JPS60216461A - Cell - Google Patents

Abstract

PURPOSE:To allow a cell to be used under the high-temperature environment by using an electrolyte made of metal ions of I or II group and a nonaqueous electrolyte mainly composed of a specific copolymer made of dimethyl siloxane and polyethylene oxide. CONSTITUTION:An electrolyte made of metal ions of I or II group is used, and a nonaqueous electrolyte mainly composed of a copolymer made of dimethyl siloxane and polyethylene oxide as expressed by a constitutional formula is used. This nonaqueous electrolyte has no boiling point, and its vapor pressure is low even at a high-temperature. Accordingly, even if a cell is stored or used at a high-temperature, the internal pressure of the cell never rises, and the deterioration of the characteristics such as leakage or blowout does not occur.

Description

【発明の詳細な説明】 （技術分野） 本発明は電池に関し、とくに高温使用に耐えうる非水電
解液を有する電波に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a battery, and particularly to a radio wave having a non-aqueous electrolyte that can withstand high-temperature use.

（従来技術） リチウム、マグネシウムなどの軽金属を負極活物質とし
、フッ化岸素、硫化銅りロム酸銀、二酸化マンガンなど
を正極活物質とし、非水系の有機電解液を用いる有機電
解質電池は、高エネルギー密度を有する電池として知ら
れ、なかでもリチウム電池は小型あるいは携帯用電子機
器のめざましい普及に伴って急速にその需要をのばして
いる。(Prior art) Organic electrolyte batteries use light metals such as lithium and magnesium as negative electrode active materials, carbon fluoride, copper sulfide silver bromate, manganese dioxide, etc. as positive electrode active materials, and use a non-aqueous organic electrolyte. BACKGROUND OF THE INVENTION Lithium batteries are known as batteries with high energy density, and demand for lithium batteries is rapidly increasing due to the remarkable spread of small and portable electronic devices.

電子機器の普及に伴い、その使用環境や使用条件も多岐
にわたり、特殊な環境における使用可能な電池も必要と
なっている。例えば高温環境もそのひとつであり、エン
ジンやモーター、あるいは熱源などの付近で使用される
電子機器が増え、これに使用される高い信頼性を有する
電池が必要となっている。With the spread of electronic devices, the environments and conditions in which they are used are becoming more diverse, and there is a need for batteries that can be used in special environments. For example, high-temperature environments are one of them, and as more and more electronic devices are used near engines, motors, or heat sources, there is a need for highly reliable batteries for use in these devices.

従来の有機電解質電池は他の水溶液系の電池に比べて使
用温度範囲の広いものであるが、使用される有機溶剤の
沸点と蒸気圧の関係で一般的に温度６０〜８０℃が高温
側の使用限界になっている。Conventional organic electrolyte batteries have a wider operating temperature range than other aqueous batteries, but due to the relationship between the boiling point and vapor pressure of the organic solvent used, the high temperature range is generally 60 to 80°C. It has reached its usage limit.

このため従来の電池はこの限界温度以上で使用した場合
には、電池の内圧が上昇し漏液を生じたり、電池性能の
劣化を招く。さらには電池が破裂するなど様々な障害を
起し、信頼性に欠けるものであった。また、使用温度範
囲内ではあっても、高い温度側での長期保存や長期使用
は電池性能を劣化させるため、そのような使用にはあま
り適していなかった＠ 高温で使用する電池として溶融塩を電解質とする一連の
固体電解質電池が開発されているが、これらは高温でし
か使用することができ力いうえに、その使用温度が高す
ぎるため、大規模な発電システムを要し、特殊用途以外
に広く実用化されるに至っていない。For this reason, when conventional batteries are used at temperatures above this limit temperature, the internal pressure of the battery increases, causing leakage and deterioration of battery performance. Furthermore, they suffered from various problems such as batteries exploding, and were unreliable. Also, even if the temperature is within the operating temperature range, long-term storage or long-term use at high temperatures deteriorates battery performance, so molten salt is not suitable for such uses. A series of solid electrolyte batteries have been developed, but these can only be used at high temperatures, and their operating temperatures are so high that they require large-scale power generation systems, making them difficult to use except for special applications. It has not yet been widely put into practical use.

（発明の目的） 本発明の目的は、かかる従来の有機電解質電池および固
体電解質電池の欠点を除去した電池を提供することにあ
る。(Object of the Invention) An object of the present invention is to provide a battery that eliminates the drawbacks of such conventional organic electrolyte batteries and solid electrolyte batteries.

（発明の構成） 本発明によれば、周期律表の１族またはＬ族に属する金
属のイオンからなる電解質と、チルシロキサンとポリ（
エチレンオキサイド）との共重合体を主成分とする非水
電解液を有することを特徴とする電池が得られる。(Structure of the Invention) According to the present invention, an electrolyte consisting of ions of metals belonging to Group 1 or L of the periodic table, tilsiloxane and poly(
A battery characterized by having a non-aqueous electrolyte mainly composed of a copolymer with ethylene oxide) can be obtained.

本発明のジメチルシロキサンとポリ（エチレンオキサイ
ド）から成る共重合体は、主鎖中にエチレンオキサイド
基を有するために誘電率が高く、種々の電解質を溶解・
解離する能力に優れている。The copolymer of dimethylsiloxane and poly(ethylene oxide) of the present invention has an ethylene oxide group in its main chain, so it has a high dielectric constant and can dissolve and dissolve various electrolytes.
Excellent ability to dissociate.

また、ジメチルシロキサン基を有しているためにガラス
転移点（Ｔｇ　）が低く、常温で低粘度の液状を呈し、
イオンの移動度が高い。In addition, because it has a dimethylsiloxane group, it has a low glass transition point (Tg) and exhibits a low viscosity liquid state at room temperature.
High ion mobility.

この非水電解液（以下電解液と称す）は溶剤の代りに液
状の高分子化合物を用いていることから、沸点を持たず
、高温中でも蒸気圧が低い。したがって高温中で電池を
保存あるいは使用しても、電池の内圧が上ることなく、
漏液・破裂や特性劣化などは起らない。Since this non-aqueous electrolyte (hereinafter referred to as electrolyte) uses a liquid polymer compound instead of a solvent, it does not have a boiling point and has a low vapor pressure even at high temperatures. Therefore, even if the battery is stored or used at high temperatures, the internal pressure of the battery will not rise.
No leakage, rupture, or characteristic deterioration occurs.

（実施例） 以下、本発明を実施例にて第１図〜第４図を参照して詳
細に説明する。(Example) Hereinafter, the present invention will be described in detail in Examples with reference to FIGS. 1 to 4.

負極活物質にリチウム、正極活物質に二酸化マンガンを
用い、第１図のようなコイン型電池を作製した場合につ
いて説明する。A case will be described in which a coin-type battery as shown in FIG. 1 is manufactured using lithium as a negative electrode active material and manganese dioxide as a positive electrode active material.

電解液は次のように準備した。The electrolyte solution was prepared as follows.

ジメチルシロキサンとポリ（エチレンオキサイド）との
共重合体は、通常の方法によりジメチルジクロルシラン
とポリ（エチレングリコール）とをベンゼン溶媒中で脱
塩酸重縮合反応し、透明で粘性を有する液体として得ら
れる。A copolymer of dimethylsiloxane and poly(ethylene oxide) is obtained as a transparent and viscous liquid by subjecting dimethyldichlorosilane and poly(ethylene glycol) to a dehydrochloric acid polycondensation reaction in a benzene solvent using a conventional method. It will be done.

ここでは、−（−ＣＨ２ＣＨ２０＋ｐで表わされるポリ
（エチレンオキサイド）のうちｐが１．３．４および９
である、モノ−、トリー、テトラ−、ノナ（エチレンオ
キサイド）を含む共重合体の合成例を示す。合成に際し
、試料の仕込み量を第１表に示した。Here, among poly(ethylene oxide) represented by -(-CH2CH20+p, p is 1.3.4 and 9
An example of synthesis of a copolymer containing mono-, tri-, tetra-, and nona (ethylene oxide) is shown below. Table 1 shows the amount of sample charged during the synthesis.

＝５− 反応条件は、初めの７２時間は揮発性のジメチルジクロ
ルシランが反応するまで温度１０℃で徐々に反応させ、
次に温度６０℃で７２時間反応を促進し、さらに減圧下
で２４時間反応させることにより各々の共重合体を得た
。この際とくにジメチルジクロルシランは水との反応性
が強いため、充分に乾燥したアルゴン不活性ガスを流し
ながら合成を行った。=5- The reaction conditions were to gradually react at a temperature of 10°C for the first 72 hours until the volatile dimethyldichlorosilane reacted;
Next, each copolymer was obtained by promoting the reaction at a temperature of 60° C. for 72 hours and further reacting under reduced pressure for 24 hours. At this time, since dimethyldichlorosilane in particular has strong reactivity with water, the synthesis was performed while flowing sufficiently dry argon inert gas.

次に、電解質濃度が５重量％になるように秤量した電解
質をベンゼンを溶媒として共重合体中に分散・溶解させ
た後、温度６０℃にて５時間ベンゼンを真空留去するこ
とによシミ解液を得た。第２表に、電解液を構成する共
重合体と電解質の組み合せ、および電導度を示した。な
お、電導度は白金電極を用いた電導度肝で周波数５０Ｈ
ｚで測定した。Next, the electrolyte weighed so that the electrolyte concentration was 5% by weight was dispersed and dissolved in the copolymer using benzene as a solvent, and then the benzene was vacuum distilled at a temperature of 60°C for 5 hours to remove stains. A solution was obtained. Table 2 shows the combinations of copolymers and electrolytes constituting the electrolytic solution and the electrical conductivity. The conductivity is measured using a platinum electrode at a frequency of 50H.
Measured at z.

正極体１は次のように準備した。Positive electrode body 1 was prepared as follows.

正極活物質の二酸化マンガン１０重量部と導電剤のアセ
チレンブラック１重音部と結着剤のテフロン粉末１重量
部と電解液３ＴＬ量部を十分に混合６− 第２表 し混合ペースト得た。この混合ペースト０．６ｇｒを圧
力２　、ＯＯＯｋｇ／ｃｔｒｉで加圧成形し、直径１７
叫厚さ約１．０簡のペレットを形成した。このベレット
をさらに電解液中に浸し十分に電解液を浸み込ませたも
のを正極体１とした。10 parts by weight of manganese dioxide as a positive electrode active material, 1 part by weight of acetylene black as a conductive agent, 1 part by weight of Teflon powder as a binder, and 3 parts by weight of an electrolyte were thoroughly mixed to obtain a mixed paste shown in Table 6-2. This mixed paste 0.6gr was pressure molded at a pressure of 2 and OOOkg/ctri, and the diameter was 17g.
A pellet having a thickness of about 1.0 mm was formed. This pellet was further immersed in an electrolytic solution so that the electrolytic solution was sufficiently permeated to form a positive electrode body 1.

隔膜２は、厚さ０．２５　ｍｍのポリプロピレン製の不
織布を直径１８叫で切り抜き、これを電解液中に２４時
間反漬し、十分に電解液を浸み込ませて準備した。The diaphragm 2 was prepared by cutting out a 0.25 mm thick polypropylene nonwoven fabric with a diameter of 18 cm, and soaking it in an electrolytic solution for 24 hours to allow it to fully soak in the electrolytic solution.

負極体３は厚さ０．５鴫のリチウムンートを直径１５ｍ
ｍに打ち抜い゛Ｃ準備した。The negative electrode body 3 is a lithium tube with a thickness of 0.5 m and a diameter of 15 m.
I punched it out to m and prepared it.

次に内側にステンレスメツシュ４ｔｌ−溶接した上下の
外装ケース５．６中に上から正極体１．隔膜２、負極体
３の順に積層して収容し、外装ケース６の端部を絶縁リ
ング７全介し°Ｃカシメて密封し、第１図のような外径
２０ｍｍｔ淳さ２．５胴のコイン型電池を作製した。Next, the positive electrode body 1.6 is inserted into the upper and lower exterior cases 5.6 with 4tl-welded stainless mesh on the inside. The diaphragm 2 and the negative electrode body 3 are stacked and housed in this order, and the end of the outer case 6 is sealed by caulking the entire insulating ring 7 through the insulation ring 7, and a coin with an outer diameter of 20 mm and a length of 2.5 mm as shown in Fig. 1 is prepared. A type battery was made.

この電池を各々温度２０℃、６０℃、１００℃の各恒温
槽に入れ、負荷抵抗２５にΩを取り付けて放電させた。The batteries were placed in thermostats at temperatures of 20° C., 60° C., and 100° C., and the load resistor 25 was set to Ω and discharged.

第２表のｂの電解液を用いた場合の各々の放電特性を第
２図のＡ、Ｅ、Ｃに、またｆの電解液を用いた場合の各
々の放電特性を第３図のＤ　、　Ｅ、Ｆに示す。The discharge characteristics when using the electrolyte b in Table 2 are shown in A, E, and C in Figure 2, and the discharge characteristics when using the electrolyte f in Table 2 are shown in D, D in Figure 3. Shown in E and F.

次に、温度１００℃の恒温槽に１０日間保存した後、常
温で負荷抵抗２５にΩを取抄付けて放電させた。ｃ、ｄ
の電解液を用いた場合の放電特性を第４図のＧ、Ｈに示
す。また、比較のために高温保存をしない電池の特性を
第４図のＱ／　、　）ｌ／に示す。Next, after storing it in a constant temperature bath at a temperature of 100° C. for 10 days, it was discharged by attaching Ω to the load resistor 25 at room temperature. c, d
The discharge characteristics when using the electrolyte are shown in G and H in FIG. For comparison, the characteristics of a battery that is not stored at high temperatures are shown in Q/, )l/ in FIG.

本実施例で作製した全ての電池は、高温保存や高温放電
の際にも漏液や破裂などの故障が表く良好な特性を示し
た。とくに高温になるほど電解液の電導度が高くなり放
電特性が向上した。゛また高温保存させても特性劣化が
ほとんど見られなかった。なお、（イ）本実施例では電
池作製までの全ての工程は、アルゴン不活性ガス雰囲気
下で行われた。All the batteries produced in this example exhibited good characteristics, with no failures such as leakage or rupture even during high-temperature storage or high-temperature discharge. In particular, the higher the temperature, the higher the conductivity of the electrolyte and the better the discharge characteristics.゛Furthermore, even when stored at high temperatures, almost no deterioration in characteristics was observed. Note that (a) in this example, all steps up to battery fabrication were performed under an argon inert gas atmosphere.

（ロ）本実施例では電池の試験温度を高温側で１００℃
までとした。絶縁リングや不織布の材質を耐熱性の優れ
たものを用いれば、さらに高い温度でも使用することが
可能である。Ｃ→本実施例では負極活物質にリチウムを
、正極活物質に二酸化マンガンを用いた電池について記
述したが、前述した他の活物質を用いた場合や電解質に
ナトリウム、カリウム、マグネシウム、カルシウムなど
の塩を用いた場合にも良好な特性を示すことは勿論であ
る。(b) In this example, the test temperature of the battery was 100°C on the high temperature side.
Up to. If the insulating ring and nonwoven fabric are made of materials with excellent heat resistance, they can be used at even higher temperatures. C → In this example, a battery using lithium as the negative electrode active material and manganese dioxide as the positive electrode active material was described, but other active materials mentioned above or sodium, potassium, magnesium, calcium, etc. as the electrolyte were described. It goes without saying that good properties are exhibited even when salt is used.

以上、本発明には次の効果がある。As described above, the present invention has the following effects.

９− （１）高温環境においても蒸気圧が極めて低く、内圧増
大による漏液や破裂の危険性がない。9- (1) The vapor pressure is extremely low even in high-temperature environments, so there is no risk of leakage or bursting due to increased internal pressure.

（１１）経時的劣化の極めて少ない高信頼性の電池が得
られる。(11) A highly reliable battery with extremely little deterioration over time can be obtained.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明によるコイン型電池の断面図、第２図〜
第４図はその放電特性である。 １・・・・・・正極体、２・・・・・・隔膜、３・・・
・・・負極体、４・・・・・・ステンレスメツシー、５
，６・・・・・・外装ケース、７・・・・・・絶縁リン
グ、Ａ、Ｄ・・・・・・温度２０℃での放電特性、Ｂ、
Ｅ・・・・・・温度６０℃での放電特性、Ｃ１Ｆ・・・
・・・温度１００℃での放電特性、Ｇ、Ｈ・・・・・・
温度ｌＯＯ℃で１０日間保存した後の常温での放電特性
、Ｇ’　、　Ｈ’・・・・・・常温での放電特性。 −１〇−FIG. 1 is a sectional view of a coin-type battery according to the present invention, and FIG.
Figure 4 shows its discharge characteristics. 1...Positive electrode body, 2...Diaphragm, 3...
... Negative electrode body, 4 ... Stainless steel mesh, 5
, 6...Exterior case, 7...Insulation ring, A, D...Discharge characteristics at a temperature of 20°C, B,
E...Discharge characteristics at a temperature of 60℃, C1F...
...Discharge characteristics at a temperature of 100℃, G, H...
Discharge characteristics at room temperature after storage at a temperature of 100°C for 10 days, G', H'...Discharge characteristics at room temperature. -10-

Claims (1)

【特許請求の範囲】[Claims] オキサイド）との共重合体を主成分とする非水電解液を
有することを％徴とする電池。A battery characterized by having a non-aqueous electrolyte whose main component is a copolymer with oxide).