JPH0433261A - Manufacture of electrode composition material - Google Patents
Manufacture of electrode composition materialInfo
- Publication number
- JPH0433261A JPH0433261A JP2137814A JP13781490A JPH0433261A JP H0433261 A JPH0433261 A JP H0433261A JP 2137814 A JP2137814 A JP 2137814A JP 13781490 A JP13781490 A JP 13781490A JP H0433261 A JPH0433261 A JP H0433261A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- powder
- slurry
- electrode composition
- active material
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002131 composite material Substances 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- 229920000570 polyether Polymers 0.000 claims abstract description 25
- 239000007772 electrode material Substances 0.000 claims abstract description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 6
- 239000011267 electrode slurry Substances 0.000 abstract description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004020 conductor Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- -1 ether compound Chemical class 0.000 description 9
- 230000010287 polarization Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002781 RbAg4I5 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明（よ 固体電池 キャパシ久 センサ、表示素子
、記録素子などの固体の電気化学素子に用いる電極組成
物の製造方法に関すも さらに詳しくは 特定のポリエ
ーテル化合物を電極活物質粒子、固体電解質粒子、熱可
塑性樹脂を含む溶媒中に添加するものであも
従来の技術
固体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など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が叙 弾性に欠ける固
体物質で素子が構成されていることか収 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よ
うな欠点を解決するた八 特開昭６３−２４５８７１号
公報にあるようへ 合成ゴムなどの熱可塑性樹脂を固体
電解質や電極活物質に混合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素子が提案されてい
も この暇電極活物質および固体電解質は電気絶縁性の
熱可塑性樹脂と混合され電極組成物として用いられも発
明が解決しようとする課題
このような電極活物質粉末 固体電解質粉末および熱可
塑性樹脂よりなる電極組成物ζよ 一般に熱可塑性樹脂
を溶解した溶剤中におのおのの粉末を分散してスラリー
状とし これを成形した後あるいは成形しながら溶剤を
散逸させて得も この際 固体電解質粉末はイオン性で
あるので水アルコ−／ｋ アセトンなどの親水性溶剤
または極性溶剤を用いて分散させると固体電解質粉末が
前記溶剤に僅かながら溶解しまた変質するのでトルエン
などの親油性の非極性溶剤が用いられも 従って、親水
性である固体電解質粉末は二次粒子を形成して熱可塑性
樹脂中に不均一に分散することが多く、電極活物質粉末
と均一に混合されず、とくく 電極組成物の電気容量を
大きくするために混合する固体電解質粉末の量を少なく
した゛場合、電極組成物内で十分なイオン伝導性が保持
され負電極の利用率が極端に低下するという問題点かあ
も また 均質な大面積の電極組成物を得ることが困難
であａ 本発明はこのような問題点を解決するものて
均質な電極組成物を得る電極組成物の製造法を提供する
ことを目的とすも
課題を解決するための手段
本発明の電極組成物の製造法は上記問題点を解決するも
ので、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を
電極活物質粉末 固体電解質粉末 および熱可塑性樹脂
を含む溶媒中に添加するものであ４
作用
このようにして得られる電極組成物は ポリエーテル化
合物が分散剤として作用し電極活物質粉末および固体電
解質粉末を均一に混合・分散させるためイオン伝導のた
めの経路が電極組成物内で均一に構築されることとなも
実施例
以下、本発明の一実施例をさらに詳細に説明する力ｔ
本発明は以下の実施例に限定されるものではな（〜 ま
な 以下の実施侭 比較例において服％はと（に断わら
ない限り重量餓 重量Ｘ 重量比を表わす。[Detailed Description of the Invention] Industrial Fields of Application The present invention relates to a method for producing an electrode composition for use in solid electrochemical devices such as solid-state batteries, capacitors, sensors, display elements, and recording elements. Conventional technology, in which a polyether compound is added to a solvent containing electrode active material particles, solid electrolyte particles, and thermoplastic resin.By using a solid electrolyte, there is no leakage, making the battery smaller and thinner.Electric double layer. Although it is possible to obtain solid-state electrochemical devices such as capacitors, the disadvantage is that the elements are constructed of solid materials that lack elasticity, making them extremely brittle and easily damaged by mechanical shock. In order to solve these drawbacks, as described in Japanese Patent Application Laid-Open No. 63-245871, flexibility can be imparted by mixing a thermoplastic resin such as synthetic rubber into the solid electrolyte or electrode active material.
Although an element that is not easily damaged by mechanical shock has been proposed, the problem to be solved by the invention is that the electrode active material and the solid electrolyte are mixed with an electrically insulating thermoplastic resin and used as an electrode composition. An electrode active material powder such as an electrode composition ζ consisting of a solid electrolyte powder and a thermoplastic resin is generally prepared by dispersing each powder in a solvent in which a thermoplastic resin is dissolved to form a slurry, which is then molded into a solvent after or during molding. In this case, since the solid electrolyte powder is ionic, if it is dispersed using a hydrophilic or polar solvent such as acetone, the solid electrolyte powder will dissolve slightly in the solvent and change its quality. Therefore, although a lipophilic non-polar solvent such as toluene is used, the hydrophilic solid electrolyte powder often forms secondary particles and is unevenly dispersed in the thermoplastic resin, and the electrode active material powder If the amount of solid electrolyte powder mixed is reduced in order to increase the capacitance of the electrode composition, sufficient ionic conductivity is maintained within the electrode composition, making it difficult to use the negative electrode. In addition, it is difficult to obtain a homogeneous electrode composition with a large area.The present invention solves these problems.
An object of the present invention is to provide a method for producing an electrode composition that yields a homogeneous electrode composition.Means for Solving the ProblemsThe method for producing an electrode composition of the present invention solves the above-mentioned problems. A polyether compound obtained by adding ethylene oxide and butylene oxide to a polyether is added to a solvent containing an electrode active material powder, a solid electrolyte powder, and a thermoplastic resin. Since the ether compound acts as a dispersant and uniformly mixes and disperses the electrode active material powder and the solid electrolyte powder, paths for ion conduction are uniformly constructed within the electrode composition. A power to explain one embodiment of the invention in further detail
The present invention is not limited to the following examples.
本実施例の電極活物質として（よ 金属鍼 金属鉱 金
属リチウムなどの単体金ｒｉＬＬｉ−Ａｌ、 ＬａＮｉ
５などの合金； 硫化楓 硫化机 銅シュブレル化合轍
銀シュブレル化合法 硫化チタン、硫化ニオス 硫化
モリブデンなどの金属硫化物； 二酸化マンガン、酸化
バナジウム 酸化コバルト、酸化クロムなどの金属酸化
物； 塩化区 ヨウ化舷 フッ化カーボンなどのハロゲ
ン化物； 活性炭、黒縁カーボンブラックなどの炭素材
料など常温で固体状の材料をあげることができも 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
固体電解質粉末として（＆ ＭＣｕ＊ ｂ−＋＋Ｃｈ
＋ｘ（ｘ＝ｏ。As the electrode active material of this example (metal acupuncture, metal ore, elemental gold such as metal lithium, riLLi-Al, LaNi
Alloys such as 5; maple sulfide, sulfide machine, copper Chevrell compound track, silver Chevrell compound method, titanium sulfide, nios sulfide, metal sulfides such as molybdenum sulfide; metal oxides such as manganese dioxide, vanadium oxide, cobalt oxide, chromium oxide; chloride, iodide Halides such as fluorinated carbon; materials that are solid at room temperature such as activated carbon and carbon materials such as black edge carbon black; It can also be used as solid electrolyte powder (&MCu*b-++Ch
+x (x=o.
２！ｒ１．ｏ、 Ｍ−Ｒｂ、 Ｋ、 ＮＨ４またはそれ
らを混合したもの）やＣｕｂ−Ｃｕ２ｅ−Ｍｏｓｓガラ
スなどの銅イオン伝導性固体電解質、ＲｂＡｇ４Ｉ５、
Ａｇ＊Ｓｉ、 ＡｇＩ−Ａｇ２０−Ｍｏｏｔガラ入 Ａ
ｇ・ｌ４ＷＯａなどの銀イオン伝導性固体電解覧 Ｌｉ
ｌ５ＬｉＩ−Ｈ２Ｏ，Ｌｉ−β−Ａ １２０ｓ、ＬｉＩ
−Ｌｉａｒ−Ｂｕｓ＄、ＰＥ０−ＬｉＣＦｍ５Ｏｓなど
のリチウムイオン伝導性固体電解覧ＨｓＭｏ＋ｔＰＯｎ
＊ ・２９ＨＲＱ、 ＨａＷ＋ｔＰＯ１・２９Ｈ２０な
ど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 平均粒径が１μｍ
以下の超微粒固体電解質粉末であっても均一に分散でき
も 熱可塑性樹脂としてζ１ １．４−ポリブタジェン
、天然ゴな ポリイソプレン、 ＳＢＲ，ＮＢＲ，ＳＢ
Ｓ、 ＳＩＳ、 ＳＥ Ｂ Ｓ、 プチルゴベ
フォスファゼンゴベ ポリエチレン、ポリプロピレン、
ポリエチレンオキシド、ポリスチレン、 １，２−ポリ
ブタジェン、ポリテトラフルオロエチレンなどを使用す
るのが好ましく℃
電極組成物の製造にあたっては分散媒として、ｎ−ヘキ
サン、ｎ−へブタン、ｎ−オクタン、シクロヘキサン、
ベンゼン、 トルエン、キシレン、酢酸エチ）Ｉ−、）
リクレンなどの親油性の非吸水性の固体電解質と反応し
ない飽和炭化水素系溶剋 芳香族炭化水素系溶剋 ハロ
ゲン化炭化水素溶剋 エステル系溶剤が用いられも
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番表
ポリアミン化合物をアルカリ触媒下で１００−１８０ｔ
、 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（よ ポリエチレンイミン
、ポリアルキレンポリアミンまた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ン、ヘ
キサメチレンテトラミン、ジプロピレントリアミンなど
をあげることがができる。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モルであム 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
は ８０／２０〜１０／９０ （＝ＥＯ／ＢＯ）であ
ム ポリエーテルの平均分子量は１０００〜１００万で
あも
本実施例の電極組成物は次のようにして得られも 熱可
塑性樹脂を親油性の溶剤に溶解し１〜２０％の溶液とし
たものへ 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 電極活物質粉
末と固体電解質粉末必要に応じ導電剤粉末と、またはあ
らかじめ所定の配合比で電極活物質粉末と固体電解質粉
末と必要に応じ導電剤粉末とを混合した混合物を加えボ
ールミ）ｋ ディスパーサなどの混合粉砕機により粉
砕混合して固形分含量が５〜９５％の電極スラリーを調
製すム またζ友 ポリエーテル化合物を溶解した親油
性の溶剤に電極活物質粉末と固体電解質粉末 必要に応
じ導電剤粉末と、またはあらかじめ所定の配合比で電極
活物質粉末と固体電解質粉末と必要に応じ導電剤粉末と
を混合した混合物を分散したスラリーと、熱可塑性樹脂
を親油性の溶剤に溶解した溶液とを混合分散することで
電極スラリーを得ることもできも
次へ このようにして得たスラリーをそのまま成急 ま
たはテフロン板とかナイロンメツシュシートとかの支持
体上に流延または塗布して成形した喪 溶剤を散逸させ
ることで電極組成物が得られも 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電極組成物として用い
ることも可能であも
これらの工程Ｃヨ 相対湿度が４０％以下の乾燥雰囲
気中で行なわれも 好ましく３上 露点がマイナス２
０℃以下の乾燥した窒素あるいはアルゴン等の不活性ガ
ス雰囲気中で行なわれも
（実施例１）
熱可塑性樹脂であり結着剤として作用する低密度ポリエ
チレン（エフセレンＶＬ−２００、密度＝０．９、住人
化学工業製）をトルエンに溶解し１０％のポリエチレン
溶液を調整し九 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ＢＯの比が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トルエンに溶解し２０％のポリエ
ーテル溶液（Ａ）を調整した ポリエーテル溶液へ 固
形分含量が５０％となるように平均粒径が１μｍの銅イ
オン伝導性固体電解質粉末（ＲｂＣｕ４Ｉ＋ 、５Ｃ１
ｓ、ｓ、 密度＝４．７）と平均粒径が０．８μｍの
銅シュブレル相化合物（Ｃｕ２Ｍｏ＠Ｓ〒、・。2! r1. copper ion conductive solid electrolytes such as Cub-Cu2e-Moss glass, RbAg4I5,
Ag*Si, AgI-Ag20-Moot glass A
List of silver ion conductive solid electrolytes such as g/l4WOa Li
l5LiI-H2O, Li-β-A 120s, LiI
-Liar-Bus$, PE0-LiCFm5Os and other lithium ion conductive solid electrolytes HsMo+tPOn
*Proton-conducting solid electrolytes such as 29HRQ, HaW+tPO1, 29H20, etc. can be used.Anything 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 average particle size is 1 μm.
Even the following ultrafine solid electrolyte powders can be uniformly dispersed. As thermoplastic resins, ζ1 1.4-polybutadiene, natural polyisoprene, SBR, NBR, SB
S, SIS, SE B S, Petit Gobe
Phosphazengobe polyethylene, polypropylene,
Preferably, polyethylene oxide, polystyrene, 1,2-polybutadiene, polytetrafluoroethylene, etc. are used as a dispersion medium in producing the electrode composition.
Benzene, toluene, xylene, ethyl acetate) I-,)
Saturated hydrocarbon solvents that do not react with lipophilic non-water-absorbing solid electrolytes such as Recuren Aromatic hydrocarbon solvents Halogenated hydrocarbon solvents Even if ester solvents are used, ethylene oxide and butylene oxide are added to polyamine compounds. List of polyether compounds obtained by addition
100-180t of polyamine compound under alkaline catalyst
As polyamine compounds, polyethyleneimine, polyalkylene polyamines or their derivatives can be used as polyalkylene polyamines, which can be obtained by addition reaction of ethylene oxide and butylene oxide at 1 to 10 atm.
Examples include diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and dipropylenetriamine. The number of moles of ethylene oxide and butylene oxide added is 2 to 150 moles per active hydrogen of the polyamine compound.The ratio of ethylene oxide (EO) to butylene oxide (BO) to be added is 80/20 to 10/90 ( = EO/BO) Even if the average molecular weight of the polyether is 10 to 1 million, the electrode composition of this example can be obtained as follows. To make a 20% solution, add a polyether compound to the entire slurry at a ratio of 0.1 to 20%, and add electrode active material powder and solid electrolyte powder, if necessary, with conductive agent powder or a predetermined solution. Add a mixture of electrode active material powder, solid electrolyte powder, and conductive agent powder if necessary in a mixing ratio, and grind and mix using a mixer such as a disperser to create an electrode slurry with a solid content of 5 to 95%. In addition, electrode active material powder and solid electrolyte powder are prepared in a lipophilic solvent in which a polyether compound is dissolved, and if necessary, conductive agent powder is added, or electrode active material powder and solid electrolyte powder are mixed in a predetermined mixing ratio in advance. Electrode slurry can be obtained by mixing and dispersing a slurry containing a mixture mixed with a conductive agent powder if necessary, and a solution containing a thermoplastic resin dissolved in a lipophilic solvent. The electrode composition can be obtained by dissipating the solvent, or by casting or coating the obtained slurry on a support such as a Teflon plate or a nylon mesh sheet. It is possible to use it as an electrode composition with the support integrated, but these steps may be carried out in a dry atmosphere with a relative humidity of 40% or less, preferably 3 or above, and a dew point of -2.
(Example 1) Low-density polyethylene (F-selen VL-200, density = 0.9), which is a thermoplastic resin and acts as a binder, A 10% polyethylene solution was prepared by dissolving ethylene oxide (EO) and butylene oxide (BO) into polyethyleneimine containing 10 N atoms in the molecule. Ratio is 30/70
A 20% polyether solution (A) was prepared by dissolving a polyether compound with an average molecular weight of 180,000 in toluene. Copper ion conductive solid electrolyte powder (RbCu4I+, 5C1
s, s, density = 4.7) and a copper Chevrel phase compound (Cu2Mo@S〒, .) with an average particle size of 0.8 μm.
密度＝ ５．８）との２：１の混合物を分散させた檄ポ
リエチレン溶液を加え固形分含量が５０％の電極粉末分
散液（Ｂ）を得九 な耘 前記銅イオン伝導性固体電解
質（よ 所定量のＲｂＣ１，ＣｕＩ、 ＣｕＣ１よりな
る混合物を２００℃で１７時間密閉ガラス容器中で加熱
反応することで得九 また 銅シュブレル相化合物ｉｔ
ＭｏＳ２． Ｃｕ、 Ｓの混合物を真空中で１００
０℃で４８時間加熱反応することで得九所定量のポリエ
ーテル溶液（Ａ）と電極粉末分散液（Ｂ）とトルエンを
混合したの板 アルミナ製のボールミル中で２４時間混
合粉砕して電極粉末のスラリーを得た 前記スラリーを
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
布した寵 ８０℃の乾燥窒素中で５時間乾燥し大きさ８
０ｘ８０ｍｒｒｈ 厚さ１５４±５μｍの電極粉末含
量が８５容積％のシート状の電極成形体（Ｂ１）を得九
（比較例１）
固体電解質分散液（Ｂ）の代わりにポリエーテルを含ま
ない電極粉末分散液（Ｃ）を用いた以外は実施例１と同
様にして電極粉末含量が８５容積％のシート状の電極成
形体（ＣＩ）を得た（実施例２）
電極粉末として銀イオン伝導性の平均粒径が８μｍのＡ
ｇｅ Ｉ ｓ １０４粉末と平均粒径が１０μｍのバナ
ジン酸銀粉末（Ａｇｅ、ＴＶ２ｘｓ）との３：２の混合
物を用（＼ ポリエーテル化合物として、 トリエチレ
ンテトラミンにＥＯとＢＯをＥＯ／ＢＯ＝８０／２０
（重量比）の割合で付加することで得た平均分子量が８
０００のポリエーテルを含む固体電解質分散液（Ｄ）を
用いた以外＆よ 実施例１と同様にして電極粉末含量が
９０容積％である厚みが１２５μｍ±１０の電極成形体
（Ｄｌ）を得た なｋ Ａｇ５１４ＷＯ４（ｉ Ａ
ｇｅｄ、 ＡｇＩ、 ＷＯｓを所定の割合で混合し４０
０℃で大気中で６時間加熱反応することで得た まｆ＝
Ａｇ・、〒Ｖ２Ｏ５はＡｇ粉末とＶ＊ Ｏｓを所定
の割合で混合し 封管中で５５０℃で６時間加熱反応す
ることで得九
（比較例２）
電極粉末分散液（Ｄ）の代わりにポリエーテルを含まな
い電極粉末分散液（Ｅ）を用いた以外は実施例２と同様
にして電極粉末含量が９０容積％のシート状の電極成形
体（Ｅｌ）を得九（実施例３）
電極粉末として、リチウムイオン伝導性の平均粒径が５
μｍのＬｉｌ・Ｆ２０粉末と平均粒径が６μｍの硫化ニ
オブ粉末（ＮｂＳ２）との１．１の混合物を用１、％
ポリエーテル化合物として、ヘキサメチレンテトラミ
ンにＥＯとＢＯをＥＯ／ＢＯ＝４０／６０の割合で付加
することで得た平均分子量が１５０００のポリエーテル
を含む電極粉末分散液（Ｆ）を用いた以外番ヨ 実施
例１と同様にして電極粉末含量が９０容積％である厚み
が８５±５μｍの電極成形体（Ｆｌ）を得島 な耘 Ｌ
ｉｌ−Ｆ２０． ＮｂＳ２は市販の試薬をエチルエーテ
ル中でボールミルにより粉砕したものを用いた
（比較例３）
電極粉末分散液（Ｆ）の代わりにポリエーテルを含まな
い電極粉末分散液（Ｇ）を用いた以外は実施例３と同様
にして電極粉末含量が９０容積％のシート状の電極成形
体（Ｇ１）を得九以下の方法により電極成形体の特性評
価を行なつ九
実施例１〜３、比較例１〜３で得られた電極成形体を直
径１０ｍｍの円板状におのおの２０枚づつ打ち抜き特性
試験用の試料とし總 実施例１および比較例１の電極円
板について、固体電解質としてＲｂＣｕａＩ＋ 、ｓＣ
ｈ、ｓ粉末１ｇｒを２００ ｋｇ／ｃｍ”の圧力で成形
した直径１０ｍｍのペレ・ソトを挟む形で上下に１枚づ
つ配置しさらにその上下に白金円板を配置した跣 全体
を５０ ｋ ｇ ／ ｃ ｍ−圧力で上下から加圧した
状態で、窒素ガス雰囲気中で１３０℃で３時間加熱し試
験電池Ｂ２（実施例１）およびＣ２（比較例１）を組み
立てた 実施例２および比較例２の電極円板について（
よ 固体電解質としてＡｇｅ Ｉ４ＷＯ４粉末を用いて
同様に試験電池Ｄ２ （実施例２）およびＦ２ （比
較例２）を組み立てた 実施例３および比較例３の電極
円板についてｔｉｔ 固体電解質としてＬｉＩ−Ｈａ
Ｏ粉末を用へ負極として厚さ０．３ｍｍ、 直径１０
ｍｍのリチウム円板を用い試験電池Ｆ２（実施例３）お
よびＧ２ （比較例３）を組み立てｔ４ Ｆ２およびＧ
２については加圧のみで加熱は行わなかった おのおの
同じものを１０個づつ組み立てた 試験電池Ｂ２、Ｃ２
について、 ０．６ｖの一定電圧テ１７時間充電した１
１ｍＡの一定電流で１０秒間放電を行な１．Ｌ 放電
直前および放電直後の電池電圧の差（分極）を測定し１
０個の電池について平均値と標準偏差値を求め九 まな
同じ電流値で０゜３ボルトまで連続放電を行ない放電
容量を束数理論容量（１００％）に対する電極活物質の
利用率を求め九 試験電池Ｄ２、Ｆ２については０゜５
０Ｖの一定電圧で１７時間充電比 ２００μＡの一定電
流値で１０秒間放電し分極の平均値と標準偏差値を求め
九 また 同じ電流値で０．３Ｖまで連続放電を行い理
論容量（１００％）に対する電極活物質の利用率を求め
た 試験電池Ｆ２およびＧ２についてｉ；Ｌ５０μＡの
一定電流で１０秒間放電し分極の平均値と標準偏差値を
求めなまた 同じ電流値で１． Ｏｖまで連続放電を行
い理論容量（１００％）に対する電極活物質の利用率を
求め九 分極値の結果を第１表 利用率の結果を第２表
に示す。また 電極成形体の曲げ強度を、長さ４０ｍｍ
幅５ｍｍの成形体を半径が５０ｍｍの曲面に沿って１秒
間に２回の割合で繰り返し折り曲げた限 破断に至るま
での回数で評価した 結果を第３表に示す。以上の測
定値は何れも２０℃での値であム
第１表 分極
実施例１
比較例１
実施例２
比較例２
実施例３
比較例３
第２表 利用率
実施例１９２
比較例１８３
実施例２８５
比較例２６８
実施例３７６
比較例３５４
理論容量を１００％とじへ
第３表 機械強度
電池 機械強度゛
実施例１１５５
比較例１１００
実施例２１４０
比較例２１００
実施例３１６０
比較例３１００
対応する比較例の曲げ強度を１０
＊
零
０とした
第１表から第３表に示した結果から明らかなよう艮 本
実施例による電極組成物は 比較例に較べ電極利用率は
高く、分極の標準偏差値は小さく電極活物質と電解質と
が均一に混合された均質な電極組成物であることがわか
も また 分極の平均値も小さくポリエーテル化合物力
丈 均一混合・分散の効果に加え イオン伝導体として
作用していると考えられム さらく 機械的強度を比較
すると、本実施例の電極組成物は従来のものに比べ大き
な強度を与えも
発明の効果
以上の実施例の説明で明かなよう＆ζ 本発明の電極組
成物の製造法によれば ポリエーテル化合物の界面活性
作用により長期間安定な電極スラリーを得ることができ
、このスラリーから溶媒を除去し固形化することで均質
な電極組成物を得ることができも また スラリーに添
加したポリエーテル化合物は電極組成物中にそのまま残
存しイオン伝導性を向上させ分極の小さい電極組成物が
得られるという効果があもAn electrode powder dispersion (B) with a solid content of 50% was obtained by adding a 2:1 mixture of copper ion-conducting solid electrolyte (density = 5.8) into an electrode powder dispersion (B) with a solid content of 50%. It is obtained by heating and reacting a mixture consisting of a predetermined amount of RbC1, CuI, and CuC1 at 200°C for 17 hours in a closed glass container.
MoS2. A mixture of Cu and S was heated to 100% in vacuo.
A plate of a mixture of a predetermined amount of polyether solution (A), electrode powder dispersion (B), and toluene was obtained by heating reaction at 0°C for 48 hours. Electrode powder was mixed and ground in an alumina ball mill for 24 hours. The slurry was coated on a smooth Teflon plate using a doctor blade and dried in dry nitrogen at 80°C for 5 hours to form a slurry of size 8.
0x80mrrh A sheet-shaped electrode molded body (B1) with a thickness of 154±5 μm and an electrode powder content of 85% by volume was obtained (Comparative Example 1) Electrode powder dispersion containing no polyether instead of the solid electrolyte dispersion (B) A sheet-shaped electrode molded body (CI) having an electrode powder content of 85% by volume was obtained in the same manner as in Example 1 except that liquid (C) was used (Example 2). A with a particle size of 8 μm
Using a 3:2 mixture of ge Is 104 powder and silver vanadate powder (Age, TV2xs) with an average particle size of 10 μm (\ As a polyether compound, add EO and BO to triethylenetetramine at EO/BO = 80 /20
The average molecular weight obtained by adding at a ratio of (weight ratio) is 8
An electrode molded body (Dl) having a thickness of 125 μm±10 and having an electrode powder content of 90% by volume was obtained in the same manner as in Example 1 except that a solid electrolyte dispersion (D) containing 000 polyether was used. Nak Ag514WO4 (i A
ged, AgI, and WOs were mixed at a predetermined ratio and 40
Maf= obtained by heating reaction in air at 0℃ for 6 hours
Ag・, V2O5 can be obtained by mixing Ag powder and V*Os at a predetermined ratio and heating and reacting in a sealed tube at 550°C for 6 hours (Comparative Example 2) Instead of electrode powder dispersion (D) A sheet-like electrode molded body (El) with an electrode powder content of 90% by volume was obtained in the same manner as in Example 2 except that an electrode powder dispersion (E) containing no polyether was used. (Example 3) Electrode As a powder, the average particle size of lithium ion conductivity is 5.
A mixture of 1.1 μm Lil F20 powder and niobium sulfide powder (NbS2) with an average particle size of 6 μm was used at 1.1%.
An electrode powder dispersion (F) containing a polyether with an average molecular weight of 15,000 obtained by adding EO and BO to hexamethylenetetramine at a ratio of EO/BO = 40/60 as a polyether compound was used. YO In the same manner as in Example 1, an electrode molded body (Fl) with a thickness of 85 ± 5 μm and an electrode powder content of 90% by volume was obtained.
il-F20. For NbS2, a commercially available reagent was used that was ground using a ball mill in ethyl ether (Comparative Example 3) Except that an electrode powder dispersion (G) containing no polyether was used instead of the electrode powder dispersion (F). A sheet-like electrode molded body (G1) having an electrode powder content of 90% by volume was obtained in the same manner as in Example 3. Characteristics of the electrode molded body were evaluated by the following methods.9 Examples 1 to 3, Comparative Example 1 20 disks each having a diameter of 10 mm were punched out from the electrode molded bodies obtained in steps 3 to 3, and used as samples for the characteristic test.For the electrode disks of Example 1 and Comparative Example 1, RbCuaI+ and sC were used as solid electrolytes.
H, S Powder 1 gr was molded under a pressure of 200 kg/cm'', and one piece of pere-soto with a diameter of 10 mm was placed on the upper and lower sides, and platinum disks were placed on the top and bottom.The entire hem was 50 kg/cm. Example 2 and Comparative Example 2 Test batteries B2 (Example 1) and C2 (Comparative Example 1) were assembled by heating at 130°C for 3 hours in a nitrogen gas atmosphere while pressurized from above and below at cm-pressure. Regarding the electrode disk (
Test batteries D2 (Example 2) and F2 (Comparative Example 2) were similarly assembled using Age I4WO4 powder as the solid electrolyte.
O powder is used as a negative electrode with a thickness of 0.3 mm and a diameter of 10 mm.
Assemble test batteries F2 (Example 3) and G2 (Comparative Example 3) using mm lithium disks t4 F2 and G
For No. 2, only pressurization was performed but no heating was performed. Ten identical batteries were assembled for each test battery B2 and C2.
1 charged for 17 hours at a constant voltage of 0.6V
1. Discharge at a constant current of 1 mA for 10 seconds. L Measure the difference in battery voltage (polarization) immediately before and after discharge.1
Calculate the average value and standard deviation value for 0 batteries. Perform continuous discharge to 0°3 volts at the same current value, and calculate the utilization rate of the electrode active material with respect to the discharge capacity and the theoretical capacity (100%) of the bundle number. 9. Test 0°5 for batteries D2 and F2
Charge ratio for 17 hours at a constant voltage of 0V Discharge for 10 seconds at a constant current value of 200 μA and calculate the average value and standard deviation of polarization. The utilization rate of the electrode active material was determined. For test batteries F2 and G2, discharge at a constant current of L50 μA for 10 seconds and determine the average value and standard deviation of polarization. Continuous discharge was performed up to Ov and the utilization rate of the electrode active material with respect to the theoretical capacity (100%) was determined.9 The results of the polarization value are shown in Table 1, and the results of the utilization rate are shown in Table 2. In addition, the bending strength of the electrode molded body was adjusted to 40 mm in length.
Table 3 shows the results of an evaluation based on the number of times a molded product with a width of 5 mm was repeatedly bent at a rate of 2 times per second along a curved surface with a radius of 50 mm until it broke. All of the above measured values are values at 20°C. Table 1 Polarization Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Table 2 Utilization Rate Example 192 Comparative Example 183 Example 285 Comparative example 268 Example 376 Comparative example 354 Theoretical capacity to 100% Table 3 Mechanical strength Battery Mechanical strength Example 1155 Comparative example 1100 Example 2140 Comparative example 2100 Example 3160 Comparative example 3100 Bending of corresponding comparative example As is clear from the results shown in Tables 1 to 3, where the strength is set to 10 * 0, the electrode composition according to this example has a higher electrode utilization rate than the comparative example, and the standard deviation of polarization is small. It can be seen that the active material and electrolyte are evenly mixed to form a homogeneous electrode composition.The average value of polarization is also small, and the polyether compound has the strength of a polyether compound.In addition to the effects of uniform mixing and dispersion, it also acts as an ion conductor. Comparing the mechanical strength, the electrode composition of this example has greater strength than the conventional one, but as is clear from the description of the example that the effect of the invention is greater than that of the electrode composition of the present invention. According to the manufacturing method, it is possible to obtain an electrode slurry that is stable for a long period of time due to the surface active action of the polyether compound, and by removing the solvent from this slurry and solidifying it, it is possible to obtain a homogeneous electrode composition. In addition, the polyether compound added to the slurry remains in the electrode composition, improving ionic conductivity and producing an electrode composition with low polarization.
Claims (1)
び固体電解質粉末を分散しスラリー状とする工程、およ
び前記スラリーから溶媒を除く工程を電極組成物の製造
法において、前記スラリー中に、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を添加する電極組成物の製造法
。A method for producing an electrode composition includes a step of dispersing an electrode active material powder and a solid electrolyte powder into a slurry in a solvent in which a thermoplastic resin is dissolved, and a step of removing the solvent from the slurry. A method for producing an electrode composition, in which a polyether compound obtained by adding ethylene oxide and butylene oxide to a compound is added.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2137814A JP2973469B2 (en) | 1990-05-28 | 1990-05-28 | Method for producing electrode composition |
| US07/706,234 US5190695A (en) | 1990-05-28 | 1991-05-28 | Methods to produce solid electrolyte and solid electrode composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2137814A JP2973469B2 (en) | 1990-05-28 | 1990-05-28 | Method for producing electrode composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0433261A true JPH0433261A (en) | 1992-02-04 |
| JP2973469B2 JP2973469B2 (en) | 1999-11-08 |
Family
ID=15207482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2137814A Expired - Fee Related JP2973469B2 (en) | 1990-05-28 | 1990-05-28 | Method for producing electrode composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2973469B2 (en) |
-
1990
- 1990-05-28 JP JP2137814A patent/JP2973469B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2973469B2 (en) | 1999-11-08 |
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