JPH0616422B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0616422B2 JPH0616422B2 JP62170345A JP17034587A JPH0616422B2 JP H0616422 B2 JPH0616422 B2 JP H0616422B2 JP 62170345 A JP62170345 A JP 62170345A JP 17034587 A JP17034587 A JP 17034587A JP H0616422 B2 JPH0616422 B2 JP H0616422B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- aqueous electrolyte
- positive electrode
- electrolyte battery
- solvent
- 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 - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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】 ＜産業上の利用分野＞ この発明は、リチウムやナトリウムなどの軽金属を負極
活物質に用いる一次ないし二次の非水電解液電池に関す
るものである。The present invention relates to a primary or secondary non-aqueous electrolyte battery using a light metal such as lithium or sodium as a negative electrode active material.
＜従来の技術＞ 上記の非水電解液電池、例えばリチウム電池は、軽量で
エネルギー密度の高いといった特長のある電池で、筒形
スパイラル形，筒形インサイドアウト形，コイン形ある
いはピン形などの形式のものが広く用いられている。そ
して、この種の電池では、上述した軽金属を活物質とす
る負極に、二酸化マンガンやフッ化カーボンなどを活物
質とした正極をセパレータを介して組合せて構成し、ま
た、プロピレンカーボネートやγ-ブチロラクトンある
いはジメトキシエタンなどの非水系の有機溶媒に、Ｌｉ
ＣｌＯ４の如きアルカリ金属塩を溶質として溶解した非
水電解液を用いている。<Prior Art> The above-mentioned non-aqueous electrolyte battery, such as a lithium battery, is a battery that is lightweight and has a high energy density, and is of a cylindrical spiral type, cylindrical inside-out type, coin type or pin type. Are widely used. In this type of battery, the above-described negative electrode using a light metal as an active material is combined with a positive electrode using manganese dioxide, fluorocarbon, or the like as an active material via a separator, and the propylene carbonate or γ-butyrolactone is also used. Alternatively, in a non-aqueous organic solvent such as dimethoxyethane, Li
A non-aqueous electrolyte solution in which an alkali metal salt such as ClO 4 is dissolved as a solute is used.
＜発明が解決しようとする問題点＞ しかしながら、非水電解液に用いられる上記有機溶媒は
可燃性であり、また上記の過塩素酸リチウムはこれら有
機溶媒と混合した状態では不安定で爆発などの危険性が
非常に高い。このため、これらを混用してなる上記従来
の非水電解液は取扱性が悪くて電池製造工程の煩雑化の
原因となる。また、電池組立中に正負極間を短絡させた
り、組立後でも例えば正極集電体と負極あるいは正極リ
ード板と負極缶とが短絡しないし電池を外部短絡させた
時などにおける電池内部よりの発熱や、火中投入した時
などにおける外部よりの加熱などによって電池温度が上
昇した場合、上記の非水電解液の爆発に起因して電池破
裂などの事故が起こる可能性が高く、電池破裂により外
部に飛散したリチウムなどの軽金属の発火による火災事
故などは免れない。特に筒形スパイラル形電池で短絡時
に流れる大電流により電池温度の上昇が急激に起こるの
で、この危険性が殊大きく、重大な発火事故を招き易
い。<Problems to be Solved by the Invention> However, the above-mentioned organic solvent used in the non-aqueous electrolyte is flammable, and the above-mentioned lithium perchlorate is unstable in a state of being mixed with these organic solvents and may cause explosion or the like. Very dangerous. For this reason, the conventional non-aqueous electrolyte prepared by mixing these is poor in handleability and complicates the battery manufacturing process. In addition, the positive and negative electrodes are short-circuited during battery assembly, and even after assembly, for example, the positive electrode current collector and negative electrode or the positive electrode lead plate and negative electrode can are not short-circuited, and heat is generated from inside the battery when the battery is externally short-circuited. Also, if the battery temperature rises due to external heating such as when thrown into a fire, it is highly possible that an accident such as a battery rupture will occur due to the explosion of the non-aqueous electrolyte described above. There is no escape from a fire accident caused by the ignition of light metals such as lithium scattered in the air. Particularly in a cylindrical spiral battery, a large current flowing at the time of a short circuit causes a rapid increase in battery temperature, and this danger is particularly large, and a serious ignition accident is likely to occur.
＜問題点を解決するための手段＞ 本発明者は上記問題を解決すべく検討した所、上記のＬ
ｉＣｌＯ４に代えてＬｉＣＦ３ＳＯ３を用い、これを次
のような溶媒に溶解して用いた時には、電池の性能低下
を招くことなく所期の目的を達成できることを知得して
この発明を完成した。<Means for Solving Problems> The present inventor has studied to solve the above problems and found that the above L
It is known that LiCF 3 SO 3 is used in place of iClO 4 , and when this is dissolved in a solvent as described below, the intended purpose can be achieved without degrading the performance of the battery. completed.
即ち、この発明の非水電解液電池は、リチウム，ナトリ
ウムなどの軽金属を活物質とする負極にセパレータを介
して正極を組合せてなる非水電解液電池において、Ｎ，
Ｎ-ジエチルフォルムアミドからなる有機溶媒に、溶質
としてＬｉＣＦ３ＳＯ３を溶解してなる非水電解液を用
いたことを要旨とする。That is, the non-aqueous electrolyte battery of the present invention is a non-aqueous electrolyte battery in which a negative electrode using a light metal such as lithium or sodium as an active material is combined with a positive electrode via a separator,
It is a gist to use a non-aqueous electrolytic solution prepared by dissolving LiCF 3 SO 3 as a solute in an organic solvent composed of N-diethylformamide.
＜作 用＞ ＬｉＣＦ３ＳＯ３は有機溶媒中で ＬｉＣｌＯ４に比べてはるかに安定で安全性が高く、上
記発火などの危険は著しく低い。そして、上記の溶媒は
引火点も６７〜６９℃と高い。従って、従来のプロピレ
ンカーボネートを主体とする系の溶媒に代えて上記組成
の有機溶媒を用い、これに上記ＬｉＣＦ３ＳＯ３を溶解
したものを電解液として使用することで、電池性能が良
好で、安全性の高い非水電解液電池となる。<Working> LiCF 3 SO 3 is much more stable and safer than LiClO 4 in an organic solvent, and the risk of ignition is extremely low. And the above-mentioned solvent also has a high flash point of 67 to 69 ° C. Therefore, by using an organic solvent having the above composition in place of the conventional solvent mainly composed of propylene carbonate and dissolving the above LiCF 3 SO 3 as an electrolyte, good battery performance is obtained, It becomes a highly safe non-aqueous electrolyte battery.
＜実施例＞ 以下に添付図面を用いてこの発明の実施例を説明する。<Example> An example of the present invention will be described below with reference to the accompanying drawings.
有底円筒状でステンレス製の正極缶１の内側に、二酸化
マンガンを主剤とする混合粉末にをシート状に成型した
正極２とリチウムシートからなる負極３とをプロピレン
不織布シートでできたセパレータ４を介して積重し且つ
渦巻状に巻回して作った発電要素５を収納し、また発電
要素底面側の負極３より導出したリード端子６を絶縁板
７を介して正極缶内底面側に折曲しこの内底面にスポッ
ト溶接する一方、本発明に係る非水電解液８を所定量注
入し、更に正極上部より導出したリード端子９を、合成
樹脂製の絶縁ガスケット１０の内側で正極缶開口部に載
置したステンレス製で皿状の端子板１１に接続する等し
て、第１図に示した如き、ＣＲ６・Ｈ型（外径14.5mm、
高さ50.5mm）のスパイラル形リチウム電池（本発明電池
Ａ）を作製した。尚、上記の非水電解液８としては、
Ｎ，Ｎ-ジエチルフォルムアミドからなる溶媒に ＬｉＣＦ３ＳＯ３を１モル／溶解させたものを用い
た。Inside a bottomed cylindrical stainless steel positive electrode can 1, a separator 4 made of a propylene nonwoven fabric sheet, a positive electrode 2 formed by molding a mixed powder containing manganese dioxide as a main component into a sheet shape, and a negative electrode 3 formed of a lithium sheet are formed. The power generating element 5 made by stacking and winding in a spiral shape is housed, and the lead terminal 6 led out from the negative electrode 3 on the bottom side of the power generating element is bent to the bottom side inside the positive electrode can via the insulating plate 7. While spot-welding to the inner bottom surface of the rod, a predetermined amount of the non-aqueous electrolyte solution 8 according to the present invention is injected, and the lead terminal 9 led out from the upper portion of the positive electrode is connected to the inside of the insulating gasket 10 made of synthetic resin to open the positive electrode can As shown in FIG. 1, CR6H type (outer diameter 14.5 mm,
A spiral lithium battery (invention battery A) having a height of 50.5 mm was produced. In addition, as the above non-aqueous electrolyte solution 8,
LiCF 3 SO 3 was dissolved in a solvent consisting of N, N-diethylformamide at 1 mol / mol and used.
一方、プロピレンカーボネートとジメトキシエタンとを
体積比で１：１の割合で混合した溶媒に、ＬｉＣｌＯ４
を１モル／溶解させたものを非水電解液として用いた
他は、上記の本発明電池Ａと同様にして、比較用のスパ
イラル形リチウム電池（比較電池Ｃ）を作った。On the other hand, LiClO 4 was added to a solvent prepared by mixing propylene carbonate and dimethoxyethane at a volume ratio of 1: 1.
A spiral lithium battery for comparison (comparative battery C) was prepared in the same manner as the battery A of the present invention except that 1 mol / mol of was used as the non-aqueous electrolyte.
そして、これらの電池Ａ，Ｃについて、環境温度２０℃
において抵抗８０Ωで連続放電させ、その時の各電池の
端子電圧（Ｖ）の放電時間（hour）に対する変化を調べ
た。この結果は第２図の通りであり、本発明電池Ａは比
較電池Ｃより高い放電性能を示した。The environmental temperature of these batteries A and C is 20 ° C.
At 80 ° C., the battery was continuously discharged, and the change in the terminal voltage (V) of each battery with respect to the discharging time (hour) was examined. The results are shown in FIG. 2, and the battery A of the present invention showed higher discharge performance than the comparative battery C.
また、以上の電池Ａ，Ｃについて、その内部抵抗ＲＡＣ
を夫々測定した所、比較電池Ｃでは0.8〜 0.9Ωであっ
たのに対し、本発明電池Ａでは 0.7〜 0.8であり、本発
明電池Ａは内部抵抗の低い、特性の優れた電池であるこ
とが確認された。Further, regarding the above batteries A and C, the internal resistance R AC
Comparative battery C had a value of 0.8 to 0.9Ω, whereas battery A of the present invention had a value of 0.7 to 0.8, indicating that battery A of the present invention has a low internal resistance and excellent characteristics. Was confirmed.
更に、これらの電池Ａ，Ｃを夫々外部短絡ないし火中投
入した所、比較電池Ｃでは温度上昇により爆発したが、
本発明電池Ａでは容易に爆発することはなかった。Furthermore, when these batteries A and C were each externally short-circuited or thrown into fire, the comparative battery C exploded due to temperature rise,
The battery A of the present invention did not explode easily.
これは次の理由によるものと思われる。即ち、比較電池
Ｃでは、短絡して、電池内部温度がリチウムの融点であ
る 186℃を超えると、溶融リチウムと過塩素酸塩帯び溶
剤が爆発的に化合して着火，爆発に至るものと考えられ
る。一方、本発明電池Ａでは着火にすら至らない。This is probably due to the following reasons. That is, in the comparative battery C, when a short circuit occurs and the battery internal temperature exceeds 186 ° C. which is the melting point of lithium, it is considered that the molten lithium and the perchlorate-bearing solvent are explosively combined to cause ignition and explosion. To be On the other hand, the battery A of the present invention does not even lead to ignition.
また、火中投入時において、比較電池Ｃでは、最初に封
口部のガスケットが溶融変形して電池内の有機溶媒が流
れ出し、着火する。そしてこの溶媒が燃えている間は溶
媒の沸点以上には電池の温度は上昇しないが、溶媒が燃
え尽きると急激に温度が上がる。この時、電池内各部に
残っている溶質として用いたＬｉＣｌＯ４がこの急激な
加熱により爆発に至る（一般に過酸化物を有機物（液
体）と混触させて蒸発乾固すると爆発に至る危険性が常
に存在する）。一方本発明電池Ａではこのような爆発が
起こらずに安全である。In addition, in the comparative battery C, when put into the fire, the gasket at the sealing portion is first melted and deformed, and the organic solvent in the battery flows out and ignites. While the solvent is burning, the temperature of the battery does not rise above the boiling point of the solvent, but when the solvent burns out, the temperature rises rapidly. At this time, LiClO 4 used as a solute remaining in various parts of the battery causes an explosion due to this rapid heating (generally, there is a risk of explosion if the peroxide is mixed with an organic substance (liquid) and evaporated to dryness). Exist). On the other hand, the battery A of the present invention is safe without causing such an explosion.
尚、以上は正極活物質に二酸化マンガンを、また負極活
物質にはリチウムを用いた例であるが、正極活物質とし
てＭｏＯ３やＣｕＯなどの金属酸化物、ＡｇＣｌ２やＣ
ｕＯｌ２などの金属塩化物、ＣｕＦ２やＮｉＦ２などの
金属弗化物、ＣｕＳやＮｉ３Ｓ２などの金属硫化物を、
また、負極活物質にはナトリウムやカリウムなどのその
他の軽金属を用いた場合にも同様な結果が得られた。In the above description, manganese dioxide is used as the positive electrode active material and lithium is used as the negative electrode active material. However, as the positive electrode active material, metal oxides such as MoO 3 and CuO, AgCl 2 and C are used.
Metal chlorides such as uOl 2 , metal fluorides such as CuF 2 and NiF 2 , metal sulfides such as CuS and Ni 3 S 2 ,
Similar results were obtained when other light metals such as sodium and potassium were used as the negative electrode active material.
また、以上は筒形スパイラル形電池についての例である
が、筒形インサイドアウト形，コイン形あるいはピン形
などの他の形式の電池の場合も同様な結果が得られるこ
とは言うまでもない。Although the above is an example of the cylindrical spiral type battery, it goes without saying that the same result can be obtained in the case of other types of batteries such as a cylindrical inside-out type, a coin type and a pin type.
次に、電解液溶媒における溶質の好ましい濃度（mol／
）を調べるため、Ｎ，Ｎ-ジエチルフォルムアミドと
スルホランをそれぞれ体積比１：１で混合した溶媒を作
り、これらにＬｉＣＦ３ＳＯ３をその溶解度（mol／
）を適宜変えてそれぞれ溶解させた時における電解液
の導電率Ｃ（ms）の温度２０℃での変化を調べた。この
結果を第３図に示した。この結果より、溶質ＬｉＣＦ３
ＳＯ３の好ましい濃度は１mol／程度であり、この濃
度とすることで非水電解液）の導電率が著しく高まり、
これを電池に用いた時には大きな性能向上が図れること
がわかった。Next, the preferred concentration of solute in the electrolyte solvent (mol /
), N, N-diethylformamide and sulfolane were mixed at a volume ratio of 1: 1 to prepare a solvent, and LiCF 3 SO 3 was added to the solvent to determine its solubility (mol / mol).
) Was appropriately changed and dissolved, and the change in conductivity C (ms) of the electrolytic solution at a temperature of 20 ° C. was examined. The results are shown in FIG. From this result, solute LiCF 3
The preferable concentration of SO 3 is about 1 mol / min. By setting this concentration, the conductivity of the non-aqueous electrolyte is remarkably increased,
It was found that a large improvement in performance can be achieved when this is used in a battery.
＜発明の効果＞ 以上のように、この発明によれば、電池性能が良好で安
全性の高い非水電解液電池を提供することができる。<Effects of the Invention> As described above, according to the present invention, it is possible to provide a non-aqueous electrolyte battery having good battery performance and high safety.
第１図は実施例の電池の断面図、第２図は実施例の電池
と比較用の電池の放電性能を示したグラフ、第３図は非
水電解液における溶質の濃度と導電率との関係を示した
グラフである。 １……正極缶、５……発電要素、８……非水電解液。FIG. 1 is a cross-sectional view of the battery of the example, FIG. 2 is a graph showing the discharge performance of the battery of the example and a battery for comparison, and FIG. 3 is a graph showing the solute concentration and conductivity in the non-aqueous electrolyte. It is a graph showing a relationship. 1 ... Positive electrode can, 5 ... Power generating element, 8 ... Non-aqueous electrolyte.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 北方 雅一 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 (56)参考文献 特開 昭59−96666（ＪＰ，Ａ) 特開 昭58−106771（ＪＰ，Ａ) 特公 昭60−31070（ＪＰ，Ｂ２) 特公 昭53−34610（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Kitakata 5-11-3 Shimbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. (56) Reference JP-A-59-96666 (JP, A) JP Sho 58-106771 (JP, A) JP 60-31070 (JP, B2) JP 53-34610 (JP, B2)
Claims (2)
質とする負極にセパレータを介して正極を組合せてなる
非水電解液電池において、Ｎ，Ｎ-ジエチルフォルムア
ミドからなる有機溶媒に、溶質としてＬｉＣＦ３ＳＯ３
を溶解してなる非水電解液を用いたことを特徴とする非
水電解液電池。1. A non-aqueous electrolyte battery comprising a negative electrode containing a light metal such as lithium or sodium as an active material and a positive electrode via a separator, wherein LiCF is used as a solute in an organic solvent composed of N, N-diethylformamide. 3 SO 3
A non-aqueous electrolyte battery, characterized by using a non-aqueous electrolyte solution obtained by dissolving.
を特徴とする特許請求の範囲第１項記載の非水電解液電
池。2. The non-aqueous electrolyte battery according to claim 1, wherein the active material of the positive electrode is manganese dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62170345A JPH0616422B2 (en) | 1987-07-08 | 1987-07-08 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62170345A JPH0616422B2 (en) | 1987-07-08 | 1987-07-08 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6414878A JPS6414878A (en) | 1989-01-19 |
| JPH0616422B2 true JPH0616422B2 (en) | 1994-03-02 |
Family
ID=15903207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62170345A Expired - Fee Related JPH0616422B2 (en) | 1987-07-08 | 1987-07-08 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0616422B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013039148A (en) | 2011-08-11 | 2013-02-28 | Topcon Corp | Microscope for ophthalmic operation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5996666A (en) * | 1982-11-25 | 1984-06-04 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
-
1987
- 1987-07-08 JP JP62170345A patent/JPH0616422B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6414878A (en) | 1989-01-19 |
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Legal Events
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |