JPH04206265A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH04206265A JPH04206265A JP2339862A JP33986290A JPH04206265A JP H04206265 A JPH04206265 A JP H04206265A JP 2339862 A JP2339862 A JP 2339862A JP 33986290 A JP33986290 A JP 33986290A JP H04206265 A JPH04206265 A JP H04206265A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- positive electrode
- electrolyte secondary
- nonaqueous electrolyte
- 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 11
- 229910001285 shape-memory alloy Inorganic materials 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 5
- 238000010030 laminating Methods 0.000 abstract description 5
- 238000004804 winding Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- -1 N1PSz and Fe0C] Chemical class 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910004337 Ti-Ni Inorganic materials 0.000 description 2
- 229910011209 Ti—Ni Inorganic materials 0.000 description 2
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 229910017535 Cu-Al-Ni Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、非水電解質二次電池の充放電サイクル寿命の
改善に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to improving the charge/discharge cycle life of non-aqueous electrolyte secondary batteries.
（発明の概要）
本発明は、非水電解質二次電池において、負極または正
極を形状記憶合金と積層することにより、負極の劣化を
抑制し、サイクル寿命の大きい非水電解質二次電池を提
供することを目的としている。(Summary of the Invention) The present invention provides a nonaqueous electrolyte secondary battery that suppresses deterioration of the negative electrode and has a long cycle life by laminating the negative electrode or the positive electrode with a shape memory alloy. The purpose is to
（従来の技術）
リチウム金属を負極活物質とする二次電池は高電圧、高
エネルギー密度であるため非水溶液を電解液として実用
に供されでいるが、サイクル特性向上のためにリチウム
をアルミニウムと合金化させて使用している。(Prior technology) Secondary batteries that use lithium metal as the negative electrode active material have high voltage and high energy density, so non-aqueous solutions have been put into practical use as electrolytes. It is used as an alloy.
（発明が解決しようとする課題）
リチウム−アルミニウム合金を負極に用いた場合、合金
化あるいは充放電に伴う体積、形状変化により負極が劣
化しサイクル寿命に制約が生しるという問題があった。(Problems to be Solved by the Invention) When a lithium-aluminum alloy is used as a negative electrode, there is a problem in that the negative electrode deteriorates due to changes in volume and shape due to alloying or charging/discharging, resulting in restrictions on cycle life.
（課題を解決するための手段）
本発明では上記問題点を解決するために、負極または正
極を形状記憶合金と積層する。(Means for Solving the Problems) In the present invention, in order to solve the above problems, a negative electrode or a positive electrode is laminated with a shape memory alloy.
（作用）
負極または正極を形状記憶合金と積層することにより、
負極に体積あるいは形状変化があっても常に圧力がかか
るようになり、負極の劣化によるサイクル寿命の低下が
抑制できる。(Function) By laminating the negative electrode or positive electrode with shape memory alloy,
Even if the negative electrode undergoes a change in volume or shape, pressure is always applied to it, thereby suppressing a decrease in cycle life due to deterioration of the negative electrode.
（実施例） 以下本発明の実施例について述べる。(Example) Examples of the present invention will be described below.
第１図は本発明の一実施例による円筒形非水電解質二次
電池の巻回状態を示す斜視図を示し、負極１は形状記憶
合金２の両側に積層され、非水；解質が含浸されている
セパレータ３と正極４と一緒ニ巻回され各種にはそれぞ
れ負極端子５、正極端子６が形成されている。このよう
にして作製した電池要素は第２図に電池断面図に示すよ
うに、電池缶７に挿入した。FIG. 1 shows a perspective view showing a rolled state of a cylindrical nonaqueous electrolyte secondary battery according to an embodiment of the present invention, in which a negative electrode 1 is laminated on both sides of a shape memory alloy 2, and is impregnated with nonaqueous and electrolyte. A separator 3 and a positive electrode 4 are wound together, and a negative electrode terminal 5 and a positive electrode terminal 6 are respectively formed on each type. The battery element thus produced was inserted into a battery can 7 as shown in the sectional view of the battery in FIG.
電池寸法は高さ５０ｍｍ、直径１４．５ｍｍである。The battery dimensions are 50 mm in height and 14.5 mm in diameter.
形状記憶合金は、Ｔｉ−Ｎｉ合金をはじめとして、Ｃｕ
−Ｚｎ−Ａｌ、Ｃｕ−Ａｌ−Ｎｉ、Ｆｅ−Ｎｉ−Ｔｉ−
Ｃｏ、Ｆ ｅ−Ｍｎ−３ｉ合金など数多くの合金があり
、本実施例では一例としてＴｉ−Ｎｉ合金の場合につい
て述べるが、もちろん、他の形状記憶合金も同様の結果
が得られることは、言うまでもない。形状記憶合金には
あらかじめ、電池組み込み状態より小さい曲率で巻回状
態を記憶させておき、形状回復Ａ度５０°Ｃ付近のもの
を使用し、厚みはＱ、１ｍｍである。Shape memory alloys include Ti-Ni alloy, Cu
-Zn-Al, Cu-Al-Ni, Fe-Ni-Ti-
There are many alloys such as Co and Fe-Mn-3i alloys, and in this example, the case of Ti-Ni alloy will be described as an example, but it goes without saying that similar results can be obtained with other shape memory alloys. stomach. The shape memory alloy was previously memorized with a winding state with a smaller curvature than the assembled state of the battery, had a shape recovery degree A of around 50°C, and had a thickness Q of 1 mm.
正極としてはＭ ｎ ０２ 、Ｖ２０Ｓ 、Ｖｂ Ｏ＋
、ｌ−Ｍ ｏ ０３ 、Ｃｒ ３０ｓなどの酸化物や７
ｉＳｚ、Ｍｏ５ｚなどの遷移金属ジカルコゲナイト、Ｎ
ｂＳｅユ、Ｍｏ３３などの遷移金属トリカルコゲナイド
、更にＮ１ＰＳｚ 、Ｆｅ０Ｃ］などの化合物、炭素お
よびポリピロール、ポリパラフェニレン、ポリチオフェ
ン、ポリアニリン等の導電性高分子があり、非水電解液
は、溶媒としてプロピレンカーボネート、エチレンカー
ボネート、Ｔ−ブチロラクトン、ノメチルスルフォキン
ド、スルフオラン、１，３−ジオキソラン、４−メチル
−１，３−ジオキソラン、テトラヒドロフラン、２−メ
チルテトラヒドロフラン、１．２−ジメトキシエタンな
どを単独または混合したもの、溶質としてはＬ ｉＡ
ｓ Ｆ ６ 、Ｌ ｉＣＩ Ｏ４、Ｌ ｉ Ｂ Ｆ ａ
、Ｌ ｉＰＦ＆ 、ＬｉＣＦ３５Ｏ１＋ 、Ｌｉ５Ｃ
Ｎ、ＬｉＡｌｃ１４４などを０．５から３モルフ１程度
添加し、その他に２−メチルフラン、チオフェン、ピロ
ール、ヘキサメチルフォスフォリツクトリアミド、クラ
ウンエーテル類などを微量添加して用いてもよい。As a positive electrode, M n 02 , V20S , Vb O+
, l-M o 03 , Cr 30s and other oxides and 7
Transition metal dichalcogenite such as iSz, Mo5z, N
There are transition metal trichalcogenides such as bSe and Mo33, compounds such as N1PSz and Fe0C], carbon and conductive polymers such as polypyrrole, polyparaphenylene, polythiophene, and polyaniline, and the nonaqueous electrolyte uses propylene carbonate as a solvent. , ethylene carbonate, T-butyrolactone, nomethylsulfoquinde, sulfolane, 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, etc., singly or in combination. The solute is LiA
s F 6 , L iCI O4, L i B Fa
, LiPF& , LiCF35O1+ , Li5C
About 0.5 to 3 morphs of N, LiAlc144, etc. may be added, and in addition, trace amounts of 2-methylfuran, thiophene, pyrrole, hexamethylphosphoric triamide, crown ethers, etc. may be added.
本実施例では以下電解液として、プロピレンカ−ボネー
ト、エチレンカーボネートおよび２−メチルテトラヒド
ロフランを体積で１：１：２の割合で混合したものに１
−ｉＰＦ、を１モル／１添加したものを用い、正極とし
てＭｎ０ｚとアセチレンブラックとフン素樹脂を重量で
８５：１０：５の割合で混合しＳＵＳ金網に塗布したも
のを使用した。負極は厚さ０．１ｍｍの厚みのアルミニ
ウム合金基体に０．１ｍｍの厚みのリチウム金属を積層
し、ＳＵＳ金網と固着してあり、電池に組み込んでから
電気化学的に合金化した。In this example, as the electrolyte, a mixture of propylene carbonate, ethylene carbonate, and 2-methyltetrahydrofuran in a volume ratio of 1:1:2 was used.
-iPF was added at 1 mol/1, and as a positive electrode, Mn0z, acetylene black, and fluorine resin were mixed in a weight ratio of 85:10:5 and coated on a SUS wire mesh. The negative electrode was made by laminating 0.1 mm thick lithium metal on a 0.1 mm thick aluminum alloy substrate, which was adhered to a SUS wire mesh, and was electrochemically alloyed after being incorporated into a battery.
第３図は充放電のサイクル特性図である。FIG. 3 is a chart of charge/discharge cycle characteristics.
充放電条件は電流１００ｍＡで充放電時間おのおの６時
間で、放電時に電池電圧２．ＯＶに達した時点を寿命と
した。The charging and discharging conditions were a current of 100mA, charging and discharging times of 6 hours each, and a battery voltage of 2. The time when OV was reached was defined as the life span.
形状記憶合金を使用しない比較例サイクル特性曲線１１
に比べ本発明実施例サイクル特性曲線１２はサイクル特
性が向上していることがわかる。Comparative example cycle characteristic curve 11 without using shape memory alloy
It can be seen that the cycle characteristic curve 12 of the example of the present invention has improved cycle characteristics compared to the above.
本実施例ではリチウムとアルミニウム合金は体積比で１
：１であが、もちろんこれに限定されない。In this example, the volume ratio of lithium and aluminum alloy is 1.
:1, but of course it is not limited to this.
以上は形状記憶合金を負極と積層した場合であるが、正
極と積層しても同様の効果がある。The above is a case where the shape memory alloy is laminated with the negative electrode, but the same effect can be obtained even if the shape memory alloy is laminated with the positive electrode.
本発明は高分子などの固体電解質にも同様の効果がある
。The present invention has similar effects on solid electrolytes such as polymers.
（発明の効果）
以上述べたように、本発明によれば、非水電解質二次電
池において負極または正極を形状記憶合金と積層するこ
とにより、負極の劣化を抑制し、サイクル寿命の大きい
非水電解質二次電池を得ることができる。(Effects of the Invention) As described above, according to the present invention, by laminating the negative electrode or the positive electrode with a shape memory alloy in a non-aqueous electrolyte secondary battery, deterioration of the negative electrode can be suppressed and the non-aqueous electrolyte can have a long cycle life. An electrolyte secondary battery can be obtained.
第１図は本発明の一実施例による円筒形非水電解質二次
電池の巻回状態を示す斜視図であり、第２図は円筒形非
水電解質二次電池の断面図であり、第３図は充放電のサ
イクル特性図である。
１−ｍ−負極
２−ｍ−形状記憶合金
３−ｍ−セパレータ
４−ｍ−正極
５−一一負極端子
６−−−正極端子
７一−−電池缶
１１−一従来例のサイクル特性曲線
１２−一本発明のサイクル特性曲線
以上
出願人 セイコー電子工業株式会社
代理人 弁理士 林 敬 之 助
゛ ６１図
第２図
を被電のづイワル什惺図
第３図FIG. 1 is a perspective view showing a rolled state of a cylindrical non-aqueous electrolyte secondary battery according to an embodiment of the present invention, FIG. 2 is a cross-sectional view of the cylindrical non-aqueous electrolyte secondary battery, and FIG. The figure is a chart of charge/discharge cycle characteristics. 1-m-negative electrode 2-m-shape memory alloy 3-m-separator 4-m-positive electrode 5--1 negative electrode terminal 6--positive electrode terminal 7--battery can 11-1 cycle characteristic curve 12 of conventional example -1 The cycle characteristic curve of the present invention Applicant: Seiko Electronic Industries Co., Ltd. Agent Patent attorney: Takayuki Hayashi
Claims (1)
を特徴とする非水電解質二次電池。A nonaqueous electrolyte secondary battery characterized in that a negative electrode or a positive electrode is laminated with a shape memory alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339862A JPH04206265A (en) | 1990-11-29 | 1990-11-29 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339862A JPH04206265A (en) | 1990-11-29 | 1990-11-29 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04206265A true JPH04206265A (en) | 1992-07-28 |
Family
ID=18331531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2339862A Pending JPH04206265A (en) | 1990-11-29 | 1990-11-29 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04206265A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7432014B2 (en) | 2003-11-05 | 2008-10-07 | Sony Corporation | Anode and battery |
-
1990
- 1990-11-29 JP JP2339862A patent/JPH04206265A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7432014B2 (en) | 2003-11-05 | 2008-10-07 | Sony Corporation | Anode and battery |
| US7459233B2 (en) | 2003-11-05 | 2008-12-02 | Sony Corporation | Anode and battery |
| US7625668B2 (en) | 2003-11-05 | 2009-12-01 | Sony Corporation | Anode and battery |
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