JPH0432159A - Nonaqueous electrolytic secondary battery - Google Patents
Nonaqueous electrolytic secondary batteryInfo
- Publication number
- JPH0432159A JPH0432159A JP2134670A JP13467090A JPH0432159A JP H0432159 A JPH0432159 A JP H0432159A JP 2134670 A JP2134670 A JP 2134670A JP 13467090 A JP13467090 A JP 13467090A JP H0432159 A JPH0432159 A JP H0432159A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- metal
- electrode
- positive electrode
- 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
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 2
- 238000007747 plating Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- -1 PS:+ Chemical class 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 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
- 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 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
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000002747 voluntary effect Effects 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特にリチウム二次電池の
負極劣化の改善に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to improvement of negative electrode deterioration of non-aqueous electrolyte secondary batteries, particularly lithium secondary batteries.
本発明は、アルミニウム材にリチウムを電気化学的に合
金化した負極の電解質と接する面に格子状の溝を設け、
その反対側の面にリチウム金属と合金化しにくい金属層
を設けた負極にするとにより、充放電に伴う負極の劣化
を防止し、充放電サイクル特性の優れた非電解質二次電
池を提供するものである。The present invention provides lattice-like grooves on the surface in contact with the electrolyte of a negative electrode made of aluminum material electrochemically alloyed with lithium,
By providing a negative electrode with a metal layer that is difficult to alloy with lithium metal on the opposite surface, deterioration of the negative electrode due to charging and discharging is prevented, and a non-electrolyte secondary battery with excellent charge-discharge cycle characteristics is provided. be.
リチウム金属を負極活性物質として用いる二次電池、所
謂リチウム二次電池は、高電圧、高エネルギ密度である
ため、非水溶液を電解質として実用に供されているが、
充放電サイクル特性向上のためリチウムはアルミニウム
と合金化されて実用している。Secondary batteries that use lithium metal as a negative electrode active material, so-called lithium secondary batteries, have high voltage and high energy density, so they are put into practical use using non-aqueous solutions as electrolytes.
In order to improve charge-discharge cycle characteristics, lithium is alloyed with aluminum and put into practical use.
リチウム−アルミニウム合金を負極に用いたとしても、
充放電に伴う体積変化により、負極に歪が生じて亀裂が
発生し、やがて崩壊に至ったりする。また、負極と集電
体との間に絶縁部を形成し、充放電サイクル特性が低下
する。Even if a lithium-aluminum alloy is used for the negative electrode,
Changes in volume associated with charging and discharging cause distortion and cracks in the negative electrode, which eventually leads to collapse. Furthermore, an insulating portion is formed between the negative electrode and the current collector, resulting in a decrease in charge/discharge cycle characteristics.
本発明は、上記課題を解決するために、電解液と接する
面に格子状の溝と、その反対の面に形成したリチウムと
電気化学的に合金化しにくい金属層とよりなるアルミニ
ウム−リチウム合金より構成された負極を持つ非水電解
質二次電池とする。In order to solve the above problems, the present invention has developed an aluminum-lithium alloy comprising lattice-like grooves on the surface in contact with the electrolyte and a metal layer that is difficult to electrochemically alloy with lithium formed on the opposite surface. This is a non-aqueous electrolyte secondary battery having a negative electrode constructed as follows.
充放電に伴うアルミニウム−リチウム合金よりなる負極
の応力・歪は、負極へのリチウムの出入りにより生じる
ものである。負極の電解質と接する面に微細な溝を格子
状に設けることにより、負極へのリチウムの出入りによ
り生じる応力・歪が緩和され、負極の電極劣化の原因と
なる亀裂の生成か抑えられる。また、負極の反対面には
、リチウムと合金化されにくい金属層が形成されている
ため、リチウムに作用されなく、負極へのリチウムの出
入りにより生じる応力・歪がその面には発生しない。Stress and strain in the negative electrode made of an aluminum-lithium alloy due to charging and discharging are caused by lithium flowing in and out of the negative electrode. By creating fine grooves in a lattice pattern on the surface of the negative electrode in contact with the electrolyte, stress and strain caused by lithium entering and leaving the negative electrode are alleviated, and the formation of cracks that can cause electrode deterioration can be suppressed. Furthermore, since a metal layer that is difficult to alloy with lithium is formed on the opposite surface of the negative electrode, it is not affected by lithium, and stress and strain caused by lithium entering and leaving the negative electrode do not occur on that surface.
以下、本発明の実施例について図面に基づいて説明する
。Embodiments of the present invention will be described below based on the drawings.
第１図は本発明の一実施例による偏平型非水電解質二次
電池の断面図を示すものである。負極１は負極缶２の内
側底面に固着した負極集電体３に圧着されている。正極
４も同様に正極缶５の内側底面に固着している正極集電
体６に圧着されている。FIG. 1 shows a sectional view of a flat nonaqueous electrolyte secondary battery according to an embodiment of the present invention. The negative electrode 1 is crimped to a negative electrode current collector 3 fixed to the inner bottom surface of the negative electrode can 2 . Similarly, the positive electrode 4 is crimped to a positive electrode current collector 6 fixed to the inner bottom surface of the positive electrode can 5 .
セパレータ７は負極１と正極４の間に設けられており、
非水電解質が含浸されている。正極缶５と負極缶２の外
形よりなる電池寸法は直径２０．０ｍ高さ３．０鶴であ
る。The separator 7 is provided between the negative electrode 1 and the positive electrode 4,
Impregnated with non-aqueous electrolyte. The dimensions of the battery, consisting of the external shapes of the positive electrode can 5 and the negative electrode can 2, are 20.0 m in diameter and 3.0 m in height.
正極４としてはＭｎＯ２、ｖ２０１、Ｖ６Ｏ１３、Ｍｏ
ｂ、、Ｃｒ３０Ｂなどの酸化物や、Ｔｉ５ｚ、ＭｏＳ２
などの遷移金属ジカルコゲナイトや、Ｎｂ５ｅｓ 、Ｍ
ｏＳ＊などの遷移金属トリカルコゲナイドや、更にＮ１
ＰＳ：＋ 、Ｆｅ０Ｃ１などの化合物や、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からなる。また、非水溶液
電解質（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、γ−ブチロラクトン、ジメチ
ルスルフオキシド、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−ジオ
キソランなどを単体または混合したものである。ン容質
としては、ＬｉＡｓＦい ＬｉＣ１０いＬｉＢＦａ 、
ｔ、ｉｐｌ’６ 、Ｌｉｃｐ３ｓｏ３、ＬｉＡＩＣ１ｍ
などを０．５から３．０モル／ｌ程度溶媒に添加し、そ
の他に２−メチルフラン、チオフェン、ピロール、ヘキ
サメチルフォリソクトリアミド、クラウンエーテル類な
どを微量添加してもよい。As the positive electrode 4, MnO2, v201, V6O13, Mo
b,, oxides such as Cr30B, Ti5z, MoS2
Transition metal dichalcogenites such as Nb5es, M
Transition metal trichalcogenides such as oS* and even N1
It consists of compounds such as PS:+, Fe0C1, and conductive polymers such as carbon and polypyrrole, polyparaphenylene, polythiophene, and polyaniline. In addition, the non-aqueous electrolyte (electrolyte solution) uses propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl sulfoxide, sulfolane, 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyl as a solvent. It is a single substance or a mixture of tetrahydrofuran, 1,2-dioxolane, etc. As for the capacity, LiAsF, LiC10, LiBFa,
t, ipl'6, Licp3so3, LiAIC1m
About 0.5 to 3.0 mol/l of 2-methylfuran, thiophene, pyrrole, hexamethylfolisoctriamide, crown ethers, etc. may also be added in trace amounts.
本実施例では以下電解質として、プロピレンカーボネー
ト、エチレンカーボネート、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ＬｉＰ
Ｆ６を１モル／７！添加したものを用いた。正極として
ＭｎＯ□とエチレンブラックと弗素樹脂を重量で８５：
１０：５の割合で混合し加圧成形したものを使用した。In this example, as an electrolyte, LiP was added to a mixture of propylene carbonate, ethylene carbonate, and 2-methyltetrahydrofuran in a volume ratio of 1:1:2.
1 mole/7 of F6! The one added was used. As a positive electrode, MnO□, ethylene black, and fluororesin were used by weight: 85:
A mixture of 10:5 and pressure molding was used.
負極１は第２図に示したように、負極１の電解質と接触
する面に、間隔およそ１００ μ調、幅およそ１５μ観
、深さ約６０μｍの格子状の溝を形成した。As shown in FIG. 2, the negative electrode 1 had lattice-like grooves with an interval of approximately 100 μm, a width of approximately 15 μm, and a depth of approximately 60 μm formed on the surface of the negative electrode 1 that was in contact with the electrolyte.
なお、負極１はメツキ電極の負極に一方の面にニッケル
ＪｉｌＯを形成した約１寵厚さのアルミニウム金属板を
装着し、その正極にリチウム金属を設けて、電気化学的
にリチウムをアルミニウム金属板に析出させて、合金化
させる。つまり、負極１用のアルミニウム合金９ができ
る。なお、格子状の溝はリチウムを電気化学的に合金化
させる前にアルミニウム金属板に形成する。負極１のア
ルミニウム合金の成分はおよそ原子比でリチウム３０ニ
アルミニウム７０である。In addition, the negative electrode 1 is a plated electrode with an aluminum metal plate of about 1 inch thick on which nickel JILO is formed on one side, and lithium metal is provided on the positive electrode, and lithium is electrochemically transferred to the aluminum metal plate. It is precipitated and alloyed. In other words, an aluminum alloy 9 for the negative electrode 1 is produced. Note that the lattice-shaped grooves are formed in the aluminum metal plate before electrochemically alloying lithium. The components of the aluminum alloy of the negative electrode 1 are approximately 30 parts lithium and 70 parts aluminum in atomic ratio.
リチウム金属と電気化学的に合金化されにくい金属とし
て本実施例ではニッケルＮにノケル箔）１０を用いたが
、材質としては、その他チタン、動、ステンレスなども
利用できる。In this example, nickel N (Nokel foil) 10 was used as a metal that is difficult to electrochemically alloy with lithium metal, but other materials such as titanium, dynamic metal, and stainless steel can also be used.
第３図は、従来の非水電解質二次電池と本実施例の非水
電解質二次電池とを充放電を繰り返し行ってとの劣化を
調べた充放電のサイクル特性図である。従来の非水電解
質二次電池には負極の格子状溝とリチウム金属と電気化
学的に合金化されにくい金属層が形成されていないもの
であり、その他は本実施例と同様な構成である。FIG. 3 is a charging/discharging cycle characteristic diagram in which the deterioration of a conventional nonaqueous electrolyte secondary battery and a nonaqueous electrolyte secondary battery of this example was investigated by repeatedly charging and discharging the battery. The conventional non-aqueous electrolyte secondary battery does not have the lattice grooves of the negative electrode and the metal layer that is difficult to be electrochemically alloyed with lithium metal, but has the same structure as the present example.
充放電条件は電流を２．０ｍ八で充放電時間を各々６時
間とし、放電６時間したときの電圧を室軸に設定してい
る。一応寿命としては放電終了時点での電圧が２，０ν
になった時点とした。The charging and discharging conditions were such that the current was 2.0m8, the charging and discharging time was 6 hours each, and the voltage after 6 hours of discharge was set on the chamber axis. As for the lifespan, the voltage at the end of discharge is 2.0ν
It was defined as the point when
溝を形成していない従来の二次電池に比べて本実施例の
サイクル特性的１１２は寿命が向上していることがわか
る。つまり、従来のものは約１４０回位であり、本実施
例は約２１０回位の寿命である。It can be seen that the cycle characteristic 112 of this example has an improved life compared to the conventional secondary battery in which no grooves are formed. That is, the life of the conventional type is about 140 times, and the life of this embodiment is about 210 times.
溝の寸法は幅５〜３０μｍ程度、深さ５〜１００μ鴎程
度の範囲が効果的であり、その範囲をこえると充放電寿
命はあまり長くはならない。また、溝間隔はおよそ３０
〜２００ μＩ程度がよい。The groove dimensions are effectively in the range of about 5 to 30 μm in width and about 5 to 100 μm in depth; beyond these ranges, the charge/discharge life will not be very long. Also, the groove spacing is approximately 30
~200 μI is preferable.
本発明のように負極１をリチウム−アルミニウム合金と
その一方（負極集電体３に面する側）にリチウム金属と
合金化しにくい金属層１０を設けた構成にすることによ
り、充放電を繰り返すことにより負極１に多少の亀裂が
生じてもその部分の材料破壊及び負極集電体３との絶縁
部形成がおこりにくくなり、サイクル特性への影響を抑
制できる。By configuring the negative electrode 1 as in the present invention with a lithium-aluminum alloy and a metal layer 10 that is difficult to alloy with lithium metal on one side (the side facing the negative electrode current collector 3), charging and discharging can be repeated. Therefore, even if some cracks occur in the negative electrode 1, material breakdown at the cracks and formation of an insulating part with the negative electrode current collector 3 are less likely to occur, and the influence on cycle characteristics can be suppressed.
本実施例では、負極１のリチウム−アルミニウム合金が
３０ ニア０のものを用いたが、勿論本発明の効果はこ
れに限定されるものではない。In this example, the lithium-aluminum alloy of the negative electrode 1 used was 30% near 0, but of course the effects of the present invention are not limited to this.
また、本実施例では、偏平型二次電池について述べたが
、円筒形等の形状のものでも適応できるものである。こ
の場合、負極１にリチウム金属とアルミニウム金属を予
め所定の形状に形成した後、電気化学的に合金化するこ
とにより得られる。Further, in this embodiment, a flat secondary battery has been described, but it is also applicable to batteries having a cylindrical shape or the like. In this case, the negative electrode 1 is obtained by forming lithium metal and aluminum metal into a predetermined shape in advance and then electrochemically alloying them.
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、電解質（電解液）に接する面に格子状の溝
を形成したりチウム−アルミニウム合金と、リチウムと
合金化されにくい金属層を他方の面に形成した負極を用
いることにより、充放電に伴う、負極の劣化を抑制し、
充放電特性の優れた非水電解質二次電池を得ることがで
きる。As described above, according to the present invention, in a non-aqueous electrolyte secondary battery, lattice-shaped grooves are formed on the surface in contact with the electrolyte (electrolyte), and lithium-aluminum alloy and metals that are difficult to alloy with lithium are formed. By using a negative electrode with a layer formed on the other side, deterioration of the negative electrode due to charging and discharging is suppressed,
A nonaqueous electrolyte secondary battery with excellent charge/discharge characteristics can be obtained.
第１図は本発明の一実施例の偏平型非水電解質二次電池
の断面図で、第２図は負極の部分斜視図で、第３図は充
放電サイクル特性図である。
１・・負極 ２・・負極缶３ ・ ・
５ ・ ・
７ ・ ・
９ ・ ・
１１ ・
１２ ・
負極集電体 ４・・正極
正極缶 ６・・正極集電体
セパレータ ８・・絶縁バ、キンリチウムーアル
ミニウム合金
ニッケル層
・従来のサイクル特性曲線
・本実施例のサイクル特性曲線
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
督−靴嗣匂ハミ（ト）
手
続
補
正
書
（自発）
平成
３年ｙ月７０日
平成
２年
特許願
第１３４６７０号
発明の名称
非水電解質二次電池
３、補正をする者
事件との関係 特許出願人
（２３２）セイコー電子工業株式会社
代表取締役 原 禮之助
６、補正の内容
（１） 明細書第５頁第１８行目乃至第６頁第２行目
の「なお、・・・・・・合金化させる。」を「負極ｌは
第一一”二部分斜視図に示すように、厚さ０．１ ｎで
、３よそ１００ μ■、幅およそ１５μｍ、深さおよそ
６０μ園に溝を格子状に形成したアルミニウム合金９を
リチウム金属と電気化学的に合金しにくい金属としての
ニッケル箔１０に形成した負極基体を上記電解液中でリ
チウム金属を対極として電気化工合金化したリチウム−
アルミニウム合金である。」と補正します。
（２）明細書第６頁第１１行目の「動」を「銅」と補正
します。
」細書第６頁第２０行目の「立」を「縦」と−まず。
補正の対象
以上FIG. 1 is a sectional view of a flat nonaqueous electrolyte secondary battery according to an embodiment of the present invention, FIG. 2 is a partial perspective view of a negative electrode, and FIG. 3 is a charge/discharge cycle characteristic diagram. 1. Negative electrode 2. Negative electrode can 3 .. 5 .. 7 .. 9 .. 11 . 12 . Negative electrode current collector 4. Positive electrode positive electrode can 6. Lithium-aluminum alloy nickel layer, conventional cycle characteristic curve, cycle characteristic curve of this example Applicant: Seiko Electronic Industries Co., Ltd. Agent Patent attorney Takayuki Hayashi Assistant Director - Shoetsugu Nouhami (T) Procedural amendment (voluntary) Patent Application No. 134670 of 1990 (Y/70/1991) Name of the invention Non-aqueous electrolyte secondary battery 3, person making an amendment Relationship to the case Patent applicant (232) Seiko Electronic Industries Co., Ltd. Representative Director Hiroyuki Hara Supplement 6, Contents of amendment (1) From page 5, line 18 to page 6, line 2 of the specification, “In addition,...alloying” was changed to “the negative electrode l is the first one.” As shown in the two-part perspective view, an aluminum alloy 9 with grooves formed in a lattice pattern having a thickness of 0.1 nm, a width of about 15 μm, and a depth of about 60 μ is electrochemically treated with lithium metal. A negative electrode base formed on nickel foil 10, which is a metal that is difficult to alloy with, is electrochemically alloyed with lithium metal in the electrolytic solution using lithium metal as a counter electrode.
It is an aluminum alloy. ” and correct it. (2) Correct the word "do" on page 6, line 11 of the specification to "copper.""Tate" on page 6, line 20 of the specification book is "tate" - first. More than subject to correction
Claims (1)
成したリチウムと電気化学的に合金化しにくい金属層と
よりなるアルミニウム−リチウム合金より構成された負
極を持つことを特徴とする非水電解質二次電池。A non-aqueous cathode comprising an aluminum-lithium alloy comprising lattice-like grooves on the surface in contact with the electrolyte and a metal layer that is difficult to electrochemically alloy with lithium formed on the opposite surface. Electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2134670A JPH0432159A (en) | 1990-05-24 | 1990-05-24 | Nonaqueous electrolytic secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2134670A JPH0432159A (en) | 1990-05-24 | 1990-05-24 | Nonaqueous electrolytic secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0432159A true JPH0432159A (en) | 1992-02-04 |
Family
ID=15133819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2134670A Pending JPH0432159A (en) | 1990-05-24 | 1990-05-24 | Nonaqueous electrolytic secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0432159A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006100794A1 (en) * | 2005-03-23 | 2006-09-28 | Mitsui Mining & Smelting Co., Ltd. | Negative electrode for rechargeable battery with nonaqueous electrolyte |
| WO2007055276A1 (en) * | 2005-11-09 | 2007-05-18 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for coin-type lithium rechargeable battery, process for producing said negative electrode, and coin-type lithium rechargeable battery |
| JP2007157704A (en) * | 2005-11-09 | 2007-06-21 | Matsushita Electric Ind Co Ltd | Negative electrode for coin type lithium secondary battery, its manufacturing method, and coin type lithium secondary battery |
-
1990
- 1990-05-24 JP JP2134670A patent/JPH0432159A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006100794A1 (en) * | 2005-03-23 | 2006-09-28 | Mitsui Mining & Smelting Co., Ltd. | Negative electrode for rechargeable battery with nonaqueous electrolyte |
| WO2007055276A1 (en) * | 2005-11-09 | 2007-05-18 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for coin-type lithium rechargeable battery, process for producing said negative electrode, and coin-type lithium rechargeable battery |
| JP2007157704A (en) * | 2005-11-09 | 2007-06-21 | Matsushita Electric Ind Co Ltd | Negative electrode for coin type lithium secondary battery, its manufacturing method, and coin type lithium secondary battery |
| US20100151321A1 (en) * | 2005-11-09 | 2010-06-17 | Teruaki Yamamoto | Negative electrode for coin-shaped lithium secondary battery, method for producing the same, and coin-shaped lithium secondary battery |
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