JP2563409B2 - Organic electrolyte battery - Google Patents

Organic electrolyte battery

Info

Publication number
JP2563409B2
JP2563409B2 JP62316611A JP31661187A JP2563409B2 JP 2563409 B2 JP2563409 B2 JP 2563409B2 JP 62316611 A JP62316611 A JP 62316611A JP 31661187 A JP31661187 A JP 31661187A JP 2563409 B2 JP2563409 B2 JP 2563409B2
Authority
JP
Japan
Prior art keywords
aluminum foil
organic electrolyte
battery
lithium
electrolyte battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP62316611A
Other languages
Japanese (ja)
Other versions
JPH01159962A (en
Inventor
秀一 西野
信晴 小柴
忠 沢井
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 JP62316611A priority Critical patent/JP2563409B2/en
Publication of JPH01159962A publication Critical patent/JPH01159962A/en
Application granted granted Critical
Publication of JP2563409B2 publication Critical patent/JP2563409B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0495—Chemical alloying
    • 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
    • H01M4/405—Alloys based on lithium
    • 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)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、有機電解質電池の改良に関するものであ
る。TECHNICAL FIELD The present invention relates to improvements in organic electrolyte batteries.

従来の技術 リチウムを活物質とする有機電解質電池は、高エネル
ギー密度を有するところから、電子ウォッチをはじめ各
種の小型電子機器用電源として注目されている。しかし
ながら、金属リチウムは、非常に活性なため、リチウム
表面へのリチウム化合物膜の形成による内部抵抗の上昇
があり、さらに放電の進行に伴なってリチウム表面積の
低下による内部抵抗の上昇がみられる。このために、電
子ウォッチなどのパルス放電を行なうと、閉路電圧の低
下が大きくなり、電池容量を最後まで有効に使用できな
くなる。2. Description of the Related Art Organic electrolyte batteries using lithium as an active material have a high energy density, and thus have attracted attention as a power source for various small electronic devices such as electronic watches. However, since metallic lithium is very active, there is an increase in internal resistance due to the formation of a lithium compound film on the lithium surface, and further an increase in internal resistance due to a decrease in lithium surface area with the progress of discharge. For this reason, when pulse discharge is applied to an electronic watch or the like, the drop in the closed circuit voltage becomes large, and the battery capacity cannot be used effectively until the end.

このような欠点を解消するために、リチウム表面にア
ルミニウム箔をはりつけ、合金属の形成により発生する
負極の微細化状態やシワ状態により負極表面積を増大さ
せ、内部抵抗を低下させるという提案がなされている。In order to eliminate such drawbacks, an aluminum foil is attached to a lithium surface, and a proposal is made to increase the negative electrode surface area due to the finely sized state or wrinkle state of the negative electrode generated by the formation of a composite metal, and to reduce the internal resistance. There is.

発明が解決しようとする問題点 しかしながら、通常のアルミニウム箔を使用するとア
ルミニウム箔の体積分の電解液が減少するため、電池の
反応効率が落ち、容量低下をまねくばかりでなく、放電
末期ではパルス放電特性の低下がおこる。また、通常の
アルミニウム箔では、リチウムとの接触面積が小さいた
め、合金化が均一に進まず、正極との対向面の合金層は
粒子が粗く、負極表面積の増加も少ないため、パルス特
性も満足いくものが得られない。さらにはアルミニウム
箔の厚みが厚くなると、アルミニウム合金化されずに残
り、リチウムの反応を阻害して放電容量を低下させる等
の問題があった。Problems to be Solved by the Invention However, when a normal aluminum foil is used, the electrolytic solution for the volume of the aluminum foil is reduced, so that the reaction efficiency of the battery is lowered and not only the capacity is lowered, but also the pulse discharge is generated at the end of discharge. Deterioration of characteristics occurs. Moreover, in the case of ordinary aluminum foil, since the contact area with lithium is small, alloying does not proceed uniformly, and the alloy layer on the surface facing the positive electrode has coarse particles and the increase in the negative electrode surface area is small, so pulse characteristics are also satisfied. I can't get anything. Further, when the thickness of the aluminum foil becomes thick, there is a problem that the aluminum foil remains without being alloyed with aluminum, hindering the reaction of lithium and lowering the discharge capacity.

本発明は上記のような問題点を解消し、電解液の減少
を少なくし、合金化を均一にして内部抵抗が低く、パル
ス放電にすぐれた有機電解質電池を提供することを目的
とする。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems, to provide an organic electrolyte battery which reduces the amount of electrolytic solution, makes alloying uniform, has a low internal resistance, and is excellent in pulse discharge.

問題点を解決するための手段 このような問題点を解決するために本発明は、あらか
じめ焼鈍、好ましくは250℃以上で焼鈍されたアルミニ
ウム箔に電気化学的エッチング法でトンネルピットを設
け、これを負極のリチウム反応表面に載置して電池を構
成したものである。Means for Solving the Problems In order to solve such problems, the present invention provides a tunnel pit by an electrochemical etching method on an aluminum foil that has been annealed in advance, preferably annealed at 250 ° C. or higher, and The battery was constructed by placing it on the lithium reaction surface of the negative electrode.

作用 このアルミニウム箔を使用して電池を構成することに
より、アルミニウム箔内部のトンネルピット中に電解液
が浸透し、電解液の減少を防いで、反応効率の低下を防
ぐ。また、アルミニウム箔の表面積がトンネルピットに
より増大することにより、アルミニウムとリチウムとの
合金化のスピードが早、均一で、微細な粒子状の合金層
を得ることができ、アルミニウム箔を厚くする場合にお
いても合金化されないアルミニウム部分が発生すること
がなくなり、内部抵抗が低くパルス放電特性にすぐれ、
安定した放電特性を得ることが可能となる。Action By constructing a battery using this aluminum foil, the electrolytic solution permeates into the tunnel pits inside the aluminum foil to prevent the electrolytic solution from decreasing and the reaction efficiency from decreasing. In addition, since the surface area of the aluminum foil is increased by the tunnel pits, the alloying of aluminum and lithium can be performed quickly, and a uniform and fine particulate alloy layer can be obtained. The aluminum part that is not alloyed is not generated, the internal resistance is low and the pulse discharge characteristics are excellent.
It is possible to obtain stable discharge characteristics.

実 施 例 以下、本発明の実施例を説明する。Examples Examples of the present invention will be described below.

第１図はリチウム一酸化銅系のボタン型有機電解質電
池を示す。第１図において、１は厚さ0.2mmの片面にニ
ッケルメッキしたステンレス鋼板を打ち抜き加工した正
極ケース、２は厚さ0.2mmの片面ニッケルメッキを施し
たステンレス鋼製封口板、３は負極活物質の金属リチウ
ムで、封口板２の内面の凹凸部に圧着固定されている。
４は酸化銅を主成分とする活物質に導電材としての黒鉛
と結着剤とを混合して成形し、これを正極ケースに位置
させ、断面Ｌ字状のステンレス製正極リング５とともに
加圧圧着した正極、６は本発明によるアルミニウム箔
で、あらかじめ300℃で焼鈍したアルミニウム箔を電気
化学的にエッチングし、貫通形のトンネルピットを有し
ている。焼鈍はアルミニウム箔の酸化防止のため窒素雰
囲気中で行なった。通常冷間圧延された硬質箔では、複
雑な転位セルが存在するが、250℃以上で焼鈍すること
により再結晶粒子が成長し、エッチングの際に、表面く
ずれが少なく箔面に対して垂直でピット数の多い箔が得
られる。箔の厚みは40μｍを使用した。７はポリプロピ
レン製のセパレータ８はポリプロピレン製のガスケット
である。電解液には、炭酸プロピレンと、１−２ジメト
キシエタンとの混合有機溶媒に、過塩素酸リチウムを溶
解した液を使用し電池サイズは、外径9.5mm,高さ2.7mm
とした。FIG. 1 shows a lithium copper monoxide-based button type organic electrolyte battery. In FIG. 1, 1 is a positive electrode case made by punching out a 0.2 mm thick nickel plated stainless steel plate, 2 is a 0.2 mm thick single sided nickel plated stainless steel sealing plate, and 3 is a negative electrode active material. The metal lithium is fixed to the concave and convex portion on the inner surface of the sealing plate 2 by pressure bonding.
Reference numeral 4 is a mixture of an active material containing copper oxide as a main component, graphite as a conductive material, and a binder, which is then molded, placed in a positive electrode case, and pressed together with a positive electrode ring 5 made of stainless steel having an L-shaped cross section. The deposited positive electrode, 6 is an aluminum foil according to the present invention, which has a through-hole tunnel pit formed by electrochemically etching an aluminum foil previously annealed at 300 ° C. Annealing was performed in a nitrogen atmosphere to prevent oxidation of the aluminum foil. Normally, in cold-rolled hard foil, there are complicated dislocation cells, but recrystallized grains grow by annealing at 250 ° C or higher, and during etching, there is little surface deformation and it is perpendicular to the foil surface. A foil with a large number of pits can be obtained. The thickness of the foil used was 40 μm. 7 is a polypropylene separator 8 is a polypropylene gasket. The electrolyte used is a solution of lithium perchlorate dissolved in a mixed organic solvent of propylene carbonate and 1-2 dimethoxyethane, and the battery size is 9.5 mm in outer diameter and 2.7 mm in height.
And

第２図イ，ロは、本発明によるアルミニウム箔の表面
の金属組織と断面の金属組織を示す写真である。2A and 2B are photographs showing the metallographic structure of the surface and the metallographic structure of the cross section of the aluminum foil according to the present invention.

第３図は上記サイズの電池を温度20℃下で30KΩの負
荷をつないで放電した場合の特性を示す。図中Ａは、本
発明のアルミニウム箔を使用した電池、Ｂは通常のアル
ミニウム箔を使用した電池、Ｃはアルミニウム箔を使用
しない電池の放電曲線である。Fig. 3 shows the characteristics when the above size battery was discharged by connecting a load of 30 KΩ at a temperature of 20 ° C. In the figure, A is a battery using the aluminum foil of the present invention, B is a battery using a normal aluminum foil, and C is a discharge curve of a battery not using the aluminum foil.

第４図は、−10℃下で5KΩの負荷を毎秒7.8msecか
け、72時間後の閉路電圧を放電深度別に示したもので、
図中Ａは本発明のアルミニウム箔を使用した電池、Ｂは
通常のアルミニウム箔を使用した電池、Ｃはアルミニウ
ム箔を使用しない電池である。Fig. 4 shows the load voltage of 5 KΩ at -10 ℃ for 7.8 msec / sec, and the closed circuit voltage after 72 hours by discharge depth.
In the figure, A is a battery using the aluminum foil of the present invention, B is a battery using a normal aluminum foil, and C is a battery not using the aluminum foil.

なお実施例では、正極活物質に酸化銅を使用した例に
ついて述べたが、正極にフッ化黒鉛，二酸化マンガン，
硫化鉄，酸化ビスマス等を使用した場合でも同様な効果
が得られた。It should be noted that in the examples, an example in which copper oxide was used as the positive electrode active material was described, but fluorinated graphite, manganese dioxide,
Similar effects were obtained when iron sulfide, bismuth oxide, etc. were used.

発明の効果 以上のように、あらかじめ250℃以上で焼鈍されたア
ルミニウム箔を電気化学的エッチングでトンネルピット
を設け、これを負極リチウムの反応表面に載置すること
によって、放電中の内部抵抗が低く、パルス特性にすぐ
れた有機電解質電池が得られた。Effects of the Invention As described above, by providing a tunnel pit by electrochemical etching of an aluminum foil that has been annealed in advance at 250 ° C. or higher, and mounting it on the reaction surface of the negative electrode lithium, the internal resistance during discharge is reduced. Thus, an organic electrolyte battery having excellent pulse characteristics was obtained.

【図面の簡単な説明】[Brief description of drawings]

第１図は本発明の実施例による有機電解質電池の縦断面
図、第２図イは本発明によるアルミニウム箔の表面の金
属組織を示す写真、第２図ロは同アルミニウム箔の断面
の金属組織を示す写真、第３図は放電カーブを示す図、
第４図は放電深度別の閉路電圧を示す図である。 １……正極ケース、２……封口板、３……負極、４……
正極、５……正極リング、６……アルミニウム箔、７…
…セパレータ、８……ガスケット。FIG. 1 is a longitudinal sectional view of an organic electrolyte battery according to an embodiment of the present invention, FIG. 2A is a photograph showing a metallographic structure of a surface of an aluminum foil according to the present invention, and FIG. 2B is a metallographic structure of a cross section of the aluminum foil. Showing the discharge curve, Fig. 3 shows the discharge curve,
FIG. 4 is a diagram showing the closed circuit voltage for each depth of discharge. 1 ... Positive case, 2 ... Sealing plate, 3 ... Negative electrode, 4 ...
Positive electrode, 5 ... Positive electrode ring, 6 ... Aluminum foil, 7 ...
… Separator, 8 …… Gasket.

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】リチウムを活物質とする負極と、有機電解
質と正極とからなる電池であって、負極の反対側表面
に、電気化学的エッチング法による貫通形のトンネルピ
ットを有するアルミニウム箔を載置したことを特徴とす
る有機電解質電池。1. A battery comprising a negative electrode using lithium as an active material, an organic electrolyte and a positive electrode, wherein an aluminum foil having a through tunnel pit formed by an electrochemical etching method is mounted on the surface opposite to the negative electrode. An organic electrolyte battery characterized by being placed. 【請求項２】電気化学的エッチングを行なうアルミニウ
ム箔が、あらかじめ焼鈍されたものであることを特徴と
する特許請求の範囲第１項に記載の有機電解質電池。2. The organic electrolyte battery according to claim 1, wherein the aluminum foil to be electrochemically etched is annealed in advance.
JP62316611A 1987-12-15 1987-12-15 Organic electrolyte battery Expired - Lifetime JP2563409B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP62316611A JP2563409B2 (en) 1987-12-15 1987-12-15 Organic electrolyte battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62316611A JP2563409B2 (en) 1987-12-15 1987-12-15 Organic electrolyte battery

Publications (2)

Publication Number Publication Date
JPH01159962A JPH01159962A (en) 1989-06-22
JP2563409B2 true JP2563409B2 (en) 1996-12-11

Family

ID=18078996

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62316611A Expired - Lifetime JP2563409B2 (en) 1987-12-15 1987-12-15 Organic electrolyte battery

Country Status (1)

Country Link
JP (1) JP2563409B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2844829B2 (en) * 1990-04-18 1999-01-13 松下電器産業株式会社 Organic electrolyte primary battery
KR20030042841A (en) * 2001-11-24 2003-06-02 핀튜브텍(주) Intercooler For Diesel Engine And Fin-Tube Manufacturing Method

Also Published As

Publication number Publication date
JPH01159962A (en) 1989-06-22

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