JPH0433951A - Solid electrolyte composition - Google Patents
Solid electrolyte compositionInfo
- Publication number
- JPH0433951A JPH0433951A JP2140936A JP14093690A JPH0433951A JP H0433951 A JPH0433951 A JP H0433951A JP 2140936 A JP2140936 A JP 2140936A JP 14093690 A JP14093690 A JP 14093690A JP H0433951 A JPH0433951 A JP H0433951A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- compound
- ion
- electrolyte composition
- polyether
- 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.)
- Granted
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 12
- -1 alkali metal salt Chemical class 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 150000001450 anions Chemical group 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract 2
- 230000005684 electric field Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 3
- 229920002873 Polyethylenimine Polymers 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 102000011781 Karyopherins Human genes 0.000 description 1
- 108010062228 Karyopherins Proteins 0.000 description 1
- 229910015028 LiAsF5 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002892 organic cations Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000008096 xylene Substances 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
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明（友 電池 キャパシター、センサー 表示素子
、記録素子等の電気化学素子に用いられる固形電解質組
成物に関すム
従来の技術
固体の電解質を用いることで液漏れがなく、小形薄形化
の電池 電気二重層キャパシタ等の固体の電気化学デバ
イスを得ることができもしかしなか社 弾性に欠ける固
体物質で素子が構成されることか収 機械的衝撃に対し
てはきわめて脆く、破損しやすい欠点があム
この様な問題を解決するた数 特開昭６３−２４５８７
１号公報にあるようにイオン伝導性の無機化合物に可塑
性樹脂を複合化することで可撓性を付与し 機械的衝撃
に対しても破損しにくい固体電解質とする試みや、ポリ
エチレンオキシド（ＰＥＯ）とアルカリ金属塩とからな
る高分子固体電解質が提案されている（”Ｆａｓｔ Ｊ
ｏｎ Ｔｒａｎｓｐｏｒｔｉｎ ５ｏｌｉｄ” ＰＪａ
ｎｉｓｈｓｔａｅｔ、ａｌ、、 Ｅｄｓ、 Ｐ、 １３
１（１９７９） Ｎｏｒｔｈ Ｈｏ１ａｎｄ Ｐｕｂｌ
ｉｓｈｉｎｇ Ｃｏ、 ）。しかしなか収イオン伝導性
の無機化合物には耐湿性をはじめとする化学的安定性に
欠けるものが多く、特にアルカリ金属イオンの伝導体で
は化学的安定性に乏しく、可塑性樹脂と複合化を行う際
の製造プロセス中で可塑性樹脂中の活性水素等の未反応
基あるいは雰囲気の微量水分・酸素により変質をきたす
ことが多く取扱が困難であるという欠点を有していも
−人 高分子固体電解質は無機系固体電解質に較べ 軽
量で、柔軟性に優れ 化学的に安定あるという特徴があ
ム
発明が解決しようとする課題
しかし一般の可塑性樹脂に較べると、均質なフィルム形
成が困難となることが多く、また均質性・成形性（フィ
ルム形成能）を高めようとするとイオン伝導性が低下す
るという欠点があった課題を解決するための手段
本発明を達成したもので、本発明の固形の電解質（友
ポリアミン化合物にエチレンオキサイド（ＥＯ）及びブ
チレンオキサイド（ＢＯ）を付加して得られるポリエー
テル化合塩 イオン交換性の層状化合物と、式ＭＸで表
されるイオン性物質（ただし、Ｍは電界の作用で固形電
解質組成物内を移動する金属イオン、プロトン、アンモ
ニウムイオンであり、Ｘは強酸のアニオンである）を少
なくとも含有する組成物であム
作用
このようにして得られる固形電解質組成物内にあっては
イオン性の化合物ＭＸはポリエーテル化合物とイオン
交換性の層状化合物とで複合体を形成し 層状化合物の
結晶の層間あるいは表面に高濃度に保持されイオン伝導
に有利な経路を形成すも 該固形電解質の製造に際し
ポリエーテル化合物は溶媒とイオン交換性の層状化合物
との混和を容易にし均一なイオン伝導経路の形成を促進
するとともく さらに イオン伝導性粉末の添加混合に
際しては該粉末の凝集を防止し 溶媒とイオン交換性の
層状化合物との均一な混合分散を可能にすも このよう
にして、高いイオン伝導性と均質性が発現される。さら
に ポリエーテル化合物のエチレンオキサイド鎖および
ブチレンオキサイド鎖とイオン交換性の層状化合物のマ
イクロポーラス構造とが絡まって良好な成形性と十分な
機械強度が付与されも
実施例
以下、本発明を実施例によりさらに詳細に説明する力（
本発明は以下の実施例に限定されるものではなｔ〜 ま
た 以下の実施例においてａ ％比は特に断わらない限
り重量訊 重量麹 重量比を表わす。[Detailed Description of the Invention] Industrial Fields of Application The present invention relates to solid electrolyte compositions used in electrochemical elements such as batteries, capacitors, sensors, display elements, and recording elements. Smaller and thinner batteries with no leakage It is possible to obtain solid electrochemical devices such as electric double layer capacitors. However, it is extremely brittle and easy to break, so there is no way to solve this problem.
As stated in Publication No. 1, an attempt was made to create a solid electrolyte that was made flexible by combining an ion-conducting inorganic compound with a plastic resin, making it less likely to be damaged by mechanical shock, and using polyethylene oxide (PEO). A polymer solid electrolyte consisting of alkali metal salt and alkali metal salt has been proposed ("Fast J
on Transportin 5solid” PJa
Nishstaet, al., Eds, P., 13
1 (1979) North Ho1 and Publ.
Ishing Co, ). However, many of the inorganic compounds with low ion conductivity lack chemical stability including moisture resistance.In particular, conductors of alkali metal ions have poor chemical stability, and when combined with plastic resins, Although it has the disadvantage that it is difficult to handle because it is often deteriorated by unreacted groups such as active hydrogen in the plastic resin or by trace amounts of moisture and oxygen in the atmosphere during the manufacturing process.
-People Polymer solid electrolytes are lighter, more flexible, and more chemically stable than inorganic solid electrolytes, which is the problem that the invention aims to solve.However, compared to general plastic resins, they are less able to form a homogeneous film. The present invention has been achieved as a means to solve the problems in which it is often difficult to improve homogeneity and formability (film-forming ability), and the ionic conductivity decreases when trying to improve homogeneity and formability (film-forming ability). The solid electrolyte (friend) of the present invention
A polyether compound salt obtained by adding ethylene oxide (EO) and butylene oxide (BO) to a polyamine compound. An ion-exchangeable layered compound and an ionic substance represented by the formula MX (where M is the result of the action of an electric field. metal ions, protons, ammonium ions that move within the solid electrolyte composition, where X is an anion of a strong acid. The ionic compound MX forms a complex with a polyether compound and an ion-exchange layered compound, and is held at a high concentration between the layers or on the surface of the layered compound's crystals, forming an advantageous path for ion conduction. When manufacturing electrolytes
The polyether compound not only facilitates the miscibility of the solvent and the ion-exchange layered compound and promotes the formation of a uniform ion-conducting path, but also prevents the aggregation of the ion-conductive powder when it is added and mixed, thereby preventing the solvent and ions from agglomerating. This enables uniform mixing and dispersion with the exchangeable layered compound.In this way, high ionic conductivity and homogeneity are achieved. Furthermore, the ethylene oxide chain and butylene oxide chain of the polyether compound are entangled with the microporous structure of the ion-exchange layered compound to provide good moldability and sufficient mechanical strength. Ability to explain in more detail (
The present invention is not limited to the following examples. Furthermore, in the following examples, a% ratio represents a weight ratio of koji to weight unless otherwise specified.
ポリアミン化合物にエチレンオキサイドとブチレンオキ
サイドを付加して得られるポリエーテル化合物（よ ポ
リアミン化合物をアルカリ触媒下で１００−１８０＼
１〜１０気圧でエチレンオキサイドおよびブチレンオキ
サイドを付加反応することにより得ることができも ポ
リアミン化合物としてＧＬ ポリエチレンイミン、ポ
リアルキレンポリアミンあるいはそれらの誘導体を用い
ることができも ポリアルキレンポリアミンとして、
ジエチレントリアミン、 トリエチレンテトラミスヘキ
サメチレンテトラミン、ジプロピレントリアミン等を挙
げることがができも エチレンオキサイドとブチレンオ
キサイドの付加モル数はポリアミン化合物の活性水素１
個当り２〜１５０モルであも 付加するエチレンオキサ
イド（ＥＯ）とブチレンオキサイド（ＢＯ）との比＋＆
８０／２０〜１０／９０ （ＥＯ／ＢＯ）であム ポ
リエーテルの平均分子量は１０００〜５００万であム
イオン性物質ＭＸとして８表 特に制限はない力（Ｌ
ｉＩ、 ＬｉＣｌ０ａ、 ＬｉＣＦｓＳＯｓ、 ＬｉＰ
Ｆａ、 ＬｉＢＦａ、 Ｌｉ５ＣＮ。A polyether compound obtained by adding ethylene oxide and butylene oxide to a polyamine compound.
GL can be obtained by addition reaction of ethylene oxide and butylene oxide at 1 to 10 atm. Polyethyleneimine, polyalkylene polyamine or derivatives thereof can be used as the polyamine compound.
Examples include diethylene triamine, triethylenetetramishexamethylenetetramine, dipropylenetriamine, etc.The number of moles of ethylene oxide and butylene oxide added is 1 active hydrogen of the polyamine compound.
Ratio of ethylene oxide (EO) to butylene oxide (BO) to be added +&
80/20 to 10/90 (EO/BO) The average molecular weight of polyether is 10 to 5 million, and Table 8 is used as an ionic substance MX.
iI, LiCl0a, LiCFsSOs, LiP
Fa, LiBFa, Li5CN.
ＬｉＡｓＦ５． ＮａＩ、 Ｎａ５ＣＮ、 ＮａＢｒ、
ＫＩ、 ＡｇＮＯｓ、 ＣｕＣ１３Ｍｇ（ＣＩＯｚ）
＊、 ＡｌＣｌ５等の可溶性の塩が用いられも特に Ｍ
Ｘが一価のアルカリ金属塩である場合はアルカリ金属イ
オンがポリエーテルとイオン交換性の層状化合物とで複
合体を形成することで化学的に安定化されるので、アル
カリ金属イオン伝導性の無機化合物に較べると取扱が簡
単であるという利点があａ
イオン交換性の層状化合物として（よ モンモリロナイ
ト、ヘクトライト、サポナイト、スメクタイト等のけい
酸塩を含む粘土鉱物 りん酸ジルコニラ収 りん酸チタ
ニウム等のりん酸エステ／ｌｚ。LiAsF5. NaI, Na5CN, NaBr,
KI, AgNOs, CuC13Mg (CIOz)
*Soluble salts such as AlCl5 may also be used, especially M
When X is a monovalent alkali metal salt, the alkali metal ion is chemically stabilized by forming a complex with polyether and an ion-exchangeable layered compound. It has the advantage of being easier to handle compared to other compounds.As an ion-exchange layered compound, clay minerals containing silicates such as montmorillonite, hectorite, saponite, and smectite, zirconyl phosphate, and phosphorus such as titanium phosphate Acid beauty salon/lz.
バナジン限 アンチモン阪 タングステン阪 あるいは
それらを第４級アンモニウム塩等の有機カチオンある
いはエチレンオキサイド、プロピレンオキサイド等の有
機の極性化合物で変性したものが挙げられも
さらに固形電解質には 化学的安定性が損なわれない限
りイオン伝導性の粉末を添加混合することができも こ
のようなイオン伝導性の粉末としては例えｉ４ Ｍｅ
Ｃｕ４Ｉｐ−ｘｃ１ｓ＊ｘ （ｘ−０，２５−１，０，
Ｍｅ−Ｒｂ、 Ｋ、 ＮＨａあるいはそれらを混合した
もの）やＣｕＩ−ＣｕｅＯ−ＭｏＯｓガラス等の銅イオ
ン伝導性固体電解ＩＬ ＲｂＡｇａｌｓ、Ａｇ＊Ｓ３
＝ ＡｇＩ−Ａｇ２ｄ−ＭｏｏｎガラＡ Ａｇ５Ｉ
ａＷ０４等の銀イオン伝導性固体電解質、ＬｉＩ、Ｌｉ
Ｉ ・Ｉ（ａＱ、 Ｌｉ−β−Ａ１２０ｓ、 Ｌｉ
ｌ−Ｌｉ２５−Ｂａｓｓ等のリチウムイオン伝導性固体
電解質、
Ｈ＊Ｍｏ＋ｔＰＯ４ｓ ・２９ＨｅＱ、 ＨｓＷ＋ａＰ
Ｏ４ｓ ・２９ＨａＯ等のプロトン導性固体電解質を用
いることができも 平均粒径が１μｍ以下の超微粒子か
ら数１０μｍの粒子のものまで何れも用いることができ
も
本発明の固体電解質組成物は次の様にして得られも イ
オン性化合物を１から５０％溶解した溶剤にイオン交換
性の層状化合物粉末を１〜５０％となるように加え 次
にＢＯ鎖およびＢＯ鎖を有するポリエーテル化合物をス
ラリー全体に対して０．１〜２０％の割合になるように
加え ディスパーサ等の混合粉砕機により粉砕混合して
固形分含量が５〜９５％の電解質スラリーを調製すム次
く このようにして得たスラリーをそのまま成形する力
＼ あるいはテフロン板とかナイロンメツシュシートと
かの支持体上に流延あるいは塗布して成形した衡 溶剤
を一部あるいは全部散逸させることで固形電解質組成物
が得られも 支持体がメツシュ状であれば支持体を一体
化したままで固形電解質組成物として用いることも可能
であム必要に応よ これらの工程は相対湿度が４０％以
下の乾燥雰囲気中で行われも
また 溶剤として（よ アセトン、メチルエチルケトン
、メチルイソブチルケトン等のケトン系溶ｉｎ−ヘキサ
ン、 ｎ−へブタン、ｎ−オクタン、 シクロヘキサン
等の飽和炭化水素系溶剋 ベンゼン、トルエン、キシレ
ン等の芳香族系溶剋 酢酸エチ／ｋ 酢酸プチノｋ
プロピレンカーボネート等のエステル系溶剋 メタノー
ノｋ エタノール、イソブロピルアルコーノｋ エチレ
ングリコール、グリセリン、ポリエチレングリコール等
のアルコール系溶剋 アセトニトリル等のニトリル類
あるいは水が用いられも
〈実施例１〉
分子内に１０個のＮ原子を含有するポリエチレンイミン
にエチレンオキサイド（ＥＯ）とブチレンオキサイド（
ＢＯ）をＥＯとＢＯＯ比が３０／７０となるように付加
して得た平均分子量が１８００００のポリエーテル化合
物をアセトニトリルに溶解し２０％のポリエーテル溶液
（Ａ）を調整した ざらへ イオン性物質としてＬｉＣ
Ｆａ Ｓｏｎを１０％溶解したポリエーテル溶液（Ａ）
に 固形分含量が３０％となるように平均粒径が２５μ
ｍのγ−りん酸ジルコニウム粉末を添加Ｌ ４０℃で
２４時間撹半混合し九 得られた電解質スラリーを平滑
なテフロン製の板の上でドクターブレードを用い塗布し
た挑 １３０℃の乾燥アルゴン気流中で１時間乾燥しさ
らに５時間真空乾燥することで、大きさ ８０／８０ｍ
瓜 厚さ２５μｍのリチウムイオン伝導性のシート状の
固形電解質成形体（Ａ１）を電池
〈実施例２〉
トリエチレンテトラミンにＥＯとＢＯをＥＯ／ＢＯ＝８
０／２０ （重量比）の割合で付加することで得た平
均分子量が８０００のポリエーテル化合物をプロピレン
カーボネート中に溶解し１０％のポリエーテル溶液（Ｂ
）を調整しな さらにイオン性物質としてＬｉＣＩＯ
４を１０％溶解したポリエーテル溶液（Ｂ）に 固形分
含量が２０％となるように平均粒径が１５μｍのモンモ
リロナイト粉末を添加し ４０℃で２４時間撹半混合し
た得られた電解質スラリーを平滑なテフロン製の板の上
で厚さ８５μへ 開口率４０％、３３０メツシユのポリ
エステルメツシュに塗布した後、 １３０℃の乾燥アル
ゴン気流中で１時間乾燥しさらに５時間真空乾燥するこ
とで、大きさ ８０／８０ｍＫ 厚さ１１０μｍのシ
ート状のリチウムイオン伝導性の固形電解質成形体（Ｂ
１）を得？。Vanadine, antimony, tungsten, or those modified with organic cations such as quaternary ammonium salts or organic polar compounds such as ethylene oxide and propylene oxide are listed, but solid electrolytes also have a risk of loss of chemical stability. Although it is possible to add and mix ion conductive powder as long as there is no
Cu4Ip-xc1s*x (x-0,25-1,0,
Copper ion conductive solid electrolyte IL such as Me-Rb, K, NHa or a mixture thereof) and CuI-CueO-MoOs glass, RbAgals, Ag*S3
= AgI-Ag2d-Moon Gala A Ag5I
Silver ion conductive solid electrolyte such as aW04, LiI, Li
I ・I(aQ, Li-β-A120s, Li
Lithium ion conductive solid electrolyte such as l-Li25-Bass, H*Mo+tPO4s ・29HeQ, HsW+aP
A proton-conducting solid electrolyte such as O4s/29HaO can be used, and any particle size ranging from ultrafine particles with an average particle size of 1 μm or less to particles of several tens of μm can be used, but the solid electrolyte composition of the present invention has the following properties. Add 1 to 50% of the ion exchange layered compound powder to a solvent in which 1 to 50% of the ionic compound is dissolved, and then add the BO chain and the polyether compound having the BO chain to the entire slurry. The electrolyte slurry is added to the electrolyte slurry at a ratio of 0.1 to 20% and mixed using a mixer such as a disperser to prepare an electrolyte slurry with a solid content of 5 to 95%. A solid electrolyte composition can be obtained by dissipating some or all of the solvent. If it is in the form of a mesh, it is possible to use it as a solid electrolyte composition with the support integrated.If necessary, these steps may be carried out in a dry atmosphere with a relative humidity of 40% or less. Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, saturated hydrocarbon solvents such as n-hebutane, n-octane, and cyclohexane, aromatic solvents such as benzene, toluene, and xylene, and acetic acid. Ethi/k acetate puchino-k
Ester-based solvents such as propylene carbonate, methanol, ethanol, isopropyl alcohol, alcohol-based solvents such as ethylene glycol, glycerin, polyethylene glycol, etc. Nitriles such as acetonitrile
Alternatively, water may be used. Example 1 Ethylene oxide (EO) and butylene oxide (
A 20% polyether solution (A) was prepared by dissolving a polyether compound with an average molecular weight of 180,000 obtained by adding BO) at an EO to BOO ratio of 30/70 in acetonitrile. as LiC
Polyether solution containing 10% Fa Son (A)
The average particle size is 25μ so that the solids content is 30%.
γ-zirconium phosphate powder was added to the mixture at 40°C for 24 hours, and the resulting electrolyte slurry was coated on a smooth Teflon plate using a doctor blade in a dry argon stream at 130°C. By drying for 1 hour and vacuum drying for another 5 hours, the size is 80/80m.
Melon A lithium ion conductive sheet-like solid electrolyte molded body (A1) with a thickness of 25 μm is used as a battery (Example 2) EO and BO are added to triethylenetetramine (EO/BO=8)
A 10% polyether solution (B
) and LiCIO as an ionic substance.
Montmorillonite powder with an average particle size of 15 μm was added to a polyether solution (B) in which 10% of 4 was dissolved so that the solid content was 20%, and the mixture was stirred and mixed at 40°C for 24 hours.The resulting electrolyte slurry was smoothed. It was coated on a polyester mesh of 330 mesh with an aperture ratio of 40% to a thickness of 85μ on a Teflon board, dried for 1 hour in a dry argon stream at 130℃, and then vacuum dried for 5 hours. 80/80mK Sheet-like lithium ion conductive solid electrolyte molded body (B
Got 1)? .
〈実施例３〉
ヘキサメチレンテトラミンにＥＯとＢＯをＥＯ／Ｐ○＝
６０／４０の割合で付加することで得た平均分子量が１
５０００のポリエーテル化合物をイオン交換水に溶解し
１０％のポリエーテル溶液（Ｃ）を調整した さら番ミ
イオン性物質としてＬｉＣＩＯ４を２０％溶解した
ポリエーテル溶液（Ｃ）に 固形分含量が２０％となる
ように平均粒径が２５μｍのＴ−りん酸ジルコニウム粉
末を添加し４０℃で２４時間撹半混合した 得られた電
解質スラリーをシリコン樹脂製の板の上で厚さ８５μｍ
開口率４０％、 ３３０メツシユのポリエステルメツ
シュに塗布した後、 ８０℃で１時間乾燥し大気中に一
昼夜放置して、大きさ８０ｘ８０ｍ爪厚さ１００μｍの
シート状の固形電解質成形体（ＣＩ）を得た この成形
体 （Ｃ１）中ではリチウムイオンのほかプロトンも伝
導イオンとして作用しているようであも
〈実施例４〉
ジプロピレンテトラミンにＥＯとＢＯＯ比がＥＯ／ＢＯ
＝８０／２０ （重量比）を付加することで得た平均分
子量が２５００００のポリエーテル化合物をイオン交換
水に溶解し１０％のポリエーテル溶液（Ｄ）を調整し丸
さら番！ イオン性物質としてＡｌＣｌ雪を２０％溶
解したポリエーテル溶液（Ｄ）に 固形分含量が２０％
となるように平均粒径が１５μｍのモンモリロナイト粉
末を添加し ４０℃で２４時間撹半混合した 得られた
電解質スラリーをシリコン樹脂製の板の上で厚さ８５μ
瓜 開口率４０％、３３０メツシユのポリエステルメツ
シュに塗布した後、 ８０℃で１時間乾燥し 大気中に
一昼夜放置して、大きさ８０ｘ８０ｒｎ爪 厚さ１００
μｍのシート状の固形電解質成形体（Ｄｌ）を電池 こ
の成形体中ではアルミニウムイオン、プロトンが伝導イ
オンとして作用しているようであム
〈実施例５〉
実施例１と同様にして得られた電解質スラリーに無機固
体電解質として平均粒径が５μｍのＬｉ−β−Ａｌｉａ
ｓ粉末を２０重量％添加して電解質スラリー（Ｅ）を得
た これを平滑なテフロン製の板の上でドクターブレー
ドを用い塗布した槻 ８０℃の乾燥アルゴン気流中で１
時間乾燥しさらに５時間真空乾燥することで、大きさ８
０ｘ８０ｍ凪厚さ５５μｍのリチウムイオン伝導性のシ
ート状の固形電解質成形体（Ｅｌ）を得た表 電気伝
導度
試料Ｎｏ、 平均値 標準偏差（Ｓ／ｃｍ）
（Ｓ／ｃｍ）
４ｘｌＯ−”
２ｘｌＯ−”
８ｘｌＯ−’
４ｘｌＯ−’
８ｘｌＯ−”
±０．２
±０゜２
±０．１
±０．５
±０．２
１Ｏ−Ｉｌ
ｘｌＯ−’
ｘｌＯ−’
ｘｌｏ−’
ｘｌＯ−＠
る。<Example 3> EO and BO in hexamethylenetetramine EO/P○=
The average molecular weight obtained by adding at a ratio of 60/40 is 1
A 10% polyether solution (C) was prepared by dissolving 5,000 polyether compounds in ion-exchanged water.The solid content was 20% in a polyether solution (C) in which 20% of LiCIO4 was dissolved as an ionic substance. T-zirconium phosphate powder with an average particle size of 25 μm was added and mixed at 40°C for 24 hours.The resulting electrolyte slurry was placed on a silicone resin plate to a thickness of 85 μm.
After applying it to a 330-mesh polyester mesh with an aperture ratio of 40%, it was dried at 80°C for 1 hour and left in the air overnight to form a sheet-like solid electrolyte molded body (CI) with a size of 80 x 80 m and a nail thickness of 100 μm. In addition to lithium ions, protons also seem to act as conductive ions in this molded body (C1) obtained (Example 4).
A polyether compound with an average molecular weight of 250,000 obtained by adding =80/20 (weight ratio) was dissolved in ion-exchanged water to prepare a 10% polyether solution (D). A polyether solution (D) in which 20% of AlCl snow as an ionic substance is dissolved has a solid content of 20%.
Montmorillonite powder with an average particle size of 15 μm was added and mixed at 40°C for 24 hours. The resulting electrolyte slurry was spread on a silicone resin plate to a thickness of 85 μm.
Melon After applying it to a polyester mesh with an opening ratio of 40% and a mesh size of 330, it was dried at 80℃ for 1 hour and left in the air for a day and night to form a nail with a size of 80x80rn and a thickness of 100mm.
A battery using a μm sheet-like solid electrolyte molded body (Dl). In this molded body, aluminum ions and protons seem to act as conductive ions. Example 5 Obtained in the same manner as Example 1. Li-β-Alia with an average particle size of 5 μm was added to the electrolyte slurry as an inorganic solid electrolyte.
Electrolyte slurry (E) was obtained by adding 20% by weight of S powder. This was coated on a smooth Teflon plate using a doctor blade.
By drying for an hour and vacuum drying for another 5 hours, the size is 8.
Table for obtaining a lithium ion conductive sheet-like solid electrolyte molded body (El) with a thickness of 0x80m and a thickness of 55μm Electrical conductivity sample No. Average value Standard deviation (S/cm)
(S/cm) 4xlO-"2xlO-"8xlO-'4xlO-'8xlO-' ±0.2 ±0゜2 ±0.1 ±0.5 ±0.2 1O-Il xlO-'xlO-' xlo -'xlO-@ru.
径１０ｍｍの円板状に１０枚づつ打ち抜きそれぞれ２枚
の白金円板で挟＆５０ｋｇ／ｃｍ”の圧力で上下から加
圧した状態で、アルゴンガス雰囲気中で振幅１００ｍＶ
、周波数１０ＫＨｚの交流信号を白金円板間に加え固形
電解質成形体円板の２０℃での交流抵抗値を測定し九
得られた電気伝導度の平均値を表に示し九
発明の効果10 disks each with a diameter of 10 mm were punched out, each sandwiched between two platinum disks, and pressurized from above and below at a pressure of 50 kg/cm'' in an argon gas atmosphere with an amplitude of 100 mV.
An AC signal with a frequency of 10 KHz was applied between the platinum discs, and the AC resistance value of the solid electrolyte molded disc at 20°C was measured.
The average value of the electrical conductivity obtained is shown in the table.9 Effects of the invention
Claims (2)
レンオキサイドを付加して得られるポリエーテル化合物
と、イオン交換性の層状化合物と、式ＭＸで表されるイ
オン性物質（ただし、Ｍは電界の作用で固形電解質組成
物内を移動する金属イオン、プロトン、アンモニウムイ
オンであり、Ｘは強酸のアニオンである）を少なくとも
含有することを特徴とする固形電解質組成物。(1) A polyether compound obtained by adding ethylene oxide and butylene oxide to a polyamine compound, an ion exchange layered compound, and an ionic substance represented by the formula MX (where M is a solid electrolyte due to the action of an electric field). A solid electrolyte composition characterized in that it contains at least a metal ion, a proton, or an ammonium ion that moves within the composition, and X is an anion of a strong acid.
求項１記載の固形電解質組成物。(2) The solid electrolyte composition according to claim 1, wherein MX is an alkali metal salt.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2140936A JP2870988B2 (en) | 1990-05-30 | 1990-05-30 | Solid electrolyte composition |
| US07/706,988 US5188768A (en) | 1990-05-30 | 1991-05-29 | Solid form electrolyte composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2140936A JP2870988B2 (en) | 1990-05-30 | 1990-05-30 | Solid electrolyte composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0433951A true JPH0433951A (en) | 1992-02-05 |
| JP2870988B2 JP2870988B2 (en) | 1999-03-17 |
Family
ID=15280264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2140936A Expired - Fee Related JP2870988B2 (en) | 1990-05-30 | 1990-05-30 | Solid electrolyte composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2870988B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118480A (en) * | 1993-10-21 | 1995-05-09 | Sony Corp | Polymer solid electrolyte |
| CN115241528A (en) * | 2022-06-28 | 2022-10-25 | 电子科技大学长三角研究院(湖州) | Preparation method of montmorillonite and polyethyleneimine modified fluorine-containing meta-aramid-based polymer electrolyte |
-
1990
- 1990-05-30 JP JP2140936A patent/JP2870988B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118480A (en) * | 1993-10-21 | 1995-05-09 | Sony Corp | Polymer solid electrolyte |
| CN115241528A (en) * | 2022-06-28 | 2022-10-25 | 电子科技大学长三角研究院(湖州) | Preparation method of montmorillonite and polyethyleneimine modified fluorine-containing meta-aramid-based polymer electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2870988B2 (en) | 1999-03-17 |
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