JPS62254302A - Lithium ion conducting polymer electrolyte - Google Patents
Lithium ion conducting polymer electrolyteInfo
- Publication number
- JPS62254302A JPS62254302A JP61097528A JP9752886A JPS62254302A JP S62254302 A JPS62254302 A JP S62254302A JP 61097528 A JP61097528 A JP 61097528A JP 9752886 A JP9752886 A JP 9752886A JP S62254302 A JPS62254302 A JP S62254302A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymer electrolyte
- lithium
- lithium ion
- molecule
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 21
- 229920001940 conductive polymer Polymers 0.000 title claims description 11
- 239000003792 electrolyte Substances 0.000 title description 11
- 239000002322 conducting polymer Substances 0.000 title 1
- 239000005518 polymer electrolyte Substances 0.000 claims description 36
- 150000002596 lactones Chemical group 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102100030393 G-patch domain and KOW motifs-containing protein Human genes 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013115 LiBFn Inorganic materials 0.000 description 1
- -1 LiPFh Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003180 beta-lactone group Chemical group 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000422 delta-lactone group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Primary Cells (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明はリチウム電池、エレクトロクロミックディス
プレイなどの電解質やリチウムイオン濃度センサー、リ
チウムイオン分離膜などの用に供されるリチウムイオン
伝導性ポリマー電解質に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a lithium ion conductive polymer electrolyte used for electrolytes such as lithium batteries and electrochromic displays, lithium ion concentration sensors, and lithium ion separation membranes. .
リチウム電池用などのリチウムイオン伝導性電解質とし
ては、Ｌ ｉ Ｃ１０ａ −炭酸プロピレンに代表され
るような液体電解質や、Ｌｉ３Ｎ、Ｌｉｌ−Ａｌ□０３
に代表されるような固体電解質が知られているが、最近
では柔軟性のあるフィルム状物に成形することが容易な
有機ポリマーをペースとしたポリマー電解質を用いる試
みがなされている。Lithium ion conductive electrolytes for lithium batteries include liquid electrolytes such as LiC10a-propylene carbonate, Li3N, Lil-Al□03
Although solid electrolytes such as those typified by are known, recently attempts have been made to use polymer electrolytes based on organic polymers that can be easily formed into flexible film-like materials.
この種のポリマー電解質は、これを超薄型化や小型化が
要請されているリチウム電池に適用すれば、電池作製の
ための作業性や封止の信頼性の面で有利となり、また低
コスト化にも役立つという利点がある。また、その柔軟
性によってリチウムイオン分離膜として賞月でき、さら
にエレクトロクロミックディスプレイなどの電解質やリ
チウムイオン濃度センサーなどとしても有用である。If this type of polymer electrolyte is applied to lithium batteries, which are required to be ultra-thin and compact, it will be advantageous in terms of workability and sealing reliability for battery production, and will also be low cost. It also has the advantage of being useful. In addition, its flexibility makes it useful as a lithium ion separation membrane, and it is also useful as an electrolyte in electrochromic displays and as a lithium ion concentration sensor.
従来、このようなポリマー電解質としては、有機ポリマ
ーとしてポリエチレンオキサイドを使用し、これとリチ
ウム塩との複合体としたものが知られている程度である
（Ｆａｓｔ Ｉｏｎ Ｔｒａｎｓｐｏｒｔ ｉｎ
５ｏｌｉｄ Ｐ１３１（１９７９））。Conventionally, the only known polymer electrolyte is a composite of polyethylene oxide as an organic polymer and lithium salt (Fast Ion Transport in
5olid P131 (1979)).
しかるに、上記従来公知のポリマー電解質は、リチウム
イオン伝導性にやや劣り、室温下で用いられることがほ
とんどのリチウム電池や前記各種用途に応用したとき、
その性能上充分に満足できないという問題があった。し
がも、有機ポリマーとしてのポリエチレンオキサイドは
その分子末端に水酸基を有しているため、これがリチウ
ムと反応するおそれがあり、この点でも満足できるもの
とはいえなかった。However, the conventionally known polymer electrolytes described above have somewhat poor lithium ion conductivity, and when applied to lithium batteries, which are mostly used at room temperature, and the various uses mentioned above,
There was a problem in that the performance was not fully satisfactory. However, since polyethylene oxide as an organic polymer has a hydroxyl group at the end of its molecule, there is a risk that this may react with lithium, and in this respect as well, it could not be said to be satisfactory.
したがって、この発明は、上記従来の有機ポリマーとは
異なる特定のポリマーを探究することにより、リチウム
イオン伝導性にすぐれかつリチウムと反応するおそれの
ない前記種々の用途に有利に適用することのできるポリ
マー電解質を提供することを目的としている。Therefore, by searching for a specific polymer different from the above-mentioned conventional organic polymers, the present invention aims to create a polymer that has excellent lithium ion conductivity and is free from the risk of reacting with lithium and can be advantageously applied to the various uses mentioned above. Its purpose is to provide electrolytes.
この発明者らは、上記の目的を達成するために鋭意検討
した結果、ポリマー電解質を構成させる有機ポリマーと
して分子内にラクトン構造を有するポリマーを用いたと
きには、リチウムイオン伝導性に非常にすぐれる、特に
室温下でも各種用途に応用可能な良好なイオン伝導性を
示し、しかもリチウムとの反応のおそれのない電解質が
得られることを知り、この発明を完成するに至った。As a result of intensive studies to achieve the above object, the inventors found that when a polymer having a lactone structure in the molecule is used as the organic polymer constituting the polymer electrolyte, it has extremely excellent lithium ion conductivity. In particular, the present invention was completed after learning that an electrolyte can be obtained that exhibits good ionic conductivity that can be applied to various uses even at room temperature, and that is free from the risk of reaction with lithium.
すなわち、この発明は、リチウム塩と有機ポリマーの複
合体からなるリチウムイオン伝導性ポリマー電解質にお
いて、上記の有機ポリマーが分子内にラクトン構造を有
するポリマーからなることを特徴とするリチウムイオン
伝勇性ポリマー電解質に係るものである。That is, the present invention provides a lithium ion conductive polymer electrolyte comprising a composite of a lithium salt and an organic polymer, wherein the organic polymer is a polymer having a lactone structure in the molecule. It is related to electrolytes.
この発明において用いられる分子内にラクトン構造を有
するポリマーとしては、ラクトン構造が側鎖中に存在す
るものと主鎖中に存在するもののいずれをも使用可能で
ある。しかし、製造および入手の容易さの面から通常は
前者のラクトン構造が側鎖中に存在するポリマーが用い
られる。これらポリマーは、その数平均分子量が３，０
００〜５ｏｏ、ｏｏｏの範囲にある常温下で固体状ない
し半固体状となるものである。As the polymer having a lactone structure in the molecule used in this invention, it is possible to use either a polymer in which the lactone structure is present in the side chain or a polymer in which the lactone structure is present in the main chain. However, from the viewpoint of ease of production and availability, the former polymer in which a lactone structure is present in the side chain is usually used. These polymers have a number average molecular weight of 3.0
It becomes solid or semi-solid at room temperature in the range of 00 to 5oo, ooo.
なお、これらポリマーのラクトン構造は、環状構造中に
−Ｃ０−０−を含むものであればよく、環を構成する原
子数はとくに限定されないが、たとえばプロピオラクト
ン（β−ラクトン）構造、ブチロラクトン（γ−ラクト
ン）構造、バレロラクトン（δ−ラクトン）構造などの
６員環以下のものが好適である。The lactone structure of these polymers may have -C0-0- in the cyclic structure, and the number of atoms constituting the ring is not particularly limited. For example, propiolactone (β-lactone) structure, butyrolactone structure, etc. (γ-lactone) structure, valerolactone (δ-lactone) structure and the like are preferably 6-membered rings or less.
この発明において特に好適なラクトン構造が側鎖中に存
在するポリマーの代表例としては、分子内にビニル基を
含むラクトンの単独重合体、ならびに上記ラクトンとこ
れと共重合可能な他のモノマーとの共重合体が挙げられ
る。上記の分子内にビニル基を含むラクトンとしては、
環を構成する原子数およびビニル基の結合位置が種々異
なるものを使用できるが、特に好ましい例として３−ビ
ニル−１・４−ブチロラクトンおよび４−ビニルト４−
ブチロラクトンがある。また、共重合可能な他のモノマ
ーとしては、（メタ）アクリロニトリルやアルキル基の
炭素数が通常１〜４程度のメタクリル酸アルキルエステ
ルなどの各種モノマーが挙げられる。これら共重合可能
なモノマーの使用割合はモノマー全体の７０モル％以下
となる範囲がよく、この割合が多くなりすぎるとラクト
ン構造による既述利点が充分に発揮されなくなる。Typical examples of polymers in which a lactone structure is present in the side chain, which are particularly suitable for the present invention, include homopolymers of lactones containing vinyl groups in the molecule, and monopolymers of lactones and other monomers copolymerizable with the lactones. Examples include copolymers. The above lactones containing a vinyl group in the molecule include:
Rings with various numbers of atoms and vinyl group bonding positions can be used, but particularly preferred examples include 3-vinyl-1,4-butyrolactone and 4-vinyl-4-
There's butyrolactone. Other copolymerizable monomers include various monomers such as (meth)acrylonitrile and methacrylic acid alkyl esters in which the alkyl group usually has about 1 to 4 carbon atoms. The proportion of these copolymerizable monomers used is preferably 70 mol% or less of the total monomers; if this proportion is too large, the above-mentioned advantages of the lactone structure will not be sufficiently exhibited.
゛ この発明において上記の分子内にラクトン構造を有
するポリマーとともにポリマー電解質を構成させるリチ
ウム塩としては、従来のポリマー電解質に用いられてい
るものがいずれも使用可能であり、その具体例としては
ＬｉＢφ、（φはフェニル基を意味する）やそのジメト
キシエタン付加物、ＬｉＢＦｎ 、ＬｉＰＦｈ、ＬｉＣ
Ｆ３ ＳＯａ 、ＬｉＡｓＦ、などが挙げられる。この
リチウム塩の使用量は、ポリマー中のラクトン構造部分
を構成するモノマー（ビニル基を含むラクトン）単位１
モルに対して通常０．０５〜１．０モル、特に好適には
０．０８〜０．４モルの範囲にあるのがよい。゛ In this invention, any of the lithium salts used in conventional polymer electrolytes can be used as the lithium salt that constitutes the polymer electrolyte together with the polymer having a lactone structure in the molecule, and specific examples include LiBφ, (φ means phenyl group) and its dimethoxyethane adducts, LiBFn, LiPFh, LiC
Examples include F3SOa, LiAsF, and the like. The amount of lithium salt used is 1 unit of monomer (lactone containing a vinyl group) constituting the lactone structure in the polymer.
The amount is generally 0.05 to 1.0 mol, particularly preferably 0.08 to 0.4 mol.
この発明のポリマー電解質は、上記の分子内にラクトン
構造を有するポリマーとリチウム塩との複合体としたも
のであるが、この複合体を得るための一般的手段として
は、上記の両成分を適宜の有機溶媒に溶解した溶液を調
製したのちに有機溶媒を連敗除去する方法がある。この
方法においては、上記溶液とした状態で分子内にラクト
ン構造を有するポリマーの分子鎖にリチウム塩が錯体的
に結合し、溶媒除去後も上記結合が保たれた複合体が得
られるものである。The polymer electrolyte of the present invention is a composite of the above-mentioned polymer having a lactone structure in its molecule and a lithium salt. As a general means for obtaining this composite, both of the above-mentioned components are suitably combined. There is a method in which a solution is prepared by dissolving the organic solvent in an organic solvent, and then the organic solvent is continuously removed. In this method, the lithium salt is bound in a complex manner to the molecular chain of the polymer having a lactone structure in the molecule in the above-mentioned solution state, and a complex is obtained in which the above-mentioned bond is maintained even after the solvent is removed. .
この複合体の形態は、用途目的や分子内にラクトン構造
を有するポリマーの性状などに応じて適宜決められる。The form of this composite is appropriately determined depending on the purpose of use and the properties of the polymer having a lactone structure in the molecule.
たとえば、リチウム電池用のポリマー電解質としてこの
電解質で正負両極間のセパレータを兼備させる場合は、
上記複合体単独からなるシート状物とするか、これにア
ルミナなどの充填剤を含ませたシート状物や上記複合体
を不織布などの支持体に保持させたシート状物とすれば
よい。これらのシート状物はいずれも柔軟性を有するも
のである。For example, if you want to use this electrolyte as a separator between the positive and negative electrodes as a polymer electrolyte for lithium batteries,
It may be a sheet-like product made of the above-described composite alone, a sheet-like product containing a filler such as alumina, or a sheet-like product in which the above-described composite is held on a support such as a nonwoven fabric. All of these sheet-like materials have flexibility.
上記のシート状物のうち複合体単独からなるものは、前
記溶液を適宜の厚みで流延したのち溶媒を連敗除去する
ことにより得られる。また、充填剤含有のシート状物は
前記溶液に充填剤を混入させる以外は上記同様にして得
られる。さらに、支持体付きのシート状物は前記溶液を
支持体に含浸させたのち溶媒を除去することにより得る
ことができる。後二者のシート状物は分子内にラクトン
構造を有するポリマーが半固体状でその形状保持性に劣
る場合の通常形態として採用されるものである。Among the above-mentioned sheet-like products, those made of the composite alone can be obtained by casting the solution to an appropriate thickness and then continuously removing the solvent. Further, a sheet-like material containing a filler can be obtained in the same manner as described above except that the filler is mixed into the solution. Further, a sheet-like article with a support can be obtained by impregnating the support with the solution and then removing the solvent. The latter two sheet-like materials are generally employed when the polymer having a lactone structure in its molecules is semi-solid and has poor shape retention.
また、リチウム電池における正極に適用する場合、前記
溶液に正極活物質などを所定割合で加え、これを成形し
たのち溶媒を連敗除去するかあるいは成形前に連敗除去
しその後成形することにより、前記複合体と正極活物質
などとが混在一体化した成形正極とすることができる。In addition, when applied to a positive electrode in a lithium battery, a positive electrode active material or the like is added to the solution in a predetermined ratio, and after molding the solution, the solvent is continuously removed, or the composite material is removed before molding and then molded. It is possible to form a molded positive electrode in which the body, positive electrode active material, etc. are mixed and integrated.
同様に、リチウムイオン分離膜などの他の用途にあって
は、上記に準じて各用途に応じた種々の形態をとれるも
のである。Similarly, for other uses such as lithium ion separation membranes, various forms can be taken according to the respective uses in accordance with the above.
このような複合体を得るために用いられる有機溶媒は、
分子内にラクトン構造を有するポリマーおよびリチウム
塩を溶解でき、かつ最終的に連敗除去できるものであれ
ば特に限定されない。しかし、微量成分の残存が電池性
能などの劣化をきたさないように複合体の用途目的に応
じて適宜の溶媒を選択するのが望ましい。たとえば、リ
チウム電池用のポリマー電解質にあっては、上記溶媒と
してジメトキシエタン、ジオキソラン、アセトニトリル
、ジメチルフォルムアミドなどの溶媒が好ましく用いら
れる。The organic solvent used to obtain such a complex is
It is not particularly limited as long as it can dissolve a polymer having a lactone structure in its molecule and a lithium salt, and can ultimately be removed continuously. However, it is desirable to select an appropriate solvent depending on the purpose of use of the composite so that residual trace components do not cause deterioration of battery performance. For example, in polymer electrolytes for lithium batteries, solvents such as dimethoxyethane, dioxolane, acetonitrile, and dimethylformamide are preferably used as the solvent.
第１図は上記したこの発明のポリマー電解質を用いたリ
チウム電池の例を示したもので、図中、１はステンレス
鋼からなる方形平板状の正極集電板、２は周辺を一面側
へ段状に折曲して主面と同じ向きの平坦状の周辺部２ａ
を設けたステンレス鋼からなる浅い方形皿状の負掻集電
板、３は両極集電板１．２の対向する周辺部１ａ；２ａ
間を封止した接着剤層である。FIG. 1 shows an example of a lithium battery using the polymer electrolyte of the present invention described above. In the figure, 1 is a rectangular flat positive electrode current collector plate made of stainless steel; A flat peripheral portion 2a that is bent into a shape and facing the same direction as the main surface.
A shallow rectangular dish-shaped negative current collector plate made of stainless steel with
This is an adhesive layer that seals the gap.
４は両極集電板１．２間に構成された空間５内において
正掻集電板１側に配されたこの発明のポリマー電解質と
正極活物質などとを既述した方法にてシート状に成形し
てなる正極、６は空間５内において負極集電板２側に装
填されたリチウムまたはリチウム合金からなる負極、７
は両極４，６間に介在させた前記この発明のポリマー電
解質をこれ単独あるいは充填剤や不織布などとともにシ
ート状に成形してなるセパレータである。Reference numeral 4 denotes a polymer electrolyte of the present invention, a positive electrode active material, etc. arranged on the side of the current collector plate 1 in the space 5 formed between the two electrode current collector plates 1 and 2, which are formed into a sheet shape by the method described above. A positive electrode formed by molding, 6 a negative electrode made of lithium or a lithium alloy loaded on the negative electrode current collector plate 2 side in the space 5, 7
This is a separator formed by forming the polymer electrolyte of the present invention, which is interposed between the two electrodes 4 and 6, alone or together with a filler, a nonwoven fabric, etc. into a sheet shape.
なお、上記正極４は、場合により正極活物質とテフロン
粉末などの結合剤や電子伝導助剤とを混合してシート状
に成形したものなどであってもよい。正極４に用いる正
極活物質としては、Ｔｉ５ｚ ％ Ｍ ＯＳ２ 、Ｖ６
０ｔａ、Ｖ ２０ ｓ 、Ｖ Ｓ ｅ 、Ｎ１Ｐｓｊな
どの１種もしくは２種以上が用いられる。The positive electrode 4 may be formed into a sheet by mixing a positive electrode active material with a binder such as Teflon powder or an electron conduction aid, as the case may be. As the positive electrode active material used for the positive electrode 4, Ti5z% MOS2, V6
One or more of Ota, V 20 s, V S e , N1Psj, etc. are used.
このように構成されるリチウム電池は、セパレータ７が
前記ポリマー電解質からなるシート状物であることによ
り、また正極４が上記電解質を含む同様のシート状物で
あることによって、電池の薄型化や電池作製のための作
業性、封止の信頼性などの向上に寄与させることができ
、また液体電解質のような漏液の心配が本質的になく、
しかも上記電解質がそのイオン伝導性にすぐれまたリチ
ウムとの反応のおそれがないものであることにより、−
次電池としての放電特性や二次電池としての充放電サイ
クル特性に非常にすぐれたものとなる。The lithium battery constructed in this manner has the advantage that the separator 7 is a sheet-like material made of the above polymer electrolyte, and the positive electrode 4 is a similar sheet-like material containing the above-mentioned electrolyte. It can contribute to improving the workability of manufacturing and the reliability of sealing, and there is essentially no fear of leakage like with liquid electrolytes.
Moreover, since the electrolyte has excellent ionic conductivity and there is no possibility of reaction with lithium, -
It has very excellent discharge characteristics as a secondary battery and charge/discharge cycle characteristics as a secondary battery.
以上のとおり、この発明によれば、リチウム塩との複合
体を構成させるための有機ポリマーとして分子内にラク
トン構造を存するポリマーを用いたことにより、リチウ
ムイオン伝導性にすぐれかつリチウムとの反応のおそれ
のないリチウム電池やその他各種の用途に有利に応用で
きるリチウムイオン伝導性ポリマー電解質を提供するこ
とができる。As described above, according to the present invention, by using a polymer having a lactone structure in its molecule as an organic polymer for forming a complex with a lithium salt, it has excellent lithium ion conductivity and is resistant to reaction with lithium. It is possible to provide a lithium ion conductive polymer electrolyte that can be advantageously applied to lithium batteries and various other uses without any fear.
以下に、この発明の実施例を比較例と対比して記述する
。Examples of the present invention will be described below in comparison with comparative examples.
実施例１
ＬｉＢφ４のジメトキシエタン付加物（モル比１：３）
１０ｇをジメチルフォルムアミド５０ｇに溶解し、これ
に数平均分子量５０，０００のポリ−（３−ビニル−１
・４−ブチロラクトン）２０ｇを添加混合して密封し、
５０℃に１時間保持した。続いて、ステンレス製バット
に流し出し、常圧下アルゴンガス気流中で５時間放置し
たのち、真空引きして溶媒を除去した。最後に、１００
℃で５時間再度真空引きして溶媒を完全に除去すること
により、厚みが約１００μｍのこの発明に係るポリマー
電解質を得た。Example 1 LiBφ4 dimethoxyethane adduct (molar ratio 1:3)
Poly-(3-vinyl-1) having a number average molecular weight of 50,000 was dissolved in 50 g of dimethylformamide.
・Add 20g of 4-butyrolactone), mix and seal.
It was held at 50°C for 1 hour. Subsequently, the mixture was poured into a stainless steel vat, left for 5 hours under normal pressure in an argon gas stream, and then vacuumed to remove the solvent. Finally, 100
The solvent was completely removed by evacuation again at .degree. C. for 5 hours, thereby obtaining a polymer electrolyte according to the present invention having a thickness of about 100 .mu.m.
実施例２
ＬｉＢφ４のジメトキシエタン付加物の代わりにＬ ｉ
Ｂ Ｆ４１．８ ｇを、またポリ−（３−ビニル＝１
・４−ブチロラクトン）の代わりに数平均分子量１００
，０００のポリ−（４−ビニル−１・４−ブチロラクト
ン）２０ｇを、それぞれ使用した以外は、実施例１と同
様にしてポリマー電解質を得た。Example 2 Instead of dimethoxyethane adduct of LiBφ4, Li
41.8 g of B F was also added to poly-(3-vinyl=1
・Number average molecular weight 100 instead of 4-butyrolactone)
A polymer electrolyte was obtained in the same manner as in Example 1, except that 20 g of poly-(4-vinyl-1,4-butyrolactone) of 1,000 ml was used in each case.
比較例
Ｌ ｉ ＣＦｉ Ｓｏ） １０ ｇをア七ト二トリル
１００ｇに溶解し、これに数平均分子１ｔｉｏｏ、ｏｏ
。Comparative Example Li CFi So) 10 g was dissolved in 100 g of acetonitrile, and number average molecules 1tioo,oo
.
のポリエチレンオキサイド２５ｇを添加混合し、以下実
施例１と同様にして比較用のポリマー電解質を得た。A comparative polymer electrolyte was obtained in the same manner as in Example 1 by adding and mixing 25 g of polyethylene oxide.
以上の実施例１．２および比較例に係るポリマー電解質
の性能を調べるために、以下のイオン伝導度試験および
放電特性試験を行った。In order to examine the performance of the polymer electrolytes according to Example 1.2 and Comparative Example above, the following ionic conductivity test and discharge characteristic test were conducted.
くイオン伝導度試験〉
実施例１．２および比較例に係る各ポリマー電解質の両
面に１０鶴角の白金板を電極として押し当てて、広範囲
の温度条件下でＩＫＨ，でのイオン伝導度を測定した。Ionic conductivity test> Ion conductivity at IKH was measured under a wide range of temperature conditions by pressing 10 square square platinum plates as electrodes on both sides of each polymer electrolyte according to Example 1.2 and Comparative Example. did.
この結果を第２図に示した。The results are shown in FIG.
図中、縦軸はイオン伝導度（Ｓ／ｃｍ）、横軸は絶対温
度の逆数（１／Ｔ） Ｘ １，０００ （Ｋ−’）であ
り、また直線−２ａは実施例１の結果、同２ｂは実施例
２の結果、曲線−２０は比較例の結果である。In the figure, the vertical axis is the ionic conductivity (S/cm), the horizontal axis is the reciprocal of absolute temperature (1/T) x 1,000 (K-'), and the straight line -2a is the result of Example 1, Curve 2b is the result of Example 2, and curve -20 is the result of Comparative Example.
〈放電特性試験〉
実施例１．２および比較例に係る各ポリマー電解質をセ
パレータとして用いた第１図に示す構成の総厚０．５ｍ
、−辺の長さ１５鰭の方形薄型のリチウム電池を作製し
た。なお、負極はリチウムとアルミニウムとの合金を、
正極は実施例１．２および比較例のポリマー電解質と同
様成分の電解質とＴ ｉ Ｓ、とを含むシート状成形物
を、それぞれ用いた。これらのリチウム電池につき、２
５゛Ｃで、２０μＡの定電流放電を行ったときの放電特
性結果を第３図に示した。図中、曲線−３ａは実施例１
の結果、同３ｂは実施例２の結果、同３ｃは比較例の結
果である。<Discharge characteristic test> Total thickness of 0.5 m of the structure shown in Fig. 1 using each polymer electrolyte according to Example 1.2 and Comparative Example as a separator.
, - A rectangular thin lithium battery with a side length of 15 fins was produced. The negative electrode is made of an alloy of lithium and aluminum.
For the positive electrode, a sheet-shaped molded product containing an electrolyte having the same components as the polymer electrolyte of Example 1.2 and Comparative Example and T i S was used. For these lithium batteries, 2
Figure 3 shows the results of discharge characteristics when a constant current discharge of 20 μA was performed at 5°C. In the figure, curve-3a is Example 1
As a result, 3b is the result of Example 2, and 3c is the result of Comparative Example.
第２図の結果から明らかなように、この発明に係る実施
例１，２のポリマー電解質は室温（２５℃；第２図の横
軸の値で約３．３５）付近においても約１０−’Ｓ／Ｃ
Ａ以上の高いイオン伝導性が得られているのに対し、比
較例のポリマー電解質は室温付近ではイオン伝導性が著
しく低下していることが判る。このため、第３図の結果
から明らかなように、この発明に係る実施例１，２のポ
リマー電解質を用いてなるリチウム電池はすぐれた放電
特性を示すが、比較例のポリマー電解質を用いたリチウ
ム電池は放電特性にかなり劣っている。As is clear from the results in FIG. 2, the polymer electrolytes of Examples 1 and 2 according to the present invention have approximately 10-' S/C
It can be seen that while a high ionic conductivity of A or higher is obtained, the ionic conductivity of the polymer electrolyte of the comparative example is significantly decreased near room temperature. Therefore, as is clear from the results shown in FIG. 3, the lithium batteries using the polymer electrolytes of Examples 1 and 2 according to the present invention exhibit excellent discharge characteristics, but the lithium batteries using the polymer electrolytes of the comparative examples show excellent discharge characteristics. Batteries have rather poor discharge characteristics.
【図面の簡単な説明】
第１図はこの発明のリチウムイオン伝導性ポリマー電解
質を用いたリチウム電池の一例を示す縦断図面、第２図
はこの発明および比較用のリチウムイオン伝導性ポリマ
ー電解質のイオン伝導度と温度との相関図、第３図はこ
の発明および比較用のリチウムイオン伝導性ポリマー電
解質を用いた第１図に示す構成のリチウム電池の放電特
性図である。
７・・・ポリマー電解質（セパレータ）特許出願人
日立マクセル株式会社
第１図
υＴｘ１０αＸＫ−リ[Brief Description of the Drawings] Figure 1 is a longitudinal cross-sectional view showing an example of a lithium battery using the lithium ion conductive polymer electrolyte of the present invention, and Figure 2 is a longitudinal cross-sectional view showing an example of a lithium battery using the lithium ion conductive polymer electrolyte of the present invention and a comparative lithium ion conductive polymer electrolyte. A correlation diagram between conductivity and temperature, and FIG. 3 is a discharge characteristic diagram of a lithium battery having the configuration shown in FIG. 1 using a lithium ion conductive polymer electrolyte of the present invention and a comparative lithium ion conductive polymer electrolyte. 7...Polymer electrolyte (separator) patent applicant
Hitachi Maxell Ltd. Figure 1 υTx10αXK-Li
Claims (2)
ウムイオン伝導性ポリマー電解質において、上記の有機
ポリマーが分子内にラクトン構造を有するポリマーから
なることを特徴とするリチウムイオン伝導性ポリマー電
解質。(1) A lithium ion conductive polymer electrolyte comprising a composite of a lithium salt and an organic polymer, wherein the organic polymer is a polymer having a lactone structure in its molecule.
にビニル基を含むラクトンの単独重合体または共重合体
からなる特許請求の範囲第（１）項記載のリチウムイオ
ン伝導性ポリマー電解質。(2) The lithium ion conductive polymer electrolyte according to claim (1), wherein the polymer having a lactone structure in the molecule is a lactone homopolymer or copolymer having a vinyl group in the molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097528A JPS62254302A (en) | 1986-04-26 | 1986-04-26 | Lithium ion conducting polymer electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097528A JPS62254302A (en) | 1986-04-26 | 1986-04-26 | Lithium ion conducting polymer electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62254302A true JPS62254302A (en) | 1987-11-06 |
Family
ID=14194749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61097528A Pending JPS62254302A (en) | 1986-04-26 | 1986-04-26 | Lithium ion conducting polymer electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62254302A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340270A (en) * | 1986-08-04 | 1988-02-20 | Yuasa Battery Co Ltd | Solid electrolyte battery |
| JPH01130473A (en) * | 1987-11-13 | 1989-05-23 | Kimoto & Co Ltd | Thin type primary battery |
| JPH04226703A (en) * | 1990-12-29 | 1992-08-17 | Showa Prefab Kk | Method and apparatus for production of concrete member with decorative body |
| JP2006022324A (en) * | 2004-06-11 | 2006-01-26 | Canon Inc | Polyhydroxyalkanoate having vinyl group, ester group, carboxyl group and sulfonic acid group and method for producing the same |
-
1986
- 1986-04-26 JP JP61097528A patent/JPS62254302A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340270A (en) * | 1986-08-04 | 1988-02-20 | Yuasa Battery Co Ltd | Solid electrolyte battery |
| JPH01130473A (en) * | 1987-11-13 | 1989-05-23 | Kimoto & Co Ltd | Thin type primary battery |
| JPH04226703A (en) * | 1990-12-29 | 1992-08-17 | Showa Prefab Kk | Method and apparatus for production of concrete member with decorative body |
| JP2006022324A (en) * | 2004-06-11 | 2006-01-26 | Canon Inc | Polyhydroxyalkanoate having vinyl group, ester group, carboxyl group and sulfonic acid group and method for producing the same |
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