JPH10189008A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH10189008A JPH10189008A JP8357963A JP35796396A JPH10189008A JP H10189008 A JPH10189008 A JP H10189008A JP 8357963 A JP8357963 A JP 8357963A JP 35796396 A JP35796396 A JP 35796396A JP H10189008 A JPH10189008 A JP H10189008A
- Authority
- JP
- Japan
- Prior art keywords
- containing compound
- lithium battery
- halogenated
- electrolyte
- halogen
- 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.)
- Pending
Links
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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- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、ハロゲン含有化合
物を単一溶媒又は混合溶媒の一成分として含有する電解
液を備えたリチウム電池に関する。The present invention relates to a lithium battery provided with an electrolyte containing a halogen-containing compound as a single solvent or as a component of a mixed solvent.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム電池が、アルカリ水溶液を電解液として使用す
るアルカリ電池と異なり、水の分解電圧を考慮する必要
がないために高電圧設計が可能であるなどの理由から、
注目されている。2. Description of the Related Art In recent years,
Lithium batteries, unlike alkaline batteries that use an alkaline aqueous solution as the electrolyte, because high voltage design is possible because it is not necessary to consider the decomposition voltage of water,
Attention has been paid.
【０００３】リチウム電池の電解液の溶媒としては、エ
チレンカーボネート、プロピレンカーボネート、ブチレ
ンカーボネート、ジメチルカーボネート、ジエチルカー
ボネート、スルホラン、１，２−ジメトキシエタン、
１，３−ジオキソランなどが使用されている。しかし、
これらの溶媒では、得られる電池特性に限界がある。こ
のため、プロピレンオキサイド、テトラヒドロフランな
どの環状エーテルを単一溶媒又は混合溶媒の一成分とし
て使用することが検討されている。[0003] As a solvent for an electrolyte of a lithium battery, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, sulfolane, 1,2-dimethoxyethane,
1,3-dioxolane and the like are used. But,
These solvents have limitations on the battery characteristics that can be obtained. For this reason, use of a cyclic ether such as propylene oxide or tetrahydrofuran as a single solvent or one component of a mixed solvent has been studied.
【０００４】しかし、環状エーテルは、リチウムとの反
応や、自身のポリマー化により劣化し易いため、これを
含む電解液を使用した場合、保存特性に関して実用上充
分満足のいく電池は得られない。このため、最近、水素
原子の一部又は全部をハロゲン原子で置換した環状エー
テル（ハロゲン化環状エーテル）が新しく提案されてい
る（特開平６−１７６７６８号公報参照）。これは、ハ
ロゲン化により環状エーテルの安定性を高めたものであ
る。However, cyclic ethers are liable to be degraded due to reaction with lithium and polymerization of themselves, so that when an electrolytic solution containing the same is used, a battery having practically satisfactory storage characteristics cannot be obtained. For this reason, recently, a cyclic ether (halogenated cyclic ether) in which part or all of the hydrogen atoms have been substituted with halogen atoms has been newly proposed (see JP-A-6-176768). This is an improvement in the stability of the cyclic ether by halogenation.
【０００５】しかしながら、ハロゲン化環状エーテルを
使用しても、実用上充分満足のいく保存特性を有するリ
チウム電池を得るには到っていないのが実情である。ハ
ロゲン化環状エーテルも、ハロゲン化していない環状エ
ーテルほどではないが、リチウムと反応するからであ
る。However, the fact is that even if a halogenated cyclic ether is used, a lithium battery having sufficiently satisfactory storage characteristics for practical use has not yet been obtained. This is because the halogenated cyclic ether also reacts with lithium, though not so much as the non-halogenated cyclic ether.
【０００６】したがって、本発明は、ハロゲン化環状エ
ーテルなどのハロゲン含有化合物を単一溶媒又は混合溶
媒の一成分として含有する電解液を備えたリチウム電池
の保存特性を改善することを目的とする。Accordingly, an object of the present invention is to improve the storage characteristics of a lithium battery provided with an electrolytic solution containing a halogen-containing compound such as a halogenated cyclic ether as one component of a single solvent or a mixed solvent.
【０００７】[0007]
【課題を解決するための手段】本発明に係るリチウム電
池（以下、「本発明電池」と称する）は、ハロゲン含有
化合物を単一溶媒又は混合溶媒の一成分として含有する
電解液を備えるリチウム電池であって、前記電解液に、
ピリジン及びその誘導体、ピラジン及びその誘導体、ア
ニリン及びその誘導体、アルキルニトリル、Ｎ，Ｎ−ジ
アルキルアセトアミド、Ｎ−アルキルホルムアミド、ト
リアルキルアミン並びにＮ−メチル−２−ピロリドンよ
りなる群から選ばれた少なくとも１種の窒素含有化合物
が添加されていることを特徴とする。SUMMARY OF THE INVENTION A lithium battery according to the present invention (hereinafter referred to as "battery of the present invention") is a lithium battery provided with an electrolytic solution containing a halogen-containing compound as a single solvent or as a component of a mixed solvent. Wherein the electrolytic solution comprises:
At least one selected from the group consisting of pyridine and its derivatives, pyrazine and its derivatives, aniline and its derivatives, alkyl nitrile, N, N-dialkylacetamide, N-alkylformamide, trialkylamine, and N-methyl-2-pyrrolidone It is characterized in that various nitrogen-containing compounds are added.
【０００８】ハロゲン含有化合物としては、ハロゲン化
プロピレンカーボネート、ハロゲン化ジメチルカーボネ
ート、ハロゲン化テトラヒドロフラン、ハロゲン化１，
２−ジメトキシエタン、ハロゲン化γ−ブチロラクトン
及びハロゲン化チオフェンが例示される。ハロゲン化プ
ロピレンカーボネートの具体例としてはトリフルオロプ
ロピレンカーボネート（Ｃ3 Ｈ3 Ｏ3 ＣＦ3 ）が、ハロ
ゲン化ジメチルカーボネートの具体例としてはジトリフ
ルオロメチルカーボネート（ＣＯ3 （ＣＦ3 ）2 ）が、
ハロゲン化テトラヒドロフランの具体例としてはテトラ
ヒドロフルフリルフロリド（Ｃ4 Ｈ7 ＯＣＨ2 Ｆ）、テ
トラヒドロフルフリルクロリド（Ｃ4 Ｈ7 ＯＣＨ2 Ｃ
ｌ）及びテトラヒドロフルフリルブロミド（Ｃ4 Ｈ7 Ｏ
ＣＨ2 Ｂｒ）が、ハロゲン化１，２−ジメトキシエタン
の具体例としては１，２−ビス（２−クロロエトキシエ
タン）（ＣＨ2 ＣｌＣＨ2 ＯＣ2 Ｈ4 ＯＣＨ2 ＣＨ2 Ｃ
ｌ）及び１，２−ビス（２−フロロエトキシエタン）
（ＣＨ2 ＦＣＨ2 ＯＣ2 Ｈ4 ＯＣＨ2 ＣＨ2 Ｆ）が、ハ
ロゲン化γ−ブチロラクトンの具体例としてはα−ブロ
モ−γ−ブチロラクトン（Ｃ4 Ｈ5 Ｏ2 Ｂｒ）及びα−
フルオロ−γ−ブチロラクトン（Ｃ4 Ｈ5 Ｏ2 Ｆ）が、
ハロゲン化チオフェンの具体例としてはヨードチオフェ
ン（Ｃ4 Ｈ3 ＳＩ）及びフルオロチオフェン（Ｃ4 Ｈ3
ＳＦ）が、それぞれ挙げられる。The halogen-containing compounds include halogenated propylene carbonate, halogenated dimethyl carbonate, halogenated tetrahydrofuran, halogenated 1,
Examples are 2-dimethoxyethane, halogenated γ-butyrolactone and halogenated thiophene. Specific examples of the halogenated propylene carbonate include trifluoropropylene carbonate (C 3 H 3 O 3 CF 3 ), and specific examples of the halogenated dimethyl carbonate include ditrifluoromethyl carbonate (CO 3 (CF 3 ) 2 ).
Specific examples of the halogenated tetrahydrofuran include tetrahydrofurfuryl fluoride (C 4 H 7 OCH 2 F) and tetrahydrofurfuryl chloride (C 4 H 7 OCH 2 C).
l) and tetrahydrofurfuryl bromide (C 4 H 7 O
CH 2 Br) is a specific example of halogenated 1,2-dimethoxyethane as 1,2-bis (2-chloroethoxyethane) (CH 2 ClCH 2 OC 2 H 4 OCH 2 CH 2 C
l) and 1,2-bis (2-fluoroethoxyethane)
(CH 2 FCH 2 OC 2 H 4 OCH 2 CH 2 F) is a specific example of the halogenated γ-butyrolactone, α-bromo-γ-butyrolactone (C 4 H 5 O 2 Br) and α-
Fluoro-γ-butyrolactone (C 4 H 5 O 2 F)
Specific examples of the halogenated thiophene include iodothiophene (C 4 H 3 SI) and fluorothiophene (C 4 H 3
SF).
【０００９】電解液としては、保存特性を改善する上
で、上記ハロゲン含有化合物を５体積％以上含有するも
のが好ましい。ハロゲン含有化合物を他の溶媒との混合
溶媒の形態で使用する場合の他の溶媒としては、エチレ
ンカーボネート、プロピレンカーボネート、ブチレンカ
ーボネート、ジメチルカーボネート、エチルメチルカー
ボネート、ジエチルカーボネート、スルホラン、１，２
−ジメトキシエタン、テトラヒドロフラン及び１，３−
ジオキソランが例示される。必要に応じてこれらの他の
溶媒を２種以上使用してもよい。As the electrolytic solution, a solution containing the above-mentioned halogen-containing compound in an amount of 5% by volume or more is preferable for improving storage characteristics. When the halogen-containing compound is used in the form of a mixed solvent with another solvent, other solvents include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 1,2
-Dimethoxyethane, tetrahydrofuran and 1,3-
Dioxolan is exemplified. If necessary, two or more of these other solvents may be used.
【００１０】電解液の電解質塩としては、ＬｉＣＦ3 Ｓ
Ｏ3 、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＣｌＯ4 、ＬｉＡ
ｓＦ6 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＣ（ＣＦ3 Ｓ
Ｏ2）3 及びＬｉＣＦ3 （ＣＦ2 ）3 ＳＯ3 が例示され
る。As the electrolyte salt of the electrolyte, LiCF 3 S
O 3 , LiPF 6 , LiBF 4 , LiClO 4 , LiA
sF 6 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 S
O 2 ) 3 and LiCF 3 (CF 2 ) 3 SO 3 are exemplified.
【００１１】本発明電池の電解液には、ピリジン（Ｃ5
Ｈ5 Ｎ）及びその誘導体〔２−ピコリン（ＣＨ3 Ｃ5 Ｈ
4 Ｎ）など〕、ピラジン（Ｃ4 Ｈ4 Ｎ2 ）及びその誘導
体〔２−メチルピラジン（ＣＨ3 Ｃ4 Ｈ3 Ｎ2 ）な
ど〕、アニリン及びその誘導体〔Ｎ，Ｎ−ジメチルアニ
リン（Ｃ6 Ｈ5 Ｎ（ＣＨ3 ）2 ）など〕、アルキルニト
リル〔アセトニトリル（ＣＨ3 ＣＮ）など〕、Ｎ，Ｎ−
ジアルキルアセトアミド（Ｎ，Ｎ−ジメチルアセトアミ
ドなど）、Ｎ−アルキルホルムアミド（Ｎ−メチルホル
ムアミド（ＨＣＯＮＨＣＨ3 ）など）、トリアルキルア
ミン〔トリメチルアミン（（ＣＨ3 ）3 Ｎ）、トリエチ
ルアミン（（Ｃ2 Ｈ5 ）3 Ｎ）、トリ−ｎ−プロピルア
ミン（（ＣＨ3 ＣＨ2 ＣＨ2 ）3 Ｎ）など〕並びにＮ−
メチル−２−ピロリドンよりなる群から選ばれた少なく
とも１種の窒素含有化合物が添加されている。The electrolyte of the battery of the present invention contains pyridine (C 5
H 5 N) and its derivatives [2-picoline (CH 3 C 5 H
4 N), etc.], pyrazine (C 4 H 4 N 2) and its derivatives [2-methyl-pyrazine (CH 3 C 4 H 3 N 2) , etc.], aniline and derivatives thereof [N, N-dimethylaniline (C 6 H 5 N (CH 3) 2 ) , etc.], and alkyl nitriles [acetonitrile (CH 3 CN)], N, N-
Dialkylacetamides (N, N-dimethylacetamide, etc.), N- alkyl formamide (N- methylformamide (HCONHCH 3), etc.), trialkylamine [trimethylamine ((CH 3) 3 N) , triethylamine ((C 2 H 5) 3 N), tri -n- propylamine ((CH 3 CH 2 CH 2 ) 3 N) , etc.] and N-
At least one nitrogen-containing compound selected from the group consisting of methyl-2-pyrrolidone is added.
【００１２】窒素含有化合物の好適な添加量は、電解液
１００重量部に対して、０．０１〜２０重量部である。
添加量が過少及び過多のいずれの場合も、保存特性を充
分に改善することが困難になる。添加量が過多の場合に
保存特性が低下するのは、余剰の窒素含有化合物が正極
及び負極と反応するためと考えられる。The preferable addition amount of the nitrogen-containing compound is 0.01 to 20 parts by weight based on 100 parts by weight of the electrolyte.
Regardless of whether the amount is too small or too large, it is difficult to sufficiently improve the storage characteristics. It is considered that the storage characteristics are deteriorated when the addition amount is excessive, because excess nitrogen-containing compounds react with the positive electrode and the negative electrode.
【００１３】本発明の特徴は、ハロゲン含有化合物を単
一溶媒又は混合溶媒の一成分として含有する電解液を備
えたリチウム電池の保存特性を改善するために、電解液
に特定の窒素含有化合物を添加した点にある。それゆ
え、正極材料、負極材料などの電池を構成する他の材料
については特に制限は無く、リチウム電池用として従来
使用され、或いは提案されている種々の材料を使用する
ことが可能である。A feature of the present invention is that in order to improve the storage characteristics of a lithium battery provided with an electrolyte containing a halogen-containing compound as a single solvent or a component of a mixed solvent, a specific nitrogen-containing compound is added to the electrolyte. It is at the point of addition. Therefore, other materials constituting the battery, such as a positive electrode material and a negative electrode material, are not particularly limited, and various materials conventionally used or proposed for lithium batteries can be used.
【００１４】正極材料としては、ＭｎＯ2 、ＬｉＣｏＯ
2 、ＬｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＶＯ2 、ＬｉＮ
ｂＯ2 等の金属酸化物が例示され、また負極材料として
は、金属リチウム；リチウム−アルミニウム合金等のリ
チウム合金；及び黒鉛、コークス等の炭素材料が例示さ
れる。As the positive electrode material, MnO 2 , LiCoO
2 , LiNiO 2 , LiMnO 2 , LiVO 2 , LiN
Examples of a metal oxide such as bO 2 and examples of a negative electrode material include lithium metal; a lithium alloy such as a lithium-aluminum alloy; and a carbon material such as graphite and coke.
【００１５】本発明は、一次電池、二次電池を問わず、
広くリチウム電池に適用可能である。The present invention is applicable to both primary and secondary batteries.
Widely applicable to lithium batteries.
【００１６】上述の如き構成の本発明電池が保存特性に
優れる理由は、定かでないが、添加せる窒素含有化合物
がハロゲン含有化合物と負極のリチウムの反応を抑制す
るためと推察される。The reason why the battery of the present invention having the above-described structure is excellent in storage characteristics is not clear, but it is presumed that the nitrogen-containing compound added suppresses the reaction between the halogen-containing compound and lithium in the negative electrode.
【００１７】[0017]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００１８】〈実験１〉この実験では、電解液への特定
の窒素含有化合物の添加が保存特性に及ぼす影響を調べ
た。<Experiment 1> In this experiment, the effect of the addition of a specific nitrogen-containing compound to the electrolytic solution on the storage characteristics was examined.
【００１９】〔正極の作製〕４００°Ｃで加熱処理した
二酸化マンガン粉末と、導電剤としての炭素粉末と、ポ
リテトラフルオロエチレン（ＰＴＦＥ）粉末とを、重量
比８５：１０：５で混合し、円盤状に加圧成形した後、
３００°Ｃで加熱処理して、正極を作製した。[Preparation of Positive Electrode] Manganese dioxide powder heated at 400 ° C., carbon powder as a conductive agent, and polytetrafluoroethylene (PTFE) powder were mixed at a weight ratio of 85: 10: 5, After pressure molding into a disk shape,
Heat treatment was performed at 300 ° C. to produce a positive electrode.
【００２０】〔負極の作製〕金属リチウムの圧延板を円
盤状に打ち抜いて、負極を作製した。[Preparation of Negative Electrode] A rolled sheet of metallic lithium was punched into a disk to prepare a negative electrode.
【００２１】〔電解液の調製〕プロピレンカーボネート
とトリフルオロプロピレンカーボネートとの体積比１：
１の混合溶媒に、ＬｉＣＦ3 ＳＯ3 （トリフルオロメタ
ンスルホン酸リチウム）を１モル／リットル溶かして、
電解液を調製した。次いで、この電解液１００重量部
に、ピリジン、ピラジン、２−ピコリン、アセトニトリ
ル、Ｎ−メチルホルムアミド、Ｎ−メチル−２−ピロリ
ドン、トリエチルアミン、トリ−ｎ−プロピルアミン又
はＮ，Ｎ−ジメチルアニリンを１重量部添加して、窒素
含有化合物を含有する電解液を調製した。[Preparation of Electrolyte Solution] The volume ratio of propylene carbonate to trifluoropropylene carbonate is 1:
1 mol / L of LiCF 3 SO 3 (lithium trifluoromethanesulfonate) is dissolved in
An electrolyte was prepared. Next, pyridine, pyrazine, 2-picoline, acetonitrile, N-methylformamide, N-methyl-2-pyrrolidone, triethylamine, tri-n-propylamine or N, N-dimethylaniline was added to 100 parts by weight of this electrolytic solution. An electrolyte solution containing a nitrogen-containing compound was prepared by adding parts by weight.
【００２２】〔リチウム電池の作製〕上記の正極、負極
及び窒素含有化合物含有電解液を用いて、扁平形の本発
明電池Ａ１〜Ａ９を作製した（電池寸法：外径２０．０
ｍｍ；厚み２．５ｍｍ）。また、別途、窒素含有化合物
を添加しなかったこと以外は先と同様にして、比較電池
Ｂ１を作製した。セパレータには、いずれもポリプロピ
レン製の多孔膜を使用した。[Preparation of Lithium Battery] Using the positive electrode, the negative electrode and the electrolyte containing a nitrogen-containing compound, flat batteries B1 to A9 of the present invention were prepared (battery dimensions: outer diameter 20.0).
mm; thickness 2.5 mm). In addition, a comparative battery B1 was produced in the same manner as above except that the nitrogen-containing compound was not separately added. For each separator, a porous film made of polypropylene was used.
【００２３】〔各電池の保存特性〕これらの各電池を
０．３ｍＡで２Ｖまで放電して、保存前の放電容量Ｄ１
を求めた。また、別途用意した各電池を６０°Ｃで２ヵ
月間保存した後、０．３ｍＡで２Ｖまで放電して、保存
後の放電容量Ｄ２を求めた。放電容量Ｄ１及びＤ２を下
式に代入して、各電池の自己放電率（％）を求めた。各
電池の自己放電率を表１に示す。自己放電率が低いもの
ほど、保存特性に優れている。[Storage characteristics of each battery] Each of these batteries was discharged to 2 V at 0.3 mA to obtain a discharge capacity D1 before storage.
I asked. Each of the separately prepared batteries was stored at 60 ° C. for 2 months, and then discharged to 2 V at 0.3 mA to obtain a discharge capacity D2 after storage. The self-discharge rate (%) of each battery was obtained by substituting the discharge capacities D1 and D2 into the following equation. Table 1 shows the self-discharge rate of each battery. The lower the self-discharge rate, the better the storage characteristics.
【００２４】 自己放電率（％）＝｛（Ｄ１−Ｄ２）／Ｄ１｝×１００Self-discharge rate (%) = {(D1−D2) / D1} × 100
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１に示すように、本発明電池Ａ１〜Ａ９
は、比較電池Ｂ１に比べて、自己放電率が低い。この事
実から、特定の窒素含有化合物を電解液に添加すること
により、リチウム電池の保存特性が改善されることが分
かる。As shown in Table 1, the batteries A1 to A9 of the present invention
Has a lower self-discharge rate than the comparative battery B1. From this fact, it can be seen that the addition of a specific nitrogen-containing compound to the electrolytic solution improves the storage characteristics of the lithium battery.
【００２７】〈実験２〉この実験では、電解液に対する
窒素含有化合物の添加量と保存特性の関係を調べた。<Experiment 2> In this experiment, the relationship between the amount of nitrogen-containing compound added to the electrolyte and the storage characteristics was examined.
【００２８】実験１と同様にして調製した電解液１００
重量部に、ピリジン、アセトニトリル又はトリエチルア
ミンを、０．００１重量部、０．０１重量部、０．１重
量部、１重量部、５重量部、１０重量部、２０重量部又
は３０重量部添加した。窒素含有化合物を含有するこれ
らの電解液を使用したこと以外は実験１と同様にして、
リチウム電池を作製し、各電池の自己放電率を求めた。
結果を表２に示す。表２には、窒素含有化合物を添加し
なかった電池（実験１の電池Ｂ１）の自己放電率も表１
より転記して示してある。Electrolyte 100 prepared in the same manner as in Experiment 1
0.001 part by weight, 0.01 part by weight, 0.1 part by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight or 30 parts by weight of pyridine, acetonitrile or triethylamine were added to parts by weight. . Except for using these electrolytes containing nitrogen-containing compounds, in the same manner as in Experiment 1,
Lithium batteries were prepared, and the self-discharge rate of each battery was determined.
Table 2 shows the results. Table 2 also shows the self-discharge rate of the battery to which no nitrogen-containing compound was added (Battery B1 of Experiment 1).
More transcribed.
【００２９】[0029]
【表２】 [Table 2]
【００３０】表２より、保存特性を改善するためには、
電解液に対するピリジン、アセトニトリル又はトリエチ
ルアミンの添加量を、電解液１００重量部に対して０．
０１〜２０重量部とすることが好ましいことが分かる。
なお、他の窒素含有化合物についても、電解液に対する
添加量はこの範囲が好ましいことを確認した。As shown in Table 2, in order to improve the storage characteristics,
The amount of pyridine, acetonitrile or triethylamine to be added to the electrolyte was adjusted to 0.1 with respect to 100 parts by weight of the electrolyte.
It is understood that it is preferable to set the content to 01 to 20 parts by weight.
In addition, it was confirmed that the addition amount of the other nitrogen-containing compounds to the electrolytic solution was preferably in this range.
【００３１】〈実験３〉この実験では、ハロゲン含有化
合物の種類と保存特性の関係を調べた。<Experiment 3> In this experiment, the relationship between the type of the halogen-containing compound and the storage characteristics was examined.
【００３２】プロピレンカーボネートと、ジトリフルオ
ロメチルカーボネート、テトラヒドロフルフリルクロリ
ド、１，２−ビス（２−クロロエトキシエタン）、テト
ラヒドロフルフリルブロミド、α−ブロモ−γ−ブチロ
ラクトン又はヨードチオフェンとの体積比１：１の混合
溶媒に、ＬｉＣＦ3 ＳＯ3 を１モル／リットル溶かし
て、電解液を調製した。次いで、各電解液１００重量部
に、ピリジンを１重量部添加して、窒素含有化合物を含
有する電解液を調製した。次いで、これらの電解液を使
用したこと以外は実験１と同様にして、リチウム電池Ａ
１０〜Ａ１５を作製し、各電池の自己放電率を求めた。
結果を表３に示す。表３には、リチウム電池Ａ１の自己
放電率も表１より転記して示してある。The volume ratio of propylene carbonate to ditrifluoromethyl carbonate, tetrahydrofurfuryl chloride, 1,2-bis (2-chloroethoxyethane), tetrahydrofurfuryl bromide, α-bromo-γ-butyrolactone or iodothiophene is 1 1 mol / liter of LiCF 3 SO 3 in a mixed solvent of 1: 1 to prepare an electrolyte solution. Next, 1 part by weight of pyridine was added to 100 parts by weight of each electrolytic solution to prepare an electrolytic solution containing a nitrogen-containing compound. Next, a lithium battery A was prepared in the same manner as in Experiment 1 except that these electrolytes were used.
10 to A15 were prepared, and the self-discharge rate of each battery was determined.
Table 3 shows the results. Table 3 also shows the self-discharge rate of the lithium battery A1 transcribed from Table 1.
【００３３】[0033]
【表３】 [Table 3]
【００３４】表３より、ハロゲン含有化合物の種類に関
わらず、窒素含有化合物を電解液に添加することにより
保存特性に優れたリチウム電池が得られることが分か
る。Table 3 shows that regardless of the type of the halogen-containing compound, a lithium battery having excellent storage characteristics can be obtained by adding the nitrogen-containing compound to the electrolytic solution.
【００３５】〈実験４〉この実験では、ハロゲン含有化
合物の含有量と保存特性の関係を調べた。<Experiment 4> In this experiment, the relationship between the content of the halogen-containing compound and the storage characteristics was examined.
【００３６】プロピレンカーボネートと、トリフルオロ
プロピレンカーボネート、テトラヒドロフルフリルクロ
リド、テトラヒドロフルフリルブロミド又はヨードチオ
フェンとの体積比が０：１００（単一溶媒）、２５：７
５、５０：５０、７５：２５、９５：５又は１００：０
（単一溶媒）の溶媒に、トリフルオロメタンスルホン酸
リチウムを１モル／リットル溶かして、電解液を調製
し、これらの各電解液１００重量部にピリジンを１重量
部添加した。次いで、これらの電解液を使用したこと以
外は実験１と同様にして、リチウム電池を作製し、各電
池の自己放電率を求めた。結果を表４に示す。The volume ratio of propylene carbonate to trifluoropropylene carbonate, tetrahydrofurfuryl chloride, tetrahydrofurfuryl bromide or iodothiophene is 0: 100 (single solvent), 25: 7
5, 50:50, 75:25, 95: 5 or 100: 0
Lithium trifluoromethanesulfonate was dissolved at 1 mol / liter in a solvent of (single solvent) to prepare electrolytic solutions, and 1 part by weight of pyridine was added to 100 parts by weight of each of these electrolytic solutions. Next, a lithium battery was prepared in the same manner as in Experiment 1 except that these electrolytic solutions were used, and the self-discharge rate of each battery was determined. Table 4 shows the results.
【００３７】[0037]
【表４】 [Table 4]
【００３８】表４より、電解液に窒素含有化合物を添加
することにより保存特性を改善するためには、ハロゲン
含有化合物を５体積％以上含有する電解液を使用するこ
とが好ましいことが分かる。From Table 4, it can be seen that in order to improve the storage characteristics by adding a nitrogen-containing compound to the electrolytic solution, it is preferable to use an electrolytic solution containing 5% by volume or more of a halogen-containing compound.
【００３９】[0039]
【発明の効果】本発明によれば、ハロゲン含有化合物を
単一溶媒又は混合溶媒の一成分として含有する電解液を
備えたリチウム電池の保存特性が改善される。According to the present invention, the storage characteristics of a lithium battery provided with an electrolyte containing a halogen-containing compound as a single solvent or as a component of a mixed solvent are improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd.
Claims (4)
媒の一成分として含有する電解液を備えたリチウム電池
において、前記電解液に、ピリジン及びその誘導体、ピ
ラジン及びその誘導体、アニリン及びその誘導体、アル
キルニトリル、Ｎ，Ｎ−ジアルキルアセトアミド、Ｎ−
アルキルホルムアミド、トリアルキルアミン並びにＮ−
メチル−２−ピロリドンよりなる群から選ばれた少なく
とも１種の窒素含有化合物が添加されていることを特徴
とするリチウム電池。1. A lithium battery comprising an electrolyte containing a halogen-containing compound as a single solvent or a component of a mixed solvent, wherein the electrolyte contains pyridine and its derivatives, pyrazine and its derivatives, aniline and its derivatives, Alkyl nitrile, N, N-dialkylacetamide, N-
Alkylformamide, trialkylamine and N-
A lithium battery to which at least one nitrogen-containing compound selected from the group consisting of methyl-2-pyrrolidone is added.
ロピレンカーボネート、ハロゲン化ジメチルカーボネー
ト、ハロゲン化テトラヒドロフラン、ハロゲン化１，２
−ジメトキシエタン、ハロゲン化γ−ブチロラクトン及
びハロゲン化チオフェンよりなる群から選ばれた少なく
とも１種のハロゲン化物である請求項１記載のリチウム
電池。2. The method of claim 1, wherein the halogen-containing compound is halogenated propylene carbonate, halogenated dimethyl carbonate, halogenated tetrahydrofuran, halogenated 1,2
The lithium battery according to claim 1, wherein the lithium battery is at least one halide selected from the group consisting of -dimethoxyethane, halogenated γ-butyrolactone, and halogenated thiophene.
部に対して、０．０１〜２０重量部添加されている請求
項１又は２記載のリチウム電池。3. The lithium battery according to claim 1, wherein the nitrogen-containing compound is added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the electrolyte.
５体積％以上含有する請求項１〜３のいずれかに記載の
リチウム電池。4. The lithium battery according to claim 1, wherein the electrolyte contains the halogen-containing compound in an amount of 5% by volume or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8357963A JPH10189008A (en) | 1996-12-27 | 1996-12-27 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8357963A JPH10189008A (en) | 1996-12-27 | 1996-12-27 | Lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10189008A true JPH10189008A (en) | 1998-07-21 |
Family
ID=18456850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8357963A Pending JPH10189008A (en) | 1996-12-27 | 1996-12-27 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10189008A (en) |
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- 1996-12-27 JP JP8357963A patent/JPH10189008A/en active Pending
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