JPH0145180B2 - - Google Patents
Info
- Publication number
- JPH0145180B2 JPH0145180B2 JP54098905A JP9890579A JPH0145180B2 JP H0145180 B2 JPH0145180 B2 JP H0145180B2 JP 54098905 A JP54098905 A JP 54098905A JP 9890579 A JP9890579 A JP 9890579A JP H0145180 B2 JPH0145180 B2 JP H0145180B2
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- electrode active
- positive electrode
- active material
- manganese dioxide
- 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
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)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウム、ナトリウムなど軽金属の
負極活物質と非水電解質を用いる電池について、
その正極活物質の改良に関するものである。
従来、この種電池の正極活物質としては、ハロ
ゲン化物、酸化物、硫化物、酸素酸塩等種々の系
統の物質が用いられていて電力、放電特性等千差
万別である。これらの中で二酸化マンガンと弗化
炭素があり、熱処理された二酸化マンガンは、か
なり高いエネルギー密度と良好な保存性を示す
が、放電々圧特性が初期は高く、終期には低く傾
斜する欠点があつた。又、一般式（CFX）ｎにて
表わされる弗化炭素も弗素化度も弗素化度を示す
Ｘの値が0.5〜1.0の範囲のものを用いることによ
り高いエネルギー密度と良好な保存性を示し、し
かも放電々圧特性の平担性も優れているが、放電
開始直後に端子電圧が一時的に低くなる欠点があ
り、又、放電々圧も平均的にやゝ低目となる欠点
を有していた。更に二酸化マンガンは多少の導電
性はあるが、放電すると導電性が悪くなること、
及び弗化炭素も弗素化度が高いものは導電性がほ
とんど無いことから、単独で用いる場合には、カ
ーボン類を混合する必要がある。ところが弗化水
素は放電すると炭素を生成するので放電が進行す
るに従い正極活物質の電気抵抗は低くなるという
相反する欠点を有していた。
本発明は上記した両活物質の特性に着目し、こ
れらの組合せ方に適切な考慮を払うことにより単
に相加平均的な特性を得るのではなく、長所を兼
ね備えた正極活物質を得るものである。
すなわち本発明は、弗化炭素と二酸化マンガン
とからなる正極活物質により、放電の初期には二
酸化マンガンが高い電圧で放電を負担し（この間
には弗化炭素はほとんど放電に寄与せずに残つて
いる。）、放電の中期になつて二酸化マンガンの動
作電圧がやゝ低くなつてきた時点から弗化炭素が
放電に加わり、二酸化マンガンの電流負荷率が低
くなる。更に放電が進行して放電の末期になると
弗化炭素が主として電流を負担するが、残余の二
酸化マンガンも負担電流が少なくなるので分極が
少ない状態で一部の電流を負担することができ
る。従来の如くこれらの活物質を単独で用いる場
合には、導電性がないことにより黒鉛やアセチレ
ンブラツクなどのカーボン類を添加しておかなけ
ればならないが、本発明におては放電の初期に二
酸化マンガンの導電性によりその必要がなく、放
電が進行して二酸化マンガンの抵抗が高くなると
入れ替りに弗化炭素が放電することにより、生じ
た遊離炭素が導電性を与えるので両方の活物質は
良好な利用率で反応することができるようにする
ものである。つまり本発明では、正極活物質中に
バインダー剤を含有するだけでカーボン類の導電
剤を添加する必要がないため、与えられた容積又
は重量のほとんどを起電物質の充填に利用すると
ができるのでエネルギー密度を高くすることが可
能となる。
第１図は二酸化マンガン又は弗化炭素にそれぞ
れ10％の黒鉛を添加した従来の正極活物質Ａ，Ｂ
と本発明よる正極活物質Ｃ，Ｄ，Ｅを用いて組立
てたリチウム電池の放電特性図である。各電池の
正極活物質の組成を表１に示す。
The present invention relates to a battery using a negative electrode active material of a light metal such as lithium or sodium and a nonaqueous electrolyte.
The present invention relates to improvement of the positive electrode active material. Conventionally, various types of materials such as halides, oxides, sulfides, and oxyacids have been used as positive electrode active materials for this type of battery, and they have a wide variety of power and discharge characteristics. Among these, there are manganese dioxide and carbon fluoride. Heat-treated manganese dioxide shows considerably high energy density and good storage stability, but has the disadvantage that the discharge pressure characteristics are high at the beginning and slope low at the end. It was hot. Furthermore, high energy density and good storage stability can be achieved by using fluorinated carbon represented by the general formula ( CF However, it has the disadvantage that the terminal voltage temporarily decreases immediately after the start of discharge, and the average discharge voltage is rather low. had. Furthermore, although manganese dioxide has some conductivity, the conductivity deteriorates when discharged.
Also, carbon fluoride with a high degree of fluorination has almost no conductivity, so when used alone, it is necessary to mix carbon. However, since hydrogen fluoride generates carbon when it is discharged, it has the contradictory drawback that the electrical resistance of the positive electrode active material decreases as the discharge progresses. The present invention focuses on the characteristics of both of the above-mentioned active materials, and by giving appropriate consideration to how to combine them, it is possible to obtain a positive electrode active material that has both advantages, rather than simply obtaining arithmetic average characteristics. be. That is, in the present invention, by using a positive electrode active material consisting of carbon fluoride and manganese dioxide, the manganese dioxide bears the burden of the discharge at a high voltage at the beginning of the discharge (during this period, the carbon fluoride hardly contributes to the discharge and remains. ), when the operating voltage of manganese dioxide becomes somewhat low in the middle of the discharge, carbon fluoride is added to the discharge, and the current load rate of manganese dioxide becomes low. As the discharge progresses further and reaches the final stage, carbon fluoride mainly bears the burden of the current, but the remaining manganese dioxide also bears less current, so it can bear part of the current with less polarization. When these active materials are used alone as in the past, it is necessary to add carbon such as graphite or acetylene black due to their lack of conductivity, but in the present invention, carbon dioxide is added at the beginning of discharge. Due to the conductivity of manganese, this is not necessary, and as the discharge progresses and the resistance of manganese dioxide increases, carbon fluoride discharges in its place, and the free carbon generated provides conductivity, so both active materials are good. This allows us to react based on usage rates. In other words, in the present invention, since the positive electrode active material only contains a binder agent and there is no need to add a conductive agent such as carbon, most of the given volume or weight can be used for filling the electromotive material. It becomes possible to increase energy density. Figure 1 shows conventional cathode active materials A and B, which are made by adding 10% graphite to manganese dioxide or carbon fluoride, respectively.
FIG. 3 is a discharge characteristic diagram of lithium batteries assembled using positive electrode active materials C, D, and E according to the present invention. Table 1 shows the composition of the positive electrode active material of each battery.
【表】
なお、本実施例において用いた正極活物質は、
二酸化マンガンが市販の電箇二酸化マンガンを
450℃にて２時間処理したものと、弗化炭素が
（CFX）ｎにおいてＸ＝1.0のものを用いた。電池
はＧ−13型とし、リチウムを負極として用い、電
解液としては過塩素酸リチウムを１モル／溶解
したプロピレンカーボネート／1.2デイメトキシ
エタン混合溶液からなる。
第１図から明らかな如く従来の正極活物質を用
いた電池Ａ，Ｂに比較して本発明に係る電池Ｃ，
Ｄ，Ｅは、何れも放電容量が大きく、特にＤにお
いては、放電々圧、持続時間共に最も優れた特性
を示している。
第２図は弗素化度の異なる弗化炭素を用いた場
合の放電特性図であつて、表−２に示した組成の
ものを用いて第１図と同様のＧ−13型電池とした
ものである。[Table] The positive electrode active materials used in this example are as follows:
Manganese dioxide is commercially available electric manganese dioxide.
One treated at 450° C. for 2 hours and one in which carbon fluoride (CF x )n was X=1.0 were used. The battery was of the G-13 type, using lithium as the negative electrode, and the electrolyte was a mixed solution of propylene carbonate/1.2 dimethoxyethane in which 1 mole of lithium perchlorate was dissolved. As is clear from FIG. 1, compared to batteries A and B using conventional positive electrode active materials, battery C according to the present invention,
Both D and E have large discharge capacities, and D in particular exhibits the best characteristics in both discharge pressure and duration. Figure 2 is a discharge characteristic diagram when using fluorocarbons with different degrees of fluorination, and a G-13 type battery similar to that in Figure 1 was made using the composition shown in Table 2. It is.
【表】
なお二酸化マンガンと弗化炭素の混合比は、
80：20とし、放電は3KΩ負荷として高率放電の
特性を調べた。この結果、第１図の低率放電では
良好な特性であつた電池Ｄ（第２図では電池Ｆ）
よりもＸ値の低い弗化炭素を用いた電池Ｇ，Ｈの
方が優れていることが分つた。この理由は、高率
放電においては導電性の良好なＸ値の低い弗化炭
素の方が適していることを示している。以上の実
験結果から比較的低率放電を対象とする場合に
は、弗化炭素のＸ値の大きいものを20％又はやゝ
少な目に加えるのがよく、比較的高率放電を対象
とする場合には、Ｘ値が0.5又はそれ以下のもの
を用いるとよいことが分る。
上記した如く本発明は、各種の活物質の中から
放電特性と放電機構両方の面から相互に放電反応
の進行を補完しあう物質とその用法を見出したも
のであつて、単に二種類の活物質を混用してそれ
らの平均的特性を得るのではなく、相乗的効果を
得るものであり、その工業的価値は大である。[Table] The mixing ratio of manganese dioxide and carbon fluoride is
The characteristics of high-rate discharge were investigated with a ratio of 80:20 and a 3KΩ load. As a result, Battery D (Battery F in Figure 2) had good characteristics at low rate discharge in Figure 1.
It was found that batteries G and H using carbon fluoride, which have a lower X value, are superior. This reason indicates that carbon fluoride, which has good conductivity and a low X value, is more suitable for high rate discharge. From the above experimental results, when targeting a relatively low rate discharge, it is best to add fluorocarbon with a large X value of 20% or slightly less, and when targeting a relatively high rate discharge It turns out that it is better to use an X value of 0.5 or less. As described above, the present invention has discovered a material that complements the progress of a discharge reaction from among various active materials in terms of both discharge characteristics and discharge mechanism, and a method for using the same. Rather than mixing substances to obtain their average properties, this method obtains a synergistic effect, and its industrial value is great.
第１図は本発明と従来の正極を用いた電池の放
電特性図、第２図は弗化炭素のＸ値を異にした正
極活物質を使用した電池の放電特性図である。
FIG. 1 is a discharge characteristic diagram of batteries using the present invention and a conventional positive electrode, and FIG. 2 is a discharge characteristic diagram of batteries using positive electrode active materials having different X values of carbon fluoride.
Claims (1)
化炭素とよりなる正極活物質、軽金属を負極活物
質とし、正極活物質中に放電反応に寄与しない導
電剤を含有しないことを特徴とする非水電解質電
池。 ２ 固体状弗化炭素の一般式（CFX）ｎにおける
Ｘ値を0.25≦×≦0.5とする特許請求の範囲第１
項記載の非水電解質電池。[Claims] 1. A positive electrode active material consisting of manganese dioxide and solid carbon fluoride with high electrical conductivity, a light metal as a negative electrode active material, and no conductive agent that does not contribute to the discharge reaction contained in the positive electrode active material. A non-aqueous electrolyte battery featuring: 2 Claim 1 in which the value of X in the general formula ( CF
The non-aqueous electrolyte battery described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9890579A JPS5624761A (en) | 1979-08-01 | 1979-08-01 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9890579A JPS5624761A (en) | 1979-08-01 | 1979-08-01 | Nonaqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5624761A JPS5624761A (en) | 1981-03-09 |
| JPH0145180B2 true JPH0145180B2 (en) | 1989-10-02 |
Family
ID=14232141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9890579A Granted JPS5624761A (en) | 1979-08-01 | 1979-08-01 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5624761A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56107472A (en) * | 1980-01-30 | 1981-08-26 | Matsushita Electric Ind Co Ltd | Nonaqueous-electrolyte battery |
| US4327166A (en) * | 1980-09-29 | 1982-04-27 | Union Carbide Corporation | Nonaqueous cell having a MNO2 /poly-carbon fluoride cathode |
| JP3167513B2 (en) * | 1993-08-03 | 2001-05-21 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| US20050048366A1 (en) * | 2003-08-27 | 2005-03-03 | Bowden William L. | Cathode material and method of manufacturing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2140207C3 (en) * | 1971-08-11 | 1975-11-27 | Farbenfabriken Bayer Ag, 5090 Leverkusen | Stabilized aromatic polycarbonate |
| JPS5475531A (en) * | 1977-11-30 | 1979-06-16 | Hitachi Ltd | Cell |
-
1979
- 1979-08-01 JP JP9890579A patent/JPS5624761A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5624761A (en) | 1981-03-09 |
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