JPH02262270A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH02262270A JPH02262270A JP1082824A JP8282489A JPH02262270A JP H02262270 A JPH02262270 A JP H02262270A JP 1082824 A JP1082824 A JP 1082824A JP 8282489 A JP8282489 A JP 8282489A JP H02262270 A JPH02262270 A JP H02262270A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte battery
- organic electrolyte
- battery according
- salt
- organic
- 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
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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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
［産業上の利用分野１
本発明は、有機電解液電池の改良に係わり、さらに詳し
くは、第一に、低温での放電特性が優秀でしかも放電中
途で電池を保存したときの劣化を防止することに配慮し
、第二に、サイクル充放電の繰り返しに耐える特性をも
たせることに配慮したものである。[Industrial Field of Application 1] The present invention relates to the improvement of organic electrolyte batteries, and more specifically, firstly, it has excellent discharge characteristics at low temperatures and prevents deterioration when the battery is stored in the middle of discharge. Secondly, consideration was given to providing characteristics that can withstand repeated charging and discharging cycles.
【従来の技術］
リチウムを負極とし、ＭｎＯ２を正極として用いたいわ
ゆるリチウム−ＭｎＯ２電池に代表される上記の有機電
解液電池は、高エネルギー密度且つ軽量で長寿命のため
近年需要が増加している。
この電池の電解質としてはＬｉＣｌＯ，がよく用いられ
、溶媒としてはプロピレンカーボネート（以下ＰＣと略
する）とジメトキシエタン（以下ＤＭＥと略する）の混
合溶媒がよく用いられるが、この種の溶媒系は、−２０
℃などの低温での電池特性が悪くなる傾向があった。
これを改善するため、最近カメラ用Ｌｉ電池の一部にＰ
ＣとＤＭＨの他にテトラヒドロフラン（以下ＴＨＥと略
する）を加えた三成分からなる混合溶媒が使用されてい
る。
この電解液系を用いることにより、低温での電池特性は
確かに走路的に向上する。特に重負荷時の効果には著し
いものがある。例えば外径１５ｎｍ、総高４０ｎｎ＋の
筒形Ｌｉ電池でパルス放電を一２０℃で行った場合、０
．６Ｍ ＬｉＣｌＯ４／ＰＣ：ＤＭＥテは、■、７ｖ終
止で９０回しか放電できないのに対し、０．６Ｍ Ｌｉ
Ｃｌ０．／ＰＣ：ＴＨＦ：ＤＭＥを用いることにより、
２００〜３００回のパルス放電が可能となる。
このように、ＰＣ：ＴＨＦ：ＤＭＥ３成分混合溶媒を使
用した電池は低温特性に優れたものである。
しかしながら、この種の電池の低温特性を評価していた
際に、本発明者らは、以下に述べる意外な事実を見い出
したのである。
即ち、この種の電池を、半分以上放電した後に放置して
おくと、低温での優れた放電特性がしだいに失われてい
き、内部抵抗も増加してしまうという現象が認められた
。この現象については、いまだ報告例が無いことから、
本発明者らは、これを究明することとした。
まず、原因となるＴＩＩＦを添加しないで、低温での放
電特性が優秀でしかも放電中途で電池を保存したときの
劣化が防止された電池を提供しようと考え、ＴＨＦを添
加しないで検討を試みたが、ＴＨＦを添加しない０．６
Ｍ ＬｉＣｌＯ４／ＰＣ：ＤＭＥでは、このような内部
抵抗の増加は少ないかわりに、前述の通り低温での特性
は期待できないものであった。
そこで、他の方法、例えば特開昭６３−１１９１６０に
提案されているように、０．５Ｍ ＬｉＣｌＯ４−０，
ＩＭ ＬｉＢＦ４／ＰＣ：Ｄ肚（１：１）を用いた電池
を作成し、−２０℃で放電試験を試みたが、１００パル
ス程度しか放電できず、結局ＴＨＦなしでは低温特性を
改善することができなかった。
以上のことから、低温特性改善のためにはやはりＴＨＦ
などの環状エーテルが必要であるとの見解に達し、環状
エーテルを含んだものであっても、半分以上放電後の内
部抵抗増大が少なくなるように改善することが必要であ
るとの見地に基づき、本発明をなすに至った。
【発明が解決しようとする問題点）
本発明は、上記従来製品が持っていた低温特性の悪さや
放電後の内部抵抗の増大などの欠点を少くすることを目
的とする。
【問題を解決するための手段】
本発明者等は、上記の目的を達成するために鋭意検討し
た結果、電解液にＴＨＦのごとき環状エーテルを含む電
池では、半分以上放電後の内部抵抗が増大することを確
認した。
この原因について究明したところ、第一に、電解液にＴ
ＨＦのごとき環状エーテルを含む場合、放電によって活
性になったＬｉが溶媒と一部反応することを見い出した
。
第二に、この反応にはＴＨＦのごとき環状エーテルが関
与していることをつきとめた。
第三に、この反応においてＴＨＦのごとき環状エーテル
がＬｉ表面に皮膜を形成するための反応場を提供する傾
向があることを発見した。
第四にまた、この反応場としての挙動はＴＨＦのような
環状エーテルを多く加えるにつれて強く現れる傾向があ
ることを見い出した。そしてこの原因はＴＨＦのＡＮ数
（アクセプター数）が低く電解液の酸性度が低下するた
めではないかと推測された。
そこで本発明者らは、このような一連の多数の事実の発
見に基づいて検討したところ、ホウ素元素を分子内に含
み、且つ電解液の酸性度を向上させる化合物を添加する
ことが効果的であるとの考えを持つに至り、環状エーテ
ルを含む有機溶媒にリチウム塩を溶解させた有機電解液
中にホウ素元素を含む化合物を添加したことを特徴とす
る有機電解液電池を提案するに至ったのでる。
本発明において用いられる、ホウ素元素を含む化合物と
しては、ＢＦ、、ＢＣｌ３、ＢＢｒ３などがあるが、中
でもＢＦ３のようにＢ−Ｆ結合を有するものが安定であ
る。ＢＦ、でも単独ではＬｉとやや反応し望ましくない
が、本発明の電解液中においては、エーテルと溶媒和（
ＴＩ（Ｆの場合ならＢＦ、・ＴＨＦ） ｔ、たり、Ｌｉ
ＣｌＯ４やＬｉＣＦ、 Ｓｏ、とある程度複塩（Ｌｉ”
ＢＦ、 Ｃｌ０Ｊ−など）を形成し通常より安定に存在
しうる。
さらに典型的には、予めＬｉＦやＬｉＣ１などのＬｉ塩
と複塩を形成させたＬｉＢＦ、、ＬｉＢＦ３Ｃ１などと
して添加することができる。
これらの複塩としてはＢＦ４−アニオンを有する塩がＬ
ｉとの反応性が少ないことから望ましく、中でもＬｉＢ
Ｆ４が最もよく知られている。
また、このＬｉＢＦ４の応用例としてＬｉ塩を他のカチ
オンで置き換えた、（Ｃ２Ｈ４）４Ｎ ＢＦ４１ （ｎ
−Ｃ４ｔｌ、）４ＮＢＦ４．（Ｃ２Ｈ，）４Ｐ ＢＦ４
なども挙げることができる。
本発明においてより高い効果を望む場合には、例えばＢ
Ｆ４−を含む塩であれば、少くとも１０−３ｍｏｌ／ｌ
以上添加することが好ましい。より望ましくは、［ＢＦ
４−／環状エーテル］のモル濃度比が、ｌＸｌ０−３以
上であることが推奨され、ＢＦ４−濃度の増大につれて
より大きな効果が得られる。
ただ、電池の放電容量を充分にとるには、ＢＦ４−濃度
が、ＬｉＣｌ０．、とＬｉＣＦ３５ｏ、の合計濃度の３
ｏパモル比）を越えない方が望ましい。
環状エーテルとして何を選択するかによって、最適な［
ＢＦ４−］の濃度はある程度具なる。
環状エーテルとして通常テトラヒドロフラン、■、３−
ジオキソラン、２−メチル−テトラヒドロフラン、４−
メチル−１，３−ジオキソランなどが挙げられるが、低
温特性向ヒのためには、テトラヒドロフランや１．３−
ジオキソランが望ましく、中でもテトラヒドロフランは
低温特性向上に最も効果が太きし）。
テトラヒドロフラン（ＴＨＦ）を環状エーテルとして用
い、ＢＦ４−をアニオンとして含むＬｉＢＦ４の場合を
例にとると、［ＬＩＢＦ４／ＴＨＦ］のモル濃度比は２
×１０−３以上であることが望ましい。
またテトラヒドロフランの全溶媒中での体積比率が０．
１以上より望ましくは０．２５以上であることが、低温
特性向上のために望ましい。
環状エーテル以外の溶媒としては、プロピレンカーボネ
ート、エチレンカーボネート、γ〜ブチロラクトンなど
のエステルの少くとも１種を用い、エステルの全溶媒中
での比率が０．０１以上（体積比）であることが望まし
い。
その他の使用可能な溶媒として、１，２−ジメトキシエ
タン、メチルジグライム、エチルグライム、メチルトリ
プライム、スルホランなどがある。
本発明において使用する負極としては、リチウムなどの
アルカリ金属またはその合金、正極としてはＭｎＯ２、
あるいは他の金属酸化物、金属硫化物を用いることがで
き、本発明はこれらの組合せの一次電池、二次電池のど
ちらにおいても有効である。
第１図はこの発明を適用した渦巻型筒形電池の構成例を
示す。この図において、１は正極、２は負極、３は正極
１を包む袋状のセパレータ、４は前記構成の有機電解液
であり、両極は帯状のものを重ねて渦巻状に捲回した状
態で負極缶をなす筒形のステンレス鋼製電池ケース５内
に装填され、その全体が電解液４に浸漬されている。
なお、この発明は、例示した渦巻型以外の各種筒形電池
、ボタン形、コイン形の如き薄型電池など、種々の電池
形態に適用可能である。
【実施例１
以下この発明を実施例に沿って説明する。
実施例１
外径１５ｍｍのステンレス鋼製の電池ケース内に、厚さ
０．１７ｎｎ＋、幅３０ｎｗｎのリチウムからなる帯状
負極と、微孔性ポリプロピレンシートからなる袋状セパ
レータに包んだ厚さ０．４ｍｍ、幅３０Ｈ１のＭｎＯ□
合剤からなる帯状正極とを重ねて渦巻状に捲回した状態
で且つ正負両極のリード体を取り付けて装填するととも
に、プロピレンカーボネートとテトラヒドロフランと１
・２−ジメトキシエタンとの体積比１：１：１の混合溶
媒に０．５モル／ｌのＬｉＣｌＯ４と０．１モル／ｌの
ＬｉＢＦ４とを電解質として溶解し、電解液を注入した
。
ついで、電池を封口し、安定化、エイジングを行い、第
１図で示す構造の渦巻型の筒形電池を作製した。
実施例２
ＬｉＣｌＯ４濃度を０．５７モル／ｌとし、ＬｉＢＦ４
濃度を０゜０３モル／ｌとした以外は実施例１と同様に
筒形電池を作成した。
比較例ｌ
ＬｉＣｌＯ４濃度を０．６モル／ｌとし、ＬｉＢＦ４を
添加しなかった以外は実施例１と同様に筒形電池を作成
した。
これらの実施例１．２および比較例１の電池を８８０ｍ
Ａｈ放電し、４ｈｒ後に１ｋＨｚでの内部抵抗を測定し
た。測定後６０℃で３日貯蔵し内部抵抗の変化を測定し
た。その結果を表１に示す。表よりＬｉＢＦ４を添加す
ることにより、放電後の貯蔵時の内部抵抗の増加がかな
り押えられることがわかる。
また１本発明は二次電池にも適用可能であり、その効果
を検討するため、サイクル試験を行った。
即ち、厚さ１００μｌで１ａａＸ１ａｎの大きさのＬＬ
極を作用極として用い、対極にもＬｉを用いて、０．５
＋ｎＡ／ａイで４時間充電（ＬＬの電着）してのち０．
５ｍＡ／−で４時間放電（Ｌｉ＋の放出）するという操
作を繰返し、作用極の放電終止電圧を測定した。第２図
の結果から明らかなようにこの発明の有機電解液（実施
例１）を使用することにより、二次電池用としてのサイ
クル特性の改善を図れるものであることが判る。[Prior Art] Demand for the above-mentioned organic electrolyte batteries, typified by the so-called lithium-MnO2 battery that uses lithium as a negative electrode and MnO2 as a positive electrode, has increased in recent years because of its high energy density, light weight, and long life. . LiClO is often used as the electrolyte in this battery, and a mixed solvent of propylene carbonate (hereinafter abbreviated as PC) and dimethoxyethane (hereinafter abbreviated as DME) is often used as the solvent, but this type of solvent system , -20
Battery characteristics tended to deteriorate at low temperatures such as °C. To improve this, some Li batteries for cameras have recently been
A mixed solvent consisting of three components is used, in which tetrahydrofuran (hereinafter abbreviated as THE) is added in addition to C and DMH. By using this electrolyte system, battery characteristics at low temperatures are certainly improved. The effect is particularly remarkable under heavy loads. For example, when pulse discharge is performed at -20°C with a cylindrical Li battery with an outer diameter of 15 nm and a total height of 40 nn+, 0
．． 6M LiClO4/PC: DMEte can only be discharged 90 times at 7V termination, whereas 0.6M Li
Cl0. By using /PC:THF:DME,
200 to 300 pulse discharges are possible. As described above, a battery using a 3-component mixed solvent of PC:THF:DME has excellent low-temperature characteristics. However, while evaluating the low-temperature characteristics of this type of battery, the present inventors discovered the unexpected fact described below. That is, a phenomenon has been observed in which if this type of battery is left undisturbed after being discharged to more than half its capacity, its excellent discharge characteristics at low temperatures are gradually lost and its internal resistance increases. Since there are no reported cases of this phenomenon,
The present inventors decided to investigate this. First, we tried to provide a battery that has excellent discharge characteristics at low temperatures and prevents deterioration when stored in the middle of discharge without adding TIIF, which is the cause of the discharge, so we tried to consider it without adding THF. but 0.6 without adding THF
In MLiClO4/PC:DME, although such an increase in internal resistance was small, the characteristics at low temperatures were not as expected as described above. Therefore, other methods such as 0.5M LiClO4-0,
A battery was created using IM LiBF4/PC:D (1:1) and a discharge test was performed at -20°C, but it was only possible to discharge about 100 pulses, and in the end it was not possible to improve the low-temperature characteristics without THF. could not. From the above, THF is still necessary to improve low-temperature characteristics.
Based on the opinion that cyclic ethers such as , the present invention was accomplished. [Problems to be Solved by the Invention] The present invention aims to reduce the drawbacks of the conventional products, such as poor low-temperature characteristics and increased internal resistance after discharge. [Means for Solving the Problem] As a result of intensive studies to achieve the above object, the present inventors have found that in batteries containing a cyclic ether such as THF in the electrolyte, the internal resistance increases after more than half discharge. It was confirmed that When we investigated the cause of this, we found that the first reason was that the electrolyte contained T.
It has been found that when a cyclic ether such as HF is included, Li activated by discharge partially reacts with the solvent. Second, they found that a cyclic ether such as THF is involved in this reaction. Third, we discovered that in this reaction, cyclic ethers such as THF tend to provide a reaction field for forming a film on the Li surface. Fourthly, we have also found that this behavior as a reaction field tends to appear more strongly as more cyclic ether such as THF is added. It was speculated that the cause of this was that the AN number (acceptor number) of THF was low and the acidity of the electrolyte solution was reduced. The inventors of the present invention conducted studies based on the discovery of a large number of facts as described above, and found that it is effective to add a compound that contains boron element in the molecule and improves the acidity of the electrolyte. We came to the idea that there is, and came to propose an organic electrolyte battery characterized by adding a compound containing the boron element to an organic electrolyte solution in which a lithium salt is dissolved in an organic solvent containing a cyclic ether. It comes out. Compounds containing the boron element used in the present invention include BF, BCl3, BBr3, etc. Among them, compounds having a BF bond such as BF3 are stable. BF alone is undesirable as it slightly reacts with Li, but in the electrolyte of the present invention, BF and solvated (
TI (BF in case of F, ・THF) t, tari, Li
ClO4, LiCF, So, and some double salts (Li”
BF, Cl0J-, etc.) and can exist more stably than usual. More typically, it can be added as LiBF, LiBF3C1, etc., which has been formed into a double salt with a Li salt such as LiF or LiC1. As these double salts, salts having BF4-anions are L
Among them, LiB is preferable because of its low reactivity with LiB.
F4 is the best known. In addition, as an application example of this LiBF4, (C2H4)4N BF41 (n
-C4tl, )4NBF4. (C2H,)4P BF4
etc. can also be mentioned. If a higher effect is desired in the present invention, for example, B
For salts containing F4-, at least 10-3 mol/l
It is preferable to add the above amount. More preferably, [BF
It is recommended that the molar concentration ratio of 4-/cyclic ether is 1X10-3 or more, and a greater effect can be obtained as the BF4- concentration increases. However, in order to obtain a sufficient discharge capacity of the battery, the BF4- concentration must be LiCl0. 3 of the total concentration of , and LiCF35o,
It is preferable not to exceed the mol ratio. Depending on what you choose as the cyclic ether, the optimal [
The concentration of BF4-] varies to some extent. The cyclic ether is usually tetrahydrofuran, ■, 3-
Dioxolane, 2-methyl-tetrahydrofuran, 4-
Examples include methyl-1,3-dioxolane, but to improve low-temperature properties, tetrahydrofuran and 1,3-dioxolane are recommended.
Dioxolane is preferable, and among them, tetrahydrofuran is the most effective in improving low-temperature properties). Taking the case of LiBF4 using tetrahydrofuran (THF) as a cyclic ether and containing BF4- as an anion, the molar concentration ratio of [LIBF4/THF] is 2.
It is desirable that it be 10-3 or more. Also, the volume ratio of tetrahydrofuran in all solvents is 0.
A value of 1 or more, more preferably 0.25 or more is desirable for improving low-temperature characteristics. As the solvent other than the cyclic ether, it is desirable to use at least one type of ester such as propylene carbonate, ethylene carbonate, and γ-butyrolactone, and the ratio of the ester in the total solvent is 0.01 or more (volume ratio). . Other usable solvents include 1,2-dimethoxyethane, methyldiglyme, ethylglyme, methyltriprime, sulfolane, and the like. The negative electrode used in the present invention is an alkali metal such as lithium or an alloy thereof, and the positive electrode is MnO2,
Alternatively, other metal oxides and metal sulfides can be used, and the present invention is effective in both primary and secondary batteries using a combination of these. FIG. 1 shows an example of the configuration of a spiral cylindrical battery to which the present invention is applied. In this figure, 1 is a positive electrode, 2 is a negative electrode, 3 is a bag-shaped separator that encloses the positive electrode 1, 4 is an organic electrolyte having the above structure, and both electrodes are formed by overlapping strips and winding them in a spiral shape. It is loaded into a cylindrical stainless steel battery case 5 that forms a negative electrode can, and is entirely immersed in an electrolytic solution 4. Note that the present invention is applicable to various battery forms, such as various cylindrical batteries other than the illustrated spiral type, and thin batteries such as button-shaped and coin-shaped batteries. [Example 1] The present invention will be described below with reference to Examples. Example 1 In a stainless steel battery case with an outer diameter of 15 mm, a band-shaped negative electrode made of lithium with a thickness of 0.17 nn+ and a width of 30 nwn was wrapped in a bag-shaped separator made of a microporous polypropylene sheet with a thickness of 0.4 mm. , MnO□ with width 30H1
A band-shaped positive electrode consisting of a mixture is stacked and wound spirally, and lead bodies of both positive and negative electrodes are attached and loaded, and propylene carbonate, tetrahydrofuran and 1
- 0.5 mol/l LiClO4 and 0.1 mol/l LiBF4 were dissolved as electrolytes in a mixed solvent with 2-dimethoxyethane at a volume ratio of 1:1:1, and the electrolyte solution was injected. The battery was then sealed, stabilized, and aged to produce a spiral cylindrical battery having the structure shown in FIG. Example 2 LiClO4 concentration was 0.57 mol/l, LiBF4
A cylindrical battery was produced in the same manner as in Example 1 except that the concentration was 0.03 mol/l. Comparative Example 1 A cylindrical battery was produced in the same manner as in Example 1 except that the LiClO4 concentration was 0.6 mol/l and LiBF4 was not added. The batteries of Example 1.2 and Comparative Example 1 were
After 4 hours of Ah discharge, the internal resistance at 1 kHz was measured. After the measurement, the sample was stored at 60°C for 3 days and the change in internal resistance was measured. The results are shown in Table 1. It can be seen from the table that by adding LiBF4, the increase in internal resistance during storage after discharge can be suppressed considerably. The present invention is also applicable to secondary batteries, and a cycle test was conducted to examine its effects. That is, LL with a thickness of 100 μl and a size of 1aa×1an
Using the electrode as a working electrode and using Li also as a counter electrode, 0.5
After charging for 4 hours at +nA/a (electrodeposition of LL), 0.
The operation of discharging at 5 mA/- for 4 hours (release of Li+) was repeated, and the final discharge voltage of the working electrode was measured. As is clear from the results shown in FIG. 2, it can be seen that by using the organic electrolyte of the present invention (Example 1), the cycle characteristics for secondary batteries can be improved.
第１図はこの発明の有機電解液電池の構成例を示すモデ
ル的な縦断面図、表１は実施例１，２、比較例１の各電
池の放電後の内部抵抗変化を示す特性表、第２図は上記
の実施例１．比較例１に用いた有機電解液についてのサ
イクル特性の試験結果を示す特性図である。
特許出願人 日立マクセル株式会社
代表者 水弁 厚
表１
第１図
＋０ ２０ １０ ４０
サイクル数（回）
第２図
手続補正書（方式）
１、事件の表示
平成１年特許願第８２８２４号
２、発明の名称
有機電解液電池
３、補正をする者
事件との関係 特許出願人
郵便番号 ５６フ
イＪ＜ラキシ ウシトラ
住所 大阪府茨木市丑寅１丁目１番８８号氏名
ピッチ
日立マクセル株式会社
フタ ナベ ヒロシ
代表者 渡 遣 宏
Ｕ先 電話（０２０７２）４−１１２７ 特許情報部
４、補正命令の日付（発送口）
５、補正の対象
（１）明細書の「発明の詳細な説明」の欄。
２）明細書の「図面の簡単な説明」の欄。
３）図面
６、補正の内容
（１）明細書第１３頁の第１６行目と第１７行目との間
に、以下の表を挿入する。
「 表１ 各電池の放電後の内部抵抗変化（２）明細書
第１３頁の第１７行目の「［図面の簡単な説明］」を「
４、図面の簡単な説明」と補正する。
（３）明細書第１３頁の第１９行目から第１４頁第１行
目までの［表１は実施例１，２、比較例１の各電池の放
電後の内部抵抗変化を示す特性表、」の記載を削除する
。
（４）図面中、表１を記載した第２図を、別紙補正図面
の通り、表１を削除した第２図に補正する。
７、添付書類の目録
（１）補正図面 １通＋Ｑ
２０ ：’ＩＱ ４０サイクル数（回）
第２図FIG. 1 is a model vertical cross-sectional view showing an example of the structure of an organic electrolyte battery of the present invention, Table 1 is a characteristic table showing internal resistance changes after discharge of each battery of Examples 1 and 2 and Comparative Example 1, FIG. 2 shows the above embodiment 1. 3 is a characteristic diagram showing test results of cycle characteristics of an organic electrolyte used in Comparative Example 1. FIG. Patent Applicant Hitachi Maxell Co., Ltd. Representative Mizuben Atsushi Table 1 Figure 1 +0 20 10 40 Number of cycles (times) Figure 2 Procedural amendment (method) 1. Indication of the case 1999 Patent Application No. 82824 2. Name of the invention Organic electrolyte battery 3. Relationship with the case of the person making the amendment Patent applicant Zip code 56 Fui J < Rakishi Ushitra Address 1-1-88 Ushitora, Ibaraki-shi, Osaka Name Pitch Hitachi Maxell Co., Ltd. Representative Hiroshi Futanabe Person: Hiroshi Watari Telephone: (02072) 4-1127 Patent Information Department 4. Date of amendment order (shipping address) 5. Subject of amendment (1) "Detailed description of the invention" column of the specification. 2) "Brief explanation of drawings" column in the specification. 3) Drawing 6, contents of amendment (1) The following table is inserted between line 16 and line 17 on page 13 of the specification. "Table 1 Internal resistance change after discharge of each battery (2) "[Brief explanation of drawings]" on page 13, line 17 of the specification"
4. A brief explanation of the drawings”. (3) From line 19 on page 13 of the specification to line 1 on page 14 [Table 1 is a characteristic table showing the internal resistance change after discharge of each battery of Examples 1 and 2 and Comparative Example 1. ," will be deleted. (4) In the drawings, Figure 2, which shows Table 1, is amended to Figure 2 with Table 1 deleted, as shown in the attached revised drawing. 7. List of attached documents (1) 1 amended drawing + Q
20:'IQ 40 cycle number (times) Figure 2
Claims (16)
させた有機電解液と、正極、負極、セパレータとを構成
要素とし、前記電解液中にホウ素元素を含む化合物を添
加したことを特徴とする有機電解液電池。(1) It is characterized in that its constituent elements are an organic electrolytic solution in which a lithium salt is dissolved in an organic solvent containing a cyclic ether, a positive electrode, a negative electrode, and a separator, and a compound containing a boron element is added to the electrolytic solution. Organic electrolyte battery.
ことを特徴とする請求項（１）記載の有機電解液電池。(2) The organic electrolyte battery according to claim 1, wherein the solvent contains 1% or more (volume ratio) of ester.
３ＳＯ＿３の少くとも一種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。(3) The lithium salt is LiClO_4 and LiCF_
The organic electrolyte battery according to claim 1, characterized in that the electrolyte is at least one type of 3SO_3.
る化合物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。(4) The organic electrolyte battery according to claim 1, wherein the compound containing the boron element is a compound having a B-F bond.
Ｆ＿３の溶媒和物及びＢＦ＿３と他の塩との複塩のうち
の少くとも一種であることを特徴とする請求項（４）記
載の有機電解液電池。(5) The compound having the BF bond is BF_3, B
The organic electrolyte battery according to claim 4, wherein the organic electrolyte battery is at least one of a solvate of F_3 and a double salt of BF_3 and another salt.
を含む塩であることを特徴とする請求項（５）記載の有
機電解液電池。(6) The double salt of BF_3 and another salt is BF_4^-
The organic electrolyte battery according to claim 5, wherein the organic electrolyte battery is a salt containing.
して、１０＾−＾３モル／ｌ以上添加したことを特徴と
する請求項（１）記載の有機電解液電池。(7) The organic electrolyte battery according to claim (1), wherein the compound containing the boron element is added to the entire electrolyte in an amount of 10^-^3 mol/l or more.
前記リチウム塩の溶解量の３０％以下であることを特徴
とする請求項（１）記載の有機電解液電池。(8) The organic electrolyte battery according to claim 1, wherein the amount of the compound containing the boron element added is 30% or less of the dissolved amount of the lithium salt in terms of molar ratio.
状エーテルに対して、モル比で１０＾−＾３以上である
ことを特徴とする請求項（１）記載の有機電解液電池。(9) The organic electrolyte battery according to claim (1), wherein the amount of the compound containing the boron element added is 10^-^3 or more in molar ratio to the cyclic ether.
ことを特徴とする請求項（１）記載の有機電解液電池。(10) The organic electrolyte battery according to claim 1, wherein the cyclic ether is tetrahydrofuran.
環状エーテルに対して、モル比で２×１０＾−＾３以上
であることを特徴とする請求項（１０）記載の有機電解
液電池。(11) The organic electrolyte battery according to claim (10), wherein the amount of the compound containing the boron element added is 2 x 10^-^3 or more in molar ratio to the cyclic ether. .
で０．１以上を含むことを特徴とする請求項（１）記載
の有機電解液電池。(12) The organic electrolyte battery according to claim 1, wherein the organic solvent contains the cyclic ether in a volume ratio of 0.1 or more.
特徴とする請求項（１）記載の有機電解液電池。(13) The organic electrolyte battery according to claim (1), wherein the lithium salt is LiClO_4.
ーテルを含むことを特徴とする請求項（１）記載の有機
電解液電池。(14) The organic electrolyte battery according to claim (1), wherein the organic solvent contains a cyclic ether, an ester, and a chain ether.
ことを特徴とする請求項（１４）記載の有機電解液電池
。(15) The organic electrolyte battery according to claim 14, wherein the ester is propylene carbonate.
とを特徴とする請求項（１４）記載の有機電解液電池。(16) The organic electrolyte battery according to claim 14, wherein the chain ether is dimethoxyethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1082824A JP2634904B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1082824A JP2634904B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02262270A true JPH02262270A (en) | 1990-10-25 |
| JP2634904B2 JP2634904B2 (en) | 1997-07-30 |
Family
ID=13785151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1082824A Expired - Lifetime JP2634904B2 (en) | 1989-03-31 | 1989-03-31 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2634904B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2717620A1 (en) * | 1994-03-21 | 1995-09-22 | Centre Nat Rech Scient | Additive limiting the corrosion of the collector in an electrochemical cell. |
| JP2004342607A (en) * | 2003-04-25 | 2004-12-02 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution for lithium battery and its manufacturing method, and lithium ion secondary battery |
| WO2008032795A1 (en) * | 2006-09-14 | 2008-03-20 | National University Corporation Shizuoka University | Electrolytic solution for electrochemical device |
| WO2008151902A1 (en) * | 2007-06-15 | 2008-12-18 | Robert Bosch Gmbh | Additives for lithium ion accumulators |
| US8986896B2 (en) | 2008-09-11 | 2015-03-24 | Toyota Jidosha Kabushiki Kaisha | Electrolyte solution and use therefor |
| US9105942B2 (en) | 2010-12-27 | 2015-08-11 | Toyota Jidosha Kabushiki Kaisha | Non-aqueous electrolyte solution and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5987772A (en) * | 1982-11-10 | 1984-05-21 | Sanyo Electric Co Ltd | Organic electrolyte battery |
| JPS63119160A (en) * | 1987-09-24 | 1988-05-23 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
-
1989
- 1989-03-31 JP JP1082824A patent/JP2634904B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5987772A (en) * | 1982-11-10 | 1984-05-21 | Sanyo Electric Co Ltd | Organic electrolyte battery |
| JPS63119160A (en) * | 1987-09-24 | 1988-05-23 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2717620A1 (en) * | 1994-03-21 | 1995-09-22 | Centre Nat Rech Scient | Additive limiting the corrosion of the collector in an electrochemical cell. |
| JP2004342607A (en) * | 2003-04-25 | 2004-12-02 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution for lithium battery and its manufacturing method, and lithium ion secondary battery |
| WO2008032795A1 (en) * | 2006-09-14 | 2008-03-20 | National University Corporation Shizuoka University | Electrolytic solution for electrochemical device |
| JPWO2008032795A1 (en) * | 2006-09-14 | 2010-01-28 | 国立大学法人静岡大学 | Electrolyte for electrochemical devices |
| US8241787B2 (en) | 2006-09-14 | 2012-08-14 | National University Corporation Shizuoka University | Liquid electrolyte for electrochemical device |
| JP5155868B2 (en) * | 2006-09-14 | 2013-03-06 | 国立大学法人静岡大学 | Electrolyte for electrochemical devices |
| WO2008151902A1 (en) * | 2007-06-15 | 2008-12-18 | Robert Bosch Gmbh | Additives for lithium ion accumulators |
| JP2010529628A (en) * | 2007-06-15 | 2010-08-26 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Additives for lithium ion batteries |
| US9318772B2 (en) | 2007-06-15 | 2016-04-19 | Robert Bosch Gmbh | Additives for lithium-ion accumulators |
| US8986896B2 (en) | 2008-09-11 | 2015-03-24 | Toyota Jidosha Kabushiki Kaisha | Electrolyte solution and use therefor |
| US9105942B2 (en) | 2010-12-27 | 2015-08-11 | Toyota Jidosha Kabushiki Kaisha | Non-aqueous electrolyte solution and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2634904B2 (en) | 1997-07-30 |
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