JPH0541252A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH0541252A JPH0541252A JP3223469A JP22346991A JPH0541252A JP H0541252 A JPH0541252 A JP H0541252A JP 3223469 A JP3223469 A JP 3223469A JP 22346991 A JP22346991 A JP 22346991A JP H0541252 A JPH0541252 A JP H0541252A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- nonwoven fabric
- group
- liquid
- secondary 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 41
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- -1 polypropylene Polymers 0.000 abstract description 26
- 239000007788 liquid Substances 0.000 abstract description 24
- 239000004743 Polypropylene Substances 0.000 abstract description 20
- 229920001155 polypropylene Polymers 0.000 abstract description 20
- 238000007789 sealing Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- 230000003068 static effect Effects 0.000 abstract description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 abstract 1
- 229910015645 LiMn Inorganic materials 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000323 polyazulene Polymers 0.000 description 1
- 229920000573 polyethylene 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
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はリチウム二次電池に係わ
り、さらに詳しくはそのセパレータの改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to improvement of its separator.
【０００２】[0002]
【従来の技術】リチウム二次電池においては、セパレー
タとしてポリプロピレン不織布などのポリオレフィン系
不織布が使用されている（たとえば、特開昭５６−５９
４５６号公報）。2. Description of the Related Art In a lithium secondary battery, a polyolefin-based nonwoven fabric such as polypropylene nonwoven fabric is used as a separator (for example, JP-A-56-59).
456 publication).
【０００３】これは、ポリオレフィン系不織布が電解液
の溶媒として使用されている有機溶媒に対する耐性が良
いという理由によるものである。This is because the polyolefin-based nonwoven fabric has good resistance to the organic solvent used as the solvent of the electrolytic solution.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ポリオ
レフィン系不織布は吸液性が悪く、セパレータとして用
いたときに、電解液注入後の吸液に時間がかかる。However, the polyolefin nonwoven fabric has a poor liquid absorbing property, and when it is used as a separator, it takes a long time to absorb the liquid after injecting the electrolytic solution.
【０００５】また、保液性にも問題があり、電池封口時
に電解液を保持しにくいため、封口時に漏液が生じやす
い。その結果、電池内の電解液が不足して内部抵抗の増
加を招くことになる。Further, there is also a problem with the liquid retaining property, and since it is difficult to hold the electrolytic solution when the battery is sealed, liquid leakage easily occurs when the battery is sealed. As a result, the electrolyte in the battery becomes insufficient, which causes an increase in internal resistance.
【０００６】さらに、充放電のサイクルが進むにしたが
って、電池内の電解液が正極および負極に移動するの
で、セパレータ内は電解液が漸次減少し、サイクル末期
においては、セパレータ内の電解液が枯渇し、内部抵抗
が上昇してサイクル特性が低下する。Further, as the charging / discharging cycle progresses, the electrolytic solution in the battery moves to the positive electrode and the negative electrode, so that the electrolytic solution in the separator gradually decreases, and at the end of the cycle, the electrolytic solution in the separator is depleted. However, the internal resistance increases and the cycle characteristics deteriorate.
【０００７】そのため、界面活性剤でポリオレフィン系
不織布を処理して、ポリオレフィン系不織布の吸液性を
向上させるようにしたが、上記処理によって吸液性が向
上するものの、サイクル数の増加に伴って界面活性剤が
電解液中に溶出して、保液性が低下するとともに、溶出
した界面活性剤によってサイクル特性が低下するという
問題が発生した。Therefore, the polyolefin non-woven fabric is treated with a surfactant to improve the liquid absorption of the polyolefin non-woven fabric. Although the liquid absorption is improved by the above treatment, the number of cycles increases as the number of cycles increases. There has been a problem that the surfactant is eluted in the electrolytic solution to lower the liquid retention property and the eluted surfactant deteriorates the cycle characteristics.
【０００８】したがって、本発明は、上記従来のリチウ
ム二次電池が持っていたセパレータの吸液性および保液
性の悪さを解決し、封口時の漏液が少なく、かつサイク
ル特性の優れたリチウム二次電池を提供することを目的
とする。Therefore, the present invention solves the inferior liquid absorption and liquid retention properties of the separator which the above-mentioned conventional lithium secondary battery has, and reduces the leakage of liquid at the time of sealing and has excellent cycle characteristics. It is intended to provide a secondary battery.
【０００９】[0009]
【課題を解決するための手段】本発明は、ポリオレフィ
ン系不織布に親水基を導入し、この親水基を導入したポ
リオレフィン系不織布をセパレータに用いることによっ
て、上記目的を達成したものである。The present invention has achieved the above object by introducing a hydrophilic group into a polyolefin-based nonwoven fabric and using the polyolefin-based nonwoven fabric into which the hydrophilic group has been introduced as a separator.
【００１０】本発明において、ポリオレフィン系不織布
に導入する親水基は、スルホン基、カルボキシル基、ポ
リオレフィン系樹脂の酸化体などであるが、ポリオレフ
ィン系不織布にこれらの親水基を導入すると、親水基の
極性によりポリオレフィン系不織布は極性を持つように
なる。In the present invention, the hydrophilic group introduced into the polyolefin-based nonwoven fabric is a sulfone group, a carboxyl group, an oxidant of a polyolefin-based resin, or the like. As a result, the polyolefin nonwoven fabric becomes polar.
【００１１】その結果、ポリオレフィン系不織布は極性
を持つ有機溶媒を使用した有機電解液との親和性が高く
なって、セパレータの吸収性が向上し、また、ポリオレ
フィン系不織布が極性を持つため、セパレータと電解液
との間に静電気が働き、セパレータの保液性が向上す
る。その結果、封口時の漏液が防止され、サイクル特性
の低下が防止されるようになる。As a result, the polyolefin-based non-woven fabric has a high affinity with an organic electrolyte using an organic solvent having a polarity, and the separator absorbability is improved. Further, since the polyolefin-based non-woven fabric has a polarity, the separator is Static electricity acts between the electrolyte and the electrolytic solution to improve the liquid retaining property of the separator. As a result, liquid leakage at the time of sealing is prevented and deterioration of cycle characteristics is prevented.
【００１２】ポリオレフィン系不織布にスルホン基を導
入するには、たとえばポリオレフィン系不織布を発煙硫
酸中に浸漬することによって行われ、またポリオレフィ
ン系不織布にカルボキシル基を導入するには、たとえば
ポリオレフィン系不織布に放射線を照射してアクリル酸
とグラフト共重合させることによって行われる。The introduction of the sulfonic acid groups into the polyolefin-based nonwoven fabric is performed, for example, by immersing the polyolefin-based nonwoven fabric in fuming sulfuric acid, and the introduction of the carboxyl group into the polyolefin-based nonwoven fabric is performed by, for example, irradiating the polyolefin-based nonwoven fabric with radiation. And is graft-copolymerized with acrylic acid.
【００１３】そして、ポリオレフィン系不織布にポリオ
レフィン系樹脂の酸化体を導入するには、たとえばポリ
オレフィン系不織布を過マンガン酸カリウム水溶液に浸
漬し、加熱して表面を酸化処理することによって行われ
る。The introduction of the polyolefin resin oxidant into the polyolefin non-woven fabric is carried out, for example, by immersing the polyolefin non-woven fabric in an aqueous potassium permanganate solution and heating it to oxidize the surface.
【００１４】ポリオレフィン系不織布としては、たとえ
ばポリプロピレン不織布、ポリエチレン不織布などが用
いられる。As the polyolefin-based nonwoven fabric, for example, polypropylene nonwoven fabric, polyethylene nonwoven fabric, etc. are used.
【００１５】本発明において、負極はリチウムまたはリ
チウム合金からなるが、このリチウム合金としては、た
とえばリチウム−アルミニウム合金、リチウム−鉛合
金、リチウム−インジウム合金、リチウム−アルミニウ
ム−ホウ素合金、リチウム−ガリウム合金などが用いら
れる。これらのリチウム合金はあらかじめ合金化してお
いたものであってもよいし、また、電池内で電解液の存
在下に電気化学的に合金化したものでもよい。In the present invention, the negative electrode is made of lithium or a lithium alloy, and examples of the lithium alloy include lithium-aluminum alloy, lithium-lead alloy, lithium-indium alloy, lithium-aluminum-boron alloy, lithium-gallium alloy. Are used. These lithium alloys may be alloyed in advance, or may be electrochemically alloyed in the battery in the presence of an electrolytic solution.
【００１６】正極や電解液には、この種の電池において
通常使用されるものをいずれも用いることができる。As the positive electrode and the electrolytic solution, any of those normally used in this type of battery can be used.
【００１７】たとえば、電解液には、１，２−ジメトキ
シエタン、１，２−ジエトキシエタン、エチレンカーボ
ネート、プロピレンカーボネート、γ−ブチロラクト
ン、テトラヒドロフラン、１，３−ジオキソラン、４−
メチル−１，３−ジオキソランなどの有機溶媒の単独ま
たは２種以上の混合溶媒に、たとえばＬｉＣｌＯ4 、Ｌ
ｉＰＦ6 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＢＦ4 、
ＬｉＣＦ3 ＳＯ3 、ＬｉＢ（Ｃ6 Ｈ5 ）4 などの電解質
の１種または２種以上を溶解させることによって調製し
た有機電解液を用いることができる。For example, the electrolytic solution contains 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene carbonate, propylene carbonate, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, 4-
In an organic solvent such as methyl-1,3-dioxolane or a mixed solvent of two or more kinds, for example, LiClO 4 , L
iPF 6, LiAsF 6, LiSbF 6 , LiBF 4,
An organic electrolytic solution prepared by dissolving one or more electrolytes such as LiCF 3 SO 3 and LiB (C 6 H 5 ) 4 can be used.
【００１８】また、正極を作製するにあたっての正極活
物質としては、たとえばポリアニリン、ポリピロール、
ポリチオフェン、ポリフェニレン、ポリアズレン、ポリ
アセチレンなどのポリマー活物質、リチウム塩と二酸化
マンガンとを焼成して得られるリチウムマンガン複合酸
化物、ＬｉＣｏＯ2 、Ｃｒ3 Ｏ8 、Ｖ2 Ｏ5 などを用い
ることができる。As the positive electrode active material for producing the positive electrode, for example, polyaniline, polypyrrole,
Polymer active materials such as polythiophene, polyphenylene, polyazulene and polyacetylene, lithium manganese composite oxide obtained by firing a lithium salt and manganese dioxide, LiCoO 2 , Cr 3 O 8 , V 2 O 5 and the like can be used.
【００１９】[0019]
【実施例】つぎに、実施例を挙げて本発明をより具体的
に説明する。なお、以下において濃度を示す％はいずれ
も重量基準によるものである。EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, all the percentages showing the concentration are based on weight.
【００２０】実施例１ 多孔度６４容量％のポリプロピレン不織布を２０％発煙
硫酸中に１時間浸漬し、スルホン化処理を施した。Example 1 A polypropylene nonwoven fabric having a porosity of 64% by volume was immersed in 20% fuming sulfuric acid for 1 hour for sulfonation treatment.
【００２１】スルホン化処理後、ポリプロピレン不織布
から発煙硫酸を除去するために、スルホン化処理後のポ
リプロピレン不織布を８０％硫酸、６０％硫酸、４０％
硫酸中に順次浸漬した後、水洗、乾燥し、スルホン基を
導入したポリプロピレン不織布を得た。In order to remove fuming sulfuric acid from the polypropylene nonwoven fabric after the sulfonation treatment, the polypropylene nonwoven fabric after the sulfonation treatment is treated with 80% sulfuric acid, 60% sulfuric acid and 40% sulfuric acid.
After being sequentially dipped in sulfuric acid, washed with water and dried to obtain a polypropylene nonwoven fabric into which a sulfo group was introduced.
【００２２】このスルホン基を導入したポリプロピレン
不織布をセパレータとして用い、正極にはリチウムマン
ガン複合酸化物を主成分とする合剤の成形体を用い、負
極にはリチウム−アルミニウム合金を用い、電解液には
プロピレンカーボネートと１，２−ジメトキシエタンと
の容量比１：１の混合溶媒にＬｉＰＦ6 を１ｍｏｌ／ｌ
を溶解させて調製した有機電解液を用いて、直径２０ｍ
ｍ、高さ１．６ｍｍで図１に示す構造のコイン形リチウ
ム二次電池を作製した。The polypropylene non-woven fabric introduced with the sulfone group is used as a separator, a molded product of a mixture containing lithium manganese composite oxide as a main component is used for the positive electrode, a lithium-aluminum alloy is used for the negative electrode, and an electrolytic solution is used. Is 1 mol / l of LiPF 6 in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane in a volume ratio of 1: 1.
20m in diameter using the organic electrolyte prepared by dissolving
A coin-type lithium secondary battery having a structure shown in FIG. 1 having a height of m and a height of 1.6 mm was produced.
【００２３】図１に示す電池について説明すると、１は
リチウム−アルミニウム合金からなる負極で、２はリチ
ウムマンガン複合酸化物を主成分とする合剤の成形体か
らなる正極である。Explaining the battery shown in FIG. 1, 1 is a negative electrode made of a lithium-aluminum alloy, and 2 is a positive electrode made of a molded product of a mixture containing lithium-manganese composite oxide as a main component.
【００２４】３はスルホン基を導入したポリプロピレン
不織布からなるセパレータであり、４はステンレス鋼製
の負極缶、５はステンレス鋼製の正極缶で、６はポリプ
ロピレン製の環状ガスケットである。Reference numeral 3 is a separator made of a polypropylene nonwoven fabric having sulfo groups introduced therein, 4 is a negative electrode can made of stainless steel, 5 is a positive electrode can made of stainless steel, and 6 is an annular gasket made of polypropylene.
【００２５】実施例２ 多孔度６４容量％のポリプロピレン不織布を放射線の照
射下でアクリル酸とグラフト共重合させて、ポリプロピ
レン不織布にカルボキシル基を導入した。Example 2 A polypropylene nonwoven fabric having a porosity of 64% by volume was graft-copolymerized with acrylic acid under irradiation of radiation to introduce a carboxyl group into the polypropylene nonwoven fabric.
【００２６】このカルボキシル基を導入したポリプロピ
レン不織布をセパレータとして用い、それ以外は実施例
１と同様の構成のコイン形リチウム二次電池を作製し
た。A coin type lithium secondary battery having the same structure as in Example 1 except that the polypropylene non-woven fabric having the carboxyl group introduced was used as a separator was prepared.
【００２７】実施例３ 多孔度６４容量％のポリプロピレン不織布を９．５％過
マンガン酸カリウム水溶液に浸漬し、３０分間煮沸した
後、水洗乾燥し、表面を酸化したポリプロピレン不織布
を得た。Example 3 A polypropylene nonwoven fabric having a porosity of 64% by volume was dipped in a 9.5% potassium permanganate aqueous solution, boiled for 30 minutes, washed with water, and dried to obtain a polypropylene nonwoven fabric having an oxidized surface.
【００２８】この表面を酸化したポリプロピレン不織布
をセパレータとして用い、それ以外は実施例１と同様の
構成のコイン形リチウム二次電池を作製した。A coin type lithium secondary battery having the same structure as in Example 1 except that the polypropylene nonwoven fabric whose surface was oxidized was used as a separator was prepared.
【００２９】比較例１ 多孔度６４容量％のポリプロピレン不織布をそのままセ
パレータとして用い、それ以外は実施例１と同様の構成
のコイン形リチウム二次電池を作製した。Comparative Example 1 A coin type lithium secondary battery having the same structure as in Example 1 except that polypropylene non-woven fabric having a porosity of 64% by volume was used as it was as a separator was produced.
【００３０】比較例２ 多孔度６４容量％のポリプロピレン不織布を界面活性剤
（ポリオキシエチレンアルキルエーテル）で親液処理し
た。Comparative Example 2 A polypropylene nonwoven fabric having a porosity of 64% by volume was lyophilic treated with a surfactant (polyoxyethylene alkyl ether).
【００３１】この界面活性剤で親液処理したポリプロピ
レン不織布をセパレータとして用い、それ以外は実施例
１と同様の構成のコイン形リチウム二次電池を作製し
た。A coin-type lithium secondary battery having the same structure as in Example 1 except that the polypropylene non-woven fabric lyophilic treated with this surfactant was used as a separator was prepared.
【００３２】上記実施例１〜３および比較例１〜２の電
池を１００個ずつ作製し、その封口時に漏液が生じるか
否かを調べた。その結果を表１に示す。なお、表１にお
いては、漏液が発生した電池の全体中に占める割合がわ
かりやすいように、分母に作製した全電池個数を示し、
分子に漏液が発生した電池個数を示す態様で、漏液発生
電池個数を表示した。100 batteries each of the above-mentioned Examples 1 to 3 and Comparative Examples 1 and 2 were produced, and it was examined whether or not liquid leakage occurred at the time of sealing them. The results are shown in Table 1. In Table 1, the total number of batteries produced in the denominator is shown so that the ratio of the leaked batteries to the whole battery can be easily understood.
The number of leak-generating batteries was indicated in a mode showing the number of batteries in which leakage occurred in the molecule.
【００３３】[0033]
【表１】 [Table 1]
【００３４】表１に示すように、ポリプロピレン不織布
をそのままセパレータとして用いた比較例１の電池で
は、１００個の電池中３２個の電池に漏液が発生した
が、実施例１〜３の電池はいずれも漏液の発生がまった
くなかった。As shown in Table 1, in the battery of Comparative Example 1 in which polypropylene nonwoven fabric was used as a separator as it was, leakage occurred in 32 of 100 batteries, but in the batteries of Examples 1 to 3, None of them leaked.
【００３５】このような結果は、実施例１〜３の電池に
用いたセパレータの吸液性および保液性が優れているこ
とによるものである。These results are due to the excellent liquid absorbing and liquid retaining properties of the separators used in the batteries of Examples 1 to 3.
【００３６】つぎに、上記実施例１〜３および比較例１
〜２の電池について電池密度１ｍＡ／ｃｍ2 、電圧範囲
３．３Ｖ〜２．０Ｖで充放電サイクル試験を行い、放電
容量が初度の６０％になるまでのサイクル数を調べた。
その結果を表２に示す。Next, the above Examples 1 to 3 and Comparative Example 1
For the batteries No. 2 to No. 2 , a charge / discharge cycle test was performed at a battery density of 1 mA / cm 2 and a voltage range of 3.3 V to 2.0 V, and the number of cycles until the discharge capacity reached 60% of the initial level was examined.
The results are shown in Table 2.
【００３７】[0037]
【表２】 [Table 2]
【００３８】表２に示す結果から明らかなように、実施
例１〜３の電池は、比較例１〜２に比べてサイクル特性
が優れている。As is clear from the results shown in Table 2, the batteries of Examples 1 to 3 are superior in cycle characteristics to Comparative Examples 1 and 2.
【００３９】このような結果は、実施例１〜３の電池に
使用されたセパレータの保液性が優れていることによる
ものである。These results are due to the excellent liquid retaining properties of the separators used in the batteries of Examples 1 to 3.
【００４０】[0040]
【発明の効果】以上説明したように、本発明では、親水
基を導入したポリオレフィン系不織布をセパレータとし
て用いることにより、セパレータの吸液性および保液性
を高めて、封口時の漏液が少なく、かつサイクル特性の
優れたリチウム二次電池を提供することができた。As described above, in the present invention, by using the hydrophilic group-introduced polyolefin non-woven fabric as the separator, the liquid absorbing property and the liquid retaining property of the separator are improved, and the liquid leakage at the time of sealing is reduced. It was possible to provide a lithium secondary battery having excellent cycle characteristics.
【図１】本発明に係るリチウム二次電池の一例を示す断
面図である。FIG. 1 is a cross-sectional view showing an example of a lithium secondary battery according to the present invention.
１ 負極 ２ 正極 ３ セパレータ 1 Negative electrode 2 Positive electrode 3 Separator
Claims (2)
極１と、正極２と、有機電解液とを備えたリチウム二次
電池において、 セパレータ３として、親水基を導入したポリオレフィン
系不織布を用いたことを特徴とするリチウム二次電池。1. A lithium secondary battery comprising a negative electrode 1 made of lithium or a lithium alloy, a positive electrode 2, and an organic electrolyte, wherein a hydrophilic non-woven polyolefin-based nonwoven fabric is used as a separator 3. And a lithium secondary battery.
よびポリオレフィン系樹脂の酸化体よりなる群から選ば
れる少なくとも１種である請求項１記載のリチウム二次
電池。2. The lithium secondary battery according to claim 1, wherein the hydrophilic group is at least one selected from the group consisting of a sulfone group, a carboxyl group and an oxidized product of a polyolefin resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3223469A JPH0541252A (en) | 1991-08-07 | 1991-08-07 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3223469A JPH0541252A (en) | 1991-08-07 | 1991-08-07 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0541252A true JPH0541252A (en) | 1993-02-19 |
Family
ID=16798630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3223469A Pending JPH0541252A (en) | 1991-08-07 | 1991-08-07 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0541252A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007052440A1 (en) * | 2005-11-02 | 2007-05-10 | Toyo Tanso Co., Ltd. | Lithium ion rechargeable battery |
| JP2010277935A (en) * | 2009-05-29 | 2010-12-09 | Nissan Motor Co Ltd | Nonaqueous electrolyte secondary battery |
| JPWO2020054648A1 (en) * | 2018-09-14 | 2021-08-30 | マクセルホールディングス株式会社 | Non-aqueous electrolyte secondary battery, its manufacturing method and non-aqueous electrolyte secondary battery system |
-
1991
- 1991-08-07 JP JP3223469A patent/JPH0541252A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007052440A1 (en) * | 2005-11-02 | 2007-05-10 | Toyo Tanso Co., Ltd. | Lithium ion rechargeable battery |
| JP2007128719A (en) * | 2005-11-02 | 2007-05-24 | Toyo Tanso Kk | Lithium ion secondary battery |
| US8057935B2 (en) | 2005-11-02 | 2011-11-15 | Toyo Tanso Co., Ltd. | Lithium ion rechargeable battery |
| JP2010277935A (en) * | 2009-05-29 | 2010-12-09 | Nissan Motor Co Ltd | Nonaqueous electrolyte secondary battery |
| JPWO2020054648A1 (en) * | 2018-09-14 | 2021-08-30 | マクセルホールディングス株式会社 | Non-aqueous electrolyte secondary battery, its manufacturing method and non-aqueous electrolyte secondary battery system |
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