JPH0326502B2 - - Google Patents
Info
- Publication number
- JPH0326502B2 JPH0326502B2 JP57078919A JP7891982A JPH0326502B2 JP H0326502 B2 JPH0326502 B2 JP H0326502B2 JP 57078919 A JP57078919 A JP 57078919A JP 7891982 A JP7891982 A JP 7891982A JP H0326502 B2 JPH0326502 B2 JP H0326502B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- discharge
- cufes
- iron disulfide
- mixture
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005486 organic electrolyte Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 8
- 229910000339 iron disulfide Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007747 plating Methods 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、有機電解質電池に係り、特にその正
極の改良に関するものである。
二硫化鉄（FeS2）を正極活物質とする有機電
解質リチウム電池は、従来のフツ化黒鉛や二酸化
マンガンなどの3V級の有機電解質リチウム電池
に比べて単位積当りの理論電気容量が約4.5Ah／
ccと極めて大きく、また放電電圧が約4.5Vで酸
化銀電池などと互換性があるなどの特徴を有して
いる。したがつて、電子ウオツチなどの電源とし
て注目されている。
電子ウオツチは、使用される電池電圧の変動が
その精度に大きな影響を与える。このため、放電
電圧の変化がより少ない電池が必要となる。しか
し、二硫化鉄を単独で正極活物質として用いた有
機電解質リチウム電池は放電電圧の平坦性に問題
がある。すなわち、この放電機構はFeS2→LixS2
→Fe＋Li2Sで、放電曲線が二段となり、前述の
ような時計の精度面での問題を有していた。
本発明は、正極活物質として二硫化鉄と
CuFeS2との混合物を用いることにより、前述の
欠点を除去したものである。
次に本発明を実施例により説明する。
次表のように、FeS2とCuFeS2とを各種の割合
で混合し、さらに導電材のアセチレンブラツクと
結着剤のポリ４フツ化エチレンを混合する。この
混合物をニツケルからなるエキスパンデツドネツ
トに連続的に加圧、充てんし、厚さ0.35mmのシー
ト状電極を作り、これを直径5.8mmに打ち抜いて
正極とした。
The present invention relates to an organic electrolyte battery, and particularly to improvements in its positive electrode. Organic electrolyte lithium batteries that use iron disulfide (FeS 2 ) as the positive electrode active material have a theoretical electrical capacity of approximately 4.5Ah per unit volume compared to conventional 3V class organic electrolyte lithium batteries such as graphite fluoride or manganese dioxide. /
It has characteristics such as being extremely large at cc, and having a discharge voltage of approximately 4.5V, making it compatible with silver oxide batteries. Therefore, it is attracting attention as a power source for electronic watches and the like. The accuracy of electronic watches is greatly affected by fluctuations in the battery voltage used. Therefore, a battery with less variation in discharge voltage is required. However, organic electrolyte lithium batteries using iron disulfide alone as a positive electrode active material have a problem in the flatness of the discharge voltage. In other words, this discharge mechanism is FeS 2 →Li x S 2
→With Fe + Li 2 S, the discharge curve became two stages, which caused the problem in terms of clock accuracy as described above. The present invention uses iron disulfide as a positive electrode active material.
By using a mixture with CuFeS 2 , the aforementioned drawbacks are eliminated. Next, the present invention will be explained by examples. As shown in the following table, FeS 2 and CuFeS 2 are mixed in various proportions, and then acetylene black as a conductive material and polytetrafluoroethylene as a binder are mixed. This mixture was continuously pressurized and filled into an expanded nickel tube to form a sheet electrode with a thickness of 0.35 mm, which was punched out to a diameter of 5.8 mm to serve as a positive electrode.
【表】
これらの正極を用いて第１図に示すボタン形電
池を組立てた。第２図において、１は厚さ0.15mm
のメツキを施したステンレス鋼からなる外径8.5
mm、高さ0.60mmの封口板、２はその内面に圧着し
た金属リチウムからなる負極である。３はポリプ
ロピレン製不織布からなるセパレータで、炭酸プ
ロピレンと１，２−ジメトキシエタンとを体積化
で１：１の割合で混合した溶媒に過塩素酸リチウ
ムを１モル／溶解させた電解液を含浸してい
る。４は前記の正極で、片面に前記のネツト５を
集電体として備えている。６は厚さ0.15mmのニツ
ケルメツキを施したステンレス鋼よりなる外径
9.5mm、高さ1.2mmのケース、７はガスケツトであ
る。
前記の各試料を用いて作製した電池を20℃にお
いて30KΩの定抵抗放電をしたときの放電曲線を
第２図に示す。
この図から明らかなように、二硫化鉄と
CuFeS2との混合物を正極活物質として用いた電
池は、放電電圧の平坦性が改良されていることが
わかる。併せて放電容量も増大している。
二硫化鉄とCuFeS2との混合物を用いることに
より、放電曲線の二段化が解消される理論的な根
拠は明らかでないが、一般的に二硫化鉄に金属酸
化物を混合した場合は、放電曲線が二段になるこ
とから、同じ硫化物であるCuFeS2を混合するこ
とにより、二硫化鉄との混成電極としてより効率
よく反応し、作動するためと考えられる。
以上のように、本発明によれば、放電電圧の平
坦性が良好となり、電子ウオツチなど機器への悪
影響を解消することができる。[Table] Using these positive electrodes, a button-shaped battery shown in FIG. 1 was assembled. In Figure 2, 1 is 0.15mm thick
Outer diameter 8.5 made of stainless steel plated with
mm, height 0.60 mm, and 2 is a negative electrode made of metallic lithium that is crimped onto the inner surface of the sealing plate. 3 is a separator made of polypropylene nonwoven fabric, which is impregnated with an electrolytic solution in which 1 mole of lithium perchlorate is dissolved in a solvent that is a mixture of propylene carbonate and 1,2-dimethoxyethane at a volume ratio of 1:1. ing. 4 is the above-mentioned positive electrode, and one side thereof is provided with the above-mentioned net 5 as a current collector. 6 is the outer diameter made of stainless steel with nickel plating with a thickness of 0.15 mm.
The case is 9.5mm long and 1.2mm high, and 7 is the gasket. FIG. 2 shows the discharge curves obtained when batteries prepared using each of the above samples were discharged at a constant resistance of 30 KΩ at 20°C. As is clear from this figure, iron disulfide and
It can be seen that the flatness of the discharge voltage is improved in the battery using the mixture with CuFeS 2 as the positive electrode active material. At the same time, the discharge capacity has also increased. The theoretical basis for eliminating the two-stage discharge curve by using a mixture of iron disulfide and CuFeS 2 is not clear, but generally speaking, when a metal oxide is mixed with iron disulfide, the discharge Since the curve has two stages, it is thought that by mixing the same sulfide, CuFeS 2 , it reacts more efficiently and operates as a hybrid electrode with iron disulfide. As described above, according to the present invention, the flatness of the discharge voltage is improved, and adverse effects on devices such as electronic watches can be eliminated.
第１図は本発明の実施例の電池の半断面図、第
２図は二硫化鉄とCuFeS2との各種混合正極を用
いた電池の放電曲線を示す。
２……負極、３……セパレータ、４……正極。
FIG. 1 is a half-sectional view of a battery according to an embodiment of the present invention, and FIG. 2 shows discharge curves of batteries using various mixed positive electrodes of iron disulfide and CuFeS 2 . 2... Negative electrode, 3... Separator, 4... Positive electrode.
Claims (1)
極を備えた有機電解質電池。1. An organic electrolyte battery with a positive electrode containing a mixture of FeS 2 and CuFeS 2 as an active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57078919A JPS58197666A (en) | 1982-05-10 | 1982-05-10 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57078919A JPS58197666A (en) | 1982-05-10 | 1982-05-10 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58197666A JPS58197666A (en) | 1983-11-17 |
| JPH0326502B2 true JPH0326502B2 (en) | 1991-04-11 |
Family
ID=13675258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57078919A Granted JPS58197666A (en) | 1982-05-10 | 1982-05-10 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58197666A (en) |
-
1982
- 1982-05-10 JP JP57078919A patent/JPS58197666A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58197666A (en) | 1983-11-17 |
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