JPS6326954A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPS6326954A JPS6326954A JP61170606A JP17060686A JPS6326954A JP S6326954 A JPS6326954 A JP S6326954A JP 61170606 A JP61170606 A JP 61170606A JP 17060686 A JP17060686 A JP 17060686A JP S6326954 A JPS6326954 A JP S6326954A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- manganese dioxide
- titanium disulfide
- battery
- positive electrode
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite 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
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material 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
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明はリチウム又はリチウム合金を負極活物質とする
非水系二次電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a non-aqueous secondary battery using lithium or a lithium alloy as a negative electrode active material.
口 従来の技術
この種電池の正極活物質としては種々提案されているが
、その中でも特にＴｉＳ２、Ｍｏｂ’ などの遷移金属
のカルコゲン化物は充放電時の可逆性罠優れるため注目
されている。しかしながら遷移金属のカルコゲン化物を
正極活物質として用いた場合、電池電圧は約１．５ｖ程
度と低いものであったっ一方、非水系−次電池ではＭｎ
Ｏ２／Ｌｊ系、（ＣＦ）ｎ／Ｌｉ ”ｌｆ＝、、５Ｏ
Ｃ６２／Ｌｉ＋のようＫＢＶ系の高電圧電池が実用化さ
れており、特に？１ｆｎ０２／Ｌｉ系電池は優れた保存
性、低コストであるという利点を奏する。そこで二酸化
マンガンを非水系二次電池の正極活物質として用いるこ
とが考えられるが、二酸化マンガンは深い深度の充放電
では可逆性に難点がある。BACKGROUND OF THE INVENTION A variety of positive electrode active materials have been proposed for this type of battery, among which chalcogenides of transition metals such as TiS2 and Mob' are attracting attention because of their excellent reversibility during charging and discharging. However, when chalcogenides of transition metals were used as positive electrode active materials, the battery voltage was as low as about 1.5V, whereas in non-aqueous secondary batteries Mn
O2/Lj system, (CF)n/Li "lf=,,5O
KBV type high voltage batteries such as C62/Li+ have been put into practical use, especially? The 1fn02/Li-based battery has the advantages of excellent storage stability and low cost. Therefore, it is possible to use manganese dioxide as a positive electrode active material for non-aqueous secondary batteries, but manganese dioxide has a drawback in reversibility in deep charging and discharging.
ハ 発明が解決しようとする間頭点
本発明は高電位を有し、且充放′屯の可逆性が良好な非
水系二次電池を提供することを目的とする。C. Problems to be Solved by the Invention It is an object of the present invention to provide a non-aqueous secondary battery that has a high potential and good reversibility in charging and discharging.
二 問題点を解決するだめの手段
正ｈｔａ物質として二酸化マンガンと二硫化チタンとの
混合物を用いる。2. A solution to the problem is to use a mixture of manganese dioxide and titanium disulfide as the HTA material.
ホ作 用
本発明電池における正極によれば、放電の初期段階では
酸化還元電位が貝に存在する二酸化マンガンの還元反応
が優先的に起こるが、その後電圧が低下することばよっ
て二硫化チタンの還元反応が競争反応的に生じ、次第に
優先的に起こるようになる。このため二酸化マンガンの
還元反応は浅い深度で止まり可逆性が保たれると共に、
二硫化チタンのみを正極活物質として用いる場合に比し
て高電位が得られる。According to the positive electrode in the battery of the present invention, in the initial stage of discharge, the redox potential preferentially causes the reduction reaction of manganese dioxide present in the shellfish, but after that, as the voltage decreases, the reduction reaction of titanium disulfide occurs. occurs as a competitive reaction, and gradually comes to occur preferentially. Therefore, the reduction reaction of manganese dioxide stops at a shallow depth, maintaining reversibility, and
A higher potential can be obtained than when using only titanium disulfide as the positive electrode active material.
へ実施例
正極の作成；
水分除去のために熱処理を施した化学二酸化マンガン８
７ｇと、同様に熱処理を施した二硫化チタン１１２ｇと
を乳鉢で２時間充分に混合したものを活物質とする。Preparation of Example Positive Electrode; Chemical manganese dioxide 8 subjected to heat treatment to remove moisture
7 g of titanium disulfide and 112 g of titanium disulfide, which had been heat-treated in the same manner, were sufficiently mixed in a mortar for 2 hours to obtain an active material.
この活物質８５重量部と、導電剤としてのグラファイト
１０重量部及び結着剤としてのフッ素樹脂粉末５重置部
を混合して正極合剤とし、この合剤を成型圧２トン／Ｌ
：ＩＡで直径２０．０ｍｍφに加圧成型した後、更に２
００〜３００℃の温度で真空熱処理して正極とする。85 parts by weight of this active material, 10 parts by weight of graphite as a conductive agent, and 5 parts of fluororesin powder as a binder are mixed to form a positive electrode mixture, and this mixture is molded under a molding pressure of 2 tons/L.
: After pressure molding with IA to a diameter of 20.0 mmφ, further 2
A positive electrode is prepared by vacuum heat treatment at a temperature of 00 to 300°C.
電池の作成；
負極はリチウム圧延板を直径２０．Ｏｗφに打抜いたも
のを用い、又電解液はプロピレンカーボネートと１．２
ジメトキシエタンとの博体槓混合溶媒に過塩素酸リチウ
ムを１モル／を溶解したものであり、ポリプロピレン製
の微孔性薄膜セパレータに含浸して用い、上記正極と組
合せて外径２５．０■φ、厚み″２．８＋ｎｍ、理論容
ｆｉ９０ｍＡＨのボタン型井水電解液電池を作成した。Making the battery: The negative electrode is a rolled lithium plate with a diameter of 20. A punched Owφ was used, and the electrolyte was propylene carbonate and 1.2
Lithium perchlorate is dissolved in a mixed solvent of dimethoxyethane and dimethoxyethane in an amount of 1 mole per mol. It is used by impregnating a microporous thin film separator made of polypropylene, and when combined with the above positive electrode, the outer diameter is 25.0 mm. A button-type well water electrolyte battery with a diameter of 2.8+ nm in thickness and a theoretical capacity of 90 mAH was prepared.
この電池を（ト）とする。Let this battery be (g).
次に本発明電池囚の優位性を調べるために比較電池を作
成した。Next, a comparative battery was created in order to investigate the superiority of the battery according to the present invention.
比較例１
熱処理を施した化学二酸化マンガンのみを正極活物質と
することを除いて他は本発明電池と同様の第１の比較電
池ＣＢ）を作成した。この電池の理論容量は１００ｍＡ
Ｈである。Comparative Example 1 A first comparative battery CB) was prepared which was the same as the battery of the present invention except that heat-treated chemical manganese dioxide was used as the positive electrode active material. The theoretical capacity of this battery is 100mA
It is H.
比較例２
熱処理を施し九二硫化チタンのみを正極活物質とするこ
とを除いて他は本発明電池と同様の第２の比較電池（Ｃ
）を作成した。この電池の理論容量は８０ｍＡＨである
。Comparative Example 2 A second comparative battery (C
)It was created. The theoretical capacity of this battery is 80mAH.
第１図はこれらの電池のサイクル特性比較図であり、サ
イクル条件は充ｔ［； ３．６ｍＡ×１６ Ｈｒ。Figure 1 is a comparison diagram of the cycle characteristics of these batteries, and the cycle conditions are: 3.6 mA x 16 Hr.
充？ＩＬＪ上電圧４．ＯＶ、ｉ電；３．Ｏ＋ｎＡＸ１６
）ｔｒとしサイクル数と放電終止電圧との関係を示す。Full? ILJ upper voltage 4. OV, i-den; 3. O+nAX16
) The relationship between the number of cycles and the end-of-discharge voltage is shown as tr.
第１図より本発男電ａ（Ａ）は比較電池［Ｆ］）（Ｃ）
に比して高゛屯位を有し、且すイクル牧が延びているこ
とがわかる。From Figure 1, the main battery a (A) is the comparative battery [F]) (C).
It can be seen that it has a higher elevation compared to the previous year, and that the Ikuru Maki is longer.
又、第２図は正極活物質中の二硫化チタンの混合比率を
変化させた時の、霜、池の放電終止電圧が１．０ｖｒ切
るまでのブイクル数の関係を示す。第２図より二硫化チ
タンの混合比率が２０〜８０モル％の範囲の時にサイク
ル特性が特に優れているのがわかる。Further, FIG. 2 shows the relationship between the number of buoys until the final discharge voltage of the frost and pond drops below 1.0 Vr when the mixing ratio of titanium disulfide in the positive electrode active material is changed. It can be seen from FIG. 2 that the cycle characteristics are particularly excellent when the mixing ratio of titanium disulfide is in the range of 20 to 80 mol %.
ト 発明の効果
上述した如く、正隊活物質として二酸化マンガンと二硫
化チタンとの混合物を用いることにより、篩′α位を胸
し、且サイクル特性に優れた非水系二次電池を得ること
ができるものでありその工業的価値は極めて大である。G. Effects of the Invention As mentioned above, by using a mixture of manganese dioxide and titanium disulfide as a positive active material, it is possible to obtain a non-aqueous secondary battery that suppresses the sieve'α position and has excellent cycle characteristics. It can be done, and its industrial value is extremely large.
尚、本発明は固体電解質をｆＦＪいる非水系二次電池に
も通用できるものである。Note that the present invention can also be applied to non-aqueous secondary batteries using fFJ solid electrolytes.
第１図は本発明電池と比軟電池とのサイクル特性比較図
、第２図は正極活物質中の二瀝化チタンの混合比率とサ
イクル数との関係を示す図でるる。
（イ）・・・本発明電池、［Ｆ］）（Ｃ）・・・比較電
池。FIG. 1 is a comparison diagram of the cycle characteristics of a battery of the present invention and a specific soft battery, and FIG. 2 is a diagram showing the relationship between the mixing ratio of titanium distalide in the positive electrode active material and the number of cycles. (A)...Battery of the present invention, [F]) (C)...Comparison battery.
Claims (2)
、二酸化マンガンと二硫化チタンとの混合物を活物質と
する正極とを備えた非水系二次電池。(1) A nonaqueous secondary battery comprising a negative electrode using lithium or a lithium alloy as an active material, and a positive electrode using a mixture of manganese dioxide and titanium disulfide as an active material.
８０モル％であることを特徴とする特許請求の範囲第（
１）項記載の非水系二次電池。(2) The mixing ratio of titanium disulfide in the positive electrode active material is 20~
Claim No. 80 mol% (
1) The non-aqueous secondary battery described in item 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61170606A JPS6326954A (en) | 1986-07-18 | 1986-07-18 | Nonaqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61170606A JPS6326954A (en) | 1986-07-18 | 1986-07-18 | Nonaqueous secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6326954A true JPS6326954A (en) | 1988-02-04 |
Family
ID=15907968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61170606A Pending JPS6326954A (en) | 1986-07-18 | 1986-07-18 | Nonaqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6326954A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006344395A (en) * | 2005-06-07 | 2006-12-21 | Toyota Motor Corp | Positive electrode for lithium secondary battery and its use and production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59165372A (en) * | 1983-03-09 | 1984-09-18 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
-
1986
- 1986-07-18 JP JP61170606A patent/JPS6326954A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59165372A (en) * | 1983-03-09 | 1984-09-18 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006344395A (en) * | 2005-06-07 | 2006-12-21 | Toyota Motor Corp | Positive electrode for lithium secondary battery and its use and production |
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