JPS6226151B2 - - Google Patents
Info
- Publication number
- JPS6226151B2 JPS6226151B2 JP54015834A JP1583479A JPS6226151B2 JP S6226151 B2 JPS6226151 B2 JP S6226151B2 JP 54015834 A JP54015834 A JP 54015834A JP 1583479 A JP1583479 A JP 1583479A JP S6226151 B2 JPS6226151 B2 JP S6226151B2
- Authority
- JP
- Japan
- Prior art keywords
- iron sulfide
- battery
- heat
- positive electrode
- treated
- 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
Links
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder 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
- 150000004763 sulfides Chemical class 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明はリチウム、マグネシウム等の軽金属を
負極活物質とし、非水系の電解液を用いる非水電
解液電池に関するものであり、特に硫化鉄をイオ
ウ雰囲気中で熱処理したるものを正極活物質とし
て用いることにより、電池特性を向上せしめるこ
とを目的とするものである。
さて、負極活物質として極めて電気陰性度の大
なる軽金属を用いるこの種電池において、正極活
物質としては金属のハロゲン化物、硫化物、酸化
物等が提案されており、且その中でも硫化鉄は資
源的にも豊富であり安価であると共に軽金属負極
とを組合せた場合、1.5V系の電池が得られ、既
存の1.5V系電池と代替しうる等の特長を有し、
極めて有望視されている。
然しながら、硫化鉄は空気中の水分と容易に反
応して酸化鉄を生成し、且この酸化鉄は電池反応
に寄与しないため満足しうる電池容量を得ること
ができなかつた。
因みに硫化鉄の試薬では数十％の酸化鉄（FeO
及びFe3O4）が混在している。
そこで本発明者は硫化鉄をイオウ雰囲気中で熱
処理した後、分析した結果酸化鉄（FeO及び
Fe3O4）はほとんど認められないことを見出し
た。
次表は市販の硫化鉄をイオウ雰囲気中で熱処理
した硫化鉄と、真空雰囲気中で熱処理した硫化鉄
とをＸ線分析した結果を示すものである。
The present invention relates to a nonaqueous electrolyte battery that uses a light metal such as lithium or magnesium as a negative electrode active material and a nonaqueous electrolyte, and in particular uses iron sulfide heat-treated in a sulfur atmosphere as a positive electrode active material. The purpose of this is to improve battery characteristics. Now, in this type of battery that uses a light metal with extremely high electronegativity as the negative electrode active material, metal halides, sulfides, oxides, etc. have been proposed as the positive electrode active material, and among these, iron sulfide is a resource. It is abundant and inexpensive, and when combined with a light metal negative electrode, a 1.5V battery can be obtained, which can replace existing 1.5V batteries.
It is viewed as extremely promising. However, iron sulfide easily reacts with moisture in the air to produce iron oxide, and this iron oxide does not contribute to battery reactions, making it impossible to obtain a satisfactory battery capacity. Incidentally, iron sulfide reagents contain several tens of percent iron oxide (FeO
and Fe 3 O 4 ) are mixed. Therefore, the present inventor heat-treated iron sulfide in a sulfur atmosphere and analyzed the results.
It was found that almost no Fe 3 O 4 ) was observed. The following table shows the results of X-ray analysis of commercially available iron sulfide heat-treated in a sulfur atmosphere and iron sulfide heat-treated in a vacuum atmosphere.
【表】
即ち、硫化鉄をイオウ雰囲気中で熱処理すれば
酸化鉄が電池活物質たる硫化鉄に還元されること
を意味する。
以下本発明の一実施例を詳述する。
負極はリチウム圧延板をアルゴン置換されたド
ライボツクス中でローラーにより0.5mm程度に圧
延し、これを20φの寸法で打抜いたものを用い
る。
正極は硫化鉄90重量％、導電剤としての黒鉛粉
末３重量％及び結着剤としてのフツ素樹脂粉末７
重量％を加えた混合粉末を加圧成型し、厚み１mm
程度で20φの寸法としたものを熱処理する。
熱処理は上記正極成型体を中央に、イオウ粉末
を周辺に配した容器を真空にし、容器を密閉した
後、300℃で３時間熱処理した。この時、容器内
はイオウ粉末より発生せる蒸気でイオウ雰囲気と
なつている。
又、電解液はプロピレンカーボネイトと1.2ジ
メトキシエタンとの等体積比混合溶媒に１モル濃
度の過塩素酸リチウムを溶解したものであり、セ
パレータにはポリプロピレン不織布を使つた。
図は本発明法により得た正極を用いた本発明電
池Ａと、真空雰囲気中において300℃で３時間熱
処理した硫化鉄正極を用いることを除いて他は同
一構造の従来電池Ｂとの20℃における5.6KΩ定
抵抗放電時の放電特性比較図を示す。
図より本発明電池によれば従来電池に比して約
10％程度電池容量が増大していることが伺える。
尚、実施例においては未処理の硫化鉄に導電剤
及び結着剤を加え、加圧成型したる後、イオウ雰
囲気中で熱処理する場合について述べたが、予じ
め硫化鉄のみをイオウ雰囲気中で熱処理したる
後、導電剤及び結着剤を加えて加圧成型し、その
後結着剤の融点付近の温度で結着させても同様の
効果が得られる。
上述した如く、本発明は非水電解液電池用正極
の製造法に係り、硫化鉄をイオウ雰囲気中で熱処
理することにより硫化鉄中に混入している酸化鉄
が電池反応に寄与する硫化鉄に還元されることに
着目し、正極活物質として硫化鉄をイオウ雰囲気
中で熱処理したるものを用いることにより電池容
量を増大させるものであり、その工業的価値は極
めて大である。[Table] This means that when iron sulfide is heat-treated in a sulfur atmosphere, iron oxide is reduced to iron sulfide, which is a battery active material. An embodiment of the present invention will be described in detail below. The negative electrode used was a lithium rolled plate rolled to about 0.5 mm with rollers in an argon-substituted dry box, and then punched out to a size of 20φ. The positive electrode contains 90% by weight of iron sulfide, 3% by weight of graphite powder as a conductive agent, and 7% by weight of fluororesin powder as a binder.
Pressure mold the mixed powder with added weight% to a thickness of 1 mm.
Heat-treat a piece with a diameter of about 20φ. The heat treatment was performed by evacuating a container in which the positive electrode molded body was placed in the center and sulfur powder was placed around the periphery, and after sealing the container, heat treatment was performed at 300° C. for 3 hours. At this time, the inside of the container has a sulfur atmosphere due to the vapor generated from the sulfur powder. The electrolytic solution was a mixture of propylene carbonate and 1.2 dimethoxyethane in an equal volume ratio and 1 molar concentration of lithium perchlorate dissolved therein, and a polypropylene nonwoven fabric was used as the separator. The figure shows the difference between battery A of the present invention, which uses a positive electrode obtained by the method of the present invention, and conventional battery B, which has the same structure except that it uses an iron sulfide positive electrode that has been heat-treated at 300°C for 3 hours in a vacuum atmosphere at 20°C. A comparison diagram of discharge characteristics during 5.6KΩ constant resistance discharge is shown. As shown in the figure, the battery of the present invention has approximately
It can be seen that the battery capacity has increased by about 10%. In the example, a conductive agent and a binder are added to untreated iron sulfide, and after pressure molding, heat treatment is performed in a sulfur atmosphere. The same effect can be obtained by heat-treating the material, adding a conductive agent and a binder, press-molding it, and then binding it at a temperature near the melting point of the binder. As mentioned above, the present invention relates to a method for manufacturing a positive electrode for a nonaqueous electrolyte battery, in which iron sulfide is heat-treated in a sulfur atmosphere to convert iron oxide mixed in the iron sulfide into iron sulfide that contributes to battery reactions. Focusing on the fact that iron sulfide is reduced, the battery capacity is increased by using iron sulfide heat-treated in a sulfur atmosphere as the positive electrode active material, and its industrial value is extremely large.
図面は本発明電池Ａと従来電池Ｂとの放電特性
比較図である。
The drawing is a comparison diagram of the discharge characteristics of the battery A of the present invention and the conventional battery B.
Claims (1)
を正極活物質として用いることを特徴とする非水
電解液電池用正極の製造法。1. A method for producing a positive electrode for a non-aqueous electrolyte battery, characterized in that iron sulfide heat-treated in a sulfur atmosphere is used as a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1583479A JPS55108171A (en) | 1979-02-13 | 1979-02-13 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1583479A JPS55108171A (en) | 1979-02-13 | 1979-02-13 | Nonaqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55108171A JPS55108171A (en) | 1980-08-19 |
| JPS6226151B2 true JPS6226151B2 (en) | 1987-06-06 |
Family
ID=11899860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1583479A Granted JPS55108171A (en) | 1979-02-13 | 1979-02-13 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55108171A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5776758A (en) * | 1980-10-31 | 1982-05-13 | Toshiba Corp | Production of positive electrode for organic solvent battery |
| JPH03152865A (en) * | 1989-11-08 | 1991-06-28 | Sanyo Electric Co Ltd | Manufacture of cell |
| KR100467454B1 (en) * | 2002-07-10 | 2005-01-24 | 삼성에스디아이 주식회사 | Positive active material composition for lithium sulfur battery and lithium sulfur battery fabricated using binder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111140A (en) * | 1974-07-18 | 1976-01-29 | Matsushita Electric Ind Co Ltd | |
| JPS52103636A (en) * | 1976-02-24 | 1977-08-31 | Du Pont | Galvanic battery using nonncompressive fes particles as cathode |
| JPS5364692A (en) * | 1976-11-20 | 1978-06-09 | Exxon Research Engineering Co | Method of making stoichiometric titanium disulfide |
-
1979
- 1979-02-13 JP JP1583479A patent/JPS55108171A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5111140A (en) * | 1974-07-18 | 1976-01-29 | Matsushita Electric Ind Co Ltd | |
| JPS52103636A (en) * | 1976-02-24 | 1977-08-31 | Du Pont | Galvanic battery using nonncompressive fes particles as cathode |
| JPS5364692A (en) * | 1976-11-20 | 1978-06-09 | Exxon Research Engineering Co | Method of making stoichiometric titanium disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55108171A (en) | 1980-08-19 |
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