JPS6331900B2 - - Google Patents
Info
- Publication number
- JPS6331900B2 JPS6331900B2 JP54133983A JP13398379A JPS6331900B2 JP S6331900 B2 JPS6331900 B2 JP S6331900B2 JP 54133983 A JP54133983 A JP 54133983A JP 13398379 A JP13398379 A JP 13398379A JP S6331900 B2 JPS6331900 B2 JP S6331900B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- manganese dioxide
- active material
- battery
- molybdenum trioxide
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 25
- 239000007774 positive electrode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000003792 electrolyte 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
Description
【発明の詳細な説明】
本発明はリチウム、ナトリウム等の軽金属を活
物質とする負極と、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つて、正極活物質と
して二酸化マンガンと三酸化モリブデンとの混合
物を焼成して得た化合物を用いることにより電池
特性を改善することを目的とするものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous electrolyte battery using a negative electrode made of a light metal such as lithium or sodium as an active material and a non-aqueous electrolyte, and the present invention relates to a non-aqueous electrolyte battery using a non-aqueous electrolyte and manganese dioxide and trichloride as the positive electrode active material. The purpose is to improve battery characteristics by using a compound obtained by firing a mixture with molybdenum oxide.
さて、この種電池の正極活物質としては既に
種々のものが提案されているが、特に金属酸化物
は安価であること及び取扱いの容易さから有力視
されており、現に二酸化マンガンを正極活物質と
して用いる非水電解液電池が実用化されている。 Now, various materials have already been proposed as positive electrode active materials for this type of battery, but metal oxides are particularly promising because they are cheap and easy to handle, and manganese dioxide is currently being used as a positive electrode active material. Non-aqueous electrolyte batteries have been put into practical use.
而して、図に示すように三酸化モリブデン単独
Ｂを正極活物質として用いた場合には電池電圧が
２段になるという欠点を有し、一方二酸化マンガ
ン単独Ｃを正極活物質として用いた場合には二酸
化モリブデン単独に比して放電容量が小さく、且
三酸化モリブデンでは、10ｍＡ／cm2という高率放
電によつてもほとんど電圧が低下しないのに対し
二酸化マンガンは著しい低下を示すという欠点が
あつた。 As shown in the figure, when molybdenum trioxide B alone is used as the positive electrode active material, there is a drawback that the battery voltage becomes two steps, while when manganese dioxide alone C is used as the positive electrode active material. Compared to molybdenum dioxide alone, it has a smaller discharge capacity, and while molybdenum trioxide has almost no drop in voltage even when discharged at a high rate of 10 mA/cm 2 , manganese dioxide shows a significant drop in voltage. It was hot.
本発明者等は斯る点に着目して実験検討した結
果、二酸化マンガンと三酸化モリブデンとの混合
物を焼成して得た化合物を正極活物質として用い
ることにより、二酸化マンガンや三酸化モリブデ
ン単或いは二酸化マンガンと三酸化モリブデンと
の単なる混合物の場合に比して電池特性、特に放
電容量を増大しうることを見出した。 As a result of experimental studies focusing on this point, the present inventors have found that by using a compound obtained by firing a mixture of manganese dioxide and molybdenum trioxide as a positive electrode active material, manganese dioxide, monomolybdenum trioxide, or It has been found that battery characteristics, particularly discharge capacity, can be increased compared to a simple mixture of manganese dioxide and molybdenum trioxide.
本発明は上記事実に基づきなされたものであり
以下その一実施例を詳述する。 The present invention has been made based on the above facts, and one embodiment thereof will be described in detail below.
実施例
二酸化マンガン87ｇと三酸化モリブデン144ｇ
を均一になるように２時間乳鉢で十分混合し250
〜400℃で焼成する。この焼成につて例えば次述
の反応式によつてMnMoO4で表わされる化合物
が得られる。Example: 87g of manganese dioxide and 144g of molybdenum trioxide
Mix thoroughly in a mortar for 2 hours until evenly mixed.
Bake at ~400℃. In this calcination, for example, a compound represented by MnMoO 4 is obtained according to the following reaction formula.
2MnO2＋2M0O3→2MnM0O4＋O2
このようにして得られた化合物を粉砕後200メ
ツシユパスしたものを正極活物質とする。 2MnO 2 +2M 0 O 3 →2MnM 0 O 4 +O 2The thus obtained compound was crushed and passed through 200 meshes to be used as a positive electrode active material.
正極活物質90重量部、アセチレンブラツク（導
電剤）６重量部、フツ素樹脂粉末（結着剤）４重
量部を混合して正極合剤とし、この正極合剤を成
型圧３トン／cm2で直径20φの導電リング上へ加圧
成型した後、更に300℃で真空熱処理して正極と
した。 90 parts by weight of the positive electrode active material, 6 parts by weight of acetylene black (conductive agent), and 4 parts by weight of fluororesin powder (binder) are mixed to form a positive electrode mixture, and this positive electrode mixture is molded under a molding pressure of 3 tons/cm 2 After pressure molding onto a conductive ring with a diameter of 20φ, it was further vacuum heat-treated at 300°C to form a positive electrode.
負極はリチウム圧延板を直径20φに打抜いたも
のを用い、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、セパレータはポリプロピレン不織布を用
いて外径25φ、高さ2.8mmの電池を作成した。尚、
電池の組立はアルゴン雰囲気下で行つた。 The negative electrode was a lithium rolled plate punched out to a diameter of 20φ, and the electrolyte was a mixture of propylene carbonate and 1,2-dimethoxyethane in an equal volume ratio with 1 molar concentration of lithium perchlorate dissolved therein. A battery with an outer diameter of 25φ and a height of 2.8 mm was created using a polypropylene nonwoven fabric as a separator. still,
Battery assembly was performed under an argon atmosphere.
図はこの電池の5.6KΩ定負荷放電性を示し図
中Ａは本発明電池、Ｂ及びＣは夫々正極活物質と
して三酸化モリブデン単独及び二酸化マンガン単
独を用いた場合の比較電池、又Ｄは正極活物質と
して二酸化マンガンと三酸化モリブデンとを単に
混合した産合物を用いた場合の比較電池である。
この特性図より本発明電池は比較電池に比して放
電容量を増大し得ることが伺える。 The figure shows the 5.6KΩ constant load discharge performance of this battery. In the figure, A is the battery of the present invention, B and C are comparative batteries using molybdenum trioxide alone and manganese dioxide alone as the positive electrode active material, respectively, and D is the positive electrode. This is a comparative battery using a simple mixture of manganese dioxide and molybdenum trioxide as an active material.
From this characteristic diagram, it can be seen that the battery of the present invention can increase the discharge capacity compared to the comparative battery.
このように容量が改善される理由は二酸化マン
ガンと三酸化モリブデンとが焼成により互いに作
用し合つて二酸化マンガンと三酸化モリブデンの
結晶構造にひずみを生じさせ、二酸化マンガンや
三酸化モリブデン単独の場合より活性になると共
に結晶構造のひずみにより放電時正極へのリチウ
ムイオンの入りこみが容易となり活物質の利用率
が向上するためであると推察される。 The reason why the capacity is improved in this way is that manganese dioxide and molybdenum trioxide interact with each other during calcination, causing distortion in the crystal structure of manganese dioxide and molybdenum trioxide, which is better than when manganese dioxide or molybdenum trioxide is used alone. This is presumed to be because as the lithium ions become active, the distortion of the crystal structure makes it easier for lithium ions to enter the positive electrode during discharge, improving the utilization rate of the active material.
上述した如く、本発明は二酸化マンガンと三酸
化モリブデンの混合物を焼成して得た化合物を活
物質として用いることを特徴とする非水電解液電
池の正極の製造法にあり、本発明法により得た正
極活物質を用いることにより、二酸化マンガンや
二酸化モリブデン単独或いは二酸化マンガンと三
酸化モリブデンとの単なる混合物を正極活物質と
して用いる場合に比して放電容量を増大し得るも
のであり、その工業的価値は大きい。 As mentioned above, the present invention relates to a method for producing a positive electrode for a non-aqueous electrolyte battery, characterized in that a compound obtained by firing a mixture of manganese dioxide and molybdenum trioxide is used as an active material. By using a positive electrode active material, the discharge capacity can be increased compared to the case where manganese dioxide, molybdenum dioxide alone, or a simple mixture of manganese dioxide and molybdenum trioxide is used as a positive electrode active material. Great value.
図面は本発明電池の放電特性を比較電池と対比
して示す図である。
The drawing is a diagram showing the discharge characteristics of the battery of the present invention in comparison with a comparative battery.
Claims (1)
物を焼成して得た化合物を活物質として用いるこ
とを特徴とする非水電解液電池の正極の製造法。1. A method for producing a positive electrode for a non-aqueous electrolyte battery, characterized in that a compound obtained by firing a mixture of manganese dioxide and molybrine trioxide is used as an active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13398379A JPS5657260A (en) | 1979-10-16 | 1979-10-16 | Nonaqueous-electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13398379A JPS5657260A (en) | 1979-10-16 | 1979-10-16 | Nonaqueous-electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5657260A JPS5657260A (en) | 1981-05-19 |
| JPS6331900B2 true JPS6331900B2 (en) | 1988-06-27 |
Family
ID=15117638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13398379A Granted JPS5657260A (en) | 1979-10-16 | 1979-10-16 | Nonaqueous-electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5657260A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956248A (en) * | 1988-08-25 | 1990-09-11 | Sanyo Electric Co., Ltd. | Non-aqueous secondary cell |
-
1979
- 1979-10-16 JP JP13398379A patent/JPS5657260A/en active Granted
Non-Patent Citations (3)
| Title |
|---|
| GEMELIN HANDBUCH=1975 * |
| JOURNAL OF THE ELECTROCHEMICAL SOCIETY=1978 * |
| POWER SOURCES 4=1972 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5657260A (en) | 1981-05-19 |
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