JPH0950802A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH0950802A JPH0950802A JP7200625A JP20062595A JPH0950802A JP H0950802 A JPH0950802 A JP H0950802A JP 7200625 A JP7200625 A JP 7200625A JP 20062595 A JP20062595 A JP 20062595A JP H0950802 A JPH0950802 A JP H0950802A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- base film
- monomer
- lithium battery
- produced
- 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
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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
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- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム電池に関
する。さらに詳しくは、携帯電話やビデオカメラ等の小
型携帯用電子機器の電源として、また電気自動車や電力
貯蔵用などの高性能電池として特に有効な、高信頼性の
リチウム電池に関する。TECHNICAL FIELD The present invention relates to a lithium battery. More specifically, the present invention relates to a highly reliable lithium battery that is particularly effective as a power source for small portable electronic devices such as mobile phones and video cameras, and as a high-performance battery for electric vehicles and power storage.
【０００２】[0002]
【従来の技術】電気機器の小型軽量化に伴い、そこで用
いられる電源電池についてもその小型軽量化が強く求め
られている。その中で固体電解質を用いたリチウム電池
は、その高い理論エネルギー密度、形状に対する自由度
が高く、注目されている電池であるが、信頼性、コスト
等の面において、必ずしも充分満足し得るものではない
ため、未だ実用化にまで至っていないのが現状である。2. Description of the Related Art With the reduction in size and weight of electrical equipment, there is a strong demand for reduction in size and weight of power supply batteries used therein. Among them, a lithium battery using a solid electrolyte is a battery that has attracted attention because of its high theoretical energy density and high degree of freedom in shape, but it is not always sufficiently satisfactory in terms of reliability, cost, etc. Since it does not exist, it is the current situation that it has not yet been put to practical use.
【０００３】これまでに、高分子固体電解質としてはポ
リエチレンオキシド（ＰＥＯ）及びその誘導体に電解液
を加えた系が広く検討されてきた。しかし、導電率を上
げるために可塑剤として電解液を加えたこれらの系は、
ゲル状で流動性を持つため強度的に問題があった。それ
に対し近年になって、電解液に溶かしたエチレンオキシ
ド鎖をもったモノマーを架橋して得られるタイプの高分
子固体電解質は、比較的容易に固体状のものが作成可能
で、その作成方法における自由度も高いため、それを用
いたリチウム電池が幾つか検討されている。これらの高
分子固体電解質を得るためのモノマー架橋方法には、加
熱によるもの、電子線照射によるもの、および紫外線照
射による方法が試みられている。加熱による方法は最も
簡便な方法であるが、予め電解液を含んだ状態からの架
橋硬化を行なう場合、電解液が一部または全て揮発して
しまったり、加熱により組成物が反応してガスが発生す
る等の問題があった。また電子線架橋の場合は、電子線
照射装置が大がかりで高価なものとなり、コスト的な問
題があった。これらの点を考慮すると、紫外線照射によ
るものが、比較的簡便安価で信頼性の高い高分子固体電
解質を得るために最適な方法と考えられる。As a solid polymer electrolyte, a system in which an electrolytic solution is added to polyethylene oxide (PEO) and its derivatives has been widely studied so far. However, these systems with electrolyte added as a plasticizer to increase conductivity are
There was a problem in strength because it was a gel and had fluidity. On the other hand, in recent years, solid polymer electrolytes of the type obtained by crosslinking monomers having ethylene oxide chains dissolved in an electrolytic solution can be prepared relatively easily in a solid state, and there is no limitation in the method of preparation. Because of its high frequency, some lithium batteries using it have been studied. As a monomer crosslinking method for obtaining these polymer solid electrolytes, heating, electron beam irradiation, and ultraviolet irradiation have been tried. The method by heating is the simplest method, but when performing cross-linking curing from a state containing an electrolytic solution in advance, the electrolytic solution may partially or completely volatilize, or the composition may react by heating to generate gas. There was a problem such as occurrence. Further, in the case of electron beam cross-linking, the electron beam irradiation device is large and expensive, which causes a cost problem. Considering these points, ultraviolet irradiation is considered to be the most suitable method for obtaining a polymer solid electrolyte that is relatively simple, inexpensive, and highly reliable.
【０００４】一方、リチウム電池については、リチウム
金属負極の場合を除き、炭素材料を活物質とした負極、
および、金属酸化物等を活物質とした正極のいずれの場
合においても、電極層内部まで電解質を存在させること
が、リチウムイオンの導電路を確保し分極を抑えるため
に必要である。そのため、電解液が電極層内部へ含浸す
る液体電解液を用いた電池と異なり、固体電解質を用い
た電池では、予め電極作成時に電解質部分をも同時に作
り込んだ複合電極とすることが望ましい。また、電解液
に溶かしたモノマーを架橋して得られる高分子固体電解
質を用いた電池においても、従来の方法ではその電極と
して、活物質と必要に応じ導電助剤と、モノマーとを含
んだ電解液を混合して印刷後、架橋硬化した電極を用い
てきた。この場合も架橋方法として前記の３種類の方法
が考えられるが、紫外線照射方法では電極組成物の厚み
がある程度以上になると活物質等の粉体に紫外線が遮ら
れ、内部では硬化が起こらないという問題があった。電
極の硬化のためには、より透過力の強い電子線または加
熱が一般に用いられてきたが、これらには前記のような
問題を解消することができなかった。そこで、架橋硬化
型以外の高分子固体電解質を用いて電極を作成し、別個
に作成した電解液に溶かしたモノマーを架橋して得られ
る高分子固体電解質膜をセパレーターとして組み合わせ
ることも可能であるが、この場合、性質の異なる高分子
電解質を接合させる必要が生じ、二層の間の良好な界面
の形成が困難であるという問題があった。On the other hand, for lithium batteries, except for a lithium metal negative electrode, a negative electrode using a carbon material as an active material,
In any case of a positive electrode using a metal oxide or the like as an active material, it is necessary to allow an electrolyte to exist inside the electrode layer in order to secure a conductive path for lithium ions and suppress polarization. Therefore, unlike a battery using a liquid electrolytic solution in which the electrolytic solution is impregnated into the electrode layer, in a battery using a solid electrolyte, it is desirable to use a composite electrode in which an electrolyte portion is also prepared at the same time when the electrode is prepared. Further, also in a battery using a polymer solid electrolyte obtained by crosslinking a monomer dissolved in an electrolytic solution, in the conventional method, as an electrode thereof, an electrolysis containing an active material, a conductive auxiliary agent if necessary, and a monomer. After mixing the liquid and printing, a crosslinked and cured electrode has been used. In this case as well, the three types of methods described above can be considered as the crosslinking method, but in the ultraviolet irradiation method, when the thickness of the electrode composition exceeds a certain level, the ultraviolet rays are blocked by the powder of the active material and the like, and curing does not occur inside. There was a problem. Electron beams or heating having a higher penetrating power have been generally used for curing the electrodes, but these problems cannot be solved. Therefore, it is possible to create an electrode using a polymer solid electrolyte other than the cross-linking type, and to combine a polymer solid electrolyte membrane obtained by crosslinking the monomers dissolved in the separately prepared electrolyte solution as a separator. However, in this case, there is a problem that it is necessary to bond polymer electrolytes having different properties, and it is difficult to form a good interface between the two layers.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上述の問題
に鑑みなされたものであり、簡易な構造で安価な、高信
頼性のリチウム電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide an inexpensive and highly reliable lithium battery having a simple structure.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記目的を達
成するため、光重合による架橋を応用した電極組成及び
その作成方法を鋭意研究した結果、ポリエチレンオキシ
ド（ＰＥＯ）を用いて、予め電極材ベースフィルムを作
成し、その上にモノマーを含んだ電解液を塗布し一定時
間後、光照射をすることが有効であることを見い出し、
本発明を完成させた。In order to achieve the above object, the present invention has conducted extensive studies on an electrode composition applying photopolymerization crosslinking and a method for producing the same. As a result, polyethylene oxide (PEO) was used in advance for electrode formation. We found that it is effective to create a material base film, apply an electrolyte solution containing a monomer on it, and irradiate with light after a certain period of time.
The present invention has been completed.
【０００７】すなわち、本発明によれば、正極、負極、
および高分子固体電解質を備えたリチウム電池におい
て、正極および負極の少なくとも一方が、ポリエチレン
オキシド（ＰＥＯ）および活物質を含むベースフィルム
に、光重合性モノマーを含んだ電解液を塗布し含浸させ
た後、光を照射して、光重合性モノマーを重合させてな
る複合電極であることを特徴とするリチウム電池が提供
される。That is, according to the present invention, the positive electrode, the negative electrode,
And in a lithium battery including a polymer solid electrolyte, at least one of a positive electrode and a negative electrode is coated with an electrolytic solution containing a photopolymerizable monomer and impregnated into a base film containing polyethylene oxide (PEO) and an active material. A lithium battery is provided which is a composite electrode formed by irradiating light to polymerize a photopolymerizable monomer.
【０００８】また、その好ましい態様として、前記ベー
スフィルムが、前記ＰＥＯおよび活物質に加えて、さら
にリチウム塩および有機溶媒からなる電解液を含有する
ものであることを特徴とするリチウム電池が提供され
る。[0008] As a preferred embodiment thereof, there is provided a lithium battery characterized in that the base film further contains an electrolyte solution containing a lithium salt and an organic solvent in addition to the PEO and the active material. It
【０００９】さらに、その好ましい態様として、前記光
重合性モノマーが、エチレンオキシド鎖を有するポリエ
ーテルのアクリレートまたはメタクリレートであること
を特徴とするリチウム電池が提供される。Further, as a preferred embodiment thereof, there is provided a lithium battery characterized in that the photopolymerizable monomer is an acrylate or methacrylate of a polyether having an ethylene oxide chain.
【００１０】[0010]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。本発明のリチウム電池は、正極および負極
の少なくとも一方が、特定のベースフィルムに光重合性
モノマーを含んだ電解液を塗布し、含浸させた後、光を
照射して、そのモノマーを硬化させてなる複合電極であ
ることを特徴とする。以下その複合電極の構成要素につ
いて具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the lithium battery of the present invention, at least one of the positive electrode and the negative electrode is formed by coating a specific base film with an electrolytic solution containing a photopolymerizable monomer, impregnating the same, and then irradiating light to cure the monomer. It is a composite electrode consisting of The components of the composite electrode will be specifically described below.
【００１１】１．ベースフィルム 本発明に用いられるベースフィルムとしては、ポリエチ
レンオキシド（ＰＥＯ）および活物質を含むものであれ
ば特に制限はない。ここで活物質とは、正極活物質又は
負極活物質を意味する。ポリオキシエチレンオキシドの
分子量は、１０5 〜１０7 のものがフィルムの製膜性及
び強度の点で好ましい。なお、必要に応じ、アセチレン
ブラック，グラファイト等の導電助剤を加えてもよい。1. Base Film The base film used in the present invention is not particularly limited as long as it contains polyethylene oxide (PEO) and an active material. Here, the active material means a positive electrode active material or a negative electrode active material. The molecular weight of polyoxyethylene oxide is preferably 10 5 to 10 7 in terms of film-forming property and strength. If necessary, a conductive auxiliary agent such as acetylene black or graphite may be added.
【００１２】また、ベースフィルムには、予めリチウム
塩および有機溶媒からなる電解液を含有させることが好
ましい。このリチウム塩としては、ＬｉＣｌＯ4 ，Ｌｉ
ＰＦ6 ，ＬｉＢＦ4 ，ＬｉＣＦ3 ＳＯ3 ，ＬｉＡｓＦ6
等を、また有機溶媒としては、エチレンカーボネート，
プロピレンカーボネート，ジエチルカーボネート，ジメ
チルカーボネート，ジメトキシエタン，テトラヒドロフ
ラン，２−メチルテトラヒドロフラン，γ−ブチロラク
トン，ジメチルホルムアミド等を挙げることができる。
これらは単独でも二種以上を混合したものであってもよ
い。Further, it is preferable that the base film previously contains an electrolytic solution containing a lithium salt and an organic solvent. Examples of the lithium salt include LiClO 4 , Li
PF 6 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6
Etc., and as the organic solvent, ethylene carbonate,
Examples thereof include propylene carbonate, diethyl carbonate, dimethyl carbonate, dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dimethylformamide and the like.
These may be used alone or as a mixture of two or more kinds.
【００１３】このべースフィルムは、前記活物質に、必
要に応じ、導電助剤を加えた粉体に、好ましくはリチウ
ム塩および有機溶媒からなる電解液を含んだＰＥＯを加
え、さらに印刷のために揮発性の有機溶剤、たとえばア
セトニトリル等を加えて得た混合スラリーを、好ましく
は直接極板金属にスクリーン印刷またはドクターブレー
ド法等により印刷し、印刷のための有機溶剤を乾燥させ
て作成することができる。なお、ベースフィルム作成時
にリチウム塩および有機溶媒、すなわち電解液を含ませ
ないでＰＥＯのみで一次形成し、後工程である光重合性
モノマーを含んだ電解液塗布時に電解液を含浸させるこ
とも可能ではあるが、後工程ですべて含浸させるとＰＥ
Ｏの膨潤により活物質等の粉体間の接合が不完全となっ
たり、十分に電極内部までの電解液が浸透しにくいとい
う問題が生ずる。そのためベースフィルムは、前記のよ
うな工程で得られる、電解液を含んだゲル状ＰＥＯを分
散させた形態としたものの方が好ましい。This base film is prepared by adding PEO containing an electrolyte solution, preferably a lithium salt and an organic solvent, to a powder prepared by adding a conductive additive to the active material, if necessary, and further for printing. A mixed slurry obtained by adding a volatile organic solvent such as acetonitrile is preferably printed directly on the electrode plate metal by screen printing or a doctor blade method, and the organic solvent for printing is dried to be prepared. it can. In addition, it is also possible to form a primary film only with PEO without including a lithium salt and an organic solvent, that is, an electrolytic solution at the time of forming a base film, and to impregnate the electrolytic solution when applying an electrolytic solution containing a photopolymerizable monomer in a subsequent step. However, if all of them are impregnated in the subsequent process, PE
Due to the swelling of O, there arises a problem that the bonding between the powders of the active material or the like becomes incomplete, or the electrolytic solution does not easily penetrate into the electrode. Therefore, it is preferable that the base film has a form in which the gelled PEO containing the electrolytic solution obtained in the above-mentioned step is dispersed.
【００１４】２．光重合性モノマー 本発明に用いられる光重合性モノマーとしては、可視
光、紫外線等によって重合し得るものであれば特に制限
はないが、たとえば紫外線重合性のエチレンオキシド鎖
を含んだポリエーテルのアクリレートまたはメタクリレ
ートが、良好な電解質を与え、かつベースフィルムのＰ
ＥＯとの整合性も良いため好ましい。さらに好ましくは
ポリエーテルの三官能性以上の多官能性アクリレートま
たはメタクリレートが十分な強度を与えるため、特に好
ましい。2. Photopolymerizable Monomer The photopolymerizable monomer used in the present invention is not particularly limited as long as it can be polymerized by visible light, ultraviolet rays, etc., for example, an acrylate of a polyether containing an ultraviolet polymerizable ethylene oxide chain or Methacrylate gives a good electrolyte and P of the base film
It is preferable because it has good compatibility with EO. More preferably, a trifunctional or higher-functional polyfunctional acrylate or methacrylate of a polyether provides sufficient strength, and is therefore particularly preferable.
【００１５】具体的には、下記式（１）〜（６）に示す
イオン伝導性高分子化合物を挙げることができる。Specific examples include ion-conductive polymer compounds represented by the following formulas (1) to (6).
【００１６】[0016]
【化１】 Embedded image
【００１７】[0017]
【化２】 Embedded image
【００１８】[0018]
【化３】 Embedded image
【００１９】[0019]
【化４】 Embedded image
【００２０】[0020]
【化５】 Embedded image
【００２１】[0021]
【化６】 [Chemical 6]
【００２２】（式（１）〜（６）中、Ｒ1 は炭素数１〜
１６の置換されていてもよい脂肪族炭化水素残基，Ｒ
2 ，Ｒ3 はアクリロイル基またはメタクリロイル基、
ｍ，ｎ，ｐ，ｑ，ｓおよびｔは１以上の整数、並びにｘ
は３〜８の整数をそれぞれ示す。）(In the formulas (1) to (6), R 1 is a carbon number of 1 to
16 optionally substituted aliphatic hydrocarbon residues, R
2 , R 3 is an acryloyl group or a methacryloyl group,
m, n, p, q, s and t are integers of 1 or more, and x
Represents an integer of 3 to 8, respectively. )
【００２３】３．電解液 本発明に用いられる電解液としては特に制限はないが、
たとえば一般にリチウム電池用に検討または使用されて
いるもの、すなわち、前述のリチウム塩、例えばＬｉＣ
Ｏ4 ，ＬｉＣＦ3 ＳＯ3 ，ＬｉＰＦ6 ，ＬｉＢＦ4 ，Ｌ
ｉＡｓＦ6 等を、有機溶媒、例えばエチレンカーボネー
ト，プロピレンカーボネート，ジエチルカーボネート，
ジメチルカーボネート，ジメトキシエタン，テトラヒド
ロフラン，２−メチルテトラヒドロフラン，γ−ブチロ
ラクトン，ジメチルホルムアミド等の単独または二種以
上に溶かしたものを挙げることができる。3. Electrolyte Solution There is no particular limitation on the electrolyte solution used in the present invention,
For example, those commonly considered or used for lithium batteries, ie the aforementioned lithium salts, eg LiC.
O 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , L
iAsF 6 or the like is mixed with an organic solvent such as ethylene carbonate, propylene carbonate, diethyl carbonate,
Examples thereof include dimethyl carbonate, dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dimethylformamide and the like, or those dissolved in two or more kinds.
【００２４】前記光重合性モノマーを含んだ電解液中
の、モノマー濃度は、高いほど硬化後の機械的強度は得
られるが、逆に電導度は低下して電池特性が悪くなるの
で、１０重量％から５０重量％の範囲が好ましい。１０
重量％未満であると硬化後のフィルムの強度が不足し、
５０重量％を超えると十分な電導度が得られない。The higher the monomer concentration in the electrolytic solution containing the photopolymerizable monomer, the higher the mechanical strength after curing is obtained, but on the contrary, the electric conductivity is lowered and the battery characteristics are deteriorated. % To 50% by weight is preferred. 10
If it is less than wt%, the strength of the film after curing will be insufficient,
If it exceeds 50% by weight, sufficient electric conductivity cannot be obtained.
【００２５】また、光重合性モノマーを含んだ電解液に
は、光照射による硬化を容易にするため、光重合開始剤
を添加することが好ましい。一般にこの開始剤は不安定
なものが多く、添加量が多いと電池特性に悪影響を及ぼ
すので、全体の溶液に対して０．１〜１．０重量％が好
ましい。この電解液のベースフィルムへの塗布、含浸方
法については、特に制限はないが、たとえばドクターブ
レード法を好適に用いることができる。Further, it is preferable to add a photopolymerization initiator to the electrolytic solution containing the photopolymerizable monomer in order to facilitate curing by light irradiation. Generally, many of these initiators are unstable, and if added in a large amount, the battery characteristics are adversely affected. Therefore, 0.1 to 1.0% by weight of the total solution is preferable. The method of applying and impregnating the base film with this electrolytic solution is not particularly limited, but for example, the doctor blade method can be preferably used.
【００２６】この場合モノマー溶液は、塗布後、電極材
料を結着させているＰＥＯに含浸、拡散し、電極内で組
成の傾斜を持った状態で光により硬化させられるので、
界面は良好なものが得られる。またモノマーが拡散する
のは上部に限られるため光照射による未硬化が問題とな
ることはない。かつ、予めベースフィルムが形成されて
いるため、全体の強度的にも問題はない複合電極が形成
される。このようにして得られた複合電極によって前記
課題が解決された電池を提供することができる。In this case, the monomer solution is, after coating, impregnated and diffused in PEO binding the electrode material, and is cured by light with a composition gradient in the electrode.
A good interface can be obtained. Further, since the monomer diffuses only in the upper portion, uncured by light irradiation does not pose a problem. In addition, since the base film is formed in advance, a composite electrode having no problem with the overall strength is formed. With the composite electrode thus obtained, it is possible to provide a battery in which the above problems are solved.
【００２７】４．光照射 本発明における光照射については特に制限はなく、通常
の露光装置、たとえば紫外線露光装置を用いることがで
きる。一般に酸素分子の存在は光重合を阻害するので、
十分な硬化を得るためにはモノマー溶液の表面を透光性
のもので覆うか、真空下、または不活性雰囲気下で行な
うことが好ましい。作業性、電解液の揮発を考慮する
と、不活性雰囲気下の露光が特に好ましい。4. Light Irradiation There is no particular limitation on the light irradiation in the present invention, and an ordinary exposure device, for example, an ultraviolet exposure device can be used. Generally, the presence of molecular oxygen inhibits photopolymerization, so
In order to obtain sufficient curing, it is preferable to cover the surface of the monomer solution with a transparent material, or to carry out under vacuum or in an inert atmosphere. In consideration of workability and volatilization of the electrolytic solution, exposure under an inert atmosphere is particularly preferable.
【００２８】本発明に用いられる複合電極は、リチウム
電池の正極および負極のいずれにも適用することができ
る。負極にリチウム金属を使用する場合には、正極だけ
にこの複合電極を適用して電池を作成することができ
る。また、負極に炭素材料等の粉体の活物質を使用する
場合には、正極および負極共にこの複合電極を適用する
ことが好ましい。正極活物質については特に制限はな
く、たとえば、ＬｉＣｏＯ2 ，ＬｉＮｉＯ2 ，ＬｉＭｎ
2 Ｏ4 ，ＬｉＣｏ0.92Ｓｎ0.08Ｏ2，ＬｉＣｏ1-xＮｉx
Ｏ2，Ｖ6Ｏ13など、リチウム電池用として汎用されてい
る正極活物質を用いることができる。The composite electrode used in the present invention can be applied to both the positive electrode and the negative electrode of a lithium battery. When lithium metal is used for the negative electrode, the composite electrode can be applied only to the positive electrode to form a battery. When a powdery active material such as a carbon material is used for the negative electrode, it is preferable to apply this composite electrode to both the positive electrode and the negative electrode. There is no particular limitation on the positive electrode active material, and for example, LiCoO 2 , LiNiO 2 , LiMn
2 O 4 , LiCo 0.92 Sn 0.08 O 2 , LiCo 1-x Ni x
A positive electrode active material generally used for lithium batteries such as O 2 and V 6 O 13 can be used.
【００２９】高分子固体電解質を用いたリチウム電池に
おいては、通常固体電解質自身が兼ねたセパレーター層
を、正極，負極間を電子伝導的に絶縁するために、電極
間に形成する必要がある。本発明のリチウム電池の場合
には、上記と同様のモノマー溶液を光硬化たとえば紫外
線硬化して独立に得られた高分子固体電解質フィルムを
セパレーターとして使用することができ、また例えば複
合電極上にさらに直接モノマー溶液を塗布硬化させてセ
パレーターとしたり、複合電極作成時にモノマー塗布量
を多くして硬化させ塗布面表層をセパレーター層とする
等の手法により形成してもよい。いずれの方法でも簡便
かつ安価にリチウム電池を作成することができる。な
お、この場合、モノマー溶液はリチウム塩および有機溶
媒からなる電解液等を含んだものであることは上記のと
おりである。In a lithium battery using a polymer solid electrolyte, it is usually necessary to form a separator layer, which also serves as the solid electrolyte itself, between the electrodes in order to electrically conductively insulate between the positive electrode and the negative electrode. In the case of the lithium battery of the present invention, a polymer solid electrolyte film independently obtained by photo-curing, for example, UV-curing a monomer solution similar to the above can be used as a separator, and further, for example, on a composite electrode. It may be formed by a method in which a monomer solution is directly applied and cured to form a separator, or when a composite electrode is prepared, the amount of monomer applied is increased and cured to form the surface layer on the coated surface as a separator layer. Either method can easily and inexpensively produce a lithium battery. In this case, as described above, the monomer solution contains an electrolytic solution containing a lithium salt and an organic solvent.
【００３０】[0030]
【実施例】以下、本発明を実施例によってさらに具体的
に説明する。正極用ベースフィルムは、コバルト酸リチ
ウムＬｉＣｏＯ2 ７６重量部、アセチレンブラック８．
４重量部、および平均分子量４×１０6 のＰＥＯ３．１
重量部を混合したものに、体積比率５０：５０のＥＣ／
ＰＣの混合溶媒に１Ｍ／ｌのＬｉＰＦ6 を溶かした電解
液１２．５重量部およびアセトニトリル６５重量部を加
え攪拌して得た混合物を、アルミニウム極板上に印刷
し、アセトニトリルを乾燥した後、極板ごと約２００ｋ
ｇ／ｃｍ2 でプレスして作成した。モノマー溶液は、そ
れぞれ溶液全体に対して、下記式（７）に示す三官能性
エチレンオキシドのアクリレート（分子量約１，６０
０）を１４．５重量％、前記電解液８０重量％、および
重合開始剤としてのメチルベンゾイルホルメート０．５
重量％を混合溶解して得た。この溶液を前記のベースフ
ィルム上に塗布して、約１５分放置後、高圧水銀灯によ
り窒素雰囲気下で約１０Ｊ／ｃｍ2 のエネルギー量の紫
外線を照射して正極複合電極を得た。銅箔極板上にリチ
ウム金属を圧着して負極とし、セパレータとして前記モ
ノマー溶液を無蛍光ガラスに挟んで約８Ｊ／ｃｍ2 のエ
ネルギー量の紫外線を照射し、架橋させて得たフィルム
を用いて、正極複合電極と組み合わせて平板型電池（約
３×４ｃｍ）を作成した。この電池を２５℃、０．５ｍ
Ａで４．２Ｖまで充電後、同じく０．５ｍＡで３．０Ｖ
まで放電を繰り返す所謂充放電試験を行なった結果を図
１に示す。この図から良好な充放電特性が得られている
ことがわかる。EXAMPLES The present invention will be described in more detail below with reference to examples. The base film for the positive electrode was 76 parts by weight of lithium cobalt oxide LiCoO 2 , and acetylene black 8.
4 parts by weight and PEO 3.1 having an average molecular weight of 4 × 10 6 .
A mixture of parts by weight and a volume ratio of 50:50 EC /
A mixture obtained by adding 12.5 parts by weight of an electrolytic solution in which 1 M / l LiPF 6 was dissolved in a mixed solvent of PC and 65 parts by weight of acetonitrile and stirring the mixture was printed on an aluminum electrode plate, and after drying acetonitrile, About 200k per electrode plate
It was made by pressing at g / cm 2 . The monomer solution was a trifunctional ethylene oxide acrylate (molecular weight of about 1,60) represented by the following formula (7) with respect to the entire solution.
0) 14.5% by weight, the electrolytic solution 80% by weight, and methyl benzoyl formate 0.5 as a polymerization initiator.
It was obtained by mixing and dissolving wt%. This solution was applied on the above base film, left for about 15 minutes, and then irradiated with ultraviolet rays having an energy amount of about 10 J / cm 2 in a nitrogen atmosphere by a high pressure mercury lamp to obtain a positive electrode composite electrode. Using a film obtained by crosslinking lithium metal on a copper foil electrode plate as a negative electrode, irradiating ultraviolet rays with an energy amount of about 8 J / cm 2 by sandwiching the monomer solution in a non-fluorescent glass as a separator and crosslinking the same. A flat plate type battery (about 3 × 4 cm) was prepared by combining with a positive electrode composite electrode. This battery at 25 ℃, 0.5m
After charging to 4.2V with A, 3.0V with 0.5mA.
FIG. 1 shows the result of a so-called charge / discharge test in which discharge is repeated up to. From this figure, it can be seen that good charge and discharge characteristics are obtained.
【００３１】[0031]
【化７】 [Chemical 7]
【００３２】[0032]
【発明の効果】以上説明したように、本発明によって、
簡易な構造で安価な、高信頼性のリチウム電池を提供す
ることができる。As described above, according to the present invention,
It is possible to provide an inexpensive and highly reliable lithium battery with a simple structure.
【図１】本発明の実施例で得られたリチウム電池の充放
電特性を示す説明図である。FIG. 1 is an explanatory diagram showing charge / discharge characteristics of a lithium battery obtained in an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｂ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location H01M 10/40 H01M 10/40 B
Claims (3)
備えたリチウム電池において、 正極および負極の少なくとも一方が、ポリエチレンオキ
シド（ＰＥＯ）および活物質を含むベースフィルムに、
光重合性モノマーを含んだ電解液を塗布し含浸させた
後、光を照射して、光重合性モノマーを重合させてなる
複合電極であることを特徴とするリチウム電池。1. A lithium battery comprising a positive electrode, a negative electrode, and a solid polymer electrolyte, wherein at least one of the positive electrode and the negative electrode is a base film containing polyethylene oxide (PEO) and an active material,
A lithium battery, which is a composite electrode obtained by applying an electrolytic solution containing a photopolymerizable monomer and impregnating it, and then irradiating light to polymerize the photopolymerizable monomer.
び活物質に加えて、さらにリチウム塩および有機溶媒か
らなる電解液を含有するものであることを特徴とする請
求項１記載のリチウム電池。2. The lithium battery according to claim 1, wherein the base film further contains an electrolytic solution containing a lithium salt and an organic solvent in addition to the PEO and the active material.
シド鎖を有するポリエーテルのアクリレートまたはメタ
クリレートであることを特徴とする請求項１または２記
載のリチウム電池。3. The lithium battery according to claim 1, wherein the photopolymerizable monomer is an acrylate or methacrylate of a polyether having an ethylene oxide chain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7200625A JPH0950802A (en) | 1995-08-07 | 1995-08-07 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7200625A JPH0950802A (en) | 1995-08-07 | 1995-08-07 | Lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0950802A true JPH0950802A (en) | 1997-02-18 |
Family
ID=16427495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7200625A Pending JPH0950802A (en) | 1995-08-07 | 1995-08-07 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0950802A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773166A (en) * | 1995-11-28 | 1998-06-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| JPH11238503A (en) * | 1998-02-20 | 1999-08-31 | Yuasa Corp | Nonaqueous electrolyte secondary battery |
| JP2002033129A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | High polymer solid electrolyte and secondary battery |
| US6358646B1 (en) * | 1998-01-27 | 2002-03-19 | Yuasa Corporation | Method of making a flat type lithium secondary battery and electrode |
| WO2002035636A1 (en) * | 2000-10-20 | 2002-05-02 | Dainippon Ink And Chemicals, Inc. | Solid polymer electrolyte and cell containing the electrolyte |
| KR100388904B1 (en) * | 2000-09-22 | 2003-06-25 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| WO2004040674A1 (en) * | 2002-10-31 | 2004-05-13 | Zeon Corporation | Solid electrolyte composition, cathode film for battery, and method for manufacturing same |
| KR100440830B1 (en) * | 2002-10-11 | 2004-07-19 | 새한에너테크 주식회사 | Structure of gel-type polymer electrolyte for lithium ion polymer batteries |
| JP2005285416A (en) * | 2004-03-29 | 2005-10-13 | Hitachi Ltd | Electrode for polymer electrolyte secondary battery and polymer electrolyte secondary battery |
| JP2006522441A (en) * | 2003-03-07 | 2006-09-28 | バスキャップ | Method for producing composite material for electrode |
| US20140186704A1 (en) * | 2011-05-23 | 2014-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Lithium ion secondary battery electrode, manufacturing process for the same, and lithium ion secondary battery using the electrode |
-
1995
- 1995-08-07 JP JP7200625A patent/JPH0950802A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773166A (en) * | 1995-11-28 | 1998-06-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
| US6358646B1 (en) * | 1998-01-27 | 2002-03-19 | Yuasa Corporation | Method of making a flat type lithium secondary battery and electrode |
| JPH11238503A (en) * | 1998-02-20 | 1999-08-31 | Yuasa Corp | Nonaqueous electrolyte secondary battery |
| JP2002033129A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | High polymer solid electrolyte and secondary battery |
| KR100388904B1 (en) * | 2000-09-22 | 2003-06-25 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| WO2002035636A1 (en) * | 2000-10-20 | 2002-05-02 | Dainippon Ink And Chemicals, Inc. | Solid polymer electrolyte and cell containing the electrolyte |
| KR100440830B1 (en) * | 2002-10-11 | 2004-07-19 | 새한에너테크 주식회사 | Structure of gel-type polymer electrolyte for lithium ion polymer batteries |
| WO2004040674A1 (en) * | 2002-10-31 | 2004-05-13 | Zeon Corporation | Solid electrolyte composition, cathode film for battery, and method for manufacturing same |
| JP2006522441A (en) * | 2003-03-07 | 2006-09-28 | バスキャップ | Method for producing composite material for electrode |
| JP4939927B2 (en) * | 2003-03-07 | 2012-05-30 | バスキャップ | Method for producing composite material for electrode |
| JP2005285416A (en) * | 2004-03-29 | 2005-10-13 | Hitachi Ltd | Electrode for polymer electrolyte secondary battery and polymer electrolyte secondary battery |
| JP4492177B2 (en) * | 2004-03-29 | 2010-06-30 | 日油株式会社 | Electrode for polymer electrolyte secondary battery and polymer electrolyte secondary battery |
| US20140186704A1 (en) * | 2011-05-23 | 2014-07-03 | Kabushiki Kaisha Toyota Jidoshokki | Lithium ion secondary battery electrode, manufacturing process for the same, and lithium ion secondary battery using the electrode |
| US9337477B2 (en) * | 2011-05-23 | 2016-05-10 | Kabushiki Kaisha Toyota Jidoshokki | Lithium secondary battery electrode including coated layer having acrylic copolymer chemically bonded to binder of active material layer and manufacturing process for the same |
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