JPS6041775A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS6041775A JPS6041775A JP58151114A JP15111483A JPS6041775A JP S6041775 A JPS6041775 A JP S6041775A JP 58151114 A JP58151114 A JP 58151114A JP 15111483 A JP15111483 A JP 15111483A JP S6041775 A JPS6041775 A JP S6041775A
- Authority
- JP
- Japan
- Prior art keywords
- nonaqueous electrolyte
- battery
- electrolyte battery
- dioxacyclohexane
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 11
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 3
- 230000007774 longterm Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- JZVUAOCDNFNSGQ-UHFFFAOYSA-N 7-methoxy-2-phenyl-1h-quinolin-4-one Chemical compound N=1C2=CC(OC)=CC=C2C(O)=CC=1C1=CC=CC=C1 JZVUAOCDNFNSGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は非水電解液電池に関し、その非水電解液の溶
媒の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to non-aqueous electrolyte batteries and to improvements in the solvent of the non-aqueous electrolyte.
（ロ）先行技術
軽金属を活物質とする負極、これに対応する正極と、溶
質と溶媒とからなる非水電解液を備える非水電解液電池
には、溶媒としてはプロピレンカーボネート、γ−ブチ
ロラクトン、■＋２−ジメトキシエタンなどを単独か又
はこれらを２以上群合して用いられ、溶質としては過塩
素酸リチウム（ＬｉＣ４Ｏ，）、ホウフッ化リチウム（
ＬｉＢＦυ、ヘキサフルオロリン酸リチウム（ＬｉＰＦ
、）などを単独又はこれらを２以上群合して用いられる
。(b) Prior art Non-aqueous electrolyte batteries comprising a negative electrode using a light metal as an active material, a corresponding positive electrode, and a non-aqueous electrolyte comprising a solute and a solvent include propylene carbonate, γ-butyrolactone, ■+2-dimethoxyethane etc. are used alone or in combination of two or more, and the solutes are lithium perchlorate (LiC4O,), lithium borofluoride (
LiBFυ, lithium hexafluorophosphate (LiPF
, ) etc. may be used singly or in combination of two or more.
さて近年に至ってこの種の電池の利用分野が拡大され、
そのため電池特性の改善が望まれているが、特に長期間
保存後の放電特性の改善が要望されている。Now, in recent years, the field of use of this type of battery has expanded,
Therefore, it is desired to improve battery characteristics, and in particular, there is a desire to improve discharge characteristics after long-term storage.
（ハ）発明の目的
この発明は上記状況においてなされたものであって、そ
の目的とするところは、長期間保存後の放電特性の改善
された非水電解液電池を提供するにある。(c) Purpose of the Invention The present invention was made under the above circumstances, and its purpose is to provide a non-aqueous electrolyte battery with improved discharge characteristics after long-term storage.
に）発明の構成
この発明は、１，３−ジオキサシクロヘキ？ンー２−オ
ンが、酸化作用や還元作用に対して安定なことに着目し
てなされたもので、軽金属を活物質とする負極、これに
対応する正極及び溶媒と溶質とからなる非水電解液を備
えた非水電解液電池であって、溶媒が１，３−ジオキサ
シクロヘキサン−２−オン単独又はそれを含む混合溶媒
であることを特徴とする特に長期保存後の放電特性の良
好な非水電解液電池を提供するものである。B) Structure of the Invention This invention is based on 1,3-dioxacyclohexa? This was developed based on the fact that N-2-ON is stable against oxidation and reduction effects, and it is a non-aqueous electrolyte consisting of a negative electrode with a light metal as an active material, a corresponding positive electrode, and a solvent and solute. 1,3-Dioxacyclohexane-2-one alone or a mixed solvent containing 1,3-dioxacyclohexane-2-one as a solvent, the non-aqueous electrolyte battery having particularly good discharge characteristics after long-term storage. The present invention provides a water electrolyte battery.
そしてこの発明の電池の非水電解液の溶媒として１．３
−ジオキサシクロヘキサン−２−オン単独で用いる場合
は特に小電流取出し用の電池として好適なものである。and 1.3 as a solvent for the non-aqueous electrolyte of the battery of this invention.
-Dioxacyclohexane-2-one, when used alone, is particularly suitable as a battery for drawing a small current.
一方１．３−ジオキサシクロヘキサン−２−オンを混合
溶媒として用いる場合の他の溶媒としては前記のような
従来の非水電解液電池に用いられている溶媒を用いるこ
とができる。 そして電池の長期保存後の放電特性を改
善するためにはｌ。On the other hand, when 1,3-dioxacyclohexan-2-one is used as a mixed solvent, the solvents used in conventional non-aqueous electrolyte batteries as described above can be used. And in order to improve the discharge characteristics of the battery after long-term storage.
３−ジオキサシクロヘキサン−２−オンを２０容量チ以
上添加するのが適切であり、４０容儀チ以上添加するの
が好ましい。 例えば１．３−ジオキサシクロヘキサン
−２−オンと１，２−ジメトーキシエタンとを等容積混
合した溶媒を用いた場合は長期保存後の放電特性が良好
で特に大電流取出し用に好適な電池が得られる。It is appropriate to add 3-dioxacyclohexan-2-one in an amount of 20 volumes or more, preferably 40 volumes or more. For example, when a solvent containing equal volumes of 1,3-dioxacyclohexane-2-one and 1,2-dimethoxyethane is used, the discharge characteristics after long-term storage are good and it is particularly suitable for drawing large currents. A battery is obtained.
また非水電解液を構成する溶質としては、従来非水電解
液電池に用いられている前記のようなリチウム塩を用い
ることができ、さらに酢酸リチウム、トリフルオロ酢酸
リチウム、シュウ酸リチウム、安息香酸リチウムなどの
よ″うなカルボン酸リチウム塩も用いることができ、こ
の場合低温時の放電特性が改善される。In addition, as the solute constituting the non-aqueous electrolyte, the above-mentioned lithium salts conventionally used in non-aqueous electrolyte batteries can be used, and lithium acetate, lithium trifluoroacetate, lithium oxalate, benzoic acid, etc. Lithium carboxylic acid salts such as lithium can also be used, in which case the discharge characteristics at low temperatures are improved.
この発明の非水電解液電池に用いられる負極活物質とし
てはリチウム、ナトリウム、マグネシウムなどの軽金摘
、また正極としては、金属の酸化物（例えば二酸化マン
ガン、三酸化モリブデンなど）、硫化物（例えば硫化銅
など）、・・ロゲン化物（ＮｉＦ、、Ｃｕ Ｆａ、Ａｇ
Ｃ１など）、フッ化黒鉛〔（ＣＦ）ｎ〕などのような従
来の非水電解液電池に用いられ又いるものが用いられる
。The negative electrode active materials used in the nonaqueous electrolyte battery of this invention include light metals such as lithium, sodium, and magnesium, and the positive electrode includes metal oxides (such as manganese dioxide and molybdenum trioxide) and sulfides ( (e.g. copper sulfide, etc.),...rogenides (NiF, Cu Fa, Ag
C1, etc.), fluorinated graphite [(CF)n], etc., which are used in conventional non-aqueous electrolyte batteries, are used.
（ホ）実施例
この発明の実施例の電池と比較例の電池を作製して長期
保存後の放電特性を比役した。(e) Example A battery according to an example of the present invention and a battery according to a comparative example were prepared and their discharge characteristics after long-term storage were compared.
負極としてリチウム圧延板を所定寸法に打抜いたものを
用い、正極として二酸化マンガン（活物質）とアセチレ
ンプシツク粉末（導電剤）とポリテトジンルオロエチレ
ン粉末（結着剤）とを８５：１０：５の重量比で混合し
た後、Ｃの混合物を加圧成形して熱処理したものを用い
た。 そして上記正負両極とポリプロピレン不織布、及
び下記表の各種組成の非水電解液を用いてボタン型非水
を用いた小電流取出し用の電池であり、ＣとＤは混合溶
媒を用いた大電流取出し用の電池である。A lithium rolled plate punched to a specified size was used as the negative electrode, and manganese dioxide (active material), acetylene plastic powder (conductive agent), and polytetodine fluoroethylene powder (binder) were used as the positive electrode. After mixing at a weight ratio of 10:5, the mixture of C was pressure molded and heat treated. The positive and negative electrodes, polypropylene non-woven fabric, and non-aqueous electrolytes with various compositions shown in the table below are used to produce button-shaped non-aqueous batteries for small current extraction, and C and D are large current extraction batteries using mixed solvents. It is a battery for.
まずＡとＢの電池について電池作製直後２５°Ｃにおい
て５にΩの定抵抗で放電したときの放電初期特性を測定
し第１し１に示しだ。 この場合Ａ 、 １両電池に差
は認められなかった。 次にＡと、Ｂ電池金６０℃の温
度下で３ケ月保存した後、２５℃において５にΩの定抵
抗で故紙しまたときの放電４′テ性を第２図に示した。First, the initial discharge characteristics of batteries A and B were measured when they were discharged at a constant resistance of 5Ω at 25°C immediately after battery fabrication, and are shown in Table 1. In this case, no difference was observed between the A and 1 batteries. Figure 2 shows the discharge characteristics of batteries A and B when they were stored for three months at a temperature of 60°C and then recycled at 25°C with a constant resistance of 5Ω.
第２図から明らかのようにこの発明の電池の一実施例
のＢ電池の方が比較例のＡ′亀電池り長期放置ゼ２の放
電特性が優れている。As is clear from FIG. 2, battery B, which is an embodiment of the battery of the present invention, has better discharge characteristics than battery A', which is a comparative example, and battery A', which is left for a long period of time.
一方ＣとＤの電池について電池作製ｌθ後２５℃におい
て５００にΩの定抵抗で放電したときの放電初期特性を
測定し第３し１に示し／こ。 この）Ｐ曾Ｃ１Ｄ両電池
に差は認められなかった。 次にＣとＤ電池を（ｉ ０
℃の己度下で３ケ月保存し、た鏝、２５℃において５０
０にΩの定抵抗で放電したときの放電特性を第４図に示
した。 第４し１かも明らかのようにこの発明の電池の
一ツ６施例のＤ電池の方が比較例のＣ電池Ｊ：り畏期放
置後の放電特性が優れている。On the other hand, the initial discharge characteristics of batteries C and D when discharged at a constant resistance of 500Ω at 25° C. after battery fabrication lθ were measured and are shown in Section 3.1. No difference was observed between the two batteries. Next, add batteries C and D (i 0
Store at 25℃ for 3 months, then heat with a trowel at 25℃
Figure 4 shows the discharge characteristics when discharged with a constant resistance of 0Ω. As is clear from No. 4 and 1, Battery D of Example 6, which is one of the batteries of the present invention, has better discharge characteristics after being left for a period of time than Battery C of Comparative Example.
（へ）発明の効果
この発明によれば、特に長期保存後の放電嚇性が優れた
非水電解液電池が得られる。(f) Effects of the Invention According to the present invention, a non-aqueous electrolyte battery which is particularly excellent in discharge threat properties after long-term storage can be obtained.
第１図と第２図はそれぞれ、小電流取り出し用の実施例
の電池Ｂと比較例電池Ａの作製直後の放電特性と６０℃
で３ケ月放置後の放電時１＝１を示すグラフであり、第
３図と第４図はそれぞれ、大電流取出し用の実施例電池
りと比較例電池Ｃの作製直後の放電特性と６０℃で３ケ
月放置後の放電特性を示すグラフである。
−嘔１［１１原−暖百Figures 1 and 2 show the discharge characteristics of Example Battery B and Comparative Example Battery A for small current extraction, respectively, and the discharge characteristics immediately after fabrication at 60°C.
This is a graph showing 1=1 during discharge after being left for 3 months at This is a graph showing the discharge characteristics after being left for three months. - 1 [11 hara - Dan Hyaku]
Claims (1)
び溶媒と溶質とからなる非水電解液を備えた非水電解液
電池であって、溶媒が１，３−ジオギザシクロヘキサン
−２−オン単独又はそれを含む混合溶媒であることを特
徴とする非水電解液電池。 ２ 混合溶媒が１，３−ジオキサシクロヘキサン−２−
オンと１，２−ジメトキシエタンとの混合物である特許
請求の範囲第１項記載の電池。[Claims] A non-aqueous electrolyte battery characterized by using Gizacyclohexane-2-one alone or a mixed solvent containing it. 2 The mixed solvent is 1,3-dioxacyclohexane-2-
The battery according to claim 1, which is a mixture of 1,2-dimethoxyethane and 1,2-dimethoxyethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58151114A JPS6041775A (en) | 1983-08-18 | 1983-08-18 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58151114A JPS6041775A (en) | 1983-08-18 | 1983-08-18 | Nonaqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6041775A true JPS6041775A (en) | 1985-03-05 |
| JPH053113B2 JPH053113B2 (en) | 1993-01-14 |
Family
ID=15511659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58151114A Granted JPS6041775A (en) | 1983-08-18 | 1983-08-18 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6041775A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0944126A1 (en) * | 1998-03-18 | 1999-09-22 | Hitachi, Ltd. | Lithium secondary battery, its electrolyte, and electric apparatus using the same |
-
1983
- 1983-08-18 JP JP58151114A patent/JPS6041775A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0944126A1 (en) * | 1998-03-18 | 1999-09-22 | Hitachi, Ltd. | Lithium secondary battery, its electrolyte, and electric apparatus using the same |
| US6475680B1 (en) * | 1998-03-18 | 2002-11-05 | Hitachi, Ltd. | Lithium secondary battery, its electrolyte, and electric apparatus using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH053113B2 (en) | 1993-01-14 |
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