JP3030053B2 - Rechargeable battery - Google Patents
Rechargeable batteryInfo
- Publication number
- JP3030053B2 JP3030053B2 JP2131673A JP13167390A JP3030053B2 JP 3030053 B2 JP3030053 B2 JP 3030053B2 JP 2131673 A JP2131673 A JP 2131673A JP 13167390 A JP13167390 A JP 13167390A JP 3030053 B2 JP3030053 B2 JP 3030053B2
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- negative electrode
- conductive polymer
- component
- elastomer
- 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.)
- Expired - Fee Related
Links
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
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は二次電池に係かり、その負極の構造に関する
ものである。The present invention relates to a secondary battery, and to a structure of a negative electrode thereof.
（ロ）従来の技術 従来の二次電池はリチウム（Li）等のアルカリ金属、
アルカリ土類金属、或るいはアルミニウムのような軽金
属を活物質とする負極と、二酸化マンガン、三酸化モリ
ブデン、五酸化バナジウム、或るいは硫化チタン等を活
物質とする正極とを備えたものであり、例えば負極活物
質であるリチウムの場合、充電の際に負極表面に樹枝状
に析出して成長したリチウムが、正極に接するようにな
り、内部短絡を引き起こしたり、充電によって電析した
活性なLiと電解液が反応してLiの充放電効率が低下し、
充放電サイクルが極めて短くなるという問題点があっ
た。(B) Conventional technology Conventional secondary batteries are alkali metals such as lithium (Li),
It comprises a negative electrode using an alkaline earth metal or a light metal such as aluminum as an active material, and a positive electrode using manganese dioxide, molybdenum trioxide, vanadium pentoxide, or titanium sulfide as an active material. Yes, for example, in the case of lithium, which is a negative electrode active material, lithium that is deposited and grown in a dendritic manner on the surface of the negative electrode during charging comes into contact with the positive electrode, causing an internal short circuit or an active electrodeposited by charging. Li reacts with the electrolyte to reduce the charge and discharge efficiency of Li,
There is a problem that the charge / discharge cycle becomes extremely short.
又、特開平１−225063号公報には負極表面に水酸化リ
チウムの被膜を形成してLi表面を保護し、サイクル特性
を向上する技術が開示され、特開平１−231265号公報に
は負極にPF6やAsF6イオンで予め処理した保護膜を用い
る技術が開示されているが、これらの膜は機械的な強度
に弱く、充放電の繰り返しによって該膜が負極表面から
剥離し、該負極の保護膜としての効果がなくなるという
問題点もあった。JP-A 1-225063 discloses a technique for forming a lithium hydroxide coating on the negative electrode surface to protect the Li surface and improve cycle characteristics, and JP-A 1-231265 discloses a technique for improving the cycle characteristics. Although a technique using a protective film previously treated with PF 6 or AsF 6 ions has been disclosed, these films are weak in mechanical strength, and the film peels off from the surface of the negative electrode due to repeated charge and discharge, and the negative electrode has There is also a problem that the effect as a protective film is lost.
（ハ）発明が解決しようとする課題 本発明が解決しようとする課題は、充放電を繰り返し
ても負極表面からの剥離が生じない負極保護膜を提供
し、該保護膜による負極表面でのLi電析を効果的に抑制
することである。(C) Problems to be Solved by the Invention The problem to be solved by the present invention is to provide a negative electrode protective film that does not peel off from the negative electrode surface even after repeated charging and discharging, and that the protective film allows Li on the negative electrode surface. The purpose is to effectively suppress electrodeposition.
（ニ）課題を解決するための手段 本発明の二次電池は、リチウム等のアルカリ金属、ア
ルカリ土類金属、或るいはアルミニウムのような軽金属
を活物質とする負極と、二酸化マンガン、三酸化モリブ
デン、五酸化バナジウム、或るいは硫化チタン等を活物
質とする正極と、電解液と、セパレータとを備え、前記
負極の表面に近い方から順に第１保護膜、第２保護膜と
し、前記負極を保護する第１保護膜と、エラストマー、
導電性ポリマー或るいはイオン伝導性ポリマーを主成分
とする第２保護膜の少なくとも２層からなる保護膜層、
若しくは、前記負極の表面に形成された、負極を保護す
る第１成分と、エラストマー、導電性ポリマー或るいは
イオン伝導性ポリマーを主成分とする第２成分との複合
保護膜層、とを有するものである。(D) Means for Solving the Problems The secondary battery of the present invention comprises a negative electrode having an active material of an alkali metal such as lithium, an alkaline earth metal, or a light metal such as aluminum, manganese dioxide, and trioxide. A positive electrode having molybdenum, vanadium pentoxide, or titanium sulfide or the like as an active material, an electrolytic solution, and a separator, and a first protective film and a second protective film sequentially from a surface closer to the surface of the negative electrode; A first protective film for protecting the negative electrode, an elastomer,
A protective film layer comprising at least two layers of a second protective film containing a conductive polymer or an ion conductive polymer as a main component,
Alternatively, it has a composite protective film layer formed on the surface of the negative electrode, the first component protecting the negative electrode, and a second component mainly composed of an elastomer, a conductive polymer, or an ion conductive polymer. Things.
上記第１保護膜若しくは第１成分としては、アルカリ
金属、或るいはアルカリ土類金属の塩、酸化物、水酸化
物、更に、燐、ヒ素、アンチモン、ビスマスより選ばれ
る少なくとも１種の化合物よりなるものを使用しうる。As the first protective film or the first component, an alkali metal or an alkaline earth metal salt, oxide, hydroxide, and at least one compound selected from phosphorus, arsenic, antimony, and bismuth Can be used.
一方、上記第２保護膜若しくは第２成分を形成するエ
ラストマーとしては、エチレンとプロピレンとの共重合
体、或るいはエチレンとプロピレンとの非共役ジエンの
共重合体を使用することができる。On the other hand, as the elastomer forming the second protective film or the second component, a copolymer of ethylene and propylene or a copolymer of non-conjugated diene of ethylene and propylene can be used.
更に、上記第２保護膜若しくは第２成分を形成する導
電性ポリマーは、ポリアニリンを使用することができ
る。Furthermore, as the conductive polymer forming the second protective film or the second component, polyaniline can be used.
そして、上記第２保護膜若しくは第２成分を形成する
イオン伝導性ポリマーとしては、ポリエチレンオキサイ
ドにリチウム塩を分散させたものを使用することができ
る。And, as the ion-conductive polymer forming the second protective film or the second component, a polymer obtained by dispersing a lithium salt in polyethylene oxide can be used.
ここで、上記リチウム塩としては、LiClO4、LiAsF6、
LiCF3SO3、LiBF4からなる群より選択された少なくとも
１つのものが好適である。Here, as the lithium salt, LiClO 4 , LiAsF 6 ,
At least one selected from the group consisting of LiCF 3 SO 3 and LiBF 4 is preferred.
（ホ）作用 上記構成を有する本発明電池は、負極の表面が第１保
護膜と第２保護膜からなる保護膜層、若しくは複合保護
膜層により保護されており、充放電サイクルによる活性
なLiの析出が抑えられて、サイクル特性が向上する。(E) Function In the battery of the present invention having the above-described structure, the surface of the negative electrode is protected by a protective film layer composed of the first protective film and the second protective film or a composite protective film layer, and the active Li by the charge / discharge cycle is activated. Is suppressed, and the cycle characteristics are improved.
（ヘ）実施例 以下本発明を図面の実施例に基づき説明する。(F) Embodiment The present invention will be described below based on an embodiment of the drawings.
第１図は本発明の電池の縦断面図を示し、１は本発明
の要旨たる負極であって、Li等のアルカリ金属、アルカ
リ土類金属、或るいはアルミニウムのような軽金属から
成り、例えばLiを活物質とする負極１が負極缶２の内底
面に固着せる負極集電体３に圧着されている。FIG. 1 is a longitudinal sectional view of a battery of the present invention, and 1 is a negative electrode as the gist of the present invention, which is composed of an alkali metal such as Li, an alkaline earth metal, or a light metal such as aluminum. A negative electrode 1 containing Li as an active material is pressure-bonded to a negative electrode current collector 3 fixed to the inner bottom surface of a negative electrode can 2.
又、４は正極であって、二酸化マンガン、三酸化モリ
ブデン、五酸化バナジウム、或るいは硫化チタン等を活
物質とし、例えば活物質としてのマンガン酸化物に、ア
セチレンブラック導電剤と、フッ素樹脂結着剤とを80:1
0:10（重量比）の割合で混合した合剤を成形したもので
あり、正極缶５の内底面に圧接されている。Reference numeral 4 denotes a positive electrode, which contains manganese dioxide, molybdenum trioxide, vanadium pentoxide, or titanium sulfide as an active material. For example, manganese oxide as an active material, an acetylene black conductive agent, and a fluororesin binder are used. 80: 1 with adhesive
It is formed by molding a mixture mixed at a ratio of 0:10 (weight ratio), and is pressed against the inner bottom surface of the positive electrode can 5.
更に、６はポリプロピレン不織布よりなるセパレータ
であって、このセパレータ６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等体積混合溶媒に過
塩素酸リチウムを１モル／溶解した非水電解液が含浸
されている。Further, reference numeral 6 denotes a separator made of a polypropylene non-woven fabric. The separator 6 contains a non-aqueous electrolyte obtained by dissolving lithium perchlorate in an equal volume mixed solvent of propylene carbonate and 1,2-dimethoxyethane at 1 mol / mol. Impregnated.
尚、７は正、負極缶２、５を電気絶縁する絶縁パッキ
ングであり、且つ組立て後の電池寸法は直径25mm、厚み
寸法3.0mmである。Reference numeral 7 denotes an insulating packing for electrically insulating the positive and negative electrode cans 2 and 5, and the dimensions of the battery after assembly are 25 mm in diameter and 3.0 mm in thickness.
次に前記負極１の作成例について説明する。 Next, an example of forming the negative electrode 1 will be described.
［作製例１］ 直径20mm、厚み1mmのLi板を2000ppmの水分を含む第１
保護膜を構成するテトラヒドロフラン（THF）中に５分
間浸漬した後、減圧乾燥し、更に第２保護膜を構成する
エラストマーとしてのエチレンとプロピレンと非共役ジ
エンとの共重合体（EPDM）をパラキシレン中に0.01g/ml
となるように溶解した溶液中に浸漬し、その後再び減圧
乾燥してEPDM膜を形成することによりLi負極１を作製し
た。この作製例の場合、エラストマーを溶解させる溶媒
としてパラキシレンを用いたが、この他にトリクレン、
ベンゼン、トルエン等のエラストマーを溶解、或るいは
膨潤させる溶媒であればよい。[Preparation Example 1] A first Li plate having a diameter of 20 mm and a thickness of 1 mm containing 2000 ppm of water was prepared.
After being immersed in tetrahydrofuran (THF) constituting the protective film for 5 minutes, dried under reduced pressure, and a copolymer of ethylene, propylene and non-conjugated diene (EPDM) as an elastomer constituting the second protective film was para-xylene. 0.01g / ml in
Then, the resultant was immersed in a solution having been dissolved so as to obtain a negative electrode 1 and then dried again under reduced pressure to form an EPDM film. In the case of this production example, paraxylene was used as a solvent for dissolving the elastomer.
Any solvent may be used as long as it dissolves or swells the elastomer such as benzene and toluene.
このようにして作製されたLi保護額はESCAによる分析
によって、厚み寸法100オングストローム程度の水酸化
リチウム膜であることが分かった。またEPDM膜の厚みは
0.5μであった。The Li protection amount fabricated in this manner was analyzed by ESCA and found to be a lithium hydroxide film having a thickness of about 100 angstroms. The thickness of the EPDM film is
0.5μ.
この負極１を用いて作製した電池を本発明電池Ａとす
る。A battery manufactured using the negative electrode 1 is referred to as Battery A of the present invention.
［作製例２］ 直径20mm、厚み寸法1mmのLi板に、EPDMをTHF中に0.01
g/mlとなるように溶解した溶液を塗布し、更に粒径５μ
以下（好ましくは0.5μ以下）の酸化マグネシウム粉末
を分散させた溶液中にEPDMが塗布されたLi板を浸漬する
ことにより、酸化マグネシウムとEPDMの複合膜（複合保
護膜層）が形成されたLi負極１を作製した。こうして作
製された負極１を用いて本発明電池Ｂを組立てた。[Preparation Example 2] EPDM was added to THF on a Li plate having a diameter of 20 mm and a thickness of 1 mm in THF.
g / ml, and apply the solution to it.
Lithium coated with EPDM is immersed in a solution in which magnesium oxide powder of not more than 0.5 μm is dispersed to form a composite film (composite protective film layer) of magnesium oxide and EPDM. A negative electrode 1 was produced. The battery B of the present invention was assembled using the negative electrode 1 thus manufactured.
［作製例３］ 直径20mm、厚み寸法1mmのLi板に、エチレンとプロピ
レンとの共重合体（EPR）をパラキシレン中に0.03g/ml
となるように溶解した溶液を塗布し、その後、炭酸バリ
ウム粉末を該パラキシレンに分散させたペーストを塗布
してEPRと炭酸バリウムとの複合膜（複合保護膜層）を
形成したLi負極１を製作した。そしてこうして作製され
た負極１を用いて本発明電池Ｃを組立てた。[Preparation Example 3] A copolymer of ethylene and propylene (EPR) was added to a Li plate having a diameter of 20 mm and a thickness of 1 mm in para-xylene at 0.03 g / ml.
And then applying a paste obtained by dispersing barium carbonate powder in the para-xylene to form a composite film (composite protective film layer) of EPR and barium carbonate. Made. The battery C of the present invention was assembled using the negative electrode 1 thus produced.
［作製例４］ 5000ppmの５塩化燐を含むTHFを負極保護膜を作製する
材料として使用する以外は、作製例１と同様にしてLi負
極１を得た。この負極１を用いて作製した電池を本発明
電池Ｄとする。[Production Example 4] A Li negative electrode 1 was obtained in the same manner as in Production Example 1 except that THF containing 5000 ppm of phosphorus pentachloride was used as a material for producing a negative electrode protective film. A battery manufactured using this negative electrode 1 is referred to as Battery D of the present invention.
［作製例５］ 1mol/のLiAsF6を含むTHFを負極保護膜を作製する材
料として使用する以外は作製例１と同様にしてLi負極１
を得た。この負極１を用いて作製した電池を本発明電池
Ｅとする。[Production Example 5] A Li negative electrode 1 was produced in the same manner as in Production Example 1 except that THF containing 1 mol / LiAsF 6 was used as a material for producing a negative electrode protective film.
I got A battery manufactured using the negative electrode 1 is referred to as Battery E of the present invention.
［作製例６］ 0.001g/mlの濃度となるようにポリアニリンを溶解し
たＮ−メチル−2,ピロリドン、を負極面上の膜を作製す
る材料として使用する以外は作製例１と同様にしてLi負
極１を得た。[Preparation Example 6] Li was prepared in the same manner as in Preparation Example 1 except that N-methyl-2, pyrrolidone in which polyaniline was dissolved to a concentration of 0.001 g / ml was used as a material for forming a film on the negative electrode surface. A negative electrode 1 was obtained.
この例において前記ポリアニリンのような導電性ポリ
マーを溶解する溶媒としては上記Ｎ−メチル−2,ピロリ
ドンにとらわれることなく、ピロリン、ピロリジン及び
それらの誘導体等の、導電性ポリマーを溶解する溶媒で
あればよい。また、この導電性ポリマーをスラリー状に
し、負極１上に塗布して膜を形成してもよい。In this example, the solvent for dissolving the conductive polymer such as polyaniline is not limited to the above-mentioned N-methyl-2, pyrrolidone, but is a solvent that dissolves the conductive polymer such as pyrroline, pyrrolidine and derivatives thereof. Good. Alternatively, the conductive polymer may be formed into a slurry and applied on the negative electrode 1 to form a film.
そして、このようにして作製された負極１を用いて組
立てられた電池を本発明電池Ｆとする。The battery assembled using the negative electrode 1 thus produced is referred to as a battery F of the present invention.
［作製例７］ 負極面上の膜としてLiClO4を分散させたポリエチレン
オキサイドを使用する以外は作製例１と同様にしてLi負
極１を得た。このようにして作製した負極を用いて組立
てた電池を本発明電池Ｇとする。[Production Example 7] A Li negative electrode 1 was obtained in the same manner as in Production Example 1, except that polyethylene oxide in which LiClO 4 was dispersed was used as a film on the negative electrode surface. The battery assembled using the negative electrode thus manufactured is referred to as Battery G of the present invention.
［比較例１］ 負極１として未処理のLi（直径20mm、厚み寸法1mm）
を用いて作製した電池を比較電池Ｈとする。[Comparative Example 1] Untreated Li (diameter 20 mm, thickness 1 mm) as negative electrode 1
A battery manufactured using the above is referred to as a comparative battery H.
［比較例２］ 直径20mm、厚み寸法1mmのLi板を2000ppmの水分を含む
テトラヒドロフラン（THF）中に５分間浸漬した後、減
圧乾燥してLi保護膜を作製したLiを用いて組立てた電池
を比較電池Ｉとする。[Comparative Example 2] A Li plate having a diameter of 20 mm and a thickness of 1 mm was immersed in tetrahydrofuran (THF) containing 2,000 ppm of water for 5 minutes, and then dried under reduced pressure to form a Li protective film. Let it be a comparative battery I.
次に前記エラストマー、導電性ポリマー、イオン伝導
性ポリマーを主成分とする膜の最適厚み寸法を検討する
ために作製例１においてパラキシレン中のEPDM濃度、及
び処理回数を変化させ、厚み寸法が0.005〜100μまでの
膜を形成した負極１を作製し、サイクル特性、及び1mA/
cm2の放電電流密度で放電したときの放電容量を測定し
た。Next, the EPDM concentration in para-xylene and the number of treatments were changed in Production Example 1 in order to examine the optimal thickness of the film containing the elastomer, the conductive polymer, and the ion-conductive polymer as main components. A negative electrode 1 on which a film of up to 100 μm was formed was prepared, and cycle characteristics and 1 mA /
The discharge capacity when discharging at a discharge current density of cm 2 was measured.
第２図は上記各電池Ａ〜Ｉのサイクル特性を示すもの
で、横軸にサイクル数、縦軸に各サイクル毎の放電終止
電圧をプロットしている。そしてこの時の試験条件は放
電容量20mAhとし、充電は3mAで3.5Vを終止電圧とした。FIG. 2 shows the cycle characteristics of each of the batteries A to I. The number of cycles is plotted on the horizontal axis, and the discharge end voltage for each cycle is plotted on the vertical axis. The test conditions at this time were a discharge capacity of 20 mAh, a charge of 3 mA, and a final voltage of 3.5 V.
かかる第２図において、本発明電池Ａ〜Ｇはサイクル
数250回でも高い放電終止電圧略2.8Vを示すが、比較電
池Ｉでは略180サイクル目から放電終止電圧の降下が見
られ、また、比較電池Ｈではもっと悪く、略80サイクル
目から放電終止電圧の降下が見られる。In FIG. 2, the batteries A to G of the present invention show a high end-of-discharge voltage of about 2.8 V even at 250 cycles, but the comparative battery I shows a drop in the end-of-discharge voltage from about the 180th cycle. In the case of the battery H, the discharge end voltage dropped from about the 80th cycle.
この理由は負極保護膜がLiと電解液との反応を抑制
し、しかも該保護膜が負極の充放電により剥離すること
を、エラストマーを主成分とする膜、或るいは導電性ポ
リマー、或るいはイオン伝導性ポリマー主成分とする膜
が抑制するので、保護膜自身の効果を損なうことがでな
くなったためであり、結果としてサイクル特性が向上し
たものと考えられる。The reason for this is that the negative electrode protective film suppresses the reaction between Li and the electrolytic solution, and that the protective film is peeled off by the charge and discharge of the negative electrode by a film containing an elastomer as a main component, a conductive polymer, or This is because the effect of the protective film itself was not impaired because the film containing the ion-conductive polymer as a main component was suppressed, and as a result, it is considered that the cycle characteristics were improved.
第３図は前記EDPM膜の厚みを変化させてサイクル特性
（日換算）、及び放電特性を測定したものである。FIG. 3 shows the results obtained by measuring the cycle characteristics (in terms of days) and the discharge characteristics while changing the thickness of the EDPM film.
この場合EDPM膜のようなエラストマーの膜厚が、0.01
〜10μの時に最も放電容量の減少が少なく、しかもサイ
クル特性が優れている。In this case, the thickness of the elastomer such as the EDPM film is 0.01
When it is 10 μm, the decrease in the discharge capacity is the smallest, and the cycle characteristics are excellent.
この理由は、エラストマー膜が薄い時には、この膜に
よって充放電による負極保護膜の剥離を十分に抑制でき
ず、サイクル特性の向上が望めないからである。一方、
エラストマー膜が厚い時には組み立てられた電池自身の
内部抵抗が上昇するので放電容量が減少するためであ
る。The reason for this is that when the elastomer film is thin, the film cannot sufficiently prevent the negative electrode protective film from being peeled off due to charge and discharge, and thus the cycle characteristics cannot be improved. on the other hand,
This is because when the elastomer film is thick, the internal resistance of the assembled battery itself increases, so that the discharge capacity decreases.
尚、上記の実施例において、負極活物質としてリチウ
ムを例示したが、Li−Al合金や、Li−Pb合金、Li−易融
合金、Li−ウッド合金、Li−Ｂ合金等のLi合金、或るい
はLi−カーボン化合物、或るいはその他のアルカリ金
属、アルカリ土類金属、及びその合金でもよい。In the above embodiment, lithium was exemplified as the negative electrode active material.However, a Li-Al alloy, a Li-Pb alloy, a Li-fusible alloy, a Li-wood alloy, a Li-alloy such as a Li-B alloy, or Or a Li-carbon compound, or other alkali metals, alkaline earth metals, and alloys thereof.
（ト）発明の効果 本発明は、以上詳述したとおり、負極の表面が第１保
護膜と第２保護膜からなる保護膜層により保護されてい
るので、第１保護膜による負極の保護効果を第２保護膜
によって維持することができる。または、負極の表面に
形成された第１成分によって負極を保護する効果を、エ
ラストマー、導電性ポリマー或るいはイオン伝導性ポリ
マーを主成分とする第２成分とで複合化を図る、即ち複
合保護膜層とすることにより、維持することができる。
この結果、優れたサイクル特性、及び放電容量特性を有
する電池を作製することが可能となる。(G) Advantageous Effects of the Invention As described in detail above, the present invention protects the surface of the negative electrode with the protective film layer composed of the first protective film and the second protective film. Can be maintained by the second protective film. Alternatively, the effect of protecting the negative electrode by the first component formed on the surface of the negative electrode can be combined with the second component containing an elastomer, a conductive polymer, or an ion-conductive polymer as a main component. It can be maintained by forming a film layer.
As a result, a battery having excellent cycle characteristics and discharge capacity characteristics can be manufactured.
第１図は本発明電池の概略を示す縦断面図、第２図は本
発明電池Ａ〜Ｇと比較電池Ｈ、Ｉとのサイクル特性を比
較した図、第３図は第２保護膜の厚みとサイクル特性、
及び放電容量特性との関係を示す図である。 １……負極、 ２……負極缶、 ４……正極、 ５……正極缶、 ６……セパレータ、 ７……絶縁パッキング。1 is a longitudinal sectional view schematically showing a battery of the present invention, FIG. 2 is a diagram comparing cycle characteristics of batteries A to G of the present invention and comparative batteries H and I, and FIG. 3 is a thickness of a second protective film. And cycle characteristics,
FIG. 4 is a diagram showing a relationship between the discharge capacity and the discharge capacity characteristics. 1 ... Negative electrode, 2 ... Negative electrode can, 4 ... Positive electrode, 5 ... Positive electrode can, 6 ... Separator, 7 ... Insulating packing.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−873（ＪＰ，Ａ) 特開 昭63−241066（ＪＰ，Ａ) 特開 平１−186754（ＪＰ，Ａ) 特開 平２−79375（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 4/02 - 4/04 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-873 (JP, A) JP-A-63-241066 (JP, A) JP-A-1-186754 (JP, A) JP-A-2- 79375 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 10/40 H01M 4/02-4/04
Claims (7)
金属、或るいはアルミニウムのような軽金属を活物質と
する負極と、二酸化マンガン、三酸化モリブデン、五酸
化バナジウム、或るいは硫化チタン等を活物質とする正
極と、電解液と、セパレータとを備え、 前記負極の表面に近い方から順に第１保護膜、第２保護
膜とし、前記負極を保護する第１保護膜と、エラストマ
ー、導電性ポリマー或るいはイオン伝導性ポリマーを主
成分とする第２保護膜の少なくとも２層からなる保護膜
層、 若しくは、前記負極の表面に形成された、負極を保護す
る第１成分と、エラストマー、導電性ポリマー或るいは
イオン伝導性ポリマーを主成分とする第２成分との複合
保護膜層、 とを有する二次電池。1. A negative electrode having an active material of an alkali metal such as lithium, an alkaline earth metal, or a light metal such as aluminum, and manganese dioxide, molybdenum trioxide, vanadium pentoxide, or titanium sulfide. A positive electrode as an active material, an electrolytic solution, and a separator; a first protective film, a second protective film, and a first protective film for protecting the negative electrode in order from a surface closer to the surface of the negative electrode; an elastomer; A protective film layer composed of at least two layers of a second protective film containing a conductive polymer or an ion conductive polymer as a main component, or a first component formed on the surface of the negative electrode for protecting the negative electrode, and an elastomer, A composite protective film layer comprising a conductive polymer or an ion-conductive polymer and a second component having a main component.
カリ金属、或るいはアルカリ土類金属の塩、酸化物、水
酸化物より形成される上記請求項記載の二次電池。2. The secondary battery according to claim 1, wherein the first protective film or the first component is formed of a salt, oxide, or hydroxide of an alkali metal or an alkaline earth metal.
ヒ素、アンチモン、ビスマスより選ばれる少なくとも１
種の化合物より形成される上記請求項記載の二次電
池。3. The method according to claim 1, wherein the first protective film or the first component comprises phosphorus,
At least one selected from arsenic, antimony, and bismuth
The rechargeable battery according to claim 1, wherein the rechargeable battery is formed from a kind of compound.
るエラストマーは、エチレンとプロピレンとの共重合
体、或るいはエチレンとプロピレンとの非共役ジエンの
共重合体より成る上記請求項記載の二次電池。4. The method according to claim 1, wherein the elastomer forming the second protective film or the second component comprises a copolymer of ethylene and propylene, or a copolymer of a non-conjugated diene of ethylene and propylene. Rechargeable battery.
る導電性ポリマーは、ポリアニリンである上記請求項
記載の二次電池。5. The secondary battery according to claim 1, wherein the conductive polymer forming the second protective film or the second component is polyaniline.
るイオン伝導性ポリマーは、ポリエチレンオキサイドに
リチウム塩を分散させたものである上記請求項記載の
二次電池。6. The secondary battery according to claim 1, wherein the ion conductive polymer forming the second protective film or the second component is obtained by dispersing a lithium salt in polyethylene oxide.
3SO3、LiBF4からなる群より選択された少なくとも１つ
のものである上記請求項記載の二次電池。7. The lithium salt is LiClO 4 , LiAsF 6 , LiCF
3 SO 3, the secondary battery of the preceding claims, wherein at least one of those selected from the group consisting of LiBF 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131673A JP3030053B2 (en) | 1990-05-22 | 1990-05-22 | Rechargeable battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131673A JP3030053B2 (en) | 1990-05-22 | 1990-05-22 | Rechargeable battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0428172A JPH0428172A (en) | 1992-01-30 |
| JP3030053B2 true JP3030053B2 (en) | 2000-04-10 |
Family
ID=15063554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131673A Expired - Fee Related JP3030053B2 (en) | 1990-05-22 | 1990-05-22 | Rechargeable battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3030053B2 (en) |
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| KR101580995B1 (en) | 2013-06-19 | 2015-12-29 | 삼성전자주식회사 | Lithium ion conductive protecting film, preparing method thereof and lithium air electrochemical battery using the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0428172A (en) | 1992-01-30 |
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