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JPS63257183A - Nonaqueous electrolytic solution battery - Google Patents

Nonaqueous electrolytic solution battery

Info

Publication number
JPS63257183A
JPS63257183A JP9015687A JP9015687A JPS63257183A JP S63257183 A JPS63257183 A JP S63257183A JP 9015687 A JP9015687 A JP 9015687A JP 9015687 A JP9015687 A JP 9015687A JP S63257183 A JPS63257183 A JP S63257183A
Authority
JP
Japan
Prior art keywords
lithium
aluminum
battery
positive electrode
negative electrode
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
JP9015687A
Other languages
Japanese (ja)
Inventor
Chikanori Ishibashi
石橋 親典
Kazuo Moriwaki
森脇 和郎
Sanehiro Furukawa
古川 修弘
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.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric 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 Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Priority to JP9015687A priority Critical patent/JPS63257183A/en
Publication of JPS63257183A publication Critical patent/JPS63257183A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/16Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives

Landscapes

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

Abstract

PURPOSE:To suppresses the increase of an internal resistance and the increase of an open circuit voltage by adding aluminum perchlorate to a nonaqueous electrolyte solution during the storage period under high temperature and humidity. CONSTITUTION:In a nonaqueous electrolytic solution battery with a negative electrode of which lithium is used as an active material, aluminum perchlorate is added in the nonaqueous electrolytic solution. Then aluminum ions replace lithium metal and lithium-aluminum film is formed on the surface of a negative electrode. Thereby even though moisture comes in from the outside the producing reaction of an insulating film of lithium hydroxide is suppressed by a lithium-aluminum film. Moreover, aluminum ions react with impurities or active parts in the positive electrode, so that the increase of an open circuit voltage after the storage which is due to the existence of impurities and active parts in the positive electrode can be suppressed.

Description

【発明の詳細な説明】 (イ)産業上の利用分野 本発明はリチウムを活物質とする負極と、非水電解液と
、正極とを備える非水電解液電池に関するものである。
DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a nonaqueous electrolyte battery comprising a negative electrode containing lithium as an active material, a nonaqueous electrolyte, and a positive electrode.

(ロ)従来の技術 非水電解′#!電池としては、三酸化マンガンやフッ化
炭巣などを正極活物質とする3、0V糸が既に実用化さ
れており、又例えば特開昭55−137669号公報に
開示されているように酸化第二銅、二硫化鉄、三酸化ビ
スマスなどの金属化合物を正極活物質とする1、5v糸
も提案されている。
(b) Conventional technology non-aqueous electrolysis'#! As for batteries, 3.0V threads using manganese trioxide or carbon fluoride as positive electrode active materials have already been put into practical use, and oxidized carbon fibers as disclosed in JP-A-55-137669 have already been put into practical use. A 1.5V yarn using a metal compound such as dicopper, iron disulfide, or bismuth trioxide as a positive electrode active material has also been proposed.

ところで、この種電池は負極活物質として水分との反応
性に冨むリチウムを用いるため電池組立   Ic際し
ては水分の混入を阻止するように配慮されている。しか
しながら、電池保存中に外部から水分が侵入し、その水
分とリチウムとが反応してリチウム極表面に水酸化リチ
ウムよりなる絶縁被膜が生成して内部抵抗が上昇し放電
容量が低下するという問題があった。
By the way, since this type of battery uses lithium, which is highly reactive with moisture, as the negative electrode active material, care is taken to prevent moisture from entering the battery when assembling the battery Ic. However, there is a problem that moisture enters from the outside while the battery is stored, and the moisture and lithium react with each other, forming an insulating film made of lithium hydroxide on the surface of the lithium electrode, increasing the internal resistance and reducing the discharge capacity. there were.

(ハ)発明が解決しようとする問題点 本発明は非水電解液電池の保存特性を改善することを主
たる目的とする。
(c) Problems to be Solved by the Invention The main object of the present invention is to improve the storage characteristics of non-aqueous electrolyte batteries.

叉に、本発明は特VCe化第二銅、二硫化鉄、三酸化ビ
スマスなどを正極活物質とする1、5v糸電旭め保存後
の開回路電圧の上昇を抑制することを目的とする。1.
5V糸電池を組立てた場合、正、&活物質の不純物また
は活性な部分のe傳で初+91の1ノ目回路電圧は約3
.OVを示し、1,5v用の回路を組込んた電子機器を
損傷する懸念がある。
In addition, the present invention aims to suppress the increase in open circuit voltage after storage of a 1.5V yarn electrode using cupric VCe, iron disulfide, bismuth trioxide, etc. as a positive electrode active material. . 1.
When a 5V thread battery is assembled, the first circuit voltage of +91 is approximately 3
.. OV, and there is a concern that electronic equipment incorporating 1.5V circuits may be damaged.

そこで従来では゛屯a徂立後、前処理放電を行なうこと
によって初期の開回路電圧の上昇部分をカットすること
が一役に行なわnている。しかしながらこの@沌を保存
していると、又開回路電圧が上昇するという問題があっ
た。
Conventionally, therefore, it has been helpful to cut the initial increase in open circuit voltage by performing a pretreatment discharge after the voltage rises. However, when this @Chaos was stored, there was a problem in that the open circuit voltage increased.

(に)問題点を解決するための手段 本発明はリチクム全f占*質とする負極を備えた非水電
解液電池において、井水電解故に過塩索酸了Jレクムヲ
/燕加したことをイ孕倣とする。
(2) Means for Solving the Problems The present invention discloses that in a non-aqueous electrolyte battery equipped with a negative electrode made of lyticum, over-salted acid was added due to well water electrolysis. I imitate her.

八 ここで過;素峻アルミニクムの添加量としては0.01
〜0.50モル/lの@囲が好ましい。
8 Here, the amount of addition of pure aluminum is 0.01.
A range of ~0.50 mol/l is preferred.

(ホ)作 用 過塩素酸アルミニウムを電解液中に添加すると、アルミ
ニウムイオンがリチクムlI&とI!挟しリチクム負極
表曲にリチクムーアルミニクム被膜が形成されることに
なり、その結果例え外部から水分が侵入してもリチクム
ーアルミニクムaSによつ上水酸化リチクム絶縁彼膜の
生成反応が抑制される。
(e) Effect When aluminum perchlorate is added to the electrolyte, aluminum ions are released into lyticum lI& and I! A lyticum aluminicum film is formed on the negative electrode surface of the sandwiched lyticum, and as a result, even if moisture enters from the outside, a lyticum aluminicum aS prevents the formation of a lyticum hydroxide insulating film. reaction is suppressed.

更に、またアルミニウムイオンが正極中の不純物や活性
な部分と反応するため、正極中の不純物や活性な部分の
存在に起因する保存後の開回路電圧の上昇を抑制するこ
とができ、特K 1.5 V糸電池に適用して有益なる
ものである。
Furthermore, since aluminum ions react with impurities and active parts in the positive electrode, it is possible to suppress the increase in open circuit voltage after storage due to the presence of impurities and active parts in the positive electrode, and the special K1 .5 It is useful when applied to V-thread batteries.

尚、過塩素酸アルミニウムのアニオンである過塩素酸イ
オンは、一般にこの種電池の溶質として用いられている
過塩素酸リチウムと同一のアニオンであり、電池特性に
悪影響を与えることはない。
Note that perchlorate ion, which is an anion of aluminum perchlorate, is the same anion as lithium perchlorate, which is generally used as a solute in this type of battery, and does not adversely affect battery characteristics.

(へ)実施例 正極は重版特級の酸化第二銅85重量%に導電剤として
の黒鉛を10重量%、結着剤としてのフッ素楕脂粉末を
5重油%夫々加えて充分混合した後、この混合物を約2
トン/−の圧力で加圧成型して径15.0醪、厚み1.
1瓢の成型体を得、この成型体を200〜300℃の温
度で熱処理したものである。
(f) The positive electrode of the example was made by adding 10% by weight of graphite as a conductive agent and 5% of 5 heavy oil oil as a binder to 85% by weight of cupric oxide of special grade reprint, and then thoroughly mixing the mixture. Mixture approx. 2
Pressure-molded with a pressure of 15.0 tons/- and a diameter of 15.0 mm and a thickness of 1.
One gourd molded body was obtained, and this molded body was heat-treated at a temperature of 200 to 300°C.

負極はリチクム板を約0.6簡の厚みに圧延し、こりリ
チクム圧延&を径15.0簡に打抜いたものである。
The negative electrode was made by rolling a lithicum plate to a thickness of about 0.6 mm, and punching out the rolled lithic cum plate to a diameter of 15.0 mm.

110シてN 解漱rよプロピレンカーボネートと1,
2ジメトキシエタンとの混合溶媒に過塩素酸リチクム1
i、oモル/を溶解し、さらに過塩葉酸アルミニウム(
!″0.10.1モル/L&加を用い、又セパレータは
ポリプロピレン不織布を用いて直径20.0嘘、厚み2
.5■の不発明電池(4)を作成した。
110 N, disassemble propylene carbonate and 1,
1 lyticum perchlorate in a mixed solvent with 2 dimethoxyethane
Dissolve i, o mol/ and further add aluminum perchlorate folic acid (
! "0.10.1 mol/L & addition, and the separator was made of polypropylene nonwoven fabric with a diameter of 20.0 mm and a thickness of 2.
.. 5 ■ uninvented batteries (4) were created.

第1図は不発明電池の縦断1m図を示し、(1)は酸化
第二24正極であって、正極東電体!21′jfr、介
して正惟缶(3+の内屈曲に圧接されている。141は
リチクム負極であって負極果゛也俸15+を介して負極
缶(6)の内底面に圧眉されている。(7)はセパレー
タ、(8)は絶縁バンキング、19)は正極回出である
Figure 1 shows a 1m vertical cross-section of the non-invention battery, and (1) is the oxidized No. 224 positive electrode, which is the positive electrode of Toden! 21'jfr, is pressed to the inner bent side of the negative electrode can (3+). 141 is a lyticum negative electrode, which is pressed to the inner bottom surface of the negative electrode can (6) through the negative electrode electrode 15+. (7) is a separator, (8) is an insulating bank, and 19) is a positive electrode outlet.

ついで本発明電池の優位性を調べるために、電解i1&
に過塩素酸アルミニウムを添加しないことを除いて他は
本発明電池と同様の比較電池[F])を作成した。
Next, in order to investigate the superiority of the battery of the present invention, electrolytic i1&
A comparative battery [F]) was prepared which was the same as the battery of the present invention except that aluminum perchlorate was not added to the battery.

第2図はこれら電池を温度60℃、晶度90%の条件下
で保存した時の内部抵抗の経時変化を示す。
FIG. 2 shows the change in internal resistance over time when these batteries were stored at a temperature of 60° C. and a crystallinity of 90%.

又、弔5図はこれら電池を組立後、理市容重の5%を前
処理放電したのちの曲回路゛電圧の経時変化を示す。
Further, Figure 5 shows the change in voltage of the curved circuit over time after these batteries were assembled and pre-discharged to 5% of the battery capacity.

第2図及び第6図より本発明電池囚は比較電池Q3>に
比して品温、高昼下の保存時における内部抵抗の上昇及
び開回路電圧の上昇を仰1v」シうることがわかる。
From FIGS. 2 and 6, it can be seen that the battery of the present invention has a higher internal resistance and open circuit voltage than the comparative battery Q3 when stored under conditions of high product temperature and high daylight. .

又、第4図は過塩素酸アルミニウムの添加量を変化させ
、温度60℃、駐度90%の条件下で1ケ月保存した後
の電池の内部抵抗を示し、第4図より過塩素酸アルミニ
ウムの添加量としては0.01〜0.50モル/Lの範
囲が好ましいことがわかる。
In addition, Figure 4 shows the internal resistance of the battery after changing the amount of aluminum perchlorate and storing it for one month at a temperature of 60°C and a parking temperature of 90%. It can be seen that the amount of addition is preferably in the range of 0.01 to 0.50 mol/L.

ムAtcts或いは塩化アルミニウムLiAtCtaが
考えられる。しかしながら、アニオンについて云えばA
tccto4)3では電池性能にS影響のない過塩素酸
(C4OJ)  イオンであるのに対し、AtC2゜ニ
ス LiALCLm  では塩素(Ct)イオンであり
Aluminum Atcts or aluminum chloride LiAtCta can be considered. However, when it comes to anions, A
In tccto4)3, perchloric acid (C4OJ) ions have no effect on battery performance, whereas in AtC2° varnish LiALCLm, chlorine (Ct) ions are used.

この塩素イオンが、例えば内部抵抗を増大させる″等の
悪影#を及ぼすことになり好ましくない。
This chlorine ion is undesirable because it causes negative effects such as, for example, increasing internal resistance.

(ト)発明の効果 上述した如く、非水電解液に過塩素酸アルミニウムを添
加することにより、非水電解液電池の保存後における内
部抵抗の上昇を抑制することができる。又、1.5v系
の非水電解液電池においては、保存後の開回路電圧の上
!4−ヲも抑制することがでさるものであり、その工業
的価値は極めて犬である。
(G) Effects of the Invention As described above, by adding aluminum perchlorate to the non-aqueous electrolyte, it is possible to suppress the increase in internal resistance of the non-aqueous electrolyte battery after storage. Also, for 1.5V non-aqueous electrolyte batteries, the open circuit voltage after storage! It is also possible to suppress 4-wo, and its industrial value is extremely low.

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

$1図は本発明電池の縦断面図、第2図乃至第3図は本
発明電池と比較電池との電池特性比較図であって、第2
図は内部抵抗と保存期間との関係を示す図、第6図は開
回路電圧の経時変化を示す図、また第4図は過塩素酸ア
ルミニウムの添加量と内部抵抗との関係を示す図である
。 (1)・・・正極、(2)・・・正極集電体、(3)・
・・正極缶、(4)・・・リチクム負極、(5)・・・
負極集電体、(6)・・・負極缶、(7)・・・セパレ
ータ、(8)・・・絶幀バッキング、囚・・・本発明電
池、03)・・・比較′屹池。
Figure 1 is a longitudinal cross-sectional view of the battery of the present invention, and Figures 2 and 3 are comparison diagrams of battery characteristics between the battery of the present invention and a comparative battery.
Figure 6 shows the relationship between internal resistance and storage period, Figure 6 shows the change in open circuit voltage over time, and Figure 4 shows the relationship between the amount of aluminum perchlorate added and internal resistance. be. (1)...Positive electrode, (2)...Positive electrode current collector, (3)...
...Positive electrode can, (4)...Lythicum negative electrode, (5)...
Negative electrode current collector, (6)... Negative electrode can, (7)... Separator, (8)... Separate backing, Prisoner... Inventive battery, 03)... Comparison's pond.

Claims (2)

【特許請求の範囲】[Claims] (1)リチウムを活物質とする負極と、非水電解液と、
正極とを備えるものであつて、前記非水電解液に過塩素
酸アルミニウムを添加したことを特徴とする非水電解液
電池。
(1) A negative electrode using lithium as an active material, a non-aqueous electrolyte,
1. A non-aqueous electrolyte battery, comprising: a positive electrode; and aluminum perchlorate added to the non-aqueous electrolyte.
(2)前記正極の活物質が酸化第二銅、二硫化鉄、三酸
化ビスマスなどのように負極のリチウムと組合せて電池
電圧が約1.5Vを示す金属化合物よりなることを特徴
とする特許請求の範囲第(1)項記載の非水電解液電池
(2) A patent characterized in that the active material of the positive electrode is made of a metal compound such as cupric oxide, iron disulfide, bismuth trioxide, etc., which exhibits a battery voltage of about 1.5 V when combined with lithium of the negative electrode. A non-aqueous electrolyte battery according to claim (1).
JP9015687A 1987-04-13 1987-04-13 Nonaqueous electrolytic solution battery Pending JPS63257183A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9015687A JPS63257183A (en) 1987-04-13 1987-04-13 Nonaqueous electrolytic solution battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9015687A JPS63257183A (en) 1987-04-13 1987-04-13 Nonaqueous electrolytic solution battery

Publications (1)

Publication Number Publication Date
JPS63257183A true JPS63257183A (en) 1988-10-25

Family

ID=13990630

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9015687A Pending JPS63257183A (en) 1987-04-13 1987-04-13 Nonaqueous electrolytic solution battery

Country Status (1)

Country Link
JP (1) JPS63257183A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5432030A (en) * 1993-12-02 1995-07-11 Eveready Battery Company, Inc. Li/FeS2 cell employing a solvent mixture of diox, DME and 3ME20X with a lithium-based solute
US5514491A (en) * 1993-12-02 1996-05-07 Eveready Battery Company, Inc. Nonaqueous cell having a lithium iodide-ether electrolyte
US5691083A (en) * 1995-06-07 1997-11-25 Eveready Battery Company, Inc. Potassium ion additives for voltage control and performance improvement in nonaqueous cells
US6218054B1 (en) 1991-08-13 2001-04-17 Eveready Battery Company, Inc. Dioxolane and dimethoxyethane electrolyte solvent system
US6482548B2 (en) * 2000-12-18 2002-11-19 Telcordia Technologies, Inc. Lithium-aluminum dual-cation rechargeable electrochemical battery cell
JP2007227221A (en) * 2006-02-24 2007-09-06 Sony Corp Lithium/iron disulphide primary cell
US9912008B2 (en) 2013-11-12 2018-03-06 Intec Energy Storage Corporation Electrical energy storage device with non-aqueous electrolyte

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218054B1 (en) 1991-08-13 2001-04-17 Eveready Battery Company, Inc. Dioxolane and dimethoxyethane electrolyte solvent system
US5432030A (en) * 1993-12-02 1995-07-11 Eveready Battery Company, Inc. Li/FeS2 cell employing a solvent mixture of diox, DME and 3ME20X with a lithium-based solute
US5514491A (en) * 1993-12-02 1996-05-07 Eveready Battery Company, Inc. Nonaqueous cell having a lithium iodide-ether electrolyte
US5691083A (en) * 1995-06-07 1997-11-25 Eveready Battery Company, Inc. Potassium ion additives for voltage control and performance improvement in nonaqueous cells
US6482548B2 (en) * 2000-12-18 2002-11-19 Telcordia Technologies, Inc. Lithium-aluminum dual-cation rechargeable electrochemical battery cell
JP2007227221A (en) * 2006-02-24 2007-09-06 Sony Corp Lithium/iron disulphide primary cell
JP4539584B2 (en) * 2006-02-24 2010-09-08 ソニー株式会社 Lithium / iron disulfide primary battery
US9912008B2 (en) 2013-11-12 2018-03-06 Intec Energy Storage Corporation Electrical energy storage device with non-aqueous electrolyte

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