JPH01307163A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH01307163A JPH01307163A JP63137824A JP13782488A JPH01307163A JP H01307163 A JPH01307163 A JP H01307163A JP 63137824 A JP63137824 A JP 63137824A JP 13782488 A JP13782488 A JP 13782488A JP H01307163 A JPH01307163 A JP H01307163A
- Authority
- JP
- Japan
- Prior art keywords
- copper oxide
- active material
- positive electrode
- lithium
- discharge
- 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 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005751 Copper oxide Substances 0.000 claims abstract description 16
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 8
- 239000011246 composite particle Substances 0.000 claims abstract description 7
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract 2
- 229910045601 alloy Inorganic materials 0.000 claims abstract 2
- -1 composed of lithium Chemical compound 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 abstract 3
- 208000028659 discharge Diseases 0.000 abstract 3
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 229910052960 marcasite Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
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、特に酸化銅／リチウム電池の
正極活物質の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to improvements in cathode active materials for organic electrolyte batteries, particularly copper oxide/lithium batteries.
従来の技術
酸化銅／リチウム電池は単位体積当りの理論電気容量が
４．２６ムｈ／ｃｃと大きく、放電電圧が１．３６〜１
．５０ Ｖであることから、汎用電池である酸化銀電池
や水銀電池との互換性を有し、しかも汎用電池に比べ保
存性、耐漏液性などに優れることから、電子ウォッチ、
電卓等の精密電子機器の電源として注目されている。The conventional copper oxide/lithium battery has a large theoretical capacity per unit volume of 4.26 μh/cc, and a discharge voltage of 1.36 to 1
．． Since it is 50 V, it is compatible with general-purpose batteries such as silver oxide batteries and mercury batteries, and has superior storage stability and leakage resistance compared to general-purpose batteries, so it is suitable for electronic watches,
It is attracting attention as a power source for precision electronic devices such as calculators.
発明が解決しようとする課題
しかし、この電池系は、電池の放電特性、特に放電の初
期に電圧が一定の値に落ち着く迄に、電圧が一時的に落
ち込むという欠点がある。この現象は、特に電子ウォッ
チなどの精密電子機器に使用する場合、ステップモータ
が作動しないといった重要な問題となる。この電圧の落
ち込み現象は、酸化銅／リチウム電池特有のものであり
、電解液を種々変えても解消されない。Problems to be Solved by the Invention However, this battery system has a drawback in the discharge characteristics of the battery, particularly in that the voltage temporarily drops before the voltage settles to a constant value at the beginning of discharge. This phenomenon poses a serious problem, especially when used in precision electronic equipment such as electronic watches, in which the step motor does not operate. This voltage drop phenomenon is unique to copper oxide/lithium batteries, and cannot be resolved even if the electrolyte is changed.
従って、この電圧の落ち込みを解消する１つの方策とし
て、酸化銅よりも高い放電電圧をもつ活物質を酸化銅と
混合し、電池の放電初期に、混合した活物質を優先的に
反応させることにより、電圧の落ち込み現象を消滅させ
ることが考えられる。Therefore, one way to eliminate this drop in voltage is to mix an active material with a higher discharge voltage than copper oxide with copper oxide, and to react preferentially with the mixed active material in the early stage of battery discharge. , it is possible to eliminate the voltage drop phenomenon.
しかし、混合活物質の場合、添加量を少くすることには
限界があり、酸化銅本来の高い電気容量を減らすことに
なる。However, in the case of mixed active materials, there is a limit to reducing the amount added, and the inherent high electric capacity of copper oxide will be reduced.
本発明は、このような酸化銅／リチウム電池特有の放電
電圧の落ち込み問題を解決するものである。The present invention solves the problem of drop in discharge voltage peculiar to copper oxide/lithium batteries.
課題を解決するための手段
この問題を解決するために本発明は、顆粒状酸化銅の表
面に、硫化第２鉄の微粉末を結着剤で固定した硫化鉄と
酸化銅とからなる複合粒子を正極活物質としたものであ
る。Means for Solving the Problem In order to solve this problem, the present invention provides composite particles consisting of iron sulfide and copper oxide, in which fine powder of ferric sulfide is fixed with a binder on the surface of granular copper oxide. was used as the positive electrode active material.
作用
この複合粒子を正極活物質に用いることにより、酸化銅
／リチウム電池特有の放電電圧の落ち込み現象を皆無に
することができると共に、正極の利用率を向上しうろこ
とが明らかとなった。It has been revealed that by using this composite particle as a positive electrode active material, it is possible to completely eliminate the drop in discharge voltage characteristic of copper oxide/lithium batteries, and to improve the utilization rate of the positive electrode.
実施例 以下、本発明の詳細な説明する。Example The present invention will be explained in detail below.
第１図は本発明の・一実施例による酸化銅／リチウム電
池の縦断面図であり、第１図において、１は厚さ０．２
ＭＭのニッケルメッキを施した８１７Ｓ４３０のステン
レス鋼製正極缶、２は厚さ０．２０の５ＵＳ３０４のス
テンレス鋼製封口板、３は正極合剤で、はぼ球状の平均
粒径１ｏｏμｍの顆粒状酸化銅１００部に、硫化第２鉄
（ｙｅｓ２）２０部を、カルボキシメチルセルローズの
５％水溶液で、ペース状にしたもので混合し、乾燥語中
において１００’Ｃで１０時間乾燥処理し得た、ＣｕＯ
とＦｅＳ２との複合粒子９ｏＭ量部に黒鉛１０重量部を
混合し、この混合物１３０Ｑを直径８．６朋に成型後、
４で示す５ＵＳ３０４ステンレス鋼製の正極リングとと
もに正極缶１内に入れ、再度成型した−６は直径６．７
Ｍ、厚さ０．９５ａの負極リチウムで、封口板２に圧着
固定したものである。６はセパレータで、ポリプロピレ
ン製の微孔フィルムを２枚使用した。７はポリプロピレ
ン製ガスケット、８は厚さ０．０５ ＭＭのポリエチレ
ン製の多孔性含液材である。電解液には炭酸プロピレン
と１．２−ジメトキシエタンを１．Ｓ：１の体積割合で
混合したものに、過塩素酸リチウムをＯＳモル／ｅ溶解
させたものを用い、正極合剤側に１ｏμｅ、負極含液材
８側に６μｌ注液している。この電池の最大外径は９．
６１１１Ｍ、総高は２．０１ｆｆｌ１１である。FIG. 1 is a longitudinal cross-sectional view of a copper oxide/lithium battery according to an embodiment of the present invention, and in FIG. 1, 1 indicates a thickness of 0.2
817S430 stainless steel positive electrode can with MM nickel plating, 2 is a 5US304 stainless steel sealing plate with a thickness of 0.20, 3 is positive electrode mixture, and spherical granular oxidation with an average particle size of 10 μm. 100 parts of copper and 20 parts of ferric sulfide (yes2) were mixed with a 5% aqueous solution of carboxymethyl cellulose in the form of a paste, and dried at 100'C for 10 hours in a dry chamber. CuO
10 parts by weight of graphite was mixed with 9 oM of composite particles of and FeS2, and after molding this mixture 130Q to a diameter of 8.6
-6, which was placed in the positive electrode can 1 together with the 5US304 stainless steel positive electrode ring shown in 4 and molded again, has a diameter of 6.7 mm.
M, a negative electrode lithium with a thickness of 0.95a, which was fixed to the sealing plate 2 by pressure. 6 is a separator, and two microporous films made of polypropylene were used. 7 is a gasket made of polypropylene, and 8 is a porous liquid-impregnated material made of polyethylene having a thickness of 0.05 MM. The electrolyte contains 1. propylene carbonate and 1,2-dimethoxyethane. Lithium perchlorate was dissolved in OS mol/e in a mixture at a volume ratio of S:1, and 1 μe and 6 μl were poured into the positive electrode mixture side and the negative electrode liquid-containing material 8 side, respectively. The maximum outer diameter of this battery is 9.
6111M, total height is 2.01ffl11.
上記構成の電池を人、正極合剤組成以外はト記購成条件
で正極活物質に市販のＣｕＯ（平均粒径８μｍ ）８０
重量部と市販（７）Ｆｅ５０（１００メツシュ通過品）
２０重量部と黒鉛１０重量部を混合した合剤１３０ツを
用いた電池をＢ、同じく正極 。A battery with the above configuration was used, and the positive electrode active material was commercially available CuO (average particle size 8 μm) 80
Part by weight and commercially available (7) Fe50 (100 mesh passed product)
A battery using 130 parts by weight of a mixture of 20 parts by weight and 10 parts by weight of graphite was used as B, which also had a positive electrode.
活物質に上記顆粒状ＱｕＯ９０重量部と黒鉛１０重承部
を混合した合剤１３０Ｑを用いた電池をＣとし、各電池
を試作し、２０°Ｃにおける１５にΩ負荷での放電を行
った。A battery using mixture 130Q, which is a mixture of 90 parts by weight of the above-mentioned granular QuO and 10 parts by weight of graphite, as an active material was designated as C. Each battery was prototyped and discharged under a load of 15Ω at 20°C.
第２図は上記ム、Ｂ、Ｃ各電池の１５にΩ負荷の放電カ
ーブを示す。顆粒状ＣｕＯを正極活物質とする電池Ｃ及
び従来市販のＣｕＯにＦ６ｓ２を混合した電池Ｂは放電
時の電圧の落ち込みが観察されるが、電池ムは観察され
なかった。FIG. 2 shows the discharge curves of the above-mentioned batteries M, B, and C under a 15Ω load. In Battery C, which uses granular CuO as the positive electrode active material, and Battery B, in which F6s2 is mixed with conventional commercially available CuO, a drop in voltage during discharge was observed, but no battery damage was observed.
発明の効果
以上のように本発明によれば、酸化銅／リチウム電池特
有の放電時の電圧の落ち込み現象を少量の硫化物の存在
により改良することができるとともに、正極利用率の向
上により考えられる放電電圧の差が観察された。Effects of the Invention As described above, according to the present invention, the voltage drop phenomenon during discharge, which is characteristic of copper oxide/lithium batteries, can be improved by the presence of a small amount of sulfide, and the positive electrode utilization rate can be improved. Differences in discharge voltage were observed.
なお実施例では、複合粒子のＣｕＯとＦｅ５０の比率は
８０重量部と２０重量部としたが、この粒子の成型性、
充填性は良く、体積当りの電気容量はＣｕＯ単独と同等
であった。In the examples, the ratio of CuO and Fe50 in the composite particles was 80 parts by weight and 20 parts by weight, but the moldability of the particles,
The filling property was good, and the electric capacity per volume was equivalent to that of CuO alone.
第１図は本発明の一実施例による有機電解質電池の縦断
面図、第２図は放電カーブを示す図である。
１・・・・・・正極缶、２・・・・・・封口板、３・・
・・・・正極、４・・・・・・正極リング、５・・・・
・・負極、６・・・・・・セパレータ、７・・・・・・
ガスケット、８・・・・・・含浸材。FIG. 1 is a longitudinal sectional view of an organic electrolyte battery according to an embodiment of the present invention, and FIG. 2 is a diagram showing a discharge curve. 1...Positive electrode can, 2...Sealing plate, 3...
...Positive electrode, 4...Positive electrode ring, 5...
...Negative electrode, 6... Separator, 7...
Gasket, 8... Impregnating material.
Claims (1)
した複合粒子を活物質とする正極と、リチウムもしくは
リチウムを主成分とする合金を活物質とする負極と、有
機電解質とからなる有機電解質電池。An organic electrolyte consisting of a positive electrode whose active material is composite particles of ferric sulfide (FeS_2) fixed on the surface of granular copper oxide, a negative electrode whose active material is lithium or an alloy mainly composed of lithium, and an organic electrolyte. electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63137824A JPH01307163A (en) | 1988-06-03 | 1988-06-03 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63137824A JPH01307163A (en) | 1988-06-03 | 1988-06-03 | Organic electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01307163A true JPH01307163A (en) | 1989-12-12 |
Family
ID=15207704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63137824A Pending JPH01307163A (en) | 1988-06-03 | 1988-06-03 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01307163A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01286253A (en) * | 1988-05-12 | 1989-11-17 | Sanyo Electric Co Ltd | Nonaqueous electrolytic battery |
-
1988
- 1988-06-03 JP JP63137824A patent/JPH01307163A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01286253A (en) * | 1988-05-12 | 1989-11-17 | Sanyo Electric Co Ltd | Nonaqueous electrolytic battery |
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