JP3086510B2 - Non-aqueous electrolyte lithium battery - Google Patents
Non-aqueous electrolyte lithium batteryInfo
- Publication number
- JP3086510B2 JP3086510B2 JP03287933A JP28793391A JP3086510B2 JP 3086510 B2 JP3086510 B2 JP 3086510B2 JP 03287933 A JP03287933 A JP 03287933A JP 28793391 A JP28793391 A JP 28793391A JP 3086510 B2 JP3086510 B2 JP 3086510B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- battery
- lithium battery
- present
- heterocyclic compound
- 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
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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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- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水系電解液リチウム
電池に係わり、詳しくは金属酸化物を主材とする正極
と、Ｌｉ又はＬｉを吸蔵放出可能な物質を主材とする負
極と、これら正負両極間に介装されたセパレータと、非
水系電解液とを備えるリチウム電池についての、非水系
電解液の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte lithium battery, and more particularly, to a positive electrode mainly composed of a metal oxide, a negative electrode mainly composed of Li or a substance capable of occluding and releasing Li, The present invention relates to improvement of a non-aqueous electrolyte for a lithium battery including a separator interposed between these positive and negative electrodes and a non-aqueous electrolyte.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
Ｌｉと水との易反応性のために水系電解液を使用するこ
とが出来ないリチウム電池の非水系電解液の一つとし
て、酸素をヘテロ元素とする複素環式化合物に過塩素酸
リチウム等の溶質を溶かしたものが実用されている。こ
れは、酸素をヘテロ元素とする複素環式化合物を用いた
場合、これとＬｉとの反応により、Ｌｉ2 Ｏ3 やＬｉ2
Ｏ主体の保護膜が負極表面上に生成することが知られて
おり、この保護膜の性質が一次電池の保存特性や二次電
池の充放電サイクル特性に大きな影響を及ぼしていると
考えられる。しかしながら、このような保護膜のみでは
被膜の緻密さや厚みなどが不均一で、良好な保護作用が
得られず、またＬｉ+ イオン導電性も不充分なため、一
次電池の保存特性や二次電池の充放電サイクル特性にお
いて満足できる性能が得られていなかった。2. Description of the Related Art
As one of the non-aqueous electrolytes for lithium batteries in which an aqueous electrolyte cannot be used due to the easy reactivity between Li and water, a heterocyclic compound containing oxygen as a hetero element such as lithium perchlorate is used. What melt | dissolved solute is used practically. This is because, when a heterocyclic compound having oxygen as a hetero element is used, Li 2 O 3 or Li 2
It is known that a protective film mainly composed of O is formed on the surface of the negative electrode, and it is considered that the properties of the protective film greatly affect the storage characteristics of the primary battery and the charge / discharge cycle characteristics of the secondary battery. However, with such a protective film alone, the denseness and thickness of the film are not uniform, so that a good protective action cannot be obtained, and the Li + ion conductivity is insufficient, so that the storage characteristics of the primary battery and the secondary battery No satisfactory performance was obtained in the charge / discharge cycle characteristics of
【０００３】上記問題を解決するために鋭意検討した結
果、本発明者らは、特定の電解液に特定の複素環式化合
物を添加剤として適量配合してなる非水系電解液をリチ
ウム電池の電解液に適用すれば、Ｌｉ表面に薄くて緻密
な良好な保護膜が形成され、その結果、電池の自己放電
を可及的に抑制することができ、保存特性に優れたリチ
ウム一次電池或いは充放電サイクル特性に優れたリチウ
ム二次電池が得られるとの知見を得た。本発明は、かか
る知見に基づきなされたものであって、その目的とする
ところは、保存特性（一次電池）或いは充放電サイクル
特性（二次電池）に優れた非水系電解液リチウム電池を
提供するにある。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a non-aqueous electrolyte prepared by mixing an appropriate amount of a specific heterocyclic compound as an additive with a specific electrolyte is used for the electrolysis of lithium batteries. When applied to a liquid, a thin and dense good protective film is formed on the Li surface, and as a result, self-discharge of the battery can be suppressed as much as possible, and a lithium primary battery or a charge / discharge having excellent storage characteristics can be obtained. It has been found that a lithium secondary battery having excellent cycle characteristics can be obtained. The present invention has been made based on such knowledge, and an object of the present invention is to provide a nonaqueous electrolyte lithium battery excellent in storage characteristics (primary battery) or charge / discharge cycle characteristics (secondary battery). It is in.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水系電解液リチウム電池は、 金属酸
化物を主材とする正極と、Ｌｉ又はＬｉを吸蔵放出可能
な物質を主材とする負極と、これら正負両極間に介装さ
れたセパレータと、非水系電解液とを備えてなる非水系
電解液リチウム電池であって、前記非水系電解液は、エ
チレンカーボネートを含有せる非水系溶媒にフッ素含有
リチウム塩を含有せる溶質を溶かして得た溶液に、チア
ゾール、チアゾリン、チアゾリジン、及び、それらの誘
導体よりなる群から選ばれた少なくとも一種のＳ及びＮ
をヘテロ元素とする複素環式化合物が添加されてなるも
のであることを特徴とする。To achieve the above object, a nonaqueous electrolyte lithium battery according to the present invention comprises a positive electrode mainly composed of a metal oxide and a material capable of occluding and releasing Li or Li. A non-aqueous electrolyte lithium battery comprising a negative electrode as a material, a separator interposed between the positive and negative electrodes, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte includes a non-aqueous electrolyte containing ethylene carbonate. In a solution obtained by dissolving a solute containing a fluorine-containing lithium salt in an aqueous solvent, thia
Sols, thiazolines, thiazolidines and their derivatives
At least one S and N selected from the group consisting of conductors
And a heterocyclic compound having a hetero element as a hetero element.
【０００５】本発明における正極材料としての金属酸化
物としては、Ｍｎ、Ｃｏ、Ｎｉ、Ｖ又はＣｒの酸化物
や、それら金属の２種又はそれ以上の複合酸化物が例示
される。これらの金属酸化物を、アセチレンブラック、
カーボンブラック等の導電剤及びポリテトラフルオロエ
チレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＦＶ）
等の結着剤と混練して正極合剤とする。[0005] Examples of the metal oxide as the positive electrode material in the present invention include oxides of Mn, Co, Ni, V, and Cr, and composite oxides of two or more of these metals. These metal oxides, acetylene black,
Conductive agent such as carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PFV)
And the like to form a positive electrode mixture.
【０００６】本発明における好適な負極材料としては、
Ｌｉ金属単体が代表的なものとして挙げられるが、その
他Ｌｉを吸蔵放出可能な物質であれば特に制限なく用い
ることができる。かかるＬｉを吸蔵放出可能な物質とし
ては、リチウム−アルミニウム合金等のリチウム合金や
炭素材料が例示される。炭素材料としては、コークス、
好ましくは純度９９％以上の精製コークス、セルロース
等を焼成してなる有機物焼成体、黒鉛、及び、グラッシ
ーカーボン（ガラス状カーボン）が挙げられる。なお、
これらの多孔質炭素材料は一種単独を用いてもよく、必
要に応じて２種以上を併用してもよい。炭素材料を用い
る場合は、ポリテトラフルオロエチレン（ＰＴＦＥ）、
ポリフッ化ビニリデン（ＰＦＶ）等の結着剤と混練して
負極合剤とする。The preferred negative electrode material in the present invention includes:
Li metal alone can be mentioned as a typical example, but any other substance capable of inserting and extracting Li can be used without any particular limitation. Examples of the substance capable of inserting and extracting Li include a lithium alloy such as a lithium-aluminum alloy and a carbon material. As carbon materials, coke,
Preferably, an organic material fired body obtained by firing refined coke or cellulose having a purity of 99% or more, graphite, and glassy carbon (glassy carbon) are included. In addition,
One of these porous carbon materials may be used alone, or two or more thereof may be used in combination as needed. When using a carbon material, polytetrafluoroethylene (PTFE),
A negative electrode mixture is obtained by kneading with a binder such as polyvinylidene fluoride (PFV).
【０００７】本発明におけるセパレータとしては、たと
えばイオン導電性に優れたポリエチレン、ポリプロピレ
ンなど、従来リチウム電池用として使用されている種々
のものを用いることができる。[0007] As the separator in the present invention, for example, various separators conventionally used for lithium batteries such as polyethylene and polypropylene having excellent ionic conductivity can be used.
【０００８】本発明においては、非水系電解液として、
エチレンカーボネートを含有せる非水系溶媒にフッ素含
有リチウム塩を含有せる溶質を溶かして得た溶液に、Ｓ
及び／又はＮをヘテロ元素とする複素環式化合物を添加
したものが用いられる。[0008] In the present invention, as the non-aqueous electrolyte,
In a solution obtained by dissolving a solute containing a fluorine-containing lithium salt in a non-aqueous solvent containing ethylene carbonate,
And / or a heterocyclic compound containing N as a hetero element is added.
【０００９】上記非水系溶媒としては、エチレンカーボ
ネートを含むものであればよく、他に特に制限はない。
かかる非水系溶媒としては、たとえばエチレンカーボネ
ート／プロピレンカーボネート、エチレンカーボネート
／ジメトキシエタン等の２成分系混合溶媒、エチレンカ
ーボネート／プロピレンカーボネート／ジメトキシエタ
ン等の３成分系混合溶媒が挙げられる。The non-aqueous solvent is not particularly limited, as long as it contains ethylene carbonate.
Examples of such non-aqueous solvents include binary mixed solvents such as ethylene carbonate / propylene carbonate and ethylene carbonate / dimethoxyethane, and ternary mixed solvents such as ethylene carbonate / propylene carbonate / dimethoxyethane.
【００１０】上記溶質としてのフッ素含有リチウム塩と
しては、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＣＦ3 ＳＯ3 、
ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＣ（ＣＦ3 ＳＯ2 ）
3 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 が例示される。これらの
フッ素含有リチウム塩は、一種単独を用いてもよく、必
要に応じて２種以上を併用してもよい。[0010] The fluorine-containing lithium salt as the solute includes LiPF 6 , LiBF 4 , LiCF 3 SO 3 ,
LiAsF 6 , LiSbF 6 , LiC (CF 3 SO 2 )
3 and LiN (CF 3 SO 2 ) 2 . One of these fluorine-containing lithium salts may be used alone, or two or more thereof may be used in combination as needed.
【００１１】[0011]
【００１２】チアゾール誘導体としては、２−メチルチ
アゾール、４−メチルチアゾールが、チアゾリン誘導体
としては、２−メチル−２−チアゾリン、４−メチル−
２−チアゾリン、２，４−ジメチルチアゾリンが、チア
ゾリジン誘導体としては、２−メチルチアゾリジン、４
−メチルチアゾリジン、２，４−ジメチルチアゾリジ
ン、２−エチルチアゾリジン、４−エチルチアゾリジン
がそれぞれ例示される。これらの複素環式化合物は、一
種単独を用いてもよく、必要に応じて２種以上を併用し
てもよい。[0012] The thiazole derivatives, 2-methylthiazole, 4-methylthiazole, and examples of the thiazoline derivative, 2-methyl-2-thiazoline, 4-methyl -
2-thiazoline and 2,4-dimethylthiazoline are exemplified by 2-methylthiazolidine as a thiazolidine derivative.
-Methylthiazolidine, 2,4-dimethylthiazolidine, 2-ethylthiazolidine, and 4-ethylthiazolidine. One of these heterocyclic compounds may be used alone, or two or more of them may be used in combination as needed.
【００１３】本発明におけるエチレンカーボネートを含
有せる非水系溶媒にフッ素含有リチウム塩を含有せる溶
質を溶かして得た溶液への複素環式化合物の好適な添加
割合は、複素環式化合物の種類によって多少異なるが、
体積比（以下における「部」についても同様）で溶液１
００部に対して、一般に複素環式化合物０．１〜５．０
部程度である。この範囲を外れると、一次電池にあって
は良好な保存特性が、また二次電池にあっては良好な充
放電サイクル特性が得られ難い傾向がある。因みに、複
素環式化合物として４−メチルチアゾールを用いる場合
の最適な添加割合は、１．０部程度である。In the present invention, the preferable addition ratio of the heterocyclic compound to the solution obtained by dissolving the solute containing the fluorine-containing lithium salt in the non-aqueous solvent containing ethylene carbonate depends on the kind of the heterocyclic compound. Different,
Solution 1 at a volume ratio (the same applies to “parts” below)
In general, the heterocyclic compound is used in an amount of 0.1 to 5.0 relative to 00 parts.
Parts. Outside this range, good storage characteristics tend to be difficult to obtain for primary batteries, and good charge / discharge cycle characteristics for secondary batteries. Incidentally, when 4-methylthiazole is used as the heterocyclic compound, the optimum addition ratio is about 1.0 part.
【００１４】[0014]
【作用】本発明に係るリチウム電池においては、非水系
電解液として、エチレンカーボネートを含有する非水系
溶媒にフッ素含有リチウム塩を含有する溶質を溶かして
得た溶液に、チアゾール、チアゾリン、チアゾリジン、
及び、それらの誘導体よりなる群から選ばれた少なくと
も一種のＳ及びＮをヘテロ元素とする複素環式化合物が
添加されたものが用いられるので、負極上のＬｉの表面
に薄くて緻密な保護膜が形成される。この保護膜によ
り、Ｌｉと電解液との反応による自己放電が抑制され、
保存特性や充放電サイクル特性が向上する。In the lithium battery according to the present invention, thiazole, thiazoline, thiazolidine, and the like are dissolved in a solution obtained by dissolving a solute containing a fluorine-containing lithium salt in a nonaqueous solvent containing ethylene carbonate as a nonaqueous electrolyte .
And at least one selected from the group consisting of their derivatives
Since a type to which a heterocyclic compound containing S and N as a hetero element is added is used, a thin and dense protective film is formed on the surface of Li on the negative electrode. By this protective film, self-discharge due to the reaction between Li and the electrolyte is suppressed,
Storage characteristics and charge / discharge cycle characteristics are improved.
【００１５】[0015]
【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より何ら限定され
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, but the present invention is not limited to the following Examples, and may be carried out by appropriately changing the scope of the present invention. Is possible.
【００１６】（Ａ）非水系電解液二次電池の作製 （実施例１） 〔正極の作製〕Ｌｉを含有させたＭｎＯ2 と、導電剤と
してのアセチレンブラックと、結着剤としてのフッ素樹
脂粉末とを、８５：１０：５の重量比で混合して正極合
剤を得た。この正極合剤を加圧成形し、得られた成形品
を２５０〜３５０°Ｃで２時間熱処理して正極を作製し
た。(A) Preparation of Nonaqueous Electrolyte Secondary Battery (Example 1) [Preparation of Positive Electrode] MnO 2 containing Li, acetylene black as a conductive agent, and fluororesin powder as a binder Were mixed at a weight ratio of 85: 10: 5 to obtain a positive electrode mixture. This positive electrode mixture was subjected to pressure molding, and the obtained molded article was heat-treated at 250 to 350 ° C for 2 hours to produce a positive electrode.
【００１７】〔負極の作製〕リチウム圧延板を所定寸法
に打ち抜いて負極を作製した。[Preparation of Negative Electrode] A negative electrode was prepared by punching a rolled lithium plate into a predetermined size.
【００１８】〔非水系電解液の調製〕表１に示すよう
に、エチレンカーボネートとジメトキシエタンとの体積
比５０：５０の混合溶媒に、溶質としてのＬｉＰＦ6 を
１モル／リットル混合して得た溶液１００部に対して、
複素環式化合物としての４−メチルチアゾールを１部添
加して非水系電解液を調製した。[Preparation of Nonaqueous Electrolyte] As shown in Table 1, LiPF 6 as a solute was mixed at 1 mol / l with a mixed solvent of ethylene carbonate and dimethoxyethane at a volume ratio of 50:50. For 100 parts of solution,
One part of 4-methylthiazole as a heterocyclic compound was added to prepare a non-aqueous electrolyte.
【００１９】[0019]
【表１】 [Table 1]
【００２０】〔二次電池の作製〕以上の正負両極及び非
水系電解液を用いて扁平形の本発明に係るリチウム二次
電池ＢＡ１を作製した。なお、セパレータとしては、ポ
リプロピレン製の微孔性薄膜を用いた。[Preparation of Secondary Battery] A flat lithium secondary battery BA1 according to the present invention was prepared using the positive and negative electrodes and the non-aqueous electrolyte described above. As the separator, a microporous thin film made of polypropylene was used.
【００２１】図１は作製した本発明に係るリチウム二次
電池ＢＡ１の断面図であり、電池ＢＡ１は、正極１、負
極２、これら両電極を離隔するセパレータ３、正極缶
４、負極缶５、フェライト系ステンレス鋼（ＳＵＳ４３
０）製の正極集電体６、それと同じ材料からなる負極集
電体７及びポリプロピレン製の絶縁パッキング８などか
らなる。正極１及び負極２は、非水系電解液を含浸した
セパレータ３を介して対向して正負両極缶４、５が形成
する電池ケース内に収容されており、正極１は正極集電
体６を介して正極缶４に、また負極２は負極集電体７を
介して負極缶５に接続され、電池ＢＡ１内部で生じた化
学エネルギーを正極缶４及び負極缶５の両端子から電気
エネルギーとして外部へ取り出し得るようになってい
る。FIG. 1 is a sectional view of a manufactured lithium secondary battery BA1 according to the present invention. The battery BA1 has a positive electrode 1, a negative electrode 2, a separator 3 separating these electrodes, a positive electrode can 4, a negative electrode can 5, Ferritic stainless steel (SUS43
0), a negative electrode current collector 7 made of the same material as the positive electrode current collector 6, and an insulating packing 8 made of polypropylene. The positive electrode 1 and the negative electrode 2 face each other via a separator 3 impregnated with a non-aqueous electrolyte, and are housed in a battery case formed by positive and negative bipolar cans 4 and 5. And the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7, and the chemical energy generated inside the battery BA 1 is externally output as electric energy from both terminals of the positive electrode can 4 and the negative electrode can 5. It can be taken out.
【００２２】（比較例１）溶質として同モル量のＬｉＣ
ｌＯ4 を用いたこと以外は、実施例１と同様にして、比
較電池ＢＣ１を作製した。Comparative Example 1 The same molar amount of LiC was used as a solute.
except for using lO 4, the same procedure as in Example 1, was prepared comparative battery BC1.
【００２３】（比較例２）混合溶媒としてプロピレンカ
ーボネートとジメトキシエタン（体積比＝１：１）とか
らなる混合溶媒を用いたこと以外は、実施例１と同様に
して、比較電池ＢＣ２を作製した。Comparative Example 2 A comparative battery BC2 was prepared in the same manner as in Example 1, except that a mixed solvent composed of propylene carbonate and dimethoxyethane (volume ratio = 1: 1) was used as the mixed solvent. .
【００２４】（比較例３）複素環式化合物を添加しなか
ったこと以外は、実施例１と同様にして、比較電池ＢＣ
３を作製した。Comparative Example 3 A comparative battery BC was prepared in the same manner as in Example 1 except that no heterocyclic compound was added.
3 was produced.
【００２５】（比較例４）混合溶媒としてプロピレンカ
ーボネートとジメトキシエタン（体積比＝１：１）とか
らなる混合溶媒を用いるとともに、複素環式化合物を添
加しなかったこと以外は、実施例１と同様にして、比較
電池ＢＣ４を作製した。Comparative Example 4 The same procedure as in Example 1 was carried out except that a mixed solvent consisting of propylene carbonate and dimethoxyethane (volume ratio = 1: 1) was used as the mixed solvent and no heterocyclic compound was added. Similarly, a comparative battery BC4 was produced.
【００２６】（実施例２）複素環式化合物として同部数
の２−メチルチアゾリンを用いたこと以外は、実施例１
と同様にして、本発明に係る電池ＢＡ２を作製した。Example 2 Example 1 was repeated except that the same number of 2-methylthiazolines was used as the heterocyclic compound.
In the same manner as in the above, a battery BA2 according to the present invention was produced.
【００２７】（比較例５）混合溶媒としてプロピレンカ
ーボネートとジメトキシエタン（体積比＝１：１）とか
らなる混合溶媒を用いたこと以外は、実施例２と同様に
して、比較電池ＢＣ５を作製した。Comparative Example 5 A comparative battery BC5 was produced in the same manner as in Example 2 except that a mixed solvent consisting of propylene carbonate and dimethoxyethane (volume ratio = 1: 1) was used as the mixed solvent. .
【００２８】（実施例３）複素環式化合物として同部数
のチアゾリジンを用いたこと以外は、実施例１と同様に
して、本発明に係る電池ＢＡ３を作製した。Example 3 A battery BA3 according to the present invention was produced in the same manner as in Example 1, except that the same number of thiazolidine was used as the heterocyclic compound.
【００２９】（比較例６）混合溶媒としてプロピレンカ
ーボネートとジメトキシエタン（体積比＝１：１）とか
らなる混合溶媒を用いたこと以外は、実施例３と同様に
して、比較電池ＢＣ６を作製した。Comparative Example 6 A comparative battery BC6 was produced in the same manner as in Example 3, except that a mixed solvent composed of propylene carbonate and dimethoxyethane (volume ratio = 1: 1) was used as the mixed solvent. .
【００３０】[0030]
【００３１】（比較例７）混合溶媒としてプロピレンカ
ーボネートとジメトキシエタン（体積比＝１：１）とか
らなる混合溶媒を用いたこと以外は、実施例４と同様に
して、比較電池ＢＣ７を作製した。Comparative Example 7 A comparative battery BC7 was produced in the same manner as in Example 4 except that a mixed solvent composed of propylene carbonate and dimethoxyethane (volume ratio = 1: 1) was used as the mixed solvent. .
【００３２】（比較例８）溶質として同モル量のＬｉＣ
ｌＯ4 を用いるともに、混合溶媒としてプロピレンカー
ボネートとジメトキシエタン（体積比＝１：１）とから
なる混合溶媒を用いたこと以外は、実施例４と同様にし
て、比較電池ＢＣ８を作製した。Comparative Example 8 The same molar amount of LiC was used as a solute.
Both used lO 4, propylene carbonate and dimethoxyethane as a mixed solvent (volume ratio = 1: 1) except for using a mixed solvent consisting of a, in the same manner as in Example 4, to prepare a comparison battery BC8.
【００３３】[0033]
【００３４】[0034]
【００３５】（実施例４） 溶質として同モル量のＬｉＣＦ3 ＳＯ3 を用いたこと以
外は、実施例１と同様にして、本発明に係る電池ＢＡ７
を作製した。 Example 4 A battery BA7 according to the present invention was prepared in the same manner as in Example 1 except that the same molar amount of LiCF 3 SO 3 was used as a solute.
Was prepared.
【００３６】（実施例５） 溶質として同モル量のＬｉＡｓＦ6 を用いたこと以外
は、実施例１と同様にして、本発明に係る電池ＢＡ８を
作製した。 Example 5 A battery BA8 according to the present invention was produced in the same manner as in Example 1 except that the same molar amount of LiAsF 6 was used as a solute.
【００３７】（各電池の充放電サイクル特性） 上記表１に、本発明に係る電池ＢＡ１〜ＢＡ３、ＢＡ
７、ＢＡ８及び比較電池ＢＣ１〜ＢＣ８の各充放電サイ
クル特性を示す。充放電サイクル特性は、電流２ｍＡで
充電４時間及び放電４時間を繰り返し行い、各充放電を
１サイクルとし、４時間の放電時間内に１．５Ｖ以下に
達した時点を電池の寿命として、その時点までの充放電
サイクル数で表した。なお、充放電サイクル数は電池５
個についての最長及び最短サイクル数をそれぞれ上限、
下限とする範囲で示したものである。表１より本発明に
係る電池ＢＡ１〜ＢＡ３、ＢＡ７、ＢＡ８は比較電池Ｂ
Ｃ１〜ＢＣ８に比し、総じて優れた充放電サイクル特性
を有していることが分かる。(Charge / Discharge Cycle Characteristics of Each Battery) Table 1 shows the batteries BA1 to BA3 and BA according to the present invention.
7 shows the charge / discharge cycle characteristics of BA8 and Comparative Batteries BC1 to BC8. The charge / discharge cycle characteristics are such that charge and discharge are repeated for 4 hours and discharge for 4 hours at a current of 2 mA, and each charge / discharge is defined as one cycle. It was represented by the number of charge / discharge cycles up to the point. The number of charge / discharge cycles is for battery 5
Maximum number of longest and shortest cycles for each piece,
It is shown in the range of the lower limit. From Table 1, the batteries BA1 to BA3, BA7 and BA8 according to the present invention are comparative batteries B
It can be seen that the battery has generally excellent charge / discharge cycle characteristics as compared with C1 to BC8.
【００３８】（Ｂ）非水系電解液一次電池の作製 （実施例６） 〔正極の作製〕 ３５０〜４３０°Ｃの温度範囲で熱処理したＭｎＯ
2 と、導電剤としてのカーボン粉末と、結着剤としての
フッ素樹脂粉末とを、８５：１０：５の重量比で混合し
て正極合剤を得た。この正極合剤を加圧成形し、得られ
た成形品を２５０〜３５０°Ｃで２時間熱処理して正極
を作製した。(B) Preparation of Nonaqueous Electrolyte Primary Battery ( Example 6 ) [Preparation of Positive Electrode] MnO heat-treated in a temperature range of 350 to 430 ° C.
2 , a carbon powder as a conductive agent, and a fluororesin powder as a binder were mixed at a weight ratio of 85: 10: 5 to obtain a positive electrode mixture. This positive electrode mixture was subjected to pressure molding, and the obtained molded article was heat-treated at 250 to 350 ° C for 2 hours to produce a positive electrode.
【００３９】〔負極の作製〕リチウム圧延板を所定寸法
に打ち抜いて負極を作製した。[Preparation of Negative Electrode] A negative electrode was prepared by punching a rolled lithium plate into a predetermined size.
【００４０】〔非水系電解液の調製〕エチレンカーボネ
ート（ＥＣ）、ブチレンカーボネート（ＢＣ）及びジメ
トキシエタン（ＤＭＥ）の体積比１５：１５：７０の混
合溶媒に、ＬｉＣＦ3 ＳＯ3を１モル／リットル溶かし
た溶液１００部に対して、４−メチルチアゾールを１部
添加して非水系電解液を調製した。[Preparation of Non-Aqueous Electrolyte] LiCF 3 SO 3 was added to a mixed solvent of ethylene carbonate (EC), butylene carbonate (BC) and dimethoxyethane (DME) at a volume ratio of 15:15:70 at a ratio of 1 mol / l. One part of 4-methylthiazole was added to 100 parts of the dissolved solution to prepare a non-aqueous electrolyte.
【００４１】〔一次電池の作製〕以上の正負両極及び非
水系電解液を用いて、図１に示したものと同様の構造の
扁平形の本発明に係るリチウム一次電池ＢＡ９を作製し
た。[Preparation of Primary Battery] Using the positive and negative electrodes and the non-aqueous electrolyte described above, a flat lithium primary battery BA9 according to the present invention having a structure similar to that shown in FIG. 1 was prepared.
【００４２】（比較例９）４−メチルチアゾールを添加
しなかったこと以外は、実施例９と同様にして、比較電
池ＢＣ９を作製した。Comparative Example 9 A comparative battery BC9 was prepared in the same manner as in Example 9 except that 4-methylthiazole was not added.
【００４３】（両電池の保存特性）図２は、本発明に係
る電池ＢＡ９及び比較電池ＢＣ９の各５個の初期の放電
特性を、縦軸に電池電圧（Ｖ）を、横軸に放電時間（ｈ
ｒ）をとってグラフに示したものであり、また図３は、
両電池を６０°Ｃに保持した恒温槽中に３箇月保存した
後の放電特性を、同様のグラフに示したものである。い
ずれの放電も外部抵抗３００オームの定抵抗放電方式に
拠った。図２より、本発明に係る電池ＢＡ９と比較電池
ＢＣ９とは、初期の放電特性に関してはいずれもハッチ
ングで示した範囲に属する特性を示し差異は認められな
いが、図３より、６０°Ｃにおいて３箇月保存した後の
放電特性に関しては、本発明に係る電池ＢＡ９の方が明
らかに優れていることが分かる。(Storage Characteristics of Both Batteries) FIG. 2 shows the initial discharge characteristics of the five batteries BA9 and the comparative battery BC9 according to the present invention, the battery voltage (V) on the vertical axis, and the discharge time on the horizontal axis. (H
r) and shown in a graph, and FIG.
The same graph shows the discharge characteristics after both batteries were stored in a thermostat maintained at 60 ° C. for 3 months. Each discharge was based on a constant resistance discharge method with an external resistance of 300 ohms. From FIG. 2, the initial discharge characteristics of the battery BA9 according to the present invention and the comparative battery BC9 all belong to the range indicated by hatching, and no difference is observed. Regarding the discharge characteristics after storage for three months, it can be seen that the battery BA9 according to the present invention is clearly superior.
【００４４】（Ｃ）複素環式化合物の添加量と充放電サ
イクル特性との関係 複素環式化合物として４−メチルチアゾールを、また溶
液としてエチレンカーボネートとジメトキシエタン（体
積比＝１：１）の混合溶媒にＬｉＰＦ6 を１モル／リッ
トル溶かしたものを用い、４−メチルチアゾールの添加
量（部）を種々変えたときのリチウム二次電池の充放電
サイクル特性を調べた。結果を表２に示す。なお、充放
電サイクル数は電池５個についての最長及び最短サイク
ル数をそれぞれ上限、下限とする範囲で示したものであ
る。(C) Relationship between the amount of heterocyclic compound added and charge / discharge cycle characteristics 4-Methylthiazole is used as the heterocyclic compound, and ethylene carbonate and dimethoxyethane (volume ratio = 1: 1) are mixed as the solution. Using 1 mol / liter of LiPF 6 dissolved in a solvent, the charge / discharge cycle characteristics of the lithium secondary battery when the addition amount (part) of 4-methylthiazole was variously changed were examined. Table 2 shows the results. Note that the number of charge / discharge cycles is a range in which the longest and shortest cycle numbers for five batteries are set as upper and lower limits, respectively.
【００４５】[0045]
【表２】 [Table 2]
【００４６】表２により、充放電サイクル数にピークが
認められ、４−メチルチアゾールの場合は、溶液１００
部に対して１．０部程度が最適であることが分かる。According to Table 2, a peak is observed in the number of charge / discharge cycles. In the case of 4-methylthiazole, the solution 100
It can be seen that about 1.0 part is optimum for the part.
【００４７】叙上の実施例では本発明を扁平型の一次及
び二次電池に適用する場合を一例として説明したが、電
池の形状に特に制限はなく、本発明は、円筒形、角形、
水平断面瓢箪形等、種々の形状のリチウム一次及び二次
電池に適用し得るものである。In the above embodiment, the case where the present invention is applied to flat primary and secondary batteries has been described as an example. However, the shape of the battery is not particularly limited.
The present invention is applicable to lithium primary and secondary batteries of various shapes such as a gourd-shaped horizontal section.
【００４８】[0048]
【発明の効果】非水系電解液として、エチレンカーボネ
ートを含有する非水系溶媒にフッ素含有リチウム塩を含
有する溶質を溶かして得た溶液に、チアゾール、チアゾ
リン、チアゾリジン、及び、それらの誘導体よりなる群
から選ばれた少なくとも一種のＳ及びＮをヘテロ元素と
する複素環式化合物が添加されたものが用いられている
ので、本発明に係る非水系電解液リチウム電池は保存特
性或いは充放電サイクル特性に優れているなど、本発明
は優れた特有の効果を奏する。As a non-aqueous electrolyte, a solution obtained by dissolving a solute containing a fluorine-containing lithium salt in a non-aqueous solvent containing ethylene carbonate is added with thiazole and thiazo.
Group consisting of phosphorus, thiazolidine, and derivatives thereof
At least one of S and N selected from
Since the non-aqueous electrolyte lithium battery according to the present invention is excellent in storage characteristics or charge / discharge cycle characteristics, the present invention has excellent unique effects because a heterocyclic compound to which a heterocyclic compound is added is used. Play.
【図１】本発明に係るリチウム二次電池ＢＡ１の断面図
である。FIG. 1 is a cross-sectional view of a lithium secondary battery BA1 according to the present invention.
【図２】本発明に係るリチウム一次電池ＢＡ９及び比較
電池ＢＣ９の初期の放電特性を示すグラフである。FIG. 2 is a graph showing initial discharge characteristics of a lithium primary battery BA9 and a comparative battery BC9 according to the present invention.
【図３】本発明に係るリチウム一次電池ＢＡ９及び比較
電池ＢＣ９の６０°Ｃで３箇月保存した後の放電特性を
示すグラフである。FIG. 3 is a graph showing discharge characteristics of a lithium primary battery BA9 and a comparative battery BC9 according to the present invention after being stored at 60 ° C. for three months.
ＢＡ１ 実施例１で作製した電池 １ 正極 ２ 負極 ３ セパレータ ４ 正極缶 ５ 負極缶 ６ 正極集電体 ７ 負極集電体 ８ 絶縁パッキング BA1 Battery prepared in Example 1 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode can 5 Negative electrode can 6 Positive current collector 7 Negative current collector 8 Insulation packing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大下 竜司 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 古川 修弘 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (56)参考文献 特開 平３−57169（ＪＰ，Ａ) 特開 平５−59963（ＪＰ，Ａ) 特開 平３−152879（ＪＰ，Ａ) 特開 昭62−222575（ＪＰ，Ａ) 特開 昭58−75778（ＪＰ，Ａ) 特開 平３−57168（ＪＰ，Ａ) 特開 平３−49166（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 6/16 H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryuji Oshita 2-18-18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Norihiro Furukawa 2--18 Keihanhondori, Moriguchi-shi, Osaka JP-A-3-57169 (JP, A) JP-A-5-59963 (JP, A) JP-A-3-152879 (JP, A) JP-A-62-222575 (JP, a) JP Akira 58-75778 (JP, a) JP flat 3-57168 (JP, a) JP flat 3-49166 (JP, a) (58 ) investigated the field (Int.Cl. 7 H01M 6/16 H01M 10/40
Claims (3)
Ｌｉを吸蔵放出可能な物質を主材とする負極と、これら
正負両極間に介装されたセパレータと、非水系電解液と
を備えてなる非水系電解液リチウム電池であって、前記
非水系電解液は、エチレンカーボネートを含有せる非水
系溶媒にフッ素含有リチウム塩を含有せる溶質を溶かし
て得た溶液に、チアゾール、チアゾリン、チアゾリジ
ン、及び、それらの誘導体よりなる群から選ばれた少な
くとも一種のＳ及びＮをヘテロ元素とする複素環式化合
物が添加されてなるものであることを特徴とする非水系
電解液リチウム電池。1. A positive electrode mainly composed of a metal oxide, a negative electrode mainly composed of Li or a substance capable of inserting and extracting Li, a separator interposed between the positive and negative electrodes, and a non-aqueous electrolyte. A non-aqueous electrolyte lithium battery comprising: wherein the non-aqueous electrolyte is a solution obtained by dissolving a solute containing a fluorine-containing lithium salt in a non-aqueous solvent containing ethylene carbonate, thiazole, thiazoline, Thiazolidy
And a few selected from the group consisting of
A non-aqueous electrolyte lithium battery comprising at least one kind of a heterocyclic compound containing S and N as a hetero element.
積部に対して、０．１〜５．０体積部添加されている請
求項１記載の非水系電解液リチウム電池。2. The solution according to claim 1, wherein said heterocyclic compound is 100 units of said solution.
The non-aqueous electrolyte lithium battery according to claim 1 , wherein 0.1 to 5.0 parts by volume of the nonaqueous electrolyte lithium battery is added to the charging part .
とプロピレンカーボネートとの混合溶媒、エチレンカー
ボネートとジメトキシエタンとの混合溶媒、又は、エチ
レンカーボネートとプロピレンカーボネートとジメトキ
シエタンとの混合溶媒である請求項１記載の非水系電解
液リチウム電池。3. The non-aqueous solvent is ethylene carbonate.
Mixed solvent of propylene carbonate and ethylene carbonate
Mixed solvent of carbonate and dimethoxyethane, or
Lencarbonate, propylene carbonate and dimethy
2. The non-aqueous electrolyte lithium battery according to claim 1, which is a mixed solvent with cyethane .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03287933A JP3086510B2 (en) | 1991-11-01 | 1991-11-01 | Non-aqueous electrolyte lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03287933A JP3086510B2 (en) | 1991-11-01 | 1991-11-01 | Non-aqueous electrolyte lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05258753A JPH05258753A (en) | 1993-10-08 |
| JP3086510B2 true JP3086510B2 (en) | 2000-09-11 |
Family
ID=17723614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03287933A Expired - Fee Related JP3086510B2 (en) | 1991-11-01 | 1991-11-01 | Non-aqueous electrolyte lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3086510B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4529274B2 (en) * | 2000-04-18 | 2010-08-25 | ソニー株式会社 | Non-aqueous electrolyte battery |
| JP2004200015A (en) * | 2002-12-19 | 2004-07-15 | Sanyo Electric Co Ltd | Electrolyte for nonaqueous battery, its manufacturing method, and nonaqueous battery electrolytic solution |
| CN103004006B (en) | 2011-07-07 | 2014-02-19 | 住友精化株式会社 | Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device |
| US20170117588A1 (en) | 2014-03-28 | 2017-04-27 | Sumitomo Seika Chemicals Co., Ltd. | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device |
| KR102571760B1 (en) | 2015-09-09 | 2023-08-28 | 스미토모 세이카 가부시키가이샤 | Additives for non-aqueous electrolyte solutions, non-aqueous electrolyte solutions, and electrical storage devices |
| CN108352572B (en) | 2015-11-06 | 2021-02-02 | 住友精化株式会社 | Additive for nonaqueous electrolyte solution, and electricity storage device |
| EP3667802A4 (en) | 2017-08-08 | 2021-04-28 | Sumitomo Seika Chemicals Co., Ltd. | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device |
-
1991
- 1991-11-01 JP JP03287933A patent/JP3086510B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05258753A (en) | 1993-10-08 |
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