JPH0760705B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0760705B2 JPH0760705B2 JP2408617A JP40861790A JPH0760705B2 JP H0760705 B2 JPH0760705 B2 JP H0760705B2 JP 2408617 A JP2408617 A JP 2408617A JP 40861790 A JP40861790 A JP 40861790A JP H0760705 B2 JPH0760705 B2 JP H0760705B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- battery
- solute
- aqueous
- 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 - Lifetime
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、リチウムを負極活物
質とする一次あるいは二次の非水電解液電池に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primary or secondary non-aqueous electrolyte battery using lithium as a negative electrode active material.
【０００２】[0002]
【従来の技術】上記の非水電解液電池は、軽量で高エネ
ルギー密度の電池であり、筒形スパイラル形，筒形イン
サイドアウト形，コイン形などの種々の形式が用いられ
ている。2. Description of the Related Art The above non-aqueous electrolyte battery is a lightweight and high energy density battery, and various types such as a cylindrical spiral type, a cylindrical inside-out type and a coin type are used.
【０００３】そして、一次電池の場合はリチウムを、ま
た二次電池の場合にはリチウムやリチウム合金（例えば
リチウム−アルミニウム合金）をそれぞれ負極に用い、
また正極には二酸化マンガンやフッ化カーボンなどを活
物質に用いる構成が採られる。Lithium is used for the primary battery, and lithium or lithium alloy (for example, lithium-aluminum alloy) is used for the negative electrode in the secondary battery.
In addition, the positive electrode may be configured to use manganese dioxide, carbon fluoride, or the like as an active material.
【０００４】この種の電池では、非水系の有機溶媒にア
ルカリ金属塩を溶質として溶解して作った非水電解液が
用いられる。In this type of battery, a non-aqueous electrolytic solution prepared by dissolving an alkali metal salt as a solute in a non-aqueous organic solvent is used.
【０００５】非水電解液の溶質には、従来は放電性能な
どの点から高導電率で防蝕効果の高いＬｉＣｌＯ4 が主
に用いられたが、これは爆発の危険性が高いため、最近
ではＬｉＢＦ4 ，ＬｉＡｓＦ6 ，ＬｉＰＦ6 ，ＬｉＣＦ
3 ＳＯ3 ，ＬｉＳｂＦ6 などの金属塩を使用することが
電池安全性の面から検討されている。As the solute of the non-aqueous electrolytic solution, LiClO 4 which has a high electric conductivity and a high anticorrosion effect has been mainly used in the past from the viewpoint of discharge performance and the like. LiBF 4 , LiAsF 6 , LiPF 6 , LiCF
The use of metal salts such as 3 SO 3 and LiSbF 6 has been studied from the viewpoint of battery safety.
【０００６】また、非水溶媒としては、例えば、特開昭
60- 253165号，特開昭56-93267号，特開昭 63-143761
号，特開昭63- 119160号，特開昭63- 119170号，特開昭
63- 168969号，特開平2- 44659号，あるいは特開平1-20
0563号などに記載されたように、プロピレンカーボネイ
ト，エチレンカーボネイト，ブチレンカーボネイト，γ
−ブチロラクトン，1,2-ジメトキシエタン，テトラヒド
ロフタン，2-メチルテトラハイドロフラン，1,3-ジオキ
ソラン，1,2-ジエトキシエタン，エトキシメトキシエタ
ンなどから２〜３種類を適宜混合したものが使用され
る。Further, as the non-aqueous solvent, for example, Japanese Patent Laid-Open No.
60-253165, JP-A-56-93267, JP-A-63-143761
No. 63-119160, 63-119170, 63-119170
63-168969, JP-A-2-44659, or JP-A 1-20
As described in No. 0563, propylene carbonate, ethylene carbonate, butylene carbonate, γ
-Butyrolactone, 1,2-dimethoxyethane, tetrahydrofutane, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,2-diethoxyethane, ethoxymethoxyethane, etc. used.
【０００７】ところが従来より使用されている上記の溶
質は、これらをそれぞれ単独で用いた場合、ＬｉＣｌＯ
4 は爆発を起こし易い，ＬｉＢＦ4 はＭｎＯ2 系との組
合わせにおいて腐蝕などの異常現象が起き易い，ＬｉＡ
ｓＦ6 は分解時などに猛毒ガスが発生する，ＬｉＰＦ6
は熱的に非常に不安定で取扱い，ＬｉＣＦ3 ＳＯ3は低
温使用時における特性劣化が顕著である，ＬｉＳｂＦ6
は塩としての溶解度が小さい、などの欠点がある。However, the above-mentioned solutes that have been conventionally used are not limited to LiClO when they are used alone.
4 is prone to explosion, LiBF 4 is prone to abnormal phenomena such as corrosion in combination with MnO 2 system, LiA
sF 6 is highly toxic gas when decomposed, LiPF 6
Is very unstable thermally, and LiCF 3 SO 3 shows significant deterioration in characteristics at low temperatures. LiSbF 6
Has the drawback of low solubility as a salt.
【０００８】このため、安全性などの面で比較的問題が
少ないＬｉＣＦ3 ＳＯ3 単独あるいはこれを主体とする
ものを溶質として用いることが有望視されている。Therefore, it is considered promising to use LiCF 3 SO 3 as a solute, which is relatively less problematic in terms of safety, or a solute mainly composed of LiCF 3 SO 3 .
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、上記の
有機溶媒２〜３種類を適宜混合した２〜３成分系の溶媒
に、例えばＬｉＣＦ3 ＳＯ3 を溶質とした非水電解液で
は、実用上十分な程度の放電性能（室温，低温ともに）
を得ることができず、特に低温での性能劣化が大きいと
いう問題がある。[0006] However, in a solvent 2-3-component appropriately mixed organic solvent 2-3 kinds of the above, for example, in LiCF 3 non-aqueous electrolyte of SO 3 was solute, practically sufficient Discharge performance (both room temperature and low temperature)
Cannot be obtained, and there is a problem that performance deterioration is large especially at low temperatures.
【００１０】これは、上記２〜３成分系の溶媒自体の導
電性が比較的低く、このため電池の内部抵抗が高くなる
ことが要因であると考えられる。特に溶質としてＬｉＣ
Ｆ3 ＳＯ3 を用いた場合は他に比較して導電性が低いの
でこの傾向が大きい。そして、この非水電解液を用いて
構成した非水電解液二次電池の場合は、放電特性の他、
サイクル効率の低下が顕著であった。It is considered that this is because the conductivity of the solvent of the above-mentioned two- to three-component system itself is relatively low, and therefore the internal resistance of the battery becomes high. LiC as a solute
This tendency is large when F 3 SO 3 is used because the conductivity is low compared to other cases. And in the case of a non-aqueous electrolyte secondary battery configured using this non-aqueous electrolyte, in addition to the discharge characteristics,
The decrease in cycle efficiency was remarkable.
【００１１】この発明は、放電性能やサイクル特性が優
れた非水電解液電池を提供することを目的とする。An object of the present invention is to provide a non-aqueous electrolyte battery having excellent discharge performance and cycle characteristics.
【００１２】[0012]
【課題を解決するための課題】本発明者は上記目的を達
成するために鋭意研究の結果、非水溶媒として次の４成
分からなるものを用いた場合には、放電性能やサイクル
特性の非常に優れた電池を作製し得ることが判った。DISCLOSURE OF THE INVENTION As a result of earnest research to achieve the above object, the present inventor has found that when a non-aqueous solvent consisting of the following four components is used, the discharge performance and cycle characteristics are extremely high. It was found that an excellent battery can be manufactured.
【００１３】即ちこの発明の非水電解液電池は、二酸化
マンガンを活物質とする正極と、リチウムを活物質とす
る負極と、非水溶媒に溶質を溶解してなる非水電解液を
備えた非水電解液電池であって、前記非水溶媒が、プロ
ピレンカーボネイトまたはブチレンカーボネイトと、エ
チレンカーボネイトと、1,3-ジオキソランと、ジメトキ
シエタンとの４成分よりなる混合溶媒であり、前記溶質
がＬｉＣＦ 3 ＳＯ 3 にＬｉＣｌＯ 4 を0.01〜 0.1 mol／
ｌ添加したものであることを要旨とするものである。[0013] In other words the non-aqueous electrolyte battery of the present invention, dioxide
A positive electrode using manganese as an active material, a negative electrode using lithium as an active material, and a non-aqueous electrolyte battery comprising a non-aqueous electrolytic solution obtained by dissolving a solute in a non-aqueous solvent, wherein the non-aqueous solvent is: and propylene carbonate or butylene carbonate, and ethylene carbonate, and 1,3-dioxolane, Ri mixed solvent der consisting four components and dimethoxyethane, wherein the solute
Add LiClO 4 to LiCF 3 SO 3 in an amount of 0.01 to 0.1 mol /
The Der Rukoto those l added it is an gist.
【００１４】[0014]
【００１５】本発明においては、溶質としてＬｉＣＦ3
ＳＯ3 を用いるが、少量のＬｉＣｌＯ4 を添加すること
が好ましい。即ち、溶質がＬｉＣＦ3 ＳＯ3 単独である
と、ＬｉＣＦ3 ＳＯ3 から遊離したフッ素やイオウと電
池内部の微量の水との反応によって特に高温保存時に電
池缶に孔食が発生する虞があり、防蝕効果のあるＬｉＣ
ｌＯ4 を少量添加することでこの種の孔食が防止でき、
また電解液の導電率が改善される。In the present invention, LiCF 3 is used as the solute.
SO 3 is used, but it is preferable to add a small amount of LiClO 4 . That is, when the solute is LiCF 3 SO 3 alone, there is a possibility that pitting corrosion may occur in the battery can especially during high temperature storage due to the reaction between fluorine and sulfur liberated from LiCF 3 SO 3 and a small amount of water inside the battery. LiC with anticorrosion effect
lO 4 prevents pitting of this kind by adding a small amount of,
In addition, the conductivity of the electrolytic solution is improved.
【００１６】この場合、ＬｉＣｌＯ4 は上記混合溶媒に
対して0.01〜 0.1 mol／ｌ添加される。0.01 mol／ｌ未
満では顕著な効果が得られず、また 0.1 mol／ｌより多
くしても得られる効果は変わらず、火中投入時などにお
いて電池が爆発し易くなったり、若し電池内部で短絡が
起きたりした場合に電池の発火事故につながるおそれが
ある。In this case, 0.01 to 0.1 mol / l of LiClO 4 is added to the above mixed solvent. 0.01 mol / l Not available
In full remarkable effect can not be obtained, also multi than 0.1 mol / l
Ku and effect does not change even obtained, which may lead to fire accident of the battery when or become liable to explode the battery in, such as during a fire is turned on, is Wakashi short circuit inside the battery was or happened.
【００１７】[0017]
【作用】上記の混合溶媒からなる非水電解液を用いるこ
とで、電池の放電性能やサイクル特性が格段に改善され
る。この詳しい理由は不明であるが、大体以下の〜
が考えられる。The discharge performance and cycle characteristics of the battery are remarkably improved by using the non-aqueous electrolyte containing the above mixed solvent. The detailed reason for this is unknown, but it is roughly the following ~
Can be considered.
【００１８】プロピレンカーボネイトやエチレンカー
ボネイトなどのエステルは、粘性が高いため、これらと
1,3-ジオキソランやジメトキシエタンなどの低粘度溶媒
と組合わせが好ましいこと。Esters such as propylene carbonate and ethylene carbonate have a high viscosity, so
It is preferably used in combination with a low viscosity solvent such as 1,3-dioxolane or dimethoxyethane.
【００１９】プロピレンカーボネイトよりエチレンカ
ーボネイトの方が誘電率が高く、また溶質の溶解性によ
り良い結果をもたらすので、少なくともプロピレンカー
ボネイトに同量程度のエチレンカーボネイトを混合する
ことが好ましいこと。Since ethylene carbonate has a higher dielectric constant than propylene carbonate and gives better results in solubility of solute, it is preferable to mix at least the same amount of ethylene carbonate with propylene carbonate.
【００２０】1,3-ジオキソランは溶質の溶解性が非常
に優れ、また粘度が低いので、溶液の導電率も高くなる
こと。尚、二酸化マンガン系のような比較的電圧の高い
系ではしばしば重合（開環重合）の問題などを起こし易
いので、混合溶媒中における容量比率は最大でも50％、
好ましくは30％以下に押さえた方が良いことが経験上知
られている。Since 1,3-dioxolane has a very good solute solubility and a low viscosity, the conductivity of the solution is also high. Since a system with relatively high voltage such as manganese dioxide often causes a problem of polymerization (ring-opening polymerization), the volume ratio in the mixed solvent is 50% at maximum.
It is known from experience that it is better to keep the content at 30% or less.
【００２１】ジメトキシエタンは非常に安定性の良い
溶媒で特性的にも優れていること。尚、ジメトキシエタ
ンは多量に用いると電解液の導電性が低下してしまう。
これは溶質の溶解性を減じるためと考えられている。Dimethoxyethane is a very stable solvent and has excellent characteristics. If a large amount of dimethoxyethane is used, the conductivity of the electrolytic solution will be reduced.
This is believed to reduce the solubility of the solute.
【００２２】そして、これら４成分からなる系の混合溶
媒を用いることで、各々の溶媒の欠点が互いに補われ、
且つこれらの相乗効果によって特性向上が図れるものと
考えられる。By using the mixed solvent of the system consisting of these four components, the drawbacks of the respective solvents are mutually compensated,
Further, it is considered that the synergistic effect of these can improve the characteristics.
【００２３】[0023]
【実施例】以下に実施例を説明する。EXAMPLES Examples will be described below.
【００２４】プロピレンカーボネイト（ＰＣ）とエチレ
ンカーボネイト（ＥＣ）と1,3-ジオキソラン（ＤＯ）と
ジメトキシエタン（ＤＭＥ）との４成分よりなる混合溶
媒に、溶質としてＬｉＣＦ3 ＳＯ3 を１mol／ｌ添加し
た系の非水電解液において、ＤＯとＤＭＥをともに 100
容量部、またＰＣとＥＣをそれぞれ０〜 100容量部と10
0〜０容量部の範囲で変えた非水電解液ａの導電率（m
s）を測定した。尚、測定は環境温度20℃で行った。1 mol / l of LiCF 3 SO 3 was added as a solute to a mixed solvent consisting of four components of propylene carbonate (PC), ethylene carbonate (EC), 1,3-dioxolane (DO) and dimethoxyethane (DME). In the non-aqueous electrolyte solution of the system
Capacity part, 0 to 100 parts for PC and EC, and 10 parts for EC
The conductivity (m of the non-aqueous electrolyte a changed in the range of 0 to 0 parts by volume)
s) was measured. The measurement was performed at an ambient temperature of 20 ° C.
【００２５】また、ＤＯとＤＭＥをともに50容量部とし
た他は同じ非水電解液ｂ、並びにＰＣとＥＣにＤＯを各
100容量部加えた混合溶媒を用いた非水電解液ｃ、ＰＣ
とＥＣにＤＭＥを各 100容量部加えた混合溶媒を用いた
非水電解液ｄについても同様な測定を行った。Also, except that both DO and DME are 50 parts by volume, the same non-aqueous electrolyte solution b, and DO for PC and EC respectively.
Non-aqueous electrolyte c, PC using 100 parts by volume of mixed solvent
The same measurement was performed on the non-aqueous electrolyte d using a mixed solvent obtained by adding 100 parts by volume of DME to EC and EC.
【００２６】この測定結果より図１(A) のグラフを得
た。図より、４成分系の非水電解液ａ，ｂの導電率が良
好であることが判る。特にＰＣとＥＣを４：６の容量比
で混合した非水電解液ａが良い結果が得られた。From the measurement results, the graph of FIG. 1 (A) was obtained. From the figure, it can be seen that the conductivity of the four-component non-aqueous electrolyte solutions a and b is good. In particular, good results were obtained with the non-aqueous electrolytic solution a in which PC and EC were mixed at a volume ratio of 4: 6.
【００２７】またＰＣ：ＥＣ：ＤＯ：ＤＭＥを容量比で
0.5 0.5：１：１の割合で混合した溶媒に、ＬｉＣＦ3
ＳＯ3 を主体とし少量のＬｉＣｌＯ4 を添加した混合溶
質を溶解した非水電解液を作った。また、溶媒として
ＰＣ：ＤＯ：ＤＭＥを容量比で 0.5 0.5： 0.5割合で混
合した他は同じ組成，ＥＣ：ＤＯ：ＤＭＥを容量比で0.
5： 0.5： 0.5割合で混合した他は同じ組成のものをそ
れぞれ用いて、非水電解液，を作った。Also, PC: EC: DO: DME in capacity ratio
0.5 0.5: 1: 1 mixed solvent, LiCF 3
A non-aqueous electrolyte solution was prepared in which a mixed solute containing SO 3 as a main component and a small amount of LiClO 4 was dissolved. Further, the same composition except that PC: DO: DME was mixed at a volume ratio of 0.5 0.5: 0.5 as a solvent, and EC: DO: DME was at a volume ratio of 0.
A non-aqueous electrolytic solution was prepared by using the same composition except that they were mixed at a ratio of 5: 0.5: 0.5.
【００２８】上記非水電解液〜で、上記混合溶質の
濃度を 0.4〜２ mol／ｌの範囲で変えた場合における導
電率（ms）の変化を測定した。結果は図１(B) の通りで
ある。The changes in the electric conductivity (ms) when the concentration of the mixed solute was changed within the range of 0.4 to 2 mol / l were measured for the above non-aqueous electrolytes. The results are shown in Fig. 1 (B).
【００２９】そして、これら非水電解液〜をそれぞ
れ電解液に用い、また正極には二酸化マンガンとグラフ
アイトとPTFE粉末を重量比で８：１：0.3混合した正極
合剤をシート状に成形したものを、負極にはリチウム
を、セパレータにはポリプロピレン製不織布をそれぞれ
用いて、図２に示したような直径14.5mm、高さ50.5mmの
円筒形スパイラル形リチウム一次電池をそれぞれ作製し
た。Then, each of these non-aqueous electrolytic solutions 1 to 3 was used as an electrolytic solution, and a positive electrode mixture containing manganese dioxide, graphite and PTFE powder mixed in a weight ratio of 8: 1: 0.3 was formed into a sheet for the positive electrode. Using lithium as the negative electrode and polypropylene non-woven fabric as the separator, a cylindrical spiral lithium primary battery having a diameter of 14.5 mm and a height of 50.5 mm as shown in FIG. 2 was produced.
【００３０】尚、上記電池に使用した非水電解液〜
で、混合溶質はＬｉＣＦ3 ＳＯ3 を１ mol／ｌにＬｉＣ
ｌＯ4 を0.07 mol／ｌ添加したものとした。また図２で
１は電池缶、２〜４はそれぞれ負極，セパレータ，正
極、５〜８はそれぞれリード板，絶縁ガスケット，封口
板，端子板である。The non-aqueous electrolyte used in the above battery
The mixed solute is LiCF 3 SO 3 in 1 mol / l LiC.
lO 4 was used as a material obtained by adding 0.07 mol / l. In FIG. 2, 1 is a battery can, 2-4 are negative electrodes, separators, positive electrodes, and 5-8 are lead plates, insulating gaskets, sealing plates, and terminal plates, respectively.
【００３１】これら３種類の電池を、温度20℃において
抵抗80Ωで端子電圧２Ｖまで放電した所、本発明に係わ
る４成分系の非水電解液を用いた電池の放電持続時間
は38.5時間であったのに対し、従来の３成分系の非水電
解液，を用いた電池では放電時間はそれぞれ33，34
であった。When these three types of batteries were discharged to a terminal voltage of 2 V at a resistance of 80 Ω at a temperature of 20 ° C., the discharge duration of the battery using the four-component non-aqueous electrolyte according to the present invention was 38.5 hours. On the other hand, the discharge time is 33, 34 respectively in the battery using the conventional three-component non-aqueous electrolyte.
Met.
【００３２】一方、上記非水電解液〜（ＬｉＣＦ3
ＳＯ3 １ mol／ｌにＬｉＣｌＯ4 を0.07 mol／ｌ添加し
た混合溶質を用いたもの）をそれぞれ使用して、直径1
4.5mm、高さ50.5mmの円筒形スパイラル形リチウム二次
電池〜を作製した。この場合、正極にはリチウム含
有の改質二酸化マンガンとグラフアイトとPTFE粉末とを
重量比で８：１： 0.3からなる正極合剤をシート状に成
形したもの、負極にはリチウム−アルミニウム合金から
なるもの、またセパレータにはポリプロピレンのマイク
ロポーラスフィルムとポリプロピレン製不織布を積層し
たものをそれぞれ用いた。On the other hand, the above non-aqueous electrolyte solution to (LiCF 3
A mixed solute obtained by adding 0.07 mol / l of LiClO 4 to 1 mol / l of SO 3 ) was used.
A cylindrical spiral lithium secondary battery having a height of 4.5 mm and a height of 50.5 mm was manufactured. In this case, the positive electrode is a sheet-shaped positive electrode mixture composed of modified manganese dioxide containing lithium, graphite and PTFE powder in a weight ratio of 8: 1: 0.3, and the negative electrode is made of a lithium-aluminum alloy. Further, as the separator, a laminate of a polypropylene microporous film and a polypropylene non-woven fabric was used.
【００３３】これらの電池〜について、電流 200mA
で端子電圧２Ｖまで放電し、また電流 200mAで端子電圧
3.6Ｖまで充電するという充放電サイクルを繰返し、各
電池のサイクル中の放電容量の推移を初回の放電容量を
100として調べた。結果は図３(A) の通りである。For these batteries, the current is 200mA.
Discharges to a terminal voltage of 2V, and at a current of 200mA, terminal voltage
The charge / discharge cycle of charging to 3.6V is repeated, and the transition of the discharge capacity of each battery during the cycle is shown as the first discharge capacity.
I checked as 100. The results are shown in Fig. 3 (A).
【００３４】更に、上記非水電解液で、混合溶質とし
てＬｉＣＦ3 ＳＯ3 １ mol／ｌに添加するＬｉＣｌＯ4
を０〜 0.1 mol／ｌの範囲した場合において、電池を60
℃で高温保存した時の内部抵抗ＲAC（Ω）の変化を図３
(B) に示した。電池としては上記図２の形式の円筒形ス
パイラル形リチウム一次電池を用いた。Further, LiClO 4 is added to 1 mol / l of LiCF 3 SO 3 as a mixed solute in the above non-aqueous electrolyte solution.
Battery in the range of 0 to 0.1 mol / l
Figure 3 shows changes in internal resistance RAC (Ω) when stored at high temperature at ℃
It is shown in (B) . As the battery, the cylindrical spiral lithium primary battery of the type shown in FIG. 2 was used.
【００３５】以上はＰＣ，ＥＣ，ＤＯ，ＤＭＥからなる
混合溶媒を用いた例であるが、ＰＣに変えてブチレンカ
ーボネイト（ＢＣ）を用いた場合も、同様な結果を得
た。The above is an example of using a mixed solvent of PC, EC, DO, and DME, but similar results were obtained when butylene carbonate (BC) was used instead of PC.
【００３６】[0036]
【発明の効果】以上の通り、この発明によれば、放電性
能やサイクル特性が優れた一次ないし二次の非水電解液
電池を提供することができる。As described above, according to the present invention, it is possible to provide a primary or secondary non-aqueous electrolyte battery having excellent discharge performance and cycle characteristics.
【図１】(A) は非水電解液に用いる溶媒の混合比率を変
えた場合における導電率の変化を示したグラフ、(B) は
混合溶媒の濃度を変えた場合の導電率の変化を示したグ
ラフである。FIG. 1 (A) is a graph showing the change in conductivity when the mixing ratio of the solvent used for the non-aqueous electrolyte is changed, and (B) is the graph showing the change in conductivity when the concentration of the mixed solvent is changed. It is the graph shown.
【図２】実施例の電池を示した説明図である。FIG. 2 is an explanatory diagram showing a battery of an example.
【図３】(A) は実施例の非水電解液二次電池などのサイ
クル特性を示したグラフ、(B) は非水電解液におけるＬ
ｉＣｌＯ4 の添加量を変えた場合の保存特性を示したグ
ラフである。FIG. 3 (A) is a graph showing cycle characteristics of the non-aqueous electrolyte secondary battery of the example, and (B) is L in the non-aqueous electrolyte.
5 is a graph showing storage characteristics when the amount of iClO 4 added is changed.
１…電池缶 ２…負極 ３…セパレータ ４…正極 ５…リード板 ６…絶縁ガスケット ７…封口板 ８…端子板 DESCRIPTION OF SYMBOLS 1 ... Battery can 2 ... Negative electrode 3 ... Separator 4 ... Positive electrode 5 ... Lead plate 6 ... Insulation gasket 7 ... Sealing plate 8 ... Terminal plate
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59−134568（ＪＰ，Ａ) 特開 平２−44659（ＪＰ，Ａ) 特開 昭52−153118（ＪＰ，Ａ) 特開 平１−236580（ＪＰ，Ａ) 特開 平４−95362（ＪＰ，Ａ)Front page continuation (72) Inventor Masakazu Kitakata, 36-1, Shimbashi, Minato-ku, Tokyo, Fuji Electric Chemical Co., Ltd. (56) Reference JP-A-59-134568 (JP, A) JP-A-2- 44659 (JP, A) JP 52-153118 (JP, A) JP 1-236580 (JP, A) JP 4-95362 (JP, A)
Claims (1)
リチウムを活物質とする負極と、非水溶媒に溶質を溶解
してなる非水電解液を備えた非水電解液電池であって、
前記非水溶媒が、プロピレンカーボネイトまたはブチレ
ンカーボネイトと、エチレンカーボネイトと、1,3-ジオ
キソランと、ジメトキシエタンとの４成分よりなる混合
溶媒であり、 前記溶質がＬｉＣＦ 3 ＳＯ 3 にＬｉＣｌＯ
4 を0.01〜 0.1 mol／ｌ添加したものであることを特徴
とする非水電解液電池。1. A positive electrode using manganese dioxide as an active material ,
A non-aqueous electrolyte battery comprising a negative electrode using lithium as an active material, and a non-aqueous electrolyte formed by dissolving a solute in a non-aqueous solvent,
The non-aqueous solvent, LiClO propylene carbonate or butylene carbonate, and ethylene carbonate, and 1,3-dioxolane, Ri mixed solvent der consisting four components and dimethoxyethane, wherein the solute is in LiCF 3 SO 3
4 0.01 to 0.1 mol / l non-aqueous electrolyte battery, characterized in der Rukoto have been added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2408617A JPH0760705B2 (en) | 1990-12-28 | 1990-12-28 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2408617A JPH0760705B2 (en) | 1990-12-28 | 1990-12-28 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04233168A JPH04233168A (en) | 1992-08-21 |
| JPH0760705B2 true JPH0760705B2 (en) | 1995-06-28 |
Family
ID=18518048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2408617A Expired - Lifetime JPH0760705B2 (en) | 1990-12-28 | 1990-12-28 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760705B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5812991B2 (en) * | 1976-06-15 | 1983-03-11 | 松下電器産業株式会社 | battery |
| JPS59134568A (en) * | 1983-01-24 | 1984-08-02 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
| JPH01236580A (en) * | 1988-03-17 | 1989-09-21 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
| JPH0677465B2 (en) * | 1988-08-01 | 1994-09-28 | 富士電気化学株式会社 | Non-aqueous electrolyte battery |
| JPH0495362A (en) * | 1990-07-31 | 1992-03-27 | Sanyo Electric Co Ltd | Nonaqueous electrolytic battery |
-
1990
- 1990-12-28 JP JP2408617A patent/JPH0760705B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04233168A (en) | 1992-08-21 |
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