JPH0711967B2 - Non-aqueous electrolyte battery - Google Patents

Non-aqueous electrolyte battery

Info

Publication number
JPH0711967B2
JPH0711967B2 JP61060004A JP6000486A JPH0711967B2 JP H0711967 B2 JPH0711967 B2 JP H0711967B2 JP 61060004 A JP61060004 A JP 61060004A JP 6000486 A JP6000486 A JP 6000486A JP H0711967 B2 JPH0711967 B2 JP H0711967B2
Authority
JP
Japan
Prior art keywords
aqueous electrolyte
battery
electrolyte battery
solvent
discharge characteristics
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
Application number
JP61060004A
Other languages
Japanese (ja)
Other versions
JPS62217567A (en
Inventor
修弘 古川
精司 吉村
昌利 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Priority to JP61060004A priority Critical patent/JPH0711967B2/en
Publication of JPS62217567A publication Critical patent/JPS62217567A/en
Publication of JPH0711967B2 publication Critical patent/JPH0711967B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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)
  • Primary Cells (AREA)

Description

【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は軽金属を活物質とする負極と、金属の酸化物、
硫化物、ハロゲン化物などを活物質とする正極と、少く
とも一つの溶媒と少くとも一つの溶質とからなる非水電
解液とを備えた非水電解液電池に係り、特に非水電解液
の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a negative electrode using a light metal as an active material, a metal oxide,
The present invention relates to a non-aqueous electrolyte battery provided with a positive electrode using a sulfide, a halide or the like as an active material, and a non-aqueous electrolyte solution containing at least one solvent and at least one solute. It is about improvement.

（ロ） 従来の技術 この種電池に用いられる非水電解液を構成する溶媒及び
溶質として種々のものが提案されている。具体的には例
えば特公昭57-32866号公報に開示されているように溶媒
としてプロピレンカーボネート、γ−ブチロラクトン、
ジメトキシエタン、ジオキソラン、テトラハイドロフラ
ンなどが知られており、これらを単独或いは二種以上混
合して用いている。又、溶質として過塩素酸リチウム、
ホウフッ化リチウム、ヘキサフルオロリン酸リチウムな
どが知られており、これらを単独或いは二種以上混合し
て用いている。(B) Conventional Technology Various solvents and solutes have been proposed as constituents of the non-aqueous electrolyte used in this type of battery. Specifically, for example, as disclosed in JP-B-57-32866, propylene carbonate as a solvent, γ-butyrolactone,
Dimethoxyethane, dioxolane, tetrahydrofuran and the like are known, and these are used alone or in combination of two or more. Also, as a solute, lithium perchlorate,
Lithium borofluoride, lithium hexafluorophosphate and the like are known, and these are used alone or in combination of two or more.

さて、近年に至ってはこの種電池の適用分野の拡大に伴
い電池特性の改善が要望されており、その一つとして保
存後の放電特性の向上が望まれている。Now, in recent years, there has been a demand for improvement in battery characteristics with the expansion of application fields of this type of battery, and as one of them, improvement in discharge characteristics after storage is desired.

（ハ） 発明が解決しようとする問題点 本発明は非水電解液を改良し、保存特性に優れた非水電
解液電池を提供することを目的とする。(C) Problems to be Solved by the Invention An object of the present invention is to improve a non-aqueous electrolyte and provide a non-aqueous electrolyte battery having excellent storage characteristics.

（ニ） 問題点を解決するための手段 非水電解液を構成する溶媒として、４位の炭素原子をハ
ロゲン化したエチレンカーボネートを用いる。(D) Means for Solving the Problems As a solvent constituting the non-aqueous electrolyte, ethylene carbonate in which the carbon atom at the 4-position is halogenated is used.

４位の炭素原子をハロゲン化したエチレンカーボネート
の具体例としてはクロロエチレンカーボネート又はブロ
モエチレンカーボネートが挙げられる。Specific examples of ethylene carbonate obtained by halogenating the 4-position carbon atom include chloroethylene carbonate and bromoethylene carbonate.

尚、この４位の炭素原子をハロゲン化したエチレンカー
ボネートを単独溶媒として用いても良く、又前述せる他
の溶媒と組合せて混合溶媒として用いても良い。例えば
1,2ジメトキシエタンとの混合溶媒として用いると保存
特性に加え高率放電特性に優れた非水電解液電池が得ら
れる。The ethylene carbonate obtained by halogenating the carbon atom at the 4-position may be used as a single solvent, or may be used as a mixed solvent in combination with the other solvent described above. For example
When used as a mixed solvent with 1,2 dimethoxyethane, a non-aqueous electrolyte battery having excellent high rate discharge characteristics in addition to storage characteristics can be obtained.

（ホ） 作用 ４位の炭素原子をハロゲン化したエチレンカーボネート
は還元作用に対して安定であるため、リチウム、ナトリ
ウムなどの軽金属による還元を受けにくく、分解され難
い。(E) Action Ethylene carbonate in which the carbon atom at the 4-position is halogenated is stable against the reducing action, and thus is less susceptible to reduction by light metals such as lithium and sodium and is less likely to be decomposed.

（ヘ） 実施例 以下、本発明の実施例について詳述する。(F) Example Hereinafter, an example of the present invention will be described in detail.

正極は350〜430℃の温度範囲で熱処理した二酸化マンガ
ンを活物質としこの二酸化マンガンと、導電剤としての
アセチレンブラックと、結着剤としてのテトラフルオロ
エチレン粉末とを85:10:5の重量比で混合した後、この
混合物を加圧成形し250〜350℃の温度範囲で熱処理した
ものを用いた。又、負極はリチウム圧延板を所定寸法に
打抜いたものを用いた。The positive electrode uses manganese dioxide heat-treated in the temperature range of 350 to 430 ° C. as an active material, and this manganese dioxide, acetylene black as a conductive agent, and tetrafluoroethylene powder as a binder have a weight ratio of 85: 10: 5. Then, the mixture was pressure-molded and heat-treated in the temperature range of 250 to 350 ° C. As the negative electrode, a rolled lithium plate punched into a predetermined size was used.

そして、前記正負極、ポリプロピレン不織布よりなるセ
パレータ及び下表の各種組成の非水電解液を用いて径2
0.0mm、厚み2.5mm、電池容量130mAHの非水電解液電池
（A1）（A2）（A3）（Ｂ）（Ｃ）を作成した。Then, the positive and negative electrodes, a separator made of a polypropylene non-woven fabric and a non-aqueous electrolyte solution having various compositions shown in the table below are used to measure the diameter 2
Non-aqueous electrolyte batteries (A 1 ) (A 2 ) (A 3 ) (B) (C) having a thickness of 0.0 mm, a thickness of 2.5 mm and a battery capacity of 130 mAH were prepared.

尚、表において1,2DMEは1,2ジメトキシエタンを意味す
る。 In the table, 1,2DME means 1,2 dimethoxyethane.

第１図及び第２図は電池（A1）（A2）（Ｂ）の放電特性
を示し、第１図は電池作成後、25℃において12KΩの定
抵抗で放電した時の放電初期特性、第２図は電池を60℃
の温度で３ケ月保存した後、25℃において12KΩの定抵
抗で放電した時の放電特性である。1 and 2 show the discharge characteristics of the batteries (A 1 ) (A 2 ) (B), and FIG. 1 shows the initial discharge characteristics when discharged at a constant resistance of 12 KΩ at 25 ° C. after the batteries were made. Figure 2 shows the battery at 60 ℃
After being stored at the temperature of 3 months and discharged at a constant resistance of 12 KΩ at 25 ° C, the discharge characteristics are shown.

第１図及び第２図より明白なるように初期の放電特性で
は差異は認められないものの、保存後の放電特性では本
発明電池（A1）（A2）の方が比較電池（Ｂ）より優れて
いる。As is clear from FIGS. 1 and 2, no difference was observed in the initial discharge characteristics, but in the discharge characteristics after storage, the batteries of the present invention (A 1 ) and (A 2 ) were better than the comparative battery (B). Are better.

又、第３図及び第４図は電池（A3）（Ｃ）の放電特性を
示し、第３図は電池作成後、25℃において500Ωの定抵
抗で放電した時の放電初期特性、第４図は電池を60℃の
温度で３ケ月保存した後、25℃において500Ωの定抵抗
で放電した時の放電特性である。Further, FIGS. 3 and 4 show the discharge characteristics of the batteries (A 3 ) and (C), and FIG. 3 shows the discharge initial characteristics when discharged at a constant resistance of 500Ω at 25 ° C. after the preparation of the battery. The figure shows the discharge characteristics when the battery was stored at a temperature of 60 ° C for 3 months and then discharged at a constant resistance of 500Ω at 25 ° C.

第３図及び第４図より明白なるように初期の高率放電特
性では差異は認められないものの、保存後の高率放電特
性では本発明電池（A3）の方が比較電池（Ｃ）より優れ
ている。As can be seen from FIGS. 3 and 4, no difference was observed in the initial high rate discharge characteristics, but in the high rate discharge characteristics after storage, the battery of the present invention (A 3 ) was better than the comparative battery (C). Are better.

以上の実施例で示すようにプロピレンカーボネートの代
わりにクロロエチレンカーボネートやブロモエチレンカ
ーボネート（構造式は下に示す）を用いると保存後の放
電特性が優れた非水電解液電池が得られるが、これはメ
チル基（CH3）を電子供与性の強いハロゲン基（Cl基、B
r基）に置換することによって炭酸基（CO3）が負極活物
質であるリチウム、ナトリウムなどの軽金属による還元
を受けにくく、分解され難いため電解液の劣化が抑えら
れることによるものと考えられる。As shown in the above examples, when chloroethylene carbonate or bromoethylene carbonate (the structural formula is shown below) is used instead of propylene carbonate, a non-aqueous electrolyte battery having excellent discharge characteristics after storage can be obtained. Is a methyl group (CH 3 ) and a halogen group (Cl group, B
It is considered that by substituting the (r group), the carbonic acid group (CO 3 ) is less likely to be reduced by the light metal such as lithium and sodium which is the negative electrode active material and is less likely to be decomposed, so that the deterioration of the electrolytic solution is suppressed.

（ト） 発明の効果 上述した如く、溶媒として４位の炭素原子をハロゲン化
したエチレンカーボネートを用いることにより非水電解
液電池の保存特性を向上しうる。 (G) Effect of the Invention As described above, the storage characteristics of the non-aqueous electrolyte battery can be improved by using ethylene carbonate in which the carbon atom at the 4-position is halogenated as the solvent.

更に４位の炭素原子うハロゲン化したエチレンカーボネ
ートと1,2ジメトキシエタンとの混合溶媒を用いると保
存特性に加え高率放電特性も改善しうるものであり、こ
の種電池の用途拡大に資するところ極めて大である。Furthermore, when a mixed solvent of halogenated ethylene carbonate and carbon dioxide at the 4-position and 1,2 dimethoxyethane is used, not only storage characteristics but also high rate discharge characteristics can be improved. It is extremely large.

尚、非水電解液電池の正極活物質として実施例では二酸
化マンガンを例示したが、これに限定されず他の金属の
酸化物（例えば三酸化モリブデン、酸化銅）、硫化物
（例えば硫化鉄、硫化銅）、ハロゲン化物（例えばフッ
化ニッケル、フッ化銅、塩化銀）、フッ化黒鉛などを用
いることができ、又負極活物質についてもナトリウム、
マグネシウムなどを用いることができる。In addition, although manganese dioxide was illustrated in the examples as the positive electrode active material of the non-aqueous electrolyte battery, the present invention is not limited to this, and oxides of other metals (such as molybdenum trioxide and copper oxide) and sulfides (such as iron sulfide, Copper sulfide), a halide (for example, nickel fluoride, copper fluoride, silver chloride), graphite fluoride, etc. can be used, and sodium is also used for the negative electrode active material.
Magnesium or the like can be used.

【図面の簡単な説明】[Brief description of drawings]

図面は電池の放電特性を示し、第１図及び第３図は初期
の放電特性、第２図及び第４図は保存後の放電特性であ
る。 (A1)(A2)(A3)……本発明電池、（Ｂ）（Ｃ）……比較電
池。The drawings show the discharge characteristics of the battery, FIGS. 1 and 3 show the initial discharge characteristics, and FIGS. 2 and 4 show the discharge characteristics after storage. (A 1 ) (A 2 ) (A 3 ) …… Invention battery, (B) (C) …… Comparison battery.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】軽金属を活物質とする負極と、正極と、少
くとも一つの溶媒と少くとも一つの溶質とからなる非水
電解液とを備えるものであって、溶媒として４位の炭素
原子をハロゲン化したエチレンカーボネートを用いるこ
とを特徴とする非水電解液電池。1. A negative electrode using a light metal as an active material, a positive electrode, and a non-aqueous electrolyte comprising at least one solvent and at least one solute, wherein the carbon atom at the 4-position is used as the solvent. A non-aqueous electrolyte battery using halogenated ethylene carbonate. 【請求項２】４位の炭素原子をハロゲン化したエチレン
カーボネートがクロロエチレンカーボネート又はブロモ
エチレンカーボネートである特許請求の範囲第項記載
の非水電解液電池。2. The nonaqueous electrolyte battery according to claim 1, wherein the ethylene carbonate obtained by halogenating the 4-position carbon atom is chloroethylene carbonate or bromoethylene carbonate. 【請求項３】溶媒として４位の炭素原子をハロゲン化し
たエチレンカーボネートと1,2ジメトキシエタンとの混
合溶媒を用いることを特徴とする特許請求の範囲第項
記載の非水電解液電池。3. The non-aqueous electrolyte battery according to claim 1, wherein a mixed solvent of ethylene carbonate halogenated at the 4-position carbon atom and 1,2 dimethoxyethane is used as the solvent.
JP61060004A 1986-03-18 1986-03-18 Non-aqueous electrolyte battery Expired - Lifetime JPH0711967B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61060004A JPH0711967B2 (en) 1986-03-18 1986-03-18 Non-aqueous electrolyte battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61060004A JPH0711967B2 (en) 1986-03-18 1986-03-18 Non-aqueous electrolyte battery

Publications (2)

Publication Number Publication Date
JPS62217567A JPS62217567A (en) 1987-09-25
JPH0711967B2 true JPH0711967B2 (en) 1995-02-08

Family

ID=13129513

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61060004A Expired - Lifetime JPH0711967B2 (en) 1986-03-18 1986-03-18 Non-aqueous electrolyte battery

Country Status (1)

Country Link
JP (1) JPH0711967B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9831532B2 (en) 2007-11-13 2017-11-28 Sony Corporation Nonaqueous electrolyte secondary battery

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100515298B1 (en) * 2003-03-24 2005-09-15 삼성에스디아이 주식회사 A non-aqueous electrolyte and a lithium secondary battery comprising the same
JP4349321B2 (en) 2004-12-10 2009-10-21 ソニー株式会社 battery
JP5419188B2 (en) 2010-03-26 2014-02-19 Ｎｅｃエナジーデバイス株式会社 Non-aqueous electrolyte secondary battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4930417A (en) * 1972-07-20 1974-03-18
JPS52153118A (en) * 1976-06-15 1977-12-20 Matsushita Electric Ind Co Ltd Battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4930417A (en) * 1972-07-20 1974-03-18
JPS52153118A (en) * 1976-06-15 1977-12-20 Matsushita Electric Ind Co Ltd Battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9831532B2 (en) 2007-11-13 2017-11-28 Sony Corporation Nonaqueous electrolyte secondary battery

Also Published As

Publication number Publication date
JPS62217567A (en) 1987-09-25

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