JPS63152886A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPS63152886A JPS63152886A JP61300481A JP30048186A JPS63152886A JP S63152886 A JPS63152886 A JP S63152886A JP 61300481 A JP61300481 A JP 61300481A JP 30048186 A JP30048186 A JP 30048186A JP S63152886 A JPS63152886 A JP S63152886A
- Authority
- JP
- Japan
- Prior art keywords
- dioxane
- solvent
- negative electrode
- active material
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- -1 panadicum pentoxide Chemical compound 0.000 description 3
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 description 2
- 241001185311 Lyticum Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
Abstract
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明はリチウム又はリチウムを含む合金を負極活物質
とする非水電解液二次電池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 non-aqueous electrolyte secondary battery using lithium or an alloy containing lithium as a negative electrode active material.
口 従来の技術
この種二次電池の正極活物質としては三酸化モリブデン
、五酸化パナジクム、チタン或いはニオブの硫化物など
が代表的なものとして知られているが、近年においては
一次電池系で実用化されている二酸化マンガンを二次電
池の正極活物質として用いることが提案されている。Conventional technology Molybdenum trioxide, panadicum pentoxide, titanium, or niobium sulfide are known as typical positive electrode active materials for this type of secondary battery, but in recent years, they have been put into practical use in primary battery systems. It has been proposed to use manganese dioxide, which has a chemical structure, as a positive electrode active material for secondary batteries.
一方、非水電解液を構成する溶媒としては持分１１１５
７−６２２７号に開示されているプロピレンカーボネー
トやｒ−ブチロラクトン、特公昭５４−１１８９０号或
いは特関昭５９−１０８２８１号に開示されている１、
３−ジオキンラン或いはそ号
のアルキル誘導体、特開ｉｌｌ：１５９−１２７３８２
Ａに開示されているテトラヒドロフラン等が知られてい
る。On the other hand, as a solvent constituting the non-aqueous electrolyte, the equity 1115
Propylene carbonate and r-butyrolactone disclosed in No. 7-6227, 1 disclosed in Japanese Patent Publication No. 54-11890 or Japanese Patent Publication No. 59-108281,
3-dioquinrane or its alkyl derivative, JP-A-ILL: 159-127382
Tetrahydrofuran disclosed in A and the like are known.
ここで、特に二酸化マンガンを正極活物質とした場合に
、前述の溶媒を組込むと次遅のような不都合がある。即
ち、プロピレンカーボネートやｒ−ブチロラクトンは負
極活物質であるリチウムと反応する溶媒である。従来の
一次電池においては負極表面に反応生成物の薄膜が形成
するのみで反応が活発に生じるということはないが、二
次電池においては充電時に、す、チクムのデンドライト
が発生して活性なリチクム面が多数露出し反応が活発に
生じて充放電サイクル特性に悪影響を与える。Here, especially when manganese dioxide is used as the positive electrode active material, incorporating the above-mentioned solvent has disadvantages such as slowdown. That is, propylene carbonate and r-butyrolactone are solvents that react with lithium, which is a negative electrode active material. In conventional primary batteries, only a thin film of reaction products is formed on the surface of the negative electrode and no active reaction occurs, but in secondary batteries, during charging, dendrites of lyticum are generated and active lyticum is formed. Many surfaces are exposed and reactions occur actively, which adversely affects charge/discharge cycle characteristics.
又、１．５ジオキソランやテトラヒドロフランは耐酸化
性が低い溶媒である。そのた睨電時に高電位となる二酸
化マンガンによって溶媒が酸化されて分解や重合が生じ
充放電サイクル特性に悪影響を与える。Furthermore, 1.5 dioxolane and tetrahydrofuran are solvents with low oxidation resistance. At the same time, the solvent is oxidized by manganese dioxide, which has a high potential during the electrification, resulting in decomposition and polymerization, which adversely affects charge-discharge cycle characteristics.
ハ 発明が解決しようとする問題点
リチウム又はリチウムを含む合金を負極活物質とし、二
酸化マンガンを正極活物質とする非水電解液二次電池の
充放電サイクル特性を向上させることを目的とする。C. Problems to be Solved by the Invention It is an object of the invention to improve the charge/discharge cycle characteristics of a nonaqueous electrolyte secondary battery that uses lithium or an alloy containing lithium as a negative electrode active material and manganese dioxide as a positive electrode active material.
二 問題点を解決する丸めの手段
本発明は非水電解液を構成するだ媒として、１゜５−ジ
オキサン若しくＨｌ、５−ジオキサンを含む混合溶媒を
用いることを要旨とするものである。2. Means for Solving Problems The gist of the present invention is to use a mixed solvent containing 1° 5-dioxane or Hl, 5-dioxane as a solvent constituting the non-aqueous electrolyte.
ホ作 用
１．５−ジオキサンを溶媒とした非水電解液を用いて電
池を組立てると、１．５−ジオキサンは負極表面で若干
還元されて保護膜を形成し、リチウム負極活物質の溶解
、析出はこの保護膜を介して生じるためリチウムのデン
ドライトの成長が抑制されると共Ｋ、耐酸化性に優れる
ため分解や重合が生じ難い。そのため前述の溶媒を用い
る場合に比して充放電サイクル特性が向上する。When a battery is assembled using a non-aqueous electrolyte containing 1,5-dioxane as a solvent, the 1,5-dioxane is slightly reduced on the negative electrode surface to form a protective film that dissolves the lithium negative electrode active material. Since precipitation occurs through this protective film, the growth of lithium dendrites is suppressed, and the oxidation resistance is excellent, making it difficult for decomposition and polymerization to occur. Therefore, the charge/discharge cycle characteristics are improved compared to the case where the above-mentioned solvent is used.
尚、１．３−ジオキサンは単独で用いても良く、又他の
溶媒と混合して用いても１．６−ジオキサンの効果か得
られる。Note that 1,3-dioxane may be used alone or in combination with other solvents to obtain the same effect as 1,6-dioxane.
へ実施例
第１図は本発明電池の半断面図を示し、！１１１２１は
ステンレス製の正負極缶であってこれらはポリプロピレ
ン製の絶縁バッキング（３）により隔離されている。（
４）はリチウム圧延板よりなる負極であって、負極缶（
２）の内底面に同省せる負極巣亀体（５）に圧着されて
いる。（６）は、二酸化マンガン活物質に＄＊剤として
のアセチレンブラック及び結看剤としてのフッ素樹脂粉
末を重量比で８０：１０：１０の割合で混合した合剤を
加圧成型してなる正極であって、正極缶（１）の内底面
に同省せる正極集亀体１７）に圧接されている。（８）
はポリプロピレン不織布よりなるセパレータであって非
水電解液が含浸されている。Embodiment FIG. 1 shows a half-sectional view of the battery of the present invention. 11121 is a positive and negative electrode can made of stainless steel, and these are isolated by an insulating backing (3) made of polypropylene. (
4) is a negative electrode made of a lithium rolled plate, and has a negative electrode can (
2) is crimped to the negative electrode nest body (5) which can be omitted. (6) is a positive electrode formed by pressure molding a mixture of manganese dioxide active material, acetylene black as a $* agent, and fluororesin powder as a binder in a weight ratio of 80:10:10. The positive electrode collecting body 17), which can be omitted, is pressed into contact with the inner bottom surface of the positive electrode can (1). (8)
is a separator made of polypropylene nonwoven fabric, and is impregnated with a non-aqueous electrolyte.
そして非水電解液として下表に示す如く種々の組成のも
のを用いて各種電池上作成した。Various types of batteries were prepared using non-aqueous electrolytes having various compositions as shown in the table below.
第２図及び第６図はこれら電池の充放電サイクル特性図
を示し、第２図は単独溶媒を用いた本発明電池（Ａ１）
と比較電池（Ｂｌ）（Ｂ２）（Ｂ５）の場合であり、第
６図は混合溶媒を用いた本発明電池（Ａ２）と比較電池
（Ｂ４）（Ｂ５）（Ｂｂ）の場合である。尚、サイクル
条件は放電電流３ｍＡで４時間放電し、充電電流３．６
ｍ Ａで充電終止電圧を３．５ｖとした。Figures 2 and 6 show charge-discharge cycle characteristics of these batteries, and Figure 2 shows the battery of the present invention (A1) using a single solvent.
and comparative batteries (Bl), (B2, and B5), and FIG. 6 shows the case of the present invention battery (A2) using a mixed solvent and comparative batteries (B4, B5, and Bb). The cycle conditions are discharging for 4 hours at a discharge current of 3 mA, and a charging current of 3.6 mA.
The charging end voltage was set to 3.5 V at mA.
第２図及び第３図より本発明電池は比較電池に比して充
放電サイクル特性が向上しているのがわかる。It can be seen from FIGS. 2 and 3 that the battery of the present invention has improved charge-discharge cycle characteristics compared to the comparative battery.
ト 発明の効果
上述した如く、リチウム又はリチウム合金を負極活物質
とし、二酸化マンガンを正極活物質とする非水電解液電
池において、非水電解液を構成する溶媒として１．３−
ジオキサン若しくは１，６−ジオキサンを含む混合だ媒
を用いることにより充放電サイクル特性を向上しうるも
のであり、この種電池の実用化に資するところ極めて大
である。G. Effects of the Invention As mentioned above, in a nonaqueous electrolyte battery using lithium or a lithium alloy as a negative electrode active material and manganese dioxide as a positive electrode active material, 1.3- as a solvent constituting the nonaqueous electrolyte.
By using a mixed medium containing dioxane or 1,6-dioxane, the charge/discharge cycle characteristics can be improved, which greatly contributes to the practical application of this type of battery.
第１図は本発明電池の半断面図、第２図及び第６図は電
池の充放電サイクル特性図を夫々示す。
（１）・・・正極缶、（２）・・・負極缶、（３）・・
・絶縁バッキング、＋４）・・・負極、（６）・・・正
極、＋８１・・・セパレータ、（ＡＴ）（Ａ２）・・・
本発明電池、（Ｂｊ）（Ｂ２）（Ｂ５）（Ｂ４）（ＢＳ
）（Ｂ６）・・・比較電池。FIG. 1 is a half-sectional view of the battery of the present invention, and FIGS. 2 and 6 are charge-discharge cycle characteristic diagrams of the battery, respectively. (1)...Positive electrode can, (2)...Negative electrode can, (3)...
・Insulating backing, +4)...Negative electrode, (6)...Positive electrode, +81...Separator, (AT) (A2)...
Batteries of the present invention, (Bj) (B2) (B5) (B4) (BS
) (B6)... Comparison battery.
Claims (1)
負極と、二酸化マンガンを活物質とする正極と、溶媒と
溶質とからなる非水電解液とを備えるものにおいて、前
記溶媒が１，３−ジオキサン若しくは１，３−ジオキサ
ンを含む混合溶媒であることを特徴とする非水電解液二
次電池。(1) An electrode comprising a negative electrode using lithium or an alloy containing lithium as an active material, a positive electrode using manganese dioxide as an active material, and a non-aqueous electrolyte consisting of a solvent and a solute, wherein the solvent is 1,3- A non-aqueous electrolyte secondary battery characterized by using a mixed solvent containing dioxane or 1,3-dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300481A JPS63152886A (en) | 1986-12-17 | 1986-12-17 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300481A JPS63152886A (en) | 1986-12-17 | 1986-12-17 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63152886A true JPS63152886A (en) | 1988-06-25 |
Family
ID=17885321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61300481A Pending JPS63152886A (en) | 1986-12-17 | 1986-12-17 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63152886A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952330A (en) * | 1989-05-25 | 1990-08-28 | Eveready Battery Company, Inc. | Nonaqueous electrolyte |
| US6066416A (en) * | 1995-11-22 | 2000-05-23 | Matsushita Electric Industrial Co., Ltd. | Nickel hydroxide positive electrode active material having a surface layer containing a solid solution nickel hydroxide with manganese incorporated therein |
| US6261720B1 (en) | 1996-09-20 | 2001-07-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for alkaline storage batteries |
| JP2008084705A (en) * | 2006-09-28 | 2008-04-10 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US8021787B2 (en) | 2006-05-31 | 2011-09-20 | Sanyo Electric Co., Ltd. | High-voltage charge type nonaqueous electrolyte secondary cell |
| US8053109B2 (en) | 2007-11-16 | 2011-11-08 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
| WO2013031712A1 (en) * | 2011-08-31 | 2013-03-07 | 三洋電機株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
-
1986
- 1986-12-17 JP JP61300481A patent/JPS63152886A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952330A (en) * | 1989-05-25 | 1990-08-28 | Eveready Battery Company, Inc. | Nonaqueous electrolyte |
| US6066416A (en) * | 1995-11-22 | 2000-05-23 | Matsushita Electric Industrial Co., Ltd. | Nickel hydroxide positive electrode active material having a surface layer containing a solid solution nickel hydroxide with manganese incorporated therein |
| US6261720B1 (en) | 1996-09-20 | 2001-07-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for alkaline storage batteries |
| US8021787B2 (en) | 2006-05-31 | 2011-09-20 | Sanyo Electric Co., Ltd. | High-voltage charge type nonaqueous electrolyte secondary cell |
| JP5127706B2 (en) * | 2006-05-31 | 2013-01-23 | 三洋電機株式会社 | High voltage rechargeable non-aqueous electrolyte secondary battery |
| JP2008084705A (en) * | 2006-09-28 | 2008-04-10 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US8053109B2 (en) | 2007-11-16 | 2011-11-08 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
| WO2013031712A1 (en) * | 2011-08-31 | 2013-03-07 | 三洋電機株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
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