JPH0630257B2 - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH0630257B2 JPH0630257B2 JP60050167A JP5016785A JPH0630257B2 JP H0630257 B2 JPH0630257 B2 JP H0630257B2 JP 60050167 A JP60050167 A JP 60050167A JP 5016785 A JP5016785 A JP 5016785A JP H0630257 B2 JPH0630257 B2 JP H0630257B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrolytic solution
- volume
- organic electrolyte
- mol
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は有機電解質溶液を電解液に用いる有機電解質
電池に関する。さらに詳しくは、電解液の熱安定性を高
めて貯蔵性能を向上させた有機電解質電池に関する。TECHNICAL FIELD The present invention relates to an organic electrolyte battery using an organic electrolyte solution as an electrolytic solution. More specifically, the present invention relates to an organic electrolyte battery in which the thermal stability of an electrolytic solution is increased and the storage performance is improved.
最近、有機電解質電池用の電解質として下記の一般式
（Ｉ） ＬｉＸＦｎ （Ｉ） （式中、ＸはＰ、Ｓｂ、ＡｓまたはＢであり、ｎはＸが
Ｐ、ＳｂまたはＡｓのとき６で、ＸがＢのとき４であ
る） で示される化合物が有機溶媒への溶解性がよく、かつ高
電導度で、しかも過塩素酸系のものより安定性が高いこ
とから注目されており、これに関して従来からも種々の
提案がなされている。たとえば、米国特許第3,607,020
号明細書ではＬｉＰＦ６、ＬｉＡｓＦ６などの合成法が
提案され、米国特許第3,907,977 号明細書ではＣＨ３Ｃ
Ｎを用いたＬｉＰＦ６、ＬｉＡｓＦ６の高純度品の合成
法および精製法が提案されている。また米国特許第3,63
9,174 号明細書ではＬｉ−Ａｌ負極／Ｃｕ２Ｓ電池系に
おいて、電解液としてＬｉＰＦ６／プロピレンカーボネ
ート、ＬｉＰＦ６／ジメチルサルホキシドなどを用いた
電池系が提案されている。Recently, as an electrolyte for an organic electrolyte battery, the following general formula (I) LiXFn (I) (wherein X is P, Sb, As or B, and n is 6 when X is P, Sb or As, It has been noted that the compound represented by (4) when X is B) has good solubility in an organic solvent, high conductivity, and higher stability than those of perchloric acid type. Various proposals have been made in the past. For example, U.S. Pat.
In the specification, synthetic methods such as LiPF 6 and LiAsF 6 are proposed. In US Pat. No. 3,907,977, CH 3 C is proposed.
There have been proposed methods for synthesizing and purifying high-purity products of LiPF 6 and LiAsF 6 using N. Also U.S. Pat.
In Li-Al anode / Cu 2 S cell lines at 9,174 Pat, LiPF 6 / propylene carbonate, LiPF 6 / dimethyl monkey Hoki cell system using a SID has been proposed as an electrolytic solution.
しかしながら、本発明者らの実験によればＬｉＰＦ６を
プロピレンカーボネート、１，３−ジオキソラン、テト
ラヒドロフラン、４−メチル−１，３−ジオキソラン、
１，２−ジメトキシエタンなどの有機溶媒に溶解した電
解液を用いたリチウム有機電解質電池は、空温では良好
な電池特性を示すものの、60℃で貯蔵した場合、電解質
であるＬｉＰＦ６が熱分解して電解液溶媒の分解ないし
は重合を引き起こして著しく電池特性を低下させるとい
う問題がある。またＬｉＰＦ６同様に前記一般式（Ｉ）
で示されるＬｉＳｂＦ６、ＬｉＡｓＦ６、ＬｉＢＦ４な
どの化合物も、ＬｉＰＦ６と同様に熱安定性面での問題
があり、高温で貯蔵した場合、熱分解して電解液溶媒の
分解ないしは重合を引き起こして電池特性を低下させる
という問題がある。However, according to the experiments by the present inventors, LiPF 6 was added to propylene carbonate, 1,3-dioxolane, tetrahydrofuran, 4-methyl-1,3-dioxolane,
A lithium organic electrolyte battery using an electrolytic solution dissolved in an organic solvent such as 1,2-dimethoxyethane shows good battery characteristics at air temperature, but when stored at 60 ° C, LiPF 6 as an electrolyte is thermally decomposed. Then, decomposition or polymerization of the electrolytic solution solvent is caused, and battery characteristics are significantly deteriorated. Further, as in LiPF 6 , the above general formula (I)
In also compounds such LiSbF 6, LiAsF 6, LiBF 4, shown there is a problem with thermal stability plane in the same manner as LiPF 6, when stored at high temperature, thermal decomposition to cause degradation or polymerization of the electrolyte solvent Therefore, there is a problem that battery characteristics are deteriorated.
この発明は上述した従来技術の問題点を解決するもの
で、前記一般式（Ｉ）で示される化合物を電解質として
用いる電解液にトリエチレンホスホルアミド、トリエチ
レンチオホスホルアミドおよびそれらの誘導体よりなる
群から選ばれた少なくとも１種を添加することにより、
電解液の熱安定性を高めて貯蔵中における電池性能の低
下が少ない有機電解質電池を提供したものである。The present invention solves the above-mentioned problems of the prior art, and includes triethylenephosphoramide, triethylenethiophosphoramide and their derivatives as an electrolyte solution using the compound represented by the general formula (I) as an electrolyte. By adding at least one selected from the group consisting of
It is an object of the present invention to provide an organic electrolyte battery in which the thermal stability of an electrolytic solution is enhanced and the deterioration of battery performance during storage is small.
本発明において、電解液の熱安定性を高めるために電解
液に添加するトリエチレンホスホルアミドは下記の構造
式を有し、 別名1,1′,1″−Phosphinylidynetrisaziridine（1,
1′,1″−ホスフィニリジントリスアジリディン）また
はTris（１−aziridinyl）phosphine oxide（トリス
（１−アジリディニル）ホスフィンオキサイド）であ
る。In the present invention, triethylenephosphoramide added to the electrolytic solution in order to increase the thermal stability of the electrolytic solution has the following structural formula, Synonyms 1,1 ′, 1 ″ −Phosphinylidynetrisaziridine (1,
1 ', 1 "-phosphinyridine trisaziridin) or Tris (1-aziridinyl) phosphine oxide (tris (1-aziridinyl) phosphine oxide).
また、トリエチレンチオホスホルアミドは下記の構造式
を有し、 別名1,1′,1″−Phoshinothioylidynetrisaziridine
（1,1′,1″−ホスフィノチオイリジントリスアジリデ
ィン）またはTris（１−aziridinyl）phosphine sulfid
e（トリス（１−アジリディニルホスフィンサルファイ
ド）である。Further, triethylenethiophosphoramide has the following structural formula, Synonyms 1,1 ′, 1 ″ −Phoshinothioylidynetrisaziridine
(1,1 ′, 1 ″ -phosphinothioyridine trisaziridin) or Tris (1-aziridinyl) phosphine sulfid
e (tris (1-aziridinylphosphine sulfide)).
これらトリエチレンホスホルアミド、トリエチレンチオ
ホスホルアミドの誘導体としては、チッ素と三員環を形
成する炭素に結合している水素原子の１個または２個が
メチル基、エチル基、プロピル基、ブチル基などで置換
したものがあげられ、その代表的な具体例としては、下
記の構造式を有する トリス（１−（２−メチル）アジリディニル）ホスフィ
ンオキサイド（Tris（１−（２−methyl）aziridinyl）
phosphine oxide）があげられる。As derivatives of these triethylenephosphoramide and triethylenethiophosphoramide, one or two of hydrogen atoms bonded to carbon forming a three-membered ring with nitrogen are methyl, ethyl, or propyl. , Those substituted with a butyl group, etc., and typical examples thereof have the following structural formulas. Tris (1- (2-methyl) aziridinyl) phosphine oxide (Tris (1- (2-methyl) aziridinyl)
phosphine oxide).
これらトリエチレンホスホルアミド、トリエチレンチオ
ホスホルアミドおよびそれらの誘導体は分子量が大き
く、分子中の酸素またはイオウがカチオン配位性を有
し、電解液中で電離している一般式（Ｉ）で示される化
合物のリチウムイオンに配位して電解液を安定化させ
る。These triethylenephosphoramide, triethylenethiophosphoramide and their derivatives have a large molecular weight, oxygen or sulfur in the molecule has a cation coordination property, and is ionized in the electrolytic solution of the general formula (I). It stabilizes the electrolytic solution by coordinating with the lithium ion of the compound represented by.
上記トリエチレンホスホルアミド、トリエチレンチオホ
スホルアミドまたはそれらの誘導体の添加量は一般式
（Ｉ）で示される化合物のモル数の0.3 〜1.5 倍モルと
するのが好ましい。これはトリエチレンホスホルアミ
ド、トリエチレンチオホスホルアミドまたはそれらの誘
導体の添加量が一般式（Ｉ）で示される化合物のモル数
の0.3 倍モルより少ないときは安定化を高める効果が充
分に発揮されず、1.5 倍モルより多いときは電池特性、
特に二次電池に用いた場合のサイクル特性が悪くなるか
らである。トリエチレンホスホルアミド、トリエチレン
チオホスホルアミド、それらの誘導体は併用してもよ
く、これらを併用する場合、添加量は上記と同じ理由に
より、合計で一般式（Ｉ）で示される化合物のモル数の
0.3 〜1.5 倍モルとするのが好ましい。The addition amount of the above-mentioned triethylenephosphoramide, triethylenethiophosphoramide or their derivatives is preferably 0.3 to 1.5 times the mole number of the compound represented by the general formula (I). This is because when the added amount of triethylenephosphoramide, triethylenethiophosphoramide or their derivatives is less than 0.3 times the number of moles of the compound represented by the general formula (I), the effect of enhancing the stabilization is sufficient. If it is not exerted and is more than 1.5 times mol, battery characteristics,
This is because the cycle characteristics deteriorate when used in a secondary battery. Triethylenephosphoramide, triethylenethiophosphoramide and their derivatives may be used in combination, and when these are used in combination, the addition amount of the compound represented by the general formula (I) is the same for the same reason as above. Number of moles
It is preferably 0.3 to 1.5 times the molar amount.
本発明において電解質として用いる一般式（Ｉ）で示さ
れる化合物の具体例は、ＸがＰ（リン）であるＬｉＰＦ
６（六フッ化リン酸リチウム）、ＸがＳｂ（アンチモ
ン）であるＬｉＳｂＦ６（六フッ化アンチモン酸リチウ
ム）、ＸがＡｓ（砒素）であるＬｉＡｓＦ６（六フッ化
砒素酸リチウム）、ＸがＢ（ホウ素）であるＬｉＢＦ４
（四フッ化ホウ酸リチウム）である。そして、電解液は
これら一般式（Ｉ）で示される化合物をたとえばプロピ
レンカーボネート、γ−ブチロラクトン、テトラヒドロ
フラン、２−メチルテトラヒドロフラン、１，２−ジメ
トキシエタン、１，２−ジエトキシエタン、１，３−ジ
オキソラン、４−メチル−１，３−ジオキソランなどの
有機溶媒の単独または混合溶媒に溶解し、それにトリエ
チレンホスホルアミド、トリエチレンチオホスホルアミ
ドまたはそれらの誘導体を添加するか、あるいは有機溶
媒にトリエチレンホスホルアミド、トリエチレンチオホ
スホルアミドまたはそれらの誘導体を添加しておいてか
ら、それに一般式（Ｉ）で示される化合物を溶解させる
ことによって調製される。要は電解液中に一般式（Ｉ）
で示される化合物とトリエチレンホスホルアミド、トリ
エチレンチオホスホルアミドまたはそれらの誘導体が含
まれていればよく、トリエチレンホスホルアミド、トリ
エチレンチオホスホルアミドまたはそれらの誘導体と一
般式（Ｉ）で示される化合物との添加の順序は問わな
い。なお電解液中の一般式（Ｉ）で示される化合物の量
は通常0.1 〜３モル／である。Specific examples of the compound represented by the general formula (I) used as the electrolyte in the present invention include LiPF 6 in which X is P (phosphorus).
6 (lithium hexafluorophosphate), X is Sb (antimony) and is LiSbF 6 (lithium hexafluoro antimonate), X is As (arsenic) LiAsF 6 (lithium hexafluoro arsenic acid), X is LiBF 4 which is B (boron)
(Lithium tetrafluoroborate). Then, the electrolytic solution contains the compound represented by the general formula (I), for example, propylene carbonate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,3-. It is dissolved in an organic solvent such as dioxolane or 4-methyl-1,3-dioxolane, alone or in a mixed solvent, and triethylenephosphoramide, triethylenethiophosphoramide or a derivative thereof is added thereto, or an organic solvent is added. It is prepared by adding triethylenephosphoramide, triethylenethiophosphoramide or a derivative thereof, and then dissolving the compound represented by the general formula (I) therein. In short, the general formula (I)
It suffices that the compound represented by the formula (1) and triethylenephosphoramide, triethylenethiophosphoramide or their derivatives are contained, and triethylenephosphoramide, triethylenethiophosphoramide or their derivatives and the general formula (I The compound may be added in any order. The amount of the compound represented by the general formula (I) in the electrolytic solution is usually 0.1 to 3 mol /.
本発明の電池において、負極活物質としては、たとえば
リチウム、リチウム−アルミニウム、リチウム−鉛、リ
チウム−ガリウム−インジウムなどのリチウム合金、ナ
トリウム、マグネシウム、アルミニウムなどの軽金属が
用いられ、正極活物質としては、たとえば二硫化チタン
（ＴｉＳ２）、二硫化モリブデン（ＭｏＳ２）、三硫化
モリブデン（ＭｏＳ３）、硫化ジルコニウム（Ｚｒ
Ｓ２）、二硫化ニオブ（ＮｂＳ２）、三硫化リンニッケ
ル（ＮｉＰＳ３）、バナジウムセレナイド（ＶＳ
ｅ２）、硫化鉄、酸化銅、フッ化炭素などが用いられ
る。In the battery of the present invention, as the negative electrode active material, for example, lithium, lithium alloys such as lithium-aluminum, lithium-lead, lithium-gallium-indium, and light metals such as sodium, magnesium, and aluminum are used, and as the positive electrode active material, , For example, titanium disulfide (TiS 2 ), molybdenum disulfide (MoS 2 ), molybdenum trisulfide (MoS 3 ), zirconium sulfide (Zr
S 2 ), niobium disulfide (NbS 2 ), phosphorus nickel trisulfide (NiPS 3 ), vanadium selenide (VS
e 2 ), iron sulfide, copper oxide, fluorocarbon, etc. are used.
つぎに、実施例をあげて本発明をさらに詳細に説明す
る。Next, the present invention will be described in more detail with reference to examples.
実施例１ 電解液として４−メチル−1,3 −ジオキソラン57.4容量
％、1,2 −ジメトキシエタン30.6容量％およびトリエチ
レンホスホルアミド18容量％からなる混合溶媒にＬｉＰ
Ｆ６を１モル／溶解した有機電解質溶液を用い、負極
にリチウム、正極に二硫化チタン合剤を用いて第１図に
示すようなリチウム有機電解質電池を組み立てた。上記
電解液においてトリエチレンホスホルアミドはＬｉＰＦ
６の約１倍モルに相当する。Example 1 As an electrolytic solution, LiP was added to a mixed solvent consisting of 57.4% by volume of 4-methyl-1,3-dioxolane, 30.6% by volume of 1,2-dimethoxyethane and 18% by volume of triethylenephosphoramide.
A lithium organic electrolyte battery as shown in FIG. 1 was assembled using an organic electrolyte solution containing 1 mol / mol of F 6 , using lithium for the negative electrode and titanium disulfide mixture for the positive electrode. In the above electrolytic solution, triethylenephosphoramide is LiPF
This corresponds to about 1 time mol of 6 .
第１図において、１は負極缶で、この負極缶１はステン
レス鋼製で表面にニッケルメッキが施されており、２は
ステンレス鋼製の負極側集電網で、上記負極缶１の内面
にスポット溶接されている。３はリチウムよりなる負極
で、４は微孔性ポリプロピレンフイルムよりなるセパレ
ータである。５はポリプロピレン不織布よりなる電解液
吸収体であり、６は二硫化チタンを正極活物質とする合
剤をペレット状に加圧成形してなる正極で、７はステン
レス鋼製の正極側集電網である。８はステンレス鋼製で
表面にニッケルメッキを施した正極缶で、９はポリプロ
ピレン製の環状ガスケットである。In FIG. 1, reference numeral 1 is a negative electrode can, and this negative electrode can 1 is made of stainless steel and the surface thereof is nickel-plated. 2 is a stainless steel negative electrode side current collecting net, which is spotted on the inner surface of the negative electrode can 1. It is welded. 3 is a negative electrode made of lithium, and 4 is a separator made of a microporous polypropylene film. Reference numeral 5 is an electrolyte absorber made of polypropylene non-woven fabric, 6 is a positive electrode formed by press-molding a mixture containing titanium disulfide as a positive electrode active material into pellets, and 7 is a stainless steel positive electrode side current collecting net. is there. Reference numeral 8 is a positive electrode can made of stainless steel and having a surface plated with nickel, and 9 is an annular gasket made of polypropylene.
実施例２ 電解液として４−メチル−1,3 −ジオキソラン66.5容量
％、1,2 −ジメトキシエタン28容量％およびトリエチレ
ンホスホルアミド5.5 容量％からなる混合溶媒にＬｉＰ
Ｆ６を１モル／溶解したものを用いたほかは実施例１
と同様のリチウム有機電解質電池を組み立てた。上記電
解液において、トリエチレンホスホルアミドはＬｉＰＦ
６の約0.3 倍モルに相当する。Example 2 As an electrolytic solution, LiP was added to a mixed solvent consisting of 66.5% by volume of 4-methyl-1,3-dioxolane, 28% by volume of 1,2-dimethoxyethane and 5.5% by volume of triethylenephosphoramide.
Example 1 except that 1 mol / mol of F 6 was used
The same lithium organic electrolyte battery was assembled. In the above electrolytic solution, triethylenephosphoramide is LiPF
This corresponds to about 0.3 times the molar amount of 6 .
実施例３ 電解液として４−メチル−1,3 −ジオキソラン50.8容量
％、1,2 −ジメトキシエタン21.7容量％およびトリエチ
レンホスホルアミド27.5容量％からなる混合溶媒にＬｉ
ＰＦ６を１モル／溶解したものを用いたほかは実施例
１と同様のリチウム有機電解質電池を組み立てた。上記
電解液において、トリエチレンホスホルアミドはＬｉＰ
Ｆ６の約1.5 倍モルに相当する。Example 3 As an electrolytic solution, Li was added to a mixed solvent of 50.8% by volume of 4-methyl-1,3-dioxolane, 21.7% by volume of 1,2-dimethoxyethane and 27.5% by volume of triethylenephosphoramide.
A lithium organic electrolyte battery was assembled in the same manner as in Example 1, except that 1 mol / mol of PF 6 was used. In the above electrolytic solution, triethylenephosphoramide is LiP
This corresponds to about 1.5 times mol of F 6 .
比較例１ 電解液として４−メチル−1,3 −ジオキソラン70容量％
および1,2 −ジメトキシエタン30容量％からなる混合溶
媒にＬｉＰＦ６を１モル／溶解したものを用いたほか
は実施例１と同様のリチウム有機電解質電池を組み立て
た。Comparative Example 1 4-Methyl-1,3-dioxolane 70% by volume as an electrolytic solution
A lithium organic electrolyte battery was assembled in the same manner as in Example 1 except that 1 mol / mol of LiPF 6 was dissolved in a mixed solvent containing 30% by volume of 1,2-dimethoxyethane.
上記実施例１〜３の電池および比較例１の電池を60℃で
貯蔵し、貯蔵に伴う開路電圧の変化と300 Ω、５秒放電
後の閉路電圧変化を調べた。開路電圧変化を第２図に、
閉路電圧変化を第３図に示す。The batteries of Examples 1 to 3 and the battery of Comparative Example 1 were stored at 60 ° C., and the change in the open circuit voltage due to the storage and the change in the closed circuit voltage after discharging 300 Ω for 5 seconds were examined. Fig. 2 shows the change in open circuit voltage.
The change in closed circuit voltage is shown in FIG.
また、実施例１〜３の電池および比較例１の電池を60℃
で貯蔵したときの10kHz 内部抵抗変化を第４図に示す。
この10kHz の内部抵抗はほぼ電解液に依存する抵抗であ
る。In addition, the batteries of Examples 1 to 3 and the battery of Comparative Example 1 were heated to 60 ° C.
Fig. 4 shows the change in internal resistance at 10 kHz when stored at.
The internal resistance of 10kHz is almost dependent on the electrolyte.
第２図および第３図に示すように、本発明の実施例１〜
３の電池は、従来電池である比較例１の電池に比べて貯
蔵に伴う開路電圧、閉路電圧の変化が少なかった。As shown in FIG. 2 and FIG.
The battery of No. 3 had less change in the open circuit voltage and the closed circuit voltage due to storage, as compared with the battery of Comparative Example 1 which is a conventional battery.
また、第４図に示すように、比較例１の電池では貯蔵日
数の増加に伴って著しい内部抵抗増加が生じたが、本発
明の実施例１〜３の電池ではいずれもそのような大きな
内部抵抗増加が認められなかった。Further, as shown in FIG. 4, in the battery of Comparative Example 1, a significant increase in internal resistance occurred as the number of days of storage increased, but in the batteries of Examples 1 to 3 of the present invention, such a large internal resistance was observed. No increase in resistance was observed.
実施例４ 電解液として４−メチル−１，３−ジオキソラン56容量
％、１，２−ジメトキシエタン24容量％およびトリエチ
レンチオホスホルアミド20容量％からなる混合溶媒にＬ
ｉＰＦ６を１モル／溶解したものを用いたほかは実施
例１と同様のリチウム有機電解質電池を組み立てた。上
記電解液においてトリエチレンチオホスホルアミドはＬ
ｉＰＦ６の約１倍モルに相当する。Example 4 As an electrolytic solution, L was added to a mixed solvent consisting of 56% by volume of 4-methyl-1,3-dioxolane, 24% by volume of 1,2-dimethoxyethane and 20% by volume of triethylenethiophosphoramide.
A lithium organic electrolyte battery similar to that of Example 1 was assembled except that 1 mol / mol of iPF 6 was used. In the above electrolyte, triethylenethiophosphoramide is L
This corresponds to about 1 time mol of iPF 6 .
実施例５ 電解液として４−メチル−１，３−ジオキソラン66容量
％、１，２−ジメトキシエタン28容量％およびトリエチ
レンチオホスホルアミド６容量％からなる混合溶媒にＬ
ｉＰＦ６を１モル／溶解したものを用いたほかは実施
例１と同様のリチウム有機電解質電池を組み立てた。上
記電解液において、トリエチレンチオホスホルアミドは
ＬｉＰＦ６の約0.3 倍モルに相当する。Example 5 As an electrolytic solution, L was added to a mixed solvent consisting of 66% by volume of 4-methyl-1,3-dioxolane, 28% by volume of 1,2-dimethoxyethane and 6% by volume of triethylenethiophosphoramide.
A lithium organic electrolyte battery similar to that of Example 1 was assembled except that 1 mol / mol of iPF 6 was used. In the electrolyte solution, triethylenethiophosphoramide corresponds to about 0.3 times mol of LiPF 6 .
実施例６ 電解液として４−メチル−１，３−ジオキソラン49容量
％、１，２−ジメトキシエタン21容量％およびトリエチ
レンチオホスホルアミド30容量％からなる混合溶媒にＬ
ｉＰＦ６を１モル／溶解したものを用いたほかは実施
例１と同様のリチウム有機電解質電池を組み立てた。上
記電解液において、トリエチレンチオホスホルアミドは
ＬｉＰＦ６の約1.5 倍に相当する。Example 6 As an electrolytic solution, L was added to a mixed solvent consisting of 49% by volume of 4-methyl-1,3-dioxolane, 21% by volume of 1,2-dimethoxyethane and 30% by volume of triethylenethiophosphoramide.
A lithium organic electrolyte battery similar to that of Example 1 was assembled except that 1 mol / mol of iPF 6 was used. In the above electrolyte, triethylenethiophosphoramide corresponds to about 1.5 times that of LiPF 6 .
上記実施例４〜６の電池および前記比較例１の電池を60
℃で貯蔵し、貯蔵に伴う開路電圧の変化と300 Ω、５秒
放電後の閉路電圧変化を調べた。開路電圧変化を第５図
に、閉路電圧変化を第６図に示す。The batteries of Examples 4 to 6 and the battery of Comparative Example 1 were replaced by 60
The sample was stored at ℃, and the change in the open circuit voltage due to the storage and the change in the closed circuit voltage after discharging at 300 Ω for 5 seconds were examined. The change in open circuit voltage is shown in FIG. 5, and the change in closed circuit voltage is shown in FIG.
また、実施例４〜６の電池および比較例１の電池を６０
℃で貯蔵したときの10kHz 内部抵抗変化を第７図に示
す。In addition, the batteries of Examples 4 to 6 and the battery of Comparative Example 1 were replaced by 60
Fig. 7 shows changes in internal resistance at 10 kHz when stored at ℃.
第５図および第６図に示すように、この実施例４〜６の
電池も、前記実施例１〜３の電池同様に従来電池である
比較例１の電池に比べて貯蔵に伴う開路電圧変化、閉路
電圧変化が少なかった。As shown in FIGS. 5 and 6, the batteries of Examples 4 to 6 also changed the open-circuit voltage accompanying storage as compared with the battery of Comparative Example 1 which was a conventional battery as in the batteries of Examples 1 to 3. , The change in closed circuit voltage was small.
また、第４図に示すように、本発明の実施例４〜６の電
池も貯蔵に伴う大きな内部抵抗増加が認められなかっ
た。Further, as shown in FIG. 4, the batteries of Examples 4 to 6 of the present invention did not show a large increase in internal resistance due to storage.
実施例７ 電解液として４−メチル−１，３−ジオキソラン56.3容
量％、１，２−ジメトキシエタン24.1容量％およびトリ
ス（１−（２−メチル）アジリディニル）ホスフィンオ
キサイド19.6容量％からなる混合溶媒にＬｉＰＦ６を１
モル／溶解したものを用いたほかは実施例１と同様の
リチウム有機電解質電池を組み立てた。上記電解液にお
いてトリス（１−（２−メチル）アジリディニル）ホス
フィンオキサイドはＬｉＰＦ６の約１倍モルに相当す
る。Example 7 As an electrolytic solution, a mixed solvent of 56.3% by volume of 4-methyl-1,3-dioxolane, 24.1% by volume of 1,2-dimethoxyethane and 19.6% by volume of tris (1- (2-methyl) aziridinyl) phosphine oxide was used. 1 LiPF 6
A lithium organic electrolyte battery was assembled in the same manner as in Example 1 except that the mol / melted product was used. In the electrolytic solution, tris (1- (2-methyl) aziridinyl) phosphine oxide corresponds to about 1-fold molar amount of LiPF 6 .
実施例８ 電解液として４−メチル−１，３−ジオキソラン65.9容
量％、１，２−ジメトキシエタン28.2容量％およびトリ
ス（１−（２−メチル）アジリディニル）ホスフィンオ
キサイド5.9 容量％からなる混合溶媒にＬｉＰＦ６を１
モル／溶解したものを用いたほかは実施例１と同様の
リチウム有機電解質電池を組み立てた。上記電解液にお
いて、トリス（１−（２−メチル）アジリディニル）ホ
スフィンオキサイドはＬｉＰＦ６の約0.3 倍モルに相当
する。Example 8 As an electrolytic solution, a mixed solvent consisting of 65.9% by volume of 4-methyl-1,3-dioxolane, 28.2% by volume of 1,2-dimethoxyethane and 5.9% by volume of tris (1- (2-methyl) aziridinyl) phosphine oxide was used. 1 LiPF 6
A lithium organic electrolyte battery was assembled in the same manner as in Example 1 except that the mol / melted product was used. In the electrolytic solution, tris (1- (2-methyl) aziridinyl) phosphine oxide corresponds to about 0.3 times mol of LiPF 6 .
実施例９ 電解液として４−メチル−１，３−ジオキソラン49.5容
量％、１，２−ジメトキシエタン21.2容量％およびトリ
ス（１−（２−メチル）アジリディニル）ホスフィンオ
キサイド29.3容量％からなる混合溶媒にＬｉＰＦ６を１
モル／溶解したものを用いたほかは実施例１と同様の
リチウム有機電解質電池を組み立てた。上記電解液にお
いて、トリス（１−（２−メチル）アジリディニル）ホ
スフィンオキサイドはＬｉＰＦ６の約1.5 倍に相当す
る。Example 9 As an electrolytic solution, a mixed solvent consisting of 49.5% by volume of 4-methyl-1,3-dioxolane, 21.2% by volume of 1,2-dimethoxyethane and 29.3% by volume of tris (1- (2-methyl) aziridinyl) phosphine oxide was used. 1 LiPF 6
A lithium organic electrolyte battery was assembled in the same manner as in Example 1 except that the mol / melted product was used. In the electrolytic solution, tris (1- (2-methyl) aziridinyl) phosphine oxide corresponds to about 1.5 times as much as LiPF 6 .
上記実施例７〜９の電池および前記比較例１の電池を60
℃で貯蔵し、貯蔵に伴う開路電圧の変化と300 Ω、５秒
放電後の閉路電圧変化を調べた。開路電圧変化を第８図
に、開路電圧変化を第９図に示す。The batteries of Examples 7 to 9 and Comparative Example 1 were replaced by 60
The sample was stored at ℃, and the change in the open circuit voltage due to the storage and the change in the closed circuit voltage after discharging at 300 Ω for 5 seconds were examined. The open circuit voltage change is shown in FIG. 8 and the open circuit voltage change is shown in FIG.
また、実施例７〜９の電池および比較例１の電池を６０
℃で貯蔵したときの10kHz 内部抵抗変化を第10図に示
す。In addition, the batteries of Examples 7 to 9 and the battery of Comparative Example 1 were used as 60
Figure 10 shows the change in internal resistance at 10 kHz when stored at ℃.
第８図および第９図に示すように、この実施例７〜９の
電池も、前記実施例１〜６の電池同様に従来電池である
比較例１の電池に比べて貯蔵に伴う開路電圧変化、閉路
電圧変化が少なかった。As shown in FIG. 8 and FIG. 9, the batteries of Examples 7 to 9 also changed the open circuit voltage accompanying storage as compared to the battery of Comparative Example 1 which is a conventional battery like the batteries of Examples 1 to 6. , The change in closed circuit voltage was small.
また、第10図に示すように、本発明の実施例７〜９の電
池も貯蔵に伴う大きな内部抵抗増加が認められなかっ
た。Further, as shown in FIG. 10, the batteries of Examples 7 to 9 of the present invention did not show a large increase in internal resistance due to storage.
〔発明の効果〕 以上説明したように、本発明ではトリエチレンホスホル
アミド、トリエチレンチオホスホルアミドおよびそれら
の誘導体よりなる群から選ばれた少なくとも１種を電解
液中に添加することによって、電解液の熱安定性を高め
て、電池の貯蔵性能を高めることができた。[Effects of the Invention] As described above, in the present invention, by adding at least one selected from the group consisting of triethylenephosphoramide, triethylenethiophosphoramide and their derivatives to the electrolytic solution, The thermal stability of the electrolyte was increased and the storage performance of the battery could be improved.
第１図は本発明に係る有機電解質電池の一例を示す断面
図であり、第２図は本発明の実施例１〜３の電池と比較
例１の電池の貯蔵に伴う開路電圧の変化を示す図であ
る。第３図は本発明の実施例１〜３の電池と比較例１の
電池の貯蔵に伴う閉路電圧の変化を示す図であり、第４
図は本発明の実施例１〜３の電池と比較例１の電池の貯
蔵に伴う10kHz 内部抵抗の変化を示す図である。第５図
は本発明の実施例４〜６の電池と比較例１の電池の貯蔵
に伴う開路電圧の変化を示す図であり、第６図は本発明
の実施例４〜６の電池と比較例１の電池の貯蔵に伴う閉
路電圧の変化を示す図である。第７図は本発明の実施例
４〜６の電池と比較例１の電池の貯蔵に伴う10kHz 内部
抵抗の変化を示す図である。第８図は本発明の実施例７
〜９の電池と比較例１の電池の貯蔵に伴う開路電圧の変
化を示す図であり、第９図は本発明の実施例７〜９の電
池と比較例１の電池の貯蔵に伴う閉路電圧の変化を示す
図である。第10図は本発明の実施例７〜９の電池と比較
例１の電池の貯蔵に伴う10kHz 内部抵抗の変化を示す図
である。 ３……負極、４……セパレータ、５……電解液吸収体、
６……正極FIG. 1 is a cross-sectional view showing an example of the organic electrolyte battery according to the present invention, and FIG. 2 shows changes in open circuit voltage due to storage of the batteries of Examples 1 to 3 of the present invention and the battery of Comparative Example 1. It is a figure. FIG. 3 is a graph showing changes in closed circuit voltage due to storage of the batteries of Examples 1 to 3 of the present invention and the battery of Comparative Example 1.
The figure is a diagram showing changes in 10 kHz internal resistance with storage of the batteries of Examples 1 to 3 of the present invention and the battery of Comparative Example 1. FIG. 5 is a diagram showing changes in open circuit voltage due to storage of the batteries of Examples 4 to 6 of the present invention and the battery of Comparative Example 1, and FIG. 6 is compared with the batteries of Examples 4 to 6 of the present invention. It is a figure which shows the change of closed circuit voltage accompanying the storage of the battery of Example 1. FIG. 7 is a diagram showing changes in the internal resistance of 10 kHz with the storage of the batteries of Examples 4 to 6 of the present invention and the battery of Comparative Example 1. FIG. 8 shows Embodiment 7 of the present invention.
9 to 9 are graphs showing changes in open circuit voltage of the batteries of Comparative Example 1 and the battery of Comparative Example 1, and FIG. 9 is a circuit diagram of the batteries of Examples 7 to 9 of the present invention and of Comparative Example 1 It is a figure which shows the change of. FIG. 10 is a diagram showing changes in 10 kHz internal resistance with storage of the batteries of Examples 7 to 9 of the present invention and the battery of Comparative Example 1. 3 ... Negative electrode, 4 ... Separator, 5 ... Electrolyte absorber,
6 ... Positive electrode
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−108276（ＪＰ，Ａ) 特開 昭58−87777（ＪＰ，Ａ) 特公 昭51−3890（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-108276 (JP, A) JP-A-58-87777 (JP, A) JP-B-51-3890 (JP, B2)
Claims (2)
Ｐ、ＳｂまたはＡｓのとき６で、ＸがＢのときは４であ
る） で示される化合物を溶解し、トリエチレンホスホルアミ
ド、トリエチレンチオホスホルアミドおよびそれらの誘
導体よりなる群から選ばれた少なくとも１種を添加した
電解液を用いたことを特徴とする有機電解質電池。1. An organic solvent comprising the general formula (I) LiXFn (I) (wherein X is P, Sb, As or B, n is 6 when X is P, Sb or As, and X is In the case of B, the compound represented by 4) was dissolved, and an electrolytic solution containing at least one selected from the group consisting of triethylenephosphoramide, triethylenethiophosphoramide and their derivatives was used. An organic electrolyte battery characterized by the above.
ンチオホスホルアミドおよびそれらの誘導体よりなる群
から選ばれた少なくとも１種の添加量が一般式（Ｉ）で
示される化合物のモル数の0.3 〜1.5 倍モルである特許
請求の範囲第１項記載の有機電解質電池。2. An addition amount of at least one selected from the group consisting of triethylenephosphoramide, triethylenethiophosphoramide and their derivatives is 0.3 to 0.3 of the number of moles of the compound represented by the general formula (I). The organic electrolyte battery according to claim 1, which has a molar ratio of 1.5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60050167A JPH0630257B2 (en) | 1985-03-12 | 1985-03-12 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60050167A JPH0630257B2 (en) | 1985-03-12 | 1985-03-12 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61208758A JPS61208758A (en) | 1986-09-17 |
| JPH0630257B2 true JPH0630257B2 (en) | 1994-04-20 |
Family
ID=12851644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60050167A Expired - Lifetime JPH0630257B2 (en) | 1985-03-12 | 1985-03-12 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0630257B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11476500B2 (en) | 2018-02-12 | 2022-10-18 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2594036B2 (en) * | 1985-10-17 | 1997-03-26 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| JPH03274670A (en) * | 1990-03-23 | 1991-12-05 | Sanyo Electric Co Ltd | Nonaqueous electrolytic battery |
| US5846673A (en) * | 1996-12-09 | 1998-12-08 | Valence Technology, Inc. | Additive to stabilize electrochemical cell |
| WO2000038265A1 (en) * | 1998-12-22 | 2000-06-29 | Mitsubishi Denki Kabushiki Kaisha | Electrolytic solution for celles and cells made by using the same |
| EP1742237B1 (en) * | 2004-04-27 | 2012-05-23 | Bridgestone Corporation | Additive for non-aqueous electrolyte solution of electric double layer capacitor, non-aqueous electrolyte solution for electric double layer capacitor and non-aqueous electrolyte solution electric double layer capacitor |
| WO2016006381A1 (en) * | 2014-07-09 | 2016-01-14 | 日本電気株式会社 | Nonaqueous electrolyte and lithium ion secondary cell |
| CN112310478B (en) * | 2020-10-23 | 2022-04-01 | 惠州锂威新能源科技有限公司 | Electrolyte and electrochemical device thereof |
| CN116235315A (en) * | 2020-11-25 | 2023-06-06 | 三星Sdi株式会社 | Additive and lithium secondary battery electrolyte and lithium secondary battery including same |
| CN114335718B (en) * | 2021-11-24 | 2024-07-26 | 惠州市豪鹏科技有限公司 | Nonaqueous electrolyte, preparation method thereof and secondary battery |
-
1985
- 1985-03-12 JP JP60050167A patent/JPH0630257B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11476500B2 (en) | 2018-02-12 | 2022-10-18 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61208758A (en) | 1986-09-17 |
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