JPH02262246A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH02262246A JPH02262246A JP1083102A JP8310289A JPH02262246A JP H02262246 A JPH02262246 A JP H02262246A JP 1083102 A JP1083102 A JP 1083102A JP 8310289 A JP8310289 A JP 8310289A JP H02262246 A JPH02262246 A JP H02262246A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- manganese dioxide
- positive electrode
- specific surface
- surface area
- 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.)
- Granted
Links
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (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−次電池、リチウム二次電池等の有
機電解液電池に関し、その正極と、電解液に添加せる溶
質との改良に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to organic electrolyte batteries such as lithium secondary batteries and lithium secondary batteries, and relates to improvements in the positive electrode and solute added to the electrolyte. It is something.
（ロ）従来の技術
ノチウム又はリチウム合金等を負極に用いた有機電解液
電池は、高エネルギー密度で低自己放電率であるという
特徴を有する。近年この種電池が広く普及するにつれて
、この種電池の高率放電特性、低温放電特性の改善が望
まれている。(b) Conventional technology Organic electrolyte batteries using notium or lithium alloys as negative electrodes are characterized by high energy density and low self-discharge rate. As this type of battery has become widespread in recent years, it has been desired to improve the high rate discharge characteristics and low temperature discharge characteristics of this type of battery.
そこで、正極活物質である二酸化マンガンの高比表面積
化を計り、電池の高率放電特性を改善することが考えら
れる。そこで、高比表面積を有する二酸化マンガンを正
極活物質として用いた場合、たしかに高率放電特性、低
温放電特性の向上が計られる。Therefore, it is possible to improve the high rate discharge characteristics of the battery by increasing the specific surface area of manganese dioxide, which is the positive electrode active material. Therefore, when manganese dioxide having a high specific surface area is used as a positive electrode active material, the high rate discharge characteristics and low temperature discharge characteristics are certainly improved.
しかしながら、高比表面積を有する二酸化マンガンは、
電池内における電極反応が進行し易いものの、有機電解
液との反応も高くなってしまう。However, manganese dioxide, which has a high specific surface area,
Although the electrode reaction within the battery progresses easily, the reaction with the organic electrolyte also becomes high.
その結果、有機電解液を分解してしまい、高温保存中に
おける電池特性の劣化が激しく、単に高比表面積を有す
る二酸化マンガンをこの種電池に用いるだけでは、電池
特性の向上が期待できない。As a result, the organic electrolyte decomposes, resulting in severe deterioration of battery characteristics during high-temperature storage, and simply using manganese dioxide, which has a high specific surface area, in this type of battery cannot be expected to improve battery characteristics.
（ハ）発明が解決しようとする課題
本発明は前記間組点に鑑みてなされたものであって、高
比表面積を有する二酸化マンガンを活を物質として正極
に用いた場合であっても、高率放電特性並びに保存特性
に優れた有機電解液電池を提供することを課題とする。(c) Problems to be Solved by the Invention The present invention has been made in view of the above-mentioned problems, and even when manganese dioxide having a high specific surface area is used as an active material in the positive electrode, a An object of the present invention is to provide an organic electrolyte battery with excellent discharge characteristics and storage characteristics.
（ニ）課題を解決するための手段
本発明の有機電解液電池は、３５０℃〜４３０℃の温度
範囲で熱処理した後の比表面積が３０１１１″／ｇ以上
である二酸化マンガンを活を物質とする正極と、フッ素
を含むリチウム塩を溶解させた有機電解液と、リチウム
もしくはリチウム合金よりなる負極とを備えたものであ
る。(d) Means for Solving the Problems The organic electrolyte battery of the present invention uses manganese dioxide as an active substance, which has a specific surface area of 30111″/g or more after heat treatment in a temperature range of 350°C to 430°C. It includes a positive electrode, an organic electrolyte in which a fluorine-containing lithium salt is dissolved, and a negative electrode made of lithium or a lithium alloy.
ここで、前記フッ素を含むリチウム塩としては、いＣＦ
ｓＳＯｓ、ＬｉＰＦ６． ＬｉＢＦ４． Ｌｉ５ｂＦｓ
、 ＬｉＡｓＦａ、ＬｉＴａＦ５． ＬｉＧｅＦ、、ｔ
、ｉ ＋Ｃ＊Ｆ＋ （５０ｇ ）＋、ＬｉｔＣｔＦｓ（
５０ｓ）＊のうちから選ばれた少なくとも１つを用いる
ことができる。Here, as the fluorine-containing lithium salt, CF
sSOs, LiPF6. LiBF4. Li5bFs
, LiAsFa, LiTaF5. LiGeF,,t
, i +C*F+ (50g)+, LitCtFs(
At least one selected from 50s)* can be used.
（ホ）作用
高比表面積を有する二酸化マンガン、即ち３５０℃〜・
１３０℃の温度範囲で熱処理した後の比表面積が３０ｍ
’／ｇ以上である二酸化マンガンを正極活物質として用
いると、この正極と電解液との接触面積が大きくなる。(e) Manganese dioxide with a high specific surface area, i.e. 350°C ~.
The specific surface area after heat treatment in the temperature range of 130℃ is 30m
When manganese dioxide having a concentration of 1/g or more is used as a positive electrode active material, the contact area between the positive electrode and the electrolyte becomes large.
その結果、正極の反応面積が増大したことになり、電池
の高率放電特性や低温放電特性が向上する（後述する第
３実験例で詳述する）。しかしながら、高温保存時の電
池の特性劣化が大きくなる。As a result, the reaction area of the positive electrode is increased, and the high rate discharge characteristics and low temperature discharge characteristics of the battery are improved (described in detail in the third experimental example below). However, the characteristics of the battery deteriorate significantly during high-temperature storage.
この特性劣化の原因は、電池内の有機電解液が正極活物
質である二酸化マンガンによって分解されるためであり
、より詳しくは、二酸化マンガンの持つ表面活性基によ
る分解に起因すると考えられる。The cause of this characteristic deterioration is that the organic electrolyte in the battery is decomposed by manganese dioxide, which is a positive electrode active material, and more specifically, it is thought to be caused by decomposition by surface active groups of manganese dioxide.
そこで、本発明の如く、フッ素を含むリチウム塩を溶解
させた有機電解液を用いることにより、前記二酸化マン
ガンの表面活性基がフッ素で置換され、活性が失なわれ
る。その結果、高比表面積を有する場合、特に比表面積
が３０ｍ’／ｇを越える二酸化マンガンを用いた場合で
あっても、保存特性の劣化が抑制される。このようにし
て、高率放電特性及び保存特性に優れた有機電解液電池
が提供できる。Therefore, by using an organic electrolytic solution in which a fluorine-containing lithium salt is dissolved, as in the present invention, the surface active groups of the manganese dioxide are replaced with fluorine, and the activity is lost. As a result, even when using manganese dioxide having a high specific surface area, especially when using manganese dioxide having a specific surface area exceeding 30 m'/g, deterioration of storage properties is suppressed. In this way, an organic electrolyte battery with excellent high rate discharge characteristics and storage characteristics can be provided.
そして、本発明において用いられるフッ素を含むリチウ
ム塩としては、ＬｉＣＦｓＳＯ＋、 ＬｉＰＦ５． Ｌ
ｉＢＦｔ、 Ｌｉ５ｂＦｉ、 ＬｉＡｓＦ５ 、 Ｌｉ
ＴａＦｇ 、 ＬｉＧｅＦｓ、Ｌｉ５ｂＦｉ （ＳＯ＋
）＋、 Ｌｉ ｒＣ４Ｆｍ （５０−） ｒのうちか
ら選ばれた少なくとも１つを用いることが好ましい。The fluorine-containing lithium salt used in the present invention includes LiCFsSO+, LiPF5. L
iBFt, Li5bFi, LiAsF5, Li
TaFg, LiGeFs, Li5bFi (SO+
)+, Li rC4Fm (50-) r is preferably used.
（へ）実施例
以下に、本発明の実施例と比較例との対比に言及し、詳
述する。(f) Examples Hereinafter, comparisons between examples of the present invention and comparative examples will be mentioned and explained in detail.
尚、ここで用いた各電池は、第１図に示す如く、扁平撃
の電池である。The batteries used here are flat-strike batteries, as shown in FIG.
次の第１実験例では、フッ素を含むリチウム塩としては
トリフルオロメタンスルホン酸リチウム（ＬｉＣＦｓＳ
Ｏｓ）を用いた場合、第２実験例では６フツ化リン酸リ
チウム（ＬｉＰＦ、）を用いた場合について詳述し、第
３実験例では二酸化マンガンの比表面積について検討し
た結果を述べる。In the following first experimental example, the lithium salt containing fluorine was lithium trifluoromethanesulfonate (LiCFsS).
In the second experimental example, the case in which lithium hexafluorophosphate (LiPF) is used will be described in detail, and in the third experimental example, the results of examining the specific surface area of manganese dioxide will be described.
◎ 第１実験例
（実施例１）
本発明の電池を、第１図に基づき詳述する。リチウム金
属からなる負極２は、負極集電体７の内面に圧着されて
おり、この負極集電体７はフェライト系ステンレス鋼（
ＳＵＳ４３０）からなる断面略コ字状の負極針５の内底
面に固着されている。１記負極缶、５の周端は、ポリプ
ロピレン製の絶縁バッキング８の内部に固定されており
、絶縁バッキング８の外周には、ステンレスからなり、
上記負極針５とは反対方向に断面略コ字状をなす正極缶
４が固定されている。この正極缶４の内底面には正極集
電体６が固定されており、この正極集電体６の内面には
正極１が固定されている。この正極１と前記負極２との
間には、電解液が含浸されたセパレータ３が介挿されて
いる。◎ First Experimental Example (Example 1) The battery of the present invention will be described in detail based on FIG. The negative electrode 2 made of lithium metal is crimped onto the inner surface of a negative electrode current collector 7, and this negative electrode current collector 7 is made of ferritic stainless steel (
It is fixed to the inner bottom surface of a negative electrode needle 5 made of SUS430 and having a substantially U-shaped cross section. The peripheral end of the negative electrode can 5 is fixed inside an insulating backing 8 made of polypropylene, and the outer periphery of the insulating backing 8 is made of stainless steel.
A positive electrode can 4 having a substantially U-shaped cross section is fixed in the opposite direction to the negative electrode needle 5 . A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 4, and a positive electrode 1 is fixed to the inner surface of this positive electrode current collector 6. A separator 3 impregnated with an electrolyte is interposed between the positive electrode 1 and the negative electrode 2.
ここで、前記正極１は、活炉物質として二酸化マンガン
を用いたものである。この二酸化マンガンは、硫酸マン
ガン、硫酸及びリン酸からなる電解浴中で電解して得た
電解二酸化マンガンを、３５０℃〜４３０℃の温度範囲
で熱処理したものであり、熱処理後の比表面積は４５ｍ
’／ｇであった。Here, the positive electrode 1 uses manganese dioxide as an active furnace material. This manganese dioxide is obtained by heat-treating electrolytic manganese dioxide obtained by electrolyzing in an electrolytic bath consisting of manganese sulfate, sulfuric acid, and phosphoric acid at a temperature range of 350°C to 430°C, and the specific surface area after heat treatment is 45 m
'/g.
この熱処理した二酸化マンガンを活物質とし、導型剤と
してのカーボン粉末と結着剤としてのフッ素樹脂粉末と
を、それぞれ８５：１０：５の重量比で混合し、加圧成
形した。そして、この加圧成形体を再度２５０℃〜３５
０℃で熱処理を行い、付着せる水分を除去し、正極１と
した。This heat-treated manganese dioxide was used as an active material, and carbon powder as a conductive agent and fluororesin powder as a binder were mixed at a weight ratio of 85:10:5, and pressure molded. Then, this pressure-molded product was heated again at 250°C to 35°C.
A heat treatment was performed at 0° C. to remove adhering moisture, and a positive electrode 1 was obtained.
一方、前記負極２は、リチウムを所定寸法に打ち抜くこ
とにより作製したものである。On the other hand, the negative electrode 2 was manufactured by punching lithium into a predetermined size.
また、有機電解液として（ま、エチレンカーボネート、
ブチレンカーボネート及び１，２−ジメトキシエタンと
の混合溶液に、トリフルオロメタンスルホン酸リチウム
（フッ素を含むリチウム塩）を１″０′／Ｉ溶解させた
ものを用いた。In addition, as an organic electrolyte (well, ethylene carbonate,
A mixed solution of butylene carbonate and 1,2-dimethoxyethane in which lithium trifluoromethanesulfonate (lithium salt containing fluorine) was dissolved at 1''0'/I was used.
これらを用いて、外径２０ｆｆＩＩ１１、厚み２，５ａ
ａ、電池容量１３０ｍＡＨを有する扁平型有機電解液電
池を得、本発明電池Ａを作製した。Using these, outer diameter 20ffII11, thickness 2.5a
a. A flat organic electrolyte battery having a battery capacity of 130 mAH was obtained, and a battery A of the present invention was fabricated.
（比較例１）
前記実施例１で用いたトリフルオロメタンスルホン酸リ
チウムに代えて、過塩素酸リチウム（濃度１”−１７，
＞を用いた以外は同様にして、比較電池Ｘを作製した。(Comparative Example 1) Lithium perchlorate (concentration 1''-17,
Comparative battery X was produced in the same manner except that > was used.
（比較例２）
前記実施例１で用いた比表面積４５ｍ’／ｇを有する二
酸化マンガン及びトリフルオロメタンスルホン酸リチウ
ムに代えて、比表面積が２０ｍ″／ｇである二酸化マン
ガン及び過塩素酸リチウム（濃度１ｍｏｆ／ｆ）を用い
た以外は同様にして、比較電池Ｙを作製した。(Comparative Example 2) Manganese dioxide and lithium perchlorate (concentration Comparative battery Y was produced in the same manner except that 1mof/f) was used.
そして、これらの電池Ａ、Ｘ、Ｙを用い、電池の放電特
性及び保存特性を比較した。Using these batteries A, X, and Y, the discharge characteristics and storage characteristics of the batteries were compared.
電池の放電特性の比較試験における条件は、電池の組立
直後、室温中において３００Ωの定抵抗で放電した時の
、電池電圧変化を測定するというものである。The conditions for the comparative test of battery discharge characteristics were to measure the change in battery voltage when discharging at a constant resistance of 300Ω at room temperature immediately after battery assembly.
一方、電池の保存特性の比較試験における条件は、電池
を組立直後、６０℃で３か月間保存（室温で４．５年間
保存した場合にほぼ相当）した後、３００Ωの定抵抗で
、放電した時の電池電圧変化を測定するというものであ
る。On the other hand, the conditions for the comparison test of battery storage characteristics were that immediately after assembly, the battery was stored at 60°C for 3 months (approximately equivalent to 4.5 years of storage at room temperature), and then discharged at a constant resistance of 300Ω. This method measures changes in battery voltage over time.
この結果を、第２図及び第３図に示す。第２図は電池の
初期放電特性図、第３図は電池の保存特性図である。The results are shown in FIGS. 2 and 3. FIG. 2 is a diagram of the initial discharge characteristics of the battery, and FIG. 3 is a diagram of the storage characteristics of the battery.
第２図の結果より、高比表面積（４５ｍ’／ｇ）を有す
る二酸化マンガンを用いた本発明電池Ａ及び比較電池Ｘ
は、比較電池Ｙに比べて、大きな放電容量を有し、放電
特性において優れたものであることがわかる。From the results shown in Fig. 2, the present invention battery A and comparative battery X using manganese dioxide having a high specific surface area (45 m'/g)
It can be seen that Comparative Battery Y has a larger discharge capacity and is superior in discharge characteristics than Comparative Battery Y.
また第３図の結果より、トリフルオロメタンスルホン酸
リチウム（フッ素を含むリチウムｋＸ）を用いた本発明
電池Ａは、過塩素酸リチウムを用いた比較電池Ｘ及び比
較電池Ｙに比べて、保存特性においても優れたものであ
ることがわかる。Furthermore, from the results shown in Fig. 3, the battery A of the present invention using lithium trifluoromethanesulfonate (lithium kX containing fluorine) has better storage characteristics than comparative batteries X and Y using lithium perchlorate. It turns out that it is also excellent.
そして、これらの結果より、本発明電池Ａは、高率放電
特性及び保存特性においても、優れたものであることが
わかる。From these results, it can be seen that the battery A of the present invention is also excellent in high rate discharge characteristics and storage characteristics.
◎ 第２実験例
（実施例２）
正極活物質として、化学二酸化マンガンを熱処理して得
た、熱処理後の比表面積が６０ｍ”／ｇである二酸化マ
ンガンを用いた。また有機電解液としては、プロピレン
カーボネートとテトラヒドロフランどの混合溶液に、６
フツ化リン酸リチウム（フッ素を含むリチウム塩）を添
加（（濃度１ ｍｏｔ／Ｒ）シたものを用いた。そして
、これらの二酸化マンガン及び電解液を用いた以外は前
記実施例１と同様にして、本発明電池Ｂを作製した。◎ Second Experimental Example (Example 2) Manganese dioxide, which was obtained by heat-treating chemical manganese dioxide and has a specific surface area of 60 m''/g after heat treatment, was used as the positive electrode active material. Also, as the organic electrolyte, In a mixed solution of propylene carbonate and tetrahydrofuran, 6
Lithium fluoride phosphate (lithium salt containing fluorine) was added ((concentration 1 mot/R)).The same procedure as in Example 1 was used except that these manganese dioxide and electrolyte were used. Thus, a battery B of the present invention was manufactured.
（比較例３）
前記実施例２で用いた６フツ化リン酸リチウムに代えて
、過塩素酸リチウム（濃度１ ｍｏｌ／ｊ）を用いた以
外は同様にして、比較電池Ｚを作製した。(Comparative Example 3) Comparative battery Z was produced in the same manner as in Example 2 except that lithium perchlorate (concentration 1 mol/j) was used instead of lithium hexafluorophosphate.
（比較例４）
前記実施例２で用いた比表面積が６０ｍ”／ｇである二
酸化マンガン及び６フツ化リン酸リチウムに代えて、比
表面積が２０ｍ″／ｇである二酸化マンガン及び過塩素
酸リチウム（濃度ｌ［［ｌｏｔ／りを用いた以外は同様
にして、比較電池Ｗを作製した。(Comparative Example 4) Manganese dioxide and lithium perchlorate having a specific surface area of 20 m''/g were used in place of the manganese dioxide and lithium hexafluorophosphate used in Example 2, which had a specific surface area of 60 m''/g. (Comparative battery W was produced in the same manner except that the concentration l[[lot/li) was used.
そして、これらの電池Ｂ、Ｚ、Ｗを用い、前記第１実験
例同様、電池の初期放電特性及び保存特性を比較とな。Using these batteries B, Z, and W, the initial discharge characteristics and storage characteristics of the batteries were compared in the same manner as in the first experimental example.
この時の電池の放電特性の比較試験における条件は、電
池を組立直後、−２０℃の低温において３にΩの定抵抗
で放電した時の、電池電圧変化を測定するというもので
ある。The conditions for this comparative test of the discharge characteristics of the batteries were to measure the change in battery voltage when the batteries were discharged at a constant resistance of 3Ω at a low temperature of -20° C. immediately after assembly.
一方、電池の保存特性の比較試験における条件は、６０
℃で３か月間保存した後、−２０℃において３にΩの定
抵抗で放電した時の、電池電圧変化を測定するというも
のである。On the other hand, the conditions in the comparative test of battery storage characteristics were 60
After storing the battery at ℃ for 3 months, the battery voltage change was measured when the battery was discharged at -20 ℃ with a constant resistance of 3Ω.
この結果を、第４図及び第５図に示す。第４図は、電池
の初期放電特性図、第５図は、電池の保存特性図である
。The results are shown in FIGS. 4 and 5. FIG. 4 is a diagram showing the initial discharge characteristics of the battery, and FIG. 5 is a diagram showing the storage characteristics of the battery.
第４図の結果より、高比表面積（６０ｍ’／ｇ）を有す
る二酸化マンガンを用いた本発明電池Ｂ及び比較電池Ｚ
は、比較電池Ｗに比べて、−２０℃という低温であって
も大きな放電容量を有し、放電特性において優れたもの
であるがわかる。From the results shown in Figure 4, it can be seen that the present invention battery B and comparative battery Z using manganese dioxide having a high specific surface area (60 m'/g)
It can be seen that compared to Comparative Battery W, Battery W had a larger discharge capacity even at a low temperature of -20°C, and was superior in discharge characteristics.
また第５図の結果より、６フツ化リン酸リチウム（フッ
素を含むリチウム塩）を用いた本発明電池Ｂは、過塩素
酸リチウムを用いた比較電池Ｚ及び比較電池Ｗに比べて
、保存特性においても優れたものであることがわかる。Furthermore, from the results shown in FIG. 5, the battery B of the present invention using lithium hexafluorophosphate (lithium salt containing fluorine) has better storage characteristics than comparative batteries Z and W using lithium perchlorate. It can be seen that it is also excellent.
そしてこれらの結果より、本発明電池Ｂは、放電特性及
び保存特性においてら、優れたものであることがわかる
。From these results, it can be seen that the battery B of the present invention has excellent discharge characteristics and storage characteristics.
◎ 第３実験例
前記第１実験例の実施例１において、使用せる二酸化マ
ンガンの比表面積を種々変化させた以外は同様にして、
電池ａ、ｂ、ｃ、ｄ及びｅを作製し、電池電圧を比較し
た。この時用いた二酸化マンガンの比表面積は、それぞ
れ１４ｍ’／ｇ、２０ｍ”７ｇ、３０ｎ＋″／ｇ、４０
ｍ″／ｇ、６０＋ｎ”／ｇであった。このような活物質
からなる正極を備えた電池を、２５℃の温度において３
００Ωの定抵抗で放電し、５時間後の各電池の放電電圧
を測定した。◎ Third Experimental Example In the same manner as in Example 1 of the first experimental example, except that the specific surface area of the manganese dioxide used was varied,
Batteries a, b, c, d, and e were produced and the battery voltages were compared. The specific surface areas of the manganese dioxide used at this time were 14 m'/g, 20 m'7 g, 30 n+'/g, and 40 m'/g, respectively.
m″/g, 60+n″/g. A battery equipped with a positive electrode made of such an active material was heated for 30 minutes at a temperature of 25°C.
The battery was discharged at a constant resistance of 00Ω, and the discharge voltage of each battery was measured after 5 hours.
この結果を、第６図に示す。第６図は、二酸化マンガン
の比表面積と、電池電圧との関係を示す図である。The results are shown in FIG. FIG. 6 is a diagram showing the relationship between the specific surface area of manganese dioxide and battery voltage.
これより比表面積３０ｍ’／ｇより小さい二酸化マンガ
ンを用いた電池ａ、ｂは、電池の放ｉｔ圧が低く、を池
容量が小さくなることがら、本発明において適するとは
言い難い。Batteries a and b using manganese dioxide having a specific surface area of less than 30 m'/g are not suitable for the present invention because the discharge pressure of the battery is low and the battery capacity is small.
しかしながら比表面積３０＋ｎ’／ｇ以上の二酸化マン
ガンを正極の活物質として用いた電池ｃ、ｄ、ｅは、電
池電圧が高く、二酸化マンガンの表面が活性であり、本
発明において好適するものである。However, batteries c, d, and e in which manganese dioxide having a specific surface area of 30+n'/g or more is used as the positive electrode active material have a high battery voltage and the surface of the manganese dioxide is active, and are suitable for the present invention.
（ト）発明の効果
本発明によれば、正極活物質として比表面積が３０ｍ’
／ｇ以上の二酸化マンガンを用い、フッ素を含むリチウ
ム塩を溶解させた有機電解液を使用することにより、初
期放電特性及び保存特性に優れた有機電解液電池を提供
することができ、その工業的価値は極めて大きい。(g) Effects of the invention According to the invention, the positive electrode active material has a specific surface area of 30 m'
By using an organic electrolyte in which a fluorine-containing lithium salt is dissolved in manganese dioxide with an amount of 2.5 g or more, it is possible to provide an organic electrolyte battery with excellent initial discharge characteristics and storage characteristics, and its industrial use. The value is extremely large.
第１図は本発明電池の縦断面図、第２図は電池の初期放
電特性図、第３図は電池の保存特性図、第４図は電池の
初期放電特性図、第５図は電池の保存特性図、・第６図
は比表面積と電池電圧との関係を示す図である。
１・・・正極、２・・・負極、３・・・セパレータ、４
・・・正極缶、５・・・負極針、６・・・正極ｉｔ体、
７・・・負極集電体、８・・・絶縁バッキング、
Ａ、Ｂ・・・本発明電池、
ｘ、ｙ、ｚ、ｗ・・・比較電池。Figure 1 is a longitudinal cross-sectional view of the battery of the present invention, Figure 2 is the initial discharge characteristic diagram of the battery, Figure 3 is the storage characteristic diagram of the battery, Figure 4 is the initial discharge characteristic diagram of the battery, and Figure 5 is the battery initial discharge characteristic diagram. Storage characteristic diagram: Figure 6 is a diagram showing the relationship between specific surface area and battery voltage. 1...Positive electrode, 2...Negative electrode, 3...Separator, 4
... Positive electrode can, 5... Negative electrode needle, 6... Positive electrode it body,
7...Negative electrode current collector, 8...Insulating backing, A, B...Battery of the present invention, x, y, z, w...Comparative battery.
Claims (2)
比表面積が３０ｍ＿２／ｇ以上である二酸化マンガンを
活物質とする正極と、フッ素を含むリチウム塩を溶解さ
せた有機電解液と、リチウムもしくはリチウム合金より
なる負極とを備えた有機電解液電池。(1) A positive electrode using manganese dioxide as an active material and having a specific surface area of 30 m_2/g or more after heat treatment in a temperature range of 350°C to 430°C, an organic electrolyte in which a fluorine-containing lithium salt is dissolved, and a lithium Or an organic electrolyte battery equipped with a negative electrode made of a lithium alloy.
Ｏ＿３、ＬｉＰＦ＿６、ＬｉＢＦ＿４、ＬｉＳｂＦ＿６
、ＬｉＡｓＦ＿６、ＬｉＴａＦ＿４、ＬｉＧｅＦ＿６、
Ｌｉ＿３Ｃ＿２Ｆ＿４（ＳＯ＿３）＿２、Ｌｉ＿２Ｃ＿
４Ｆ■（ＳＯ＿３）、のうちから選ばれた少なくとも１
つであることを特徴とする請求項（１）記載の有機電解
液電池。(2) The fluorine-containing lithium salt is LiCF_3S
O_3, LiPF_6, LiBF_4, LiSbF_6
, LiAsF_6, LiTaF_4, LiGeF_6,
Li_3C_2F_4(SO_3)_2, Li_2C_
At least one selected from 4F■(SO_3)
The organic electrolyte battery according to claim 1, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1083102A JPH07105233B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1083102A JPH07105233B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02262246A true JPH02262246A (en) | 1990-10-25 |
| JPH07105233B2 JPH07105233B2 (en) | 1995-11-13 |
Family
ID=13792831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1083102A Expired - Lifetime JPH07105233B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07105233B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311472A1 (en) * | 2007-06-13 | 2008-12-18 | Sony Corporation | Anode and method of manufacturing the same, and battery and method of manufacturing the same |
| CN113228368A (en) * | 2018-12-28 | 2021-08-06 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01120767A (en) * | 1987-11-04 | 1989-05-12 | Sony Corp | Organic electrolyte battery |
-
1989
- 1989-03-31 JP JP1083102A patent/JPH07105233B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01120767A (en) * | 1987-11-04 | 1989-05-12 | Sony Corp | Organic electrolyte battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080311472A1 (en) * | 2007-06-13 | 2008-12-18 | Sony Corporation | Anode and method of manufacturing the same, and battery and method of manufacturing the same |
| US9118062B2 (en) * | 2007-06-13 | 2015-08-25 | Sony Corporation | Anode and method of manufacturing the same, and battery and method of manufacturing the same |
| CN113228368A (en) * | 2018-12-28 | 2021-08-06 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07105233B2 (en) | 1995-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS63187569A (en) | Nonaqueous secondary battery | |
| JPH0487156A (en) | Nonaqueous electrolyte battery | |
| JP2001176558A (en) | Non-aqueous electrolyte secondary battery | |
| JP5094084B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP2705529B2 (en) | Organic electrolyte secondary battery | |
| JPH04206267A (en) | Nonaqueous electrolyte secondary battery | |
| JP3565478B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3713066B2 (en) | Non-aqueous electrolyte and lithium secondary battery using the same | |
| JP3348175B2 (en) | Organic electrolyte secondary battery | |
| JPH0462764A (en) | Nonaqueous electrolyte cell | |
| JPH05174872A (en) | Nonaqueous electrolyte secondary battery | |
| JPH04332480A (en) | Nonaqueous secondary battery | |
| JP2983580B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0495362A (en) | Nonaqueous electrolytic battery | |
| JPH05314977A (en) | Non-aqueous electrolyte secondary battery | |
| JPH06295724A (en) | Method for producing lithium manganate for lithium secondary battery | |
| JPH0343960A (en) | Nonaqueous electrolyte battery | |
| JPH02253560A (en) | Battery | |
| JP3273569B2 (en) | Lithium battery | |
| JPS63114065A (en) | Organic electrolyte secondary battery | |
| JP3620287B2 (en) | Organic electrolyte secondary battery | |
| JP3650016B2 (en) | Lithium battery | |
| JPH0475267A (en) | Nonaqueous secondary battery | |
| JP2664477B2 (en) | Non-aqueous electrolyte battery | |
| JP2638849B2 (en) | Non-aqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091113 Year of fee payment: 14 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091113 Year of fee payment: 14 |