JPH01107473A - Lithium ion conductive polymer electrolyte - Google Patents
Lithium ion conductive polymer electrolyteInfo
- Publication number
- JPH01107473A JPH01107473A JP62265810A JP26581087A JPH01107473A JP H01107473 A JPH01107473 A JP H01107473A JP 62265810 A JP62265810 A JP 62265810A JP 26581087 A JP26581087 A JP 26581087A JP H01107473 A JPH01107473 A JP H01107473A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymer electrolyte
- lithium ion
- lithium
- room temperature
- 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
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 229920001940 conductive polymer Polymers 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000620 organic polymer Polymers 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 24
- 159000000002 lithium salts Chemical class 0.000 claims description 24
- 229920006037 cross link polymer Polymers 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
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イ
スプレィなどの電解質や、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途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 is a lithium ion conductive material used in electrolytes such as lithium batteries and electrochromic displays, lithium ion concentration sensors, and lithium ion separation membranes. Concerning polymer electrolytes.
リチウム電池などのリチウムイオン伝導性電解質として
は、ＬｉＣｌ０ｇ／プロピレンカーボネートに代表され
るような液体電解質や、Ｌｉ５Ｎ。Lithium ion conductive electrolytes for lithium batteries include liquid electrolytes such as LiCl0g/propylene carbonate, and Li5N.
Ｌｉ１−Ａｌｔｏｓなど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に
形成することが容易な有機ポリマーをベースとしたポリ
マー電解質を用いる試みがなされている。Solid electrolytes such as Li1-Altos are known, but recently attempts have been made to use polymer electrolytes based on organic polymers that can be easily formed into a flexible film.
この種のポリマー電解質は、これらを超薄膜化や小型化
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利用でき、さらにエ
レクトロクロミックデイスプレィ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 require ultra-thin films and miniaturization, it will be advantageous in terms of workability and sealing reliability for battery production, and will also reduce costs. There are also some useful benefits. In addition, due to its flexibility, it can be used as a lithium ion separation membrane, and is also useful as an electrolyte for electrochromic displays and as a lithium ion concentration sensor.
従来、このようなポリマー電解質のひとつとして、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（Ｆ
ａｓｔ Ｉｏｎ Ｔｒａｎｓｐｏｒｔ ｉｎ ５ｏｌｉ
ｄＰ、１３１（１９７９）） 。Conventionally, one known polymer electrolyte is a composite of polyethylene oxide as an organic polymer and lithium salt (F).
ast Ion Transport in 5oli
dP, 131 (1979)).
しかしながら、上記のポリエチレンオキサイド−リチウ
ム塩系のポリマー電解質は、６０℃以上の高温では溶融
して比較的良好なリチウムイオン伝導性を示すものの、
２５℃程度の室温下ではリチウムイオン伝導性が低く、
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
述のごとき各種用途に応用したときに、性能上充分に満
足できないという問題があった。However, although the above-mentioned polyethylene oxide-lithium salt-based polymer electrolyte melts at high temperatures of 60°C or higher and exhibits relatively good lithium ion conductivity,
Lithium ion conductivity is low at room temperature of about 25℃,
When applied to lithium batteries, which are mostly used at room temperature, and the various uses mentioned above, there is a problem in that the performance is not fully satisfactory.
したがって、この発明は、リチウムイオン伝導性ポリマ
ー電解質における有機ポリマーとして、上記ポリエチレ
ンオキサイドとは異なる特定のポリマーを用いることに
より、室温下においても良好なリチウムイオン伝導性を
示すポリマー電解質を提供することを目的とする。Therefore, the present invention aims to provide a polymer electrolyte that exhibits good lithium ion conductivity even at room temperature by using a specific polymer different from the above-mentioned polyethylene oxide as an organic polymer in a lithium ion conductive polymer electrolyte. purpose.
この発明者らは、上記の目的を達成するために鋭意研究
を重ねた結果、ポリマー電解質を構成させる有機ポリマ
ーとして、ポリグリセリンにポリエチレングリコール、
ポリプロピレングリコール、エチレンオキサイド−プロ
ピレンオキサイド共重合体などのポリエーテルグリコー
ルを付加させたポリマーを用いるときは、室温下におい
ても良好なリチウムイオン伝導性を示すポリマー電解質
が得られることを見出し、この発明を完成するにいたっ
た。As a result of extensive research in order to achieve the above object, the inventors found that polyethylene glycol, polyglycerin, and
It was discovered that when using a polymer to which polyether glycol such as polypropylene glycol or ethylene oxide-propylene oxide copolymer is added, a polymer electrolyte that exhibits good lithium ion conductivity even at room temperature can be obtained, and the present invention was developed based on this discovery. It was completed.
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、ポリグリセリンにポリエ
ーテルグリコールを付加した一般式（ｆ）
（式中、Ｒはポリエチレングリコール、ポリプロピレン
グリコールまたはエチレンオキサイド−プロピレンオキ
サイド共重合体であり、口は５０以下である）
で示されるポリマーであ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に関するものである。That is, the present invention provides a lithium ion conductive polymer electrolyte consisting of a composite of a lithium salt and an organic polymer, in which the organic polymer has the general formula (f) in which polyether glycol is added to polyglycerin (wherein R is The present invention relates to a lithium ion conductive polymer electrolyte, which is polyethylene glycol, polypropylene glycol, or an ethylene oxide-propylene oxide copolymer, and has a diameter of 50 or less.
上記一般式（１）で示されるポリマーは、主鎖に従来使
用のポリエチレンオキサイドと同様のポリエチレンオキ
サイド構造をとり、側鎖にポリエチレングリコール、ポ
リプロピレングリコール、エチレンオキサイド−プロピ
レンオキサイド共重合体などのポリエーテルグリコール
を付加させた構造をとっていて、該側鎖には室温下で液
状でイオン伝導性の良好なポリエーテルグリコールを付
加させることができるので、主鎖および側鎖、特に側鎖
が良好なリチウムイオン伝導体として機能し、かつ側鎖
のポリエーテルグリコールによりポリマーの結晶化度が
低くなって、室温下でも結晶化が起こりにくいので、側
鎖の良好なリチウムイオン伝導性を低下させず、室温下
においても良好なリチウムイオン伝導性を示すポリマー
電解質を提供し得る。The polymer represented by the above general formula (1) has a polyethylene oxide structure similar to conventionally used polyethylene oxide in the main chain, and a polyether such as polyethylene glycol, polypropylene glycol, or ethylene oxide-propylene oxide copolymer in the side chain. It has a glycol-added structure, and polyether glycol, which is liquid at room temperature and has good ion conductivity, can be added to the side chain, so the main chain and side chains, especially the side chains, have good properties. It functions as a lithium ion conductor, and the polyether glycol in the side chain reduces the crystallinity of the polymer, making it difficult for crystallization to occur even at room temperature, so it does not reduce the good lithium ion conductivity of the side chain. A polymer electrolyte that exhibits good lithium ion conductivity even at room temperature can be provided.
また、上記−触式（１）で示されるポリマーの中で、室
温で液状のものは、架橋剤で架橋するこ、とによって、
液状のものの有する良好なイオン伝導性を低下させるこ
となく、固体状にし、室温下においても特に良好なリチ
ウムイオン伝導性を示すポリマー電解質を得ることがで
きる。Furthermore, among the polymers represented by formula (1) above, those that are liquid at room temperature can be crosslinked with a crosslinking agent.
It is possible to obtain a polymer electrolyte in a solid state that exhibits particularly good lithium ion conductivity even at room temperature without reducing the good ion conductivity of a liquid state.
この発明において、前記一般式（，１）で示されるポリ
マーのポリエーテルグリコール（Ｒ）の数平均分子量は
、ポリエーテルグリコールがポリエチレングリコールの
場合、１ 、０００以下、特に２００〜８００程度のも
のを用いることが好ましい、これは、ポリエチレングリ
コールの分子量が１ 、０００を岨えると固体状になっ
て、架橋する前のイオン伝導度が低くなることと、分子
量が小さくなりすぎると架橋した時に架橋点間の距離が
短くなり、リチウムのイオン移動がしにくくなって、イ
オン伝導度が低下するからである。一方、ポリエーテル
グリコールが、ポリプロピレングリコールまたはエチレ
ンオキサイド−プロピレンオキサイドの共重合体の場合
、数平均分子量が２００〜１０，０００、特に１ 、０
００〜８．０００のものを用いるのが好ましい。In this invention, the number average molecular weight of the polyether glycol (R) of the polymer represented by the general formula (1) is 1,000 or less, particularly about 200 to 800, when the polyether glycol is polyethylene glycol. This is because when the molecular weight of polyethylene glycol exceeds 1,000, it becomes solid and the ionic conductivity before cross-linking becomes low, and when the molecular weight becomes too small, cross-linking points will be lost when cross-linking. This is because the distance between them becomes shorter, making it difficult for lithium ions to move, resulting in a decrease in ionic conductivity. On the other hand, when the polyether glycol is polypropylene glycol or an ethylene oxide-propylene oxide copolymer, the number average molecular weight is 200 to 10,000, particularly 1,0.
00 to 8.000 is preferably used.
ポリプロピレングリコールまたはエチレンオキサイド−
プロピレンオキサイド共重合体が上記の分子量範囲で好
ましいのは、分子量増加による架橋前のポリマーのイオ
ン伝導度の低下と架橋後の架橋点間の距離の増加（イオ
ン移動のしやすさの増加）との兼ね合いによるものであ
り、上記範囲内でイオン伝導性が特に大きくなるからで
ある。Polypropylene glycol or ethylene oxide
The propylene oxide copolymer is preferable in the above molecular weight range because of a decrease in the ionic conductivity of the polymer before crosslinking due to an increase in molecular weight and an increase in the distance between crosslinking points after crosslinking (increase in the ease of ion movement). This is because the ionic conductivity becomes particularly high within the above range.
一般式（１）において、ｎは５０以下であるが、これは
ｎが５０を超えると主鎖のポリエーテルの結晶性が高く
なりイオン伝導性が低くなって使用しがたくなる。なお
、ｎは２以上であればよく、モノマー（つまり、ｎ＝１
）でなければよい。In the general formula (1), n is 50 or less, but if n exceeds 50, the crystallinity of the main chain polyether becomes high and the ionic conductivity becomes low, making it difficult to use. Note that n may be 2 or more, and monomer (that is, n=1
).
一般式（りで示されるポリマーを架橋する際の架橋剤と
しては、ポリマー中の水酸基と付加・縮合反応を起こす
２官能を有する有機物が用いられる。このような２官能
を有する有機物としては、ジイソシアナート、ジアミン
、ジカルボン酸、ジカルボン酸塩化物、メチロール化合
物、エピクロルヒドリンなどがあげられる。そして、上
記ジイソシアナートとしては、例えばヘキサメチレンジ
イソシアナート、２．４−）リレンジイソシアナート、
メチレンビス（４−フェニルイソシアナート）、キシリ
レンジイソシアナートなどが用いられ、ジアミンとして
は、例えばエチレンジアミン、テトラメチレンジアミン
などが用いられる。ジカルボン酸としては、例えばシュ
ウ酸、マロン酸、コハク酸、フタル酸、イソフタル酸、
テレフタル酸などが用いられ、ジカルボン酸塩化物とし
ては、例えば塩化スクシネルなどが用いられ、メチロー
ル化合物としては、例えばジメチル尿素などが用いられ
る。As a crosslinking agent for crosslinking a polymer represented by the general formula (2), an organic substance having a difunctionality that causes an addition/condensation reaction with a hydroxyl group in the polymer is used. Examples include isocyanates, diamines, dicarboxylic acids, dicarboxylic acid chlorides, methylol compounds, epichlorohydrin, etc. Examples of the diisocyanates include hexamethylene diisocyanate, 2.4-)lylene diisocyanate,
Methylene bis(4-phenyl isocyanate), xylylene diisocyanate, etc. are used, and as the diamine, for example, ethylene diamine, tetramethylene diamine, etc. are used. Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid,
Terephthalic acid or the like is used, the dicarboxylic acid chloride is, for example, succinel chloride, and the methylol compound is, for example, dimethylurea.
ポリマー電解質は、一般式（１）で示されるポリマーと
リチウム塩と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蒸発除去するか、または一般式（１
）で示されるポリマーを架橋剤で架橋した架橋ポリマー
を適当なリチウム塩の有機溶媒溶液に浸漬し、リチウム
塩溶液をポリマー中に浸透させた後、有機溶媒を蒸発除
去することによって作製される。このようなポリマーと
リチウム塩との有機溶媒による溶解または架橋ポリマー
のリチウム塩溶液への浸漬により、ポリマーのエーテル
酸素（−０−）にリチウム塩が錯体を形成して結合し、
溶媒除去後も上記結合が保持されて有機ポリマーとリチ
ウム塩との複合体が得られる。The polymer electrolyte can be prepared by preparing a solution in which a polymer represented by the general formula (1) and a lithium salt are dissolved in an appropriate organic solvent, and then removing the organic solvent by evaporation, or
) is crosslinked with a crosslinking agent by immersing the crosslinked polymer in an appropriate organic solvent solution of a lithium salt, allowing the lithium salt solution to permeate into the polymer, and then evaporating and removing the organic solvent. By dissolving such a polymer and lithium salt in an organic solvent or by immersing the crosslinked polymer in a lithium salt solution, the lithium salt forms a complex and binds to the ether oxygen (-0-) of the polymer,
Even after the solvent is removed, the above-mentioned bonds are retained and a composite of the organic polymer and lithium salt is obtained.
上記の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、例えばＬｉＣＦｚＳ０２ 、Ｌ １ｃＦｓ
ｓＯｔ 、Ｌ ｉＢｒ、Ｌｉｌ、Ｌｉ５ＣＮ、Ｌ ｌＢ
Ｆ４ 、Ｌ ｉ Ｃ１０４、Ｌ １ＡｓＦ、などがあげ
られ、上記リチウム塩を溶解する溶媒としては、リチウ
ム塩を充分に溶解し、かつポリマーと反応しない有機溶
媒、例えばアセトニトリル、ジオキソラン、ｌ、２−ジ
メトキシエタン、テトラヒドロフラン、メタノール、ア
セトンなどが用いられる。このリチウム塩の使用量は、
上記一般式（１）で示されるポリマーのエーテル酸素（
−０−）１モルに対して０．０２〜０．２モル、特に０
．０５〜０．１モルの範囲にするのが好ましい、これは
、リチウム塩の増加によるリチウムイオンのキャリアー
濃度の増大と、リチウム塩の増加によるリチウムイオン
の移動度の低下との兼ね合いに基づくものであり、上記
範囲内でリチウムイオン伝導度が大きくなるからである
。Any of the lithium salts used in conventional polymer electrolytes can be used as the above lithium salt, and specific examples thereof include LiCFzS02, L1cFs, etc.
sOt, L iBr, Lil, Li5CN, L lB
Examples of the solvent for dissolving the lithium salt include organic solvents that sufficiently dissolve the lithium salt and do not react with the polymer, such as acetonitrile, dioxolane, and l,2-dimethoxy. Ethane, tetrahydrofuran, methanol, acetone, etc. are used. The amount of lithium salt used is
The ether oxygen of the polymer represented by the above general formula (1) (
-0-) 0.02 to 0.2 mol per 1 mol, especially 0
．． The range is preferably from 0.05 to 0.1 mol. This is based on the balance between an increase in the carrier concentration of lithium ions due to an increase in the lithium salt and a decrease in the mobility of lithium ions due to an increase in the lithium salt. This is because the lithium ion conductivity increases within the above range.
ポリマー電解質の形態は、その用途目的などによって適
宜法められる０例えば、この発明のポリマー電解質をリ
チウム電池用の電解質として用いかつ正負両極間のセパ
レータとしての機能を兼ねさせる場合は、ポリマー電解
質をシート状に形成すればよい、このシート状のポリマ
ー電解質を得るには、一般式（１）で示されるポリマー
とリチウム塩との有機溶媒溶液を適宜な基板上に流延し
、有機溶媒を蒸発除去するか、あるいは一般式（１）で
示されるポリマーを架橋剤で架橋した架橋ポリマーをシ
ート状に形成し、該シート状の架橋ポリマーをリチウム
塩の有機溶媒溶液に浸漬し、浸漬後、有ｉ溶媒を蒸発除
去すればよい。上記シートとしては一般にフィルムと呼
ばれるようなミクロンオーダーのきわめて薄いものを作
製することができる。The form of the polymer electrolyte is determined as appropriate depending on its intended use. For example, when the polymer electrolyte of the present invention is used as an electrolyte for a lithium battery and also serves as a separator between positive and negative electrodes, the polymer electrolyte may be formed into a sheet. To obtain this sheet-like polymer electrolyte, an organic solvent solution of the polymer represented by general formula (1) and a lithium salt is cast onto a suitable substrate, and the organic solvent is removed by evaporation. Alternatively, a crosslinked polymer represented by the general formula (1) is crosslinked with a crosslinking agent to form a sheet, and the sheet crosslinked polymer is immersed in an organic solvent solution of lithium salt, and after immersion, The solvent may be removed by evaporation. As the above-mentioned sheet, an extremely thin sheet on the order of microns, generally called a film, can be produced.
また、この発明のポリマー電解質をリチウム塩の正極に
適用する場合は、一般式（１）で示されるポリマーとリ
チウム塩との有機溶媒溶液に正極活物質などを所定割合
で加え、有機溶媒を蒸発除去したのちシート状などの所
望形状に成形するか、または一般式（１）で示されるポ
リマー、架橋剤、正極活物質などを所定割合で加えた後
、ポリマーを架橋させ、所望形状に成形後、得られた成
形体をリチウム塩の有機溶媒溶液に浸漬し、浸漬後、有
機溶媒を蒸発除去すればよい、そうすることによって、
ポリマー電解質が正極活物質などと混在−棒体した成形
体を得ることができる。In addition, when applying the polymer electrolyte of the present invention to a lithium salt positive electrode, a positive electrode active material or the like is added in a predetermined ratio to an organic solvent solution of the polymer represented by general formula (1) and a lithium salt, and the organic solvent is evaporated. After removing it, it is molded into a desired shape such as a sheet, or after adding a polymer represented by general formula (1), a crosslinking agent, a positive electrode active material, etc. in a predetermined ratio, the polymer is crosslinked and molded into a desired shape. , the obtained molded body is immersed in an organic solvent solution of lithium salt, and after immersion, the organic solvent is removed by evaporation. By doing so,
A molded body in which a polymer electrolyte is mixed with a positive electrode active material and the like can be obtained.
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すもので、図中、■はステンレス鋼
からなる方形平板状の正極集電機、２は周辺を一面側へ
段状に折曲した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極集電板
、３は両極集電板ｌ、２の対向する周辺部１ａ、２８間
を封止する接着剤層である。Figure 1 shows an example of a lithium battery using the polymer electrolyte of the present invention described above. A shallow rectangular dish-shaped negative electrode current collector plate made of stainless steel with a flat peripheral part 2a in the same direction as the bent main surface, 3 is a bipolar current collector plate l, and 2 is between the opposing peripheral parts 1a and 28. This is the adhesive layer that seals the
４は両極集電板ｌ、２間に構成された空間５内において
正極集電板１側に配されたこの発明のボＩＪ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は正極４、負極６間に介在させた前記この発明のポリ
マー電解質をシート状に成形してなるセパレータである
。Reference numeral 4 denotes both electrode current collector plates l, and the bomber IJ electrolyte of the present invention and positive electrode active material, etc., arranged on the positive electrode current collector plate 1 side in the space 5 formed between the two electrodes are formed into a sheet form by the method described above. 6 is a negative electrode made of lithium or lithium alloy loaded on the negative electrode current collector plate 2 side in the space 5;
7 is a separator formed by molding the polymer electrolyte of the present invention interposed between the positive electrode 4 and the negative electrode 6 into a sheet shape.
なお、上記正極４は、場合により正極活物質とポリテト
ラフルオロエチレン粉末などの結着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、例えばＴｌ５ｚ
、Ｍｏ５ｔ、Ｖ＊Ｏ＋ｓ、ｖ２０３、ＶＳｅ、Ｎ１ＰＳ
ｓ、ポリアニリン、ポリピロール、ポリチオフェンなど
の１種もしくは２１１以上が用いられる。In addition, the above-mentioned positive electrode 4 may be formed into a sheet by mixing a positive electrode active material with a binder such as polytetrafluoroethylene powder or an electron conduction aid, depending on the case. As the positive electrode active material, for example, Tl5z
, Mo5t, V*O+s, v203, VSe, N1PS
One or more of s, polyaniline, polypyrrole, polythiophene, etc., or 211 or more 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が上記ポリマー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業の
ための作業性、封止の信輔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
にないといった種々の利点を有する上に、上記電解質が
そのイオン伝導性にすぐれていることにより、−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。In the lithium battery constructed in this way, the separator 7 is a sheet-like material made of the polymer electrolyte, and the positive electrode 4 is a similar sheet-like material containing the polymer electrolyte, so that the battery can be made thinner. The above-mentioned electrolyte has various advantages such as being able to contribute to improving workability for battery work and reliability of sealing, and essentially not having to worry about leakage unlike liquid electrolyte. Due to its excellent ionic conductivity, it has excellent discharge characteristics as a secondary battery and excellent charge/discharge cycle characteristics as a secondary battery.
以上のとおり、この発明によれば、リチウム塩と複合体
を構成させる有機ポリマーとして、ポリグリセリンにポ
リエーテルグリコールを付加した一ａ式（１）で示され
るポリマーを用いることにより、室温下においても良好
なリチウムイオン伝導性を示す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 represented by Formula 1a (1) in which polyether glycol is added to polyglycerin as an organic polymer constituting a complex with a lithium salt, even at room temperature A polymer electrolyte exhibiting good lithium ion conductivity can be provided.
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
数平均分子３１５，０００のユニグリＡ Ｖ −６４５
（商品名、日本油脂（株）製）を１００℃で２時間真空
乾燥した。このユニグリＡ Ｖ−６４５（商品名）の構
造式は次に示すとおりである。Example 1 UNIGRI AV-645 with number average molecular weight of 315,000
(trade name, manufactured by NOF Corporation) was vacuum dried at 100° C. for 2 hours. The structural formula of UNIGRI AV-645 (trade name) is as shown below.
上記ユニグリＡ Ｖ−６４５（商品名）９．２６ｇト２
．４−トリレンジイソシアナー）０．５ｇを三角フラス
コに入れ、マグネチックスクーラーで撹拌後、得られた
粘性溶液状混合物をアルミニウム板上に滴下し、アルゴ
ンガスフロー中で、ホットプレート上にて８０°Ｃで８
時間反応させて架橋体（架橋ポリマーという）を得た。The above Unigri A V-645 (product name) 9.26g 2
．． 4-Tolylene diisocyaner) was placed in an Erlenmeyer flask, stirred with a magnetic cooler, the resulting viscous solution mixture was dropped onto an aluminum plate, and heated to 80% on a hot plate in an argon gas flow. 8 at °C
A crosslinked product (referred to as a crosslinked polymer) was obtained by reacting for a period of time.
得られた架橋ポリマーをアルミニウム板からはがし、ア
セトン中に浸漬して、未反応の２．４−）リレンジイソ
シアナートをアセトンに溶解して除去した。つぎにエタ
ノール中に浸漬し、未反応のＮＧＯ基をエタノールと反
応させた。ついで架橋ポリマーを濃度３重量％のｌ５ｉ
ｃＦｓｓＯｓアセトン溶液中に８時間浸漬し、ＬｉＣＦ
３５Ｏｚ溶液を架橋ポリマー中に浸透させた後６０℃に
加熱してアセトンを蒸発除去して厚さ５０ａｍのシート
状のポリマー電解質を得た。The obtained crosslinked polymer was peeled off from the aluminum plate and immersed in acetone to remove unreacted 2,4-)lylene diisocyanate by dissolving it in acetone. Next, it was immersed in ethanol to cause unreacted NGO groups to react with ethanol. The crosslinked polymer was then mixed with l5i at a concentration of 3% by weight.
LiCF was soaked in cFssOs acetone solution for 8 hours.
A 35Oz solution was permeated into the crosslinked polymer and then heated to 60°C to evaporate the acetone to obtain a sheet-like polymer electrolyte with a thickness of 50am.
実施例２
＋３１”Ｉ ユニグリＡＶ−６４５（商品名）に代え
て数平均分子量１，１００のユニグリＡＶ−６１１（商
品名、日本油脂（株）製）を１．５８ｇ使用した以外は
実施例】と同様にしてポリマー電解質を得た。上記ユニ
グリＡ Ｖ −６１０商品名）の構造式は次に示すとお
りである。Example 2 +31"I Example except that 1.58 g of UNIGRI AV-611 (trade name, manufactured by NOF Corporation) with a number average molecular weight of 1,100 was used instead of UNIGRI AV-645 (trade name)] A polymer electrolyte was obtained in the same manner as above.The structural formula of UNIGRI AV-610 (trade name) is as shown below.
実施例３
ユニグリＡ Ｖ−６４５（商品名）に代えて数平均分子
量２．０００のユニグリＡ Ｖ−６２０（商品名、日本
油脂（株）製）を２．８７ｇ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。上記ユニグリＡＶ−
６２０（商品名）の構造式は次に示すとおりである。Example 3 Same as Example 1 except that 2.87g of UNIGRI A V-620 (trade name, manufactured by NOF Corporation) having a number average molecular weight of 2.000 was used instead of UNIGRI A V-645 (trade name). A polymer electrolyte was obtained in the same manner. The above Unigri AV-
The structural formula of 620 (trade name) is as shown below.
実施例４
ユニグリＡＶ−６４５（商品名）に代えて数平均分子量
７，０００のユニグリＡ Ｖ−６７０（商品名、日本油
脂（株）製）を１０ｇ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。上記ユニグリＡＶ−６７０
（商品名）の構造式は次に示すとおりである。Example 4 The same procedure as in Example 1 was carried out, except that 10 g of UNIGRI AV-670 (trade name, manufactured by NOF Corporation) having a number average molecular weight of 7,000 was used in place of UNIGRI AV-645 (trade name). A polymer electrolyte was obtained. Above Unigri AV-670
The structural formula of (product name) is as shown below.
】
実施例５
数平均分子量７Ｑ、ＱＱＱ（７）ユニグＩＪ Ａ−Ｖ−
６７０Ｔ （商品名、日本油脂（株）製）を１００°Ｃ
で２時間真空乾燥した。このユニグリＡＶ−６７０Ｔ
（商品名）の構造式は次に示すとおりである。] Example 5 Number average molecular weight 7Q, QQQ (7) UNIG IJ AV-
670T (product name, manufactured by NOF Corporation) at 100°C
It was vacuum dried for 2 hours. This Unigri AV-670T
The structural formula of (product name) is as shown below.
上記コニグリＡＶ−６７０７（商品名）ＩｇとＬｉＣＦ
ｓ Ｓ Ｏｓ Ｏ，２３６ｇをアセトニトリル５ｍｌ
に溶解し、マグネチックスターラーで撹拌して均一に混
合した。得られた粘性溶液状混合物をガラス基板上に滴
下し、常圧下、アルゴンガスフロー中で５時間放置した
後、真空度Ｉ Ｘｌ０−’ｔｏｒｒ、温度１２０℃で１
０時間処理して、アセトニトリルを蒸発Ｈ除去し、厚さ
２０μｍのシート状のポリマー電解質を得た。Coniguri AV-6707 (product name) Ig and LiCF
s S Os O, 236g, acetonitrile 5ml
and stirred with a magnetic stirrer to mix uniformly. The obtained viscous solution-like mixture was dropped onto a glass substrate, left for 5 hours under normal pressure in an argon gas flow, and then heated at a vacuum degree of I Xl0-'torr and a temperature of 120°C.
After treatment for 0 hours, acetonitrile was removed by evaporation to obtain a sheet-like polymer electrolyte with a thickness of 20 μm.
実施例６
ユニグリＡＶ−６７０７（商品名）に代えて数平均分子
量３５．０００＜７）ＬニゲＩＪＡＶ−６３５Ｔ （商
品名、日本油脂（株）製）を１ｇ使用し、かつＬｉＣＦ
。Example 6 1 g of L Nige IJAV-635T (trade name, manufactured by NOF Corporation) (number average molecular weight 35.000 < 7) was used in place of Unigri AV-6707 (trade name), and LiCF
.
５０３の量を０．２３７ｇに変えた以外は実施例５と同
様にしてポリマー電解質を得た。上記ユニグリＡＶ−６
３５Ｔ （商品名）の構造式は次に示すとおりである。A polymer electrolyte was obtained in the same manner as in Example 5 except that the amount of 503 was changed to 0.237 g. Above Unigri AV-6
The structural formula of 35T (trade name) is as shown below.
比較例１
数平均分子量６００ 、０００のポリエチレンオキサイ
ドＩｇとＬ １ｃＦｓｓＯｓ Ｏ，３２６ｇをアセト
ニトリル５ｍｌに溶解し、マグネチックスターラーで撹
拌して均一に溶解した。この溶液をガラス基板上に滴下
し、常圧下アルゴンガスフロー中で５時間放置した後、
真空度Ｉ Ｘｌ０−’ｔｏｒｒ、温度１２０℃で１０時
間処理して、アセトニトリルを蒸発除去し、厚さ２０μ
ｍのシート状のポリマー電解質を得た。Comparative Example 1 Polyethylene oxide Ig having a number average molecular weight of 600.000 and 326 g of L1cFssOs O were dissolved in 5 ml of acetonitrile and stirred with a magnetic stirrer to uniformly dissolve. After dropping this solution onto a glass substrate and leaving it for 5 hours in an argon gas flow under normal pressure,
Processed for 10 hours at a vacuum degree of I
A sheet-like polymer electrolyte of m was obtained.
上記実施例１〜６および比較例１の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電池
の内部抵抗試験を行った。In order to examine the performance of the polymer electrolytes of Examples 1 to 6 and Comparative Example 1, the following ionic conductivity test and battery internal resistance test were conducted.
（イオン伝導度試験）
実施例１〜４の各ポリマー電解質はＡｕ板でサンドイン
チ状に挾み、実施例５〜６および比較例１のポリマー電
解質はその上にＡｕ＜Ｌ型電極を蒸着法で形成し、電極
間の交流インピーダンスを測定し、複素インピーダンス
解析（Ｃｏｌｅ−Ｃｏｌｅプロット）を行い、室温（２
５℃）でのイオン伝導度を決定した。結果は第１表に示
すとおりである。(Ionic conductivity test) Each of the polymer electrolytes of Examples 1 to 4 was sandwiched between Au plates in the form of a sandwich, and the polymer electrolytes of Examples 5 to 6 and Comparative Example 1 were coated with Au<L type electrodes by vapor deposition. The alternating current impedance between the electrodes was measured, and complex impedance analysis (Cole-Cole plot) was performed.
The ionic conductivity at 5°C was determined. The results are shown in Table 1.
第 １ 表
また、種々の温度条件下でのイオン伝導度を上記同様に
して測定した結果は、第２図に示すとおりである。第２
図において、縦軸はイオン伝導度（Ｓ／ｃｍ）であり、
横軸は絶対温度の逆数１０”／Ｔ （Ｋ−１）である、
また、曲線２ａは実施例１の結果、曲線２ｂは実施例２
の結果、曲線２ｃは実施例３の結果、曲線２ｄは実施例
４の結果、曲線２ｅは実施例５の結果、曲線２ｆは実施
例６の結果、曲線２ｇは比較例１の結果である。Table 1 Further, the results of measuring the ionic conductivity under various temperature conditions in the same manner as above are shown in FIG. Second
In the figure, the vertical axis is ionic conductivity (S/cm),
The horizontal axis is the reciprocal of absolute temperature 10”/T (K-1),
Also, curve 2a is the result of Example 1, and curve 2b is the result of Example 2.
As a result, curve 2c is the result of Example 3, curve 2d is the result of Example 4, curve 2e is the result of Example 5, curve 2f is the result of Example 6, and curve 2g is the result of Comparative Example 1.
〈電池の内部抵抗試験）
実施例１〜６および比較例１の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０．５−１−
辺の長さ１５＋＋＋ｍの正方形薄型のリチウム電池を作
製した。(Internal resistance test of battery) Total thickness of the structure shown in FIG. 1 using the polymer electrolytes of Examples 1 to 6 and Comparative Example 1 as a separator: 0.5-1-
A square thin lithium battery with a side length of 15+++ m was produced.
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１〜６および比較例１と同組成のポリマー電解
質と二硫化チタン（ＴＩＳ、）とを含むシート状成形物
をそれぞれ用いた。An alloy of lithium and aluminum was used as the negative electrode, and a sheet-shaped molded product containing a polymer electrolyte having the same composition as in Examples 1 to 6 and Comparative Example 1 and titanium disulfide (TIS) was used as the positive electrode.
これらのリチウム電池について、２５℃、６０℃、１０
０℃での内部抵抗を測定した結果を第２表に示す。For these lithium batteries, 25℃, 60℃, 10℃
Table 2 shows the results of measuring the internal resistance at 0°C.
第 ２ 表
以上の試験結果から明らかなように、この発明の実施例
１〜６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８．０Ｘ１Ｇ−
’ 〜１．ＯＸｌ０−’Ｓ／ＣＩ程度の高いイオン伝導
性を示したが、ポリエチレンオキサイドをポリマー成分
とする比較例１のポリマー電解質は、室温でのイオン伝
導度が１．０Ｘ１０−＠Ｓ／ｃｍであり、この発明の実
施例１〜６のポリマー電解質に比べて、イオン伝導度が
低かうた。As is clear from the test results in Table 2 and above, the polymer electrolytes of Examples 1 to 6 of the present invention had a temperature of about 8.0 .0X1G-
'~1. Although the polymer electrolyte of Comparative Example 1 containing polyethylene oxide as a polymer component had an ionic conductivity as high as OXl0-'S/CI, the ionic conductivity at room temperature was 1.0X10-@S/cm. The ionic conductivity was lower than that of the polymer electrolytes of Examples 1 to 6 of this invention.
また、第２表に示すように、この発明の実施例１〜６の
ポリマー電解質を用いたリチウム電池の室温（２５℃）
での内部抵抗は、１１．１〜８．９００Ωであったが、
比較例１のポリマー電解質を用いたリチウム電池の室温
（２５℃）での内部抵抗は８９．０００Ωと非常に大き
かった。Furthermore, as shown in Table 2, lithium batteries using the polymer electrolytes of Examples 1 to 6 of the present invention were prepared at room temperature (25°C).
The internal resistance was 11.1 to 8.900Ω, but
The internal resistance of the lithium battery using the polymer electrolyte of Comparative Example 1 at room temperature (25° C.) was as large as 89.000Ω.
特に分子量が小さいポリマーを架橋剤で架橋した架橋ポ
リマーをポリマー成分として用いた実施例１〜４のポリ
マー電解質は、イオン伝導度が大きく、また、それらを
電解質として用いたリチウム電池の室温下での内部抵抗
は他のものに比べて非常に小さかった。In particular, the polymer electrolytes of Examples 1 to 4, in which crosslinked polymers with low molecular weights were crosslinked with a crosslinking agent, had high ionic conductivity, and the ion conductivity of lithium batteries using them as electrolytes was high at room temperature. Internal resistance was very small compared to others.
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面図である。
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関係を示す図
である。
７・・・セパレータ （ポリマー電解質）第 １
図FIG. 1 is a longitudinal sectional view showing an example of a lithium battery using the lithium ion conductive polymer electrolyte of the present invention. FIG. 2 is a diagram showing the relationship between ionic conductivity and temperature of lithium ion conductive polymer electrolytes of the present invention and comparative lithium ion conductive polymer electrolytes. 7... Separator (polymer electrolyte) 1st
figure
Claims (2)
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、ポリグリセリンにポリエーテルグリコー
ルを付加した一般式（Ｉ） ▲数式、化学式、表等があります▼（Ｉ） （式中、Ｒはポリエチレングリコール、ポリプロピレン
グリコールまたはエチレンオキサイド−プロピレンオキ
サイド共重合体であり、ｎは５０以下である） で示されるポリマーであ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) In a lithium ion conductive polymer electrolyte consisting of a composite of a lithium salt and an organic polymer, the above organic polymer has the general formula (I) in which polyether glycol is added to polyglycerin. ▲ Numerical formulas, chemical formulas, tables, etc. ▼(I) (wherein R is polyethylene glycol, polypropylene glycol or ethylene oxide-propylene oxide copolymer, and n is 50 or less) A lithium ion conductive polymer characterized by being a polymer represented by: Polymer electrolyte.
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、ポリグリセリンにポリエーテルグリコー
ルを付加した一般式（Ｉ） ▲数式、化学式、表等があります▼（Ｉ） （式中、Ｒはポリエチレングリコール、ポリプロピレン
グリコールまたはエチレンオキサイド−プロピレンオキ
サイド共重合体であり、ｎは５０以下である） で示されるポリマーを架橋剤で架橋した架橋ポリマーで
あ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。(2) In a lithium ion conductive polymer electrolyte consisting of a composite of a lithium salt and an organic polymer, the above organic polymer has the general formula (I) in which polyether glycol is added to polyglycerin. ▲ Numerical formulas, chemical formulas, tables, etc. ▼(I) (wherein R is polyethylene glycol, polypropylene glycol, or ethylene oxide-propylene oxide copolymer, and n is 50 or less) It is a crosslinked polymer obtained by crosslinking the polymer shown by the following with a crosslinking agent. A lithium ion conductive polymer electrolyte featuring:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62265810A JPH01107473A (en) | 1987-10-20 | 1987-10-20 | Lithium ion conductive polymer electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62265810A JPH01107473A (en) | 1987-10-20 | 1987-10-20 | Lithium ion conductive polymer electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01107473A true JPH01107473A (en) | 1989-04-25 |
Family
ID=17422365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62265810A Pending JPH01107473A (en) | 1987-10-20 | 1987-10-20 | Lithium ion conductive polymer electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01107473A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516339A (en) * | 1993-02-05 | 1996-05-14 | Eveready Battery Company, Inc. | Process for making electrochemical cells using a polymer electrolyte |
-
1987
- 1987-10-20 JP JP62265810A patent/JPH01107473A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516339A (en) * | 1993-02-05 | 1996-05-14 | Eveready Battery Company, Inc. | Process for making electrochemical cells using a polymer electrolyte |
| US5660950A (en) * | 1993-02-05 | 1997-08-26 | Eveready Battery Company | Electrochemical cells using a polymer electrolyte |
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