JPS63301467A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPS63301467A JPS63301467A JP13851987A JP13851987A JPS63301467A JP S63301467 A JPS63301467 A JP S63301467A JP 13851987 A JP13851987 A JP 13851987A JP 13851987 A JP13851987 A JP 13851987A JP S63301467 A JPS63301467 A JP S63301467A
- Authority
- JP
- Japan
- Prior art keywords
- organic electrolyte
- pyridine
- active substance
- sulfide
- metal oxide
- 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
Links
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000011149 active material Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 6
- -1 polypropylene carbonate Polymers 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 4
- 229920000379 polypropylene carbonate Polymers 0.000 abstract 4
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は正極活物質に二酸化マンガン、酸化銅等の金属
酸化物および硫化鉄、硫化銅等の金属硫化物を用い、負
極活物質にリチウム、カリウム等の１経金属金用い、′
電解液としてプロピレンカーボネート（以下ＰＣと略す
）を主としてテトラヒドロフラン、１，２−ジメトキシ
エタン（以下ＤＭＥと略す）、１．３−ジオキンラン等
のエーテルやエチレンカーボネート、γ−ブチルラクト
ン等のエステルを混合した溶媒中に過塩素酸リチウム。Detailed Description of the Invention: Industrial Field of Application The present invention uses metal oxides such as manganese dioxide and copper oxide, and metal sulfides such as iron sulfide and copper sulfide as positive electrode active materials, and uses lithium and potassium as negative electrode active materials. Using 1 grade metal gold such as '
As an electrolytic solution, propylene carbonate (hereinafter abbreviated as PC) was mainly mixed with ethers such as tetrahydrofuran, 1,2-dimethoxyethane (hereinafter abbreviated as DME), 1,3-dioquinrane, and esters such as ethylene carbonate and γ-butyl lactone. Lithium perchlorate in solvent.
ホウフッ化リチウム等の無機塩を溶解したものを用いる
有機電解質７に池、特に負極にリチウム電池いる有機電
解質リチウム電池の改良に関するものである。This invention relates to the improvement of organic electrolyte lithium batteries in which the organic electrolyte 7 uses a dissolved inorganic salt such as lithium fluoroborate, particularly in which the negative electrode is a lithium battery.
従来の技術
従来有機電解質リチウム電池の正極としては、取り扱い
の容易さから固体活物質が特に注目され、なかでも、フ
ッ化炭素、二酸化マンガン、硫化鉄。Conventional technology Conventional organic electrolyte Solid active materials have attracted particular attention as positive electrodes for lithium batteries due to their ease of handling, among them carbon fluoride, manganese dioxide, and iron sulfide.
酸化銅を正極活物質としたリチウム電池はすでに実用化
されている。しかしながらこれらの９ち、二酸化マンガ
ン、酸化銅などの金属酸化物、硫化鉄などの金属硫化物
全正極活物質とし電解液の溶媒にＰＣを単独または混合
物として用いた場合、正極活物質上でＰＣの加水分解が
おこり二酸化炭素を発生するために、長期保存、特に高
温での長期保存では電池のふくれや漏液全ひき起こした
り内部抵抗が増大したりした。従来この問題の解決法と
して、正極活物質全高温で熱処理した後に用いていたが
、熱処理温度全土けるほど７Ｅ池の放７Ｅ電圧や放１五
容量が低下するため、放′、Ｅ特性を維持するためには
二酸化炭素の発生度合いとの妥協点となる温度でしか熱
処理できなかった。Lithium batteries that use copper oxide as a positive electrode active material are already in practical use. However, if these 9 are made of metal oxides such as manganese dioxide, copper oxide, or metal sulfides such as iron sulfide as all positive electrode active materials, and if PC is used alone or as a mixture as the electrolyte solvent, PC will be removed on the positive electrode active material. Hydrolysis occurs and generates carbon dioxide, so long-term storage, especially at high temperatures, can cause the battery to swell, leak, or increase internal resistance. Conventionally, as a solution to this problem, the positive electrode active material was used after being heat-treated at a high temperature, but as the heat treatment temperature increases, the 7E voltage and 15 capacity of the 7E cell decrease, so it is necessary to maintain the radiation and E characteristics. In order to achieve this, heat treatment could only be carried out at a temperature that was a compromise with the degree of carbon dioxide generation.
発明が解決しようとする問題点
前述のような温度での正極活物質の熱処理は二酸化炭素
の発生に基づく問題の根本的な解決にはならない。すな
わち、電池の構成方法、形状や、高温保存の条件によっ
ては充分な耐漏液性や形状安定性が得られないことにな
る。本発明は１π解液にピリジン全添加することによっ
てＰＣの分解を抑制することにより、高温長期保存にお
ける耐漏液性、形状安定性を向上することを目的とする
ものである。Problems to be Solved by the Invention Heat treatment of the positive electrode active material at the above-mentioned temperatures does not fundamentally solve the problems caused by the generation of carbon dioxide. That is, sufficient leakage resistance and shape stability may not be obtained depending on the battery construction method, shape, and high-temperature storage conditions. The purpose of the present invention is to suppress the decomposition of PC by completely adding pyridine to the 1π solution, thereby improving leakage resistance and shape stability during long-term storage at high temperatures.
問題点を解決するための手段
この問題点を解決するために本発明は有機電解液中にピ
リジンを添加したものである。Means for Solving the Problem In order to solve this problem, the present invention adds pyridine to the organic electrolyte.
作用
この構成により、熱処理した正極活物質の金属酸化物も
しくは金属硫化物の表面活性サイトにピリジンを吸着さ
せることによってＰＣの吸着を阻害してＰＣの分解を抑
制したものである。これによＶ、従来と同様の正極活物
質熱処理温度でも高温長期保存における耐漏液性、形状
安定性が向」ニすることとなる。Function: With this configuration, pyridine is adsorbed to the surface active sites of the metal oxide or metal sulfide of the heat-treated positive electrode active material, thereby inhibiting the adsorption of PC and suppressing the decomposition of PC. As a result, leakage resistance and shape stability during high-temperature long-term storage are improved even at the same heat treatment temperature for the positive electrode active material as in the conventional case.
実施例
図に本発明の一実施例である円筒形ＭｎＯ２／Ｌ工１Ｅ
池の断面図を示す。The example diagram shows cylindrical MnO2/L work 1E, which is an example of the present invention.
A cross-sectional view of the pond is shown.
図中、１は正極であり、これは熱処理しｆｒ、 ＭｎＯ
２粉末に導電剤として黒鉛粉末とケッチェンブラックの
混合体を約１０重量多添加し、結着剤にポリ四弗化エチ
レンを加えて、水で十分混練した合剤を圧延ローラーで
ンート化した後、図示していないが金属性の多孔性正極
集電体に圧入した７−１・状極板からなる。使用に尚っ
てはこの極［１１０℃で一次乾燥し所定の寸法に切断し
た後、極板の中央部の合剤を所定の幅剥離し、その部分
へ正極リード板２を溶接する。この正極リード板２を溶
接した部分及び正極板１の長さ方向の一端に絶縁テープ
を表裏共に張ジつけて補強する。この正イウ板を二次乾
燥として２５０℃で真空乾燥する。このようにして作っ
た正極板の長さ方向のテープ全張っていない端部を巻芯
側にして微水性ポリプロピレン製のセパレータ３を介し
て負極リチウム４と対向させて渦巻状の電極群を構成す
る。In the figure, 1 is the positive electrode, which is heat treated fr, MnO
A mixture of graphite powder and Ketjen black was added as a conductive agent to the 2 powder by about 10% by weight, polytetrafluoroethylene was added as a binder, and the mixture was sufficiently kneaded with water and then rolled into a paste using a rolling roller. After that, although not shown, it consists of a 7-1-shaped electrode plate press-fitted into a metallic porous positive electrode current collector. In use, this electrode is first dried at 110° C., cut into a predetermined size, the mixture at the center of the electrode plate is peeled off to a predetermined width, and the positive electrode lead plate 2 is welded to that part. Insulating tape is pasted on both the front and back of the welded portion of the positive electrode lead plate 2 and one lengthwise end of the positive electrode plate 1 for reinforcement. This solid iron plate is vacuum-dried at 250° C. as secondary drying. The end of the positive electrode plate in the length direction where the tape is not fully stretched is placed on the winding core side and is opposed to the negative electrode lithium 4 through a separator 3 made of slightly aqueous polypropylene to form a spiral electrode group. do.
構成後、図示していないが負極リチウムのリード板を穴
あき底部絶縁板を介して鉄にニッケルメッキした′電池
ケース６の内底部に接するように挿入し、電極群中央部
の巻芯跡空間を利用してスポット溶接する。以上のよう
にして電極群を電池ケース５に収納した後、上部絶縁リ
ング６を配置し′ｌＴｉｌＴｉスケースれをする。Ａβ
ラミネート７を熱溶着した端子側キャップ８をカンノ、
ガスケット９をはめこんだ内側キャンプ１ｏに正極リー
ド板２全スポツト溶接した後ＰＣ： 、ＤＭＥの混合溶
媒に２体積係のピリジン全添加し０．６モル／ｌとなる
様にＬ工ＣｌＯ４を溶解した電解液の所定量を注液して
封口する。After configuration, the negative electrode lithium lead plate (not shown) is inserted through the perforated bottom insulating plate so as to be in contact with the inner bottom of the nickel-plated iron battery case 6, and the core trace space in the center of the electrode group is inserted. spot weld using. After the electrode group is housed in the battery case 5 as described above, the upper insulating ring 6 is placed and the case is removed. Aβ
Attach the terminal side cap 8 to which the laminate 7 is heat-welded.
After all spots of the positive electrode lead plate 2 are welded to the inner camp 1o in which the gasket 9 is fitted, PC: Add 2 parts by volume of pyridine to a mixed solvent of DME and dissolve ClO4 at a concentration of 0.6 mol/l. Pour a predetermined amount of the electrolyte solution into the container and seal it.
以上のようにして作製した′＋ｔＡＡサイズの電池で従
来のピリジンを添加しない″電解液を用いた一程池と比
較した。The '+tAA size battery produced as described above was compared with a conventional battery using a '+tAA size electrolyte without the addition of pyridine.
二酸化マンガンの熱処理温度全３４０℃、４００℃とし
た時のそれぞれの条件において電Ｍ液にピリジンを添加
した場合としない場合の計４通りの電池の５人、０．６
秒放電の閉回路’７１圧と７０℃で１ケ月保存したとき
の漏液率を表１に示す。The heat treatment temperature of manganese dioxide was 340°C and 400°C, respectively. 5 people tested batteries in 4 different cases with and without adding pyridine to the electrolytic M solution. 0.6
Table 1 shows the leakage rate when stored for one month at closed circuit '71 pressure of second discharge and 70°C.
（以下余 白）
人の７Ｆ池では閉回路電圧は高く放″１１（特性は良好
であるが７０℃で１ｔ月保存すると電池内部で二酸化炭
素が発生するために図１中７のＡβラミネートが押し上
げられ端子側キャップ８の内ｆｌｌ１１への刃突起に当
たって破れ、漏液するものが８０ｃｉｌ）ヲ占めた。−
万Ｃの’ｉ［池では漏液率は格段に減するが閉回路電圧
が低下した。これに対しピリジンを添加したＢ、Ｄの電
池では表１のようになった。(Left below) In a human 7F pond, the closed circuit voltage is high and the discharge is ``11 (The characteristics are good, but when stored at 70℃ for 1 ton, carbon dioxide is generated inside the battery, so the Aβ laminate shown in 7 in Figure 1 is 80 cil) were pushed up and hit the blade protrusion on the inner flll11 of the terminal side cap 8, causing it to tear and leaking.-
In the case of 10,000C, the leakage rate was significantly reduced, but the closed circuit voltage was reduced. On the other hand, in the batteries B and D to which pyridine was added, the results were as shown in Table 1.
すなわち３４０ ’Ｃで熱処理したＭｎＯ２を使った場
合（Ｂ）閉回路電圧を低下させることなく漏液率をＣの
４００℃で熱処理したＭｎＯ２に使ったＣの場合とほぼ
同等にまで低減し、また４０ｏ℃で熱処理したＭｎＯ２
全使ったＤの場合には漏液率をＯチに１で低減させるこ
とができた。In other words, when MnO2 heat-treated at 340'C is used (B), the leakage rate is reduced to almost the same as that of C using MnO2 heat-treated at 400'C without reducing the closed circuit voltage, and MnO2 heat treated at 40oC
In the case of D, which was fully used, the leakage rate could be reduced by 1.
発明の効果
以上のように本発明によれば、金属酸化物もしくは金属
硫化物を活物質とする有機電４Ｍ、質”、Ｅ池の長期保
存、特に高温での長期保存特性を向上することができる
という効果が得られる。Effects of the Invention As described above, according to the present invention, it is possible to improve long-term storage, especially long-term storage characteristics at high temperatures, of organic batteries using metal oxides or metal sulfides as active materials. You can get the effect that you can.
図は本発明の実施例における円筒形リチウム電池の断面
図である。
１・・・・・・正極、３・・・・・・セパレータ、４・
・・・・・負極リチウム、７・・・・・・Ａ７Ｉ ラミ
ネート、８・・・・・・端子側キャップＯ
代理人の氏名 弁理士 中 尾 敏 男 ほか１名ｔ−
〔向
２−− ｒ／ ｌへド・汲
３°゛−でハ゛し一ター
４−一一寒不シリ÷・う４
Ｓ−−−４ｔうで１−人
Ｇ−ｆ二るや亨で、奪う（す）フ゛
７−Ｖｌｌバキート
ざ−−ｐ？６−＋ｓ印１←・７フ゛
ｑ−−一刀°ス’７１ｖｌ−The figure is a cross-sectional view of a cylindrical lithium battery according to an embodiment of the present invention. 1...Positive electrode, 3...Separator, 4...
...Negative electrode lithium, 7...A7I laminate, 8...Terminal side cap O Name of agent: Patent attorney Toshio Nakao and one other person t-
[Direction 2--r/l to do/pull 3°--to increase one ter 4-11 Kanfushiri ÷ U4 S----4t arm 1-person G-f two or more , take away (su) fi 7-Vll Bakitoza--p? 6-+s mark 1←・7 ゛q--Ittou °su'71vl-
Claims (1)
属を活物質とする負極およびプロピレンカーボネートを
含む有機電解液を有する電池において、電解液にピリジ
ンを添加したことを特徴とする有機電解質電池。An organic electrolyte battery comprising a positive electrode using a metal oxide or sulfide as an active material, a negative electrode using a light metal as an active material, and an organic electrolyte solution containing propylene carbonate, characterized in that pyridine is added to the electrolyte solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13851987A JPS63301467A (en) | 1987-06-02 | 1987-06-02 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13851987A JPS63301467A (en) | 1987-06-02 | 1987-06-02 | Organic electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63301467A true JPS63301467A (en) | 1988-12-08 |
Family
ID=15224041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13851987A Pending JPS63301467A (en) | 1987-06-02 | 1987-06-02 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63301467A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999030379A1 (en) * | 1997-12-10 | 1999-06-17 | The Secretary Of State For Defence | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
-
1987
- 1987-06-02 JP JP13851987A patent/JPS63301467A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999030379A1 (en) * | 1997-12-10 | 1999-06-17 | The Secretary Of State For Defence | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
| GB2346256A (en) * | 1997-12-10 | 2000-08-02 | Secr Defence | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
| GB2346256B (en) * | 1997-12-10 | 2001-08-22 | Secr Defence | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
| US6596441B1 (en) | 1997-12-10 | 2003-07-22 | Qinetiq Limited | Electrochemical cell comprising a liquid organic electrolyte with a conductive additive |
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