JPS63181259A - Manufacture of positive electrode body for cell - Google Patents
Manufacture of positive electrode body for cellInfo
- Publication number
- JPS63181259A JPS63181259A JP62012273A JP1227387A JPS63181259A JP S63181259 A JPS63181259 A JP S63181259A JP 62012273 A JP62012273 A JP 62012273A JP 1227387 A JP1227387 A JP 1227387A JP S63181259 A JPS63181259 A JP S63181259A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode body
- general formula
- acryloyl
- alkyl group
- 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 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 abstract description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 2
- 230000036425 denaturation Effects 0.000 abstract 2
- 238000004925 denaturation Methods 0.000 abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 1
- VETIYACESIPJSO-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOC(=O)C=C VETIYACESIPJSO-UHFFFAOYSA-N 0.000 description 1
- WBIOHYFEXBPYSK-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCOCCO WBIOHYFEXBPYSK-UHFFFAOYSA-N 0.000 description 1
- TVFJLSWPPLFHKR-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCC(O)OC1=CC=CC=C1 TVFJLSWPPLFHKR-UHFFFAOYSA-N 0.000 description 1
- QUASZQPLPKGIJY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOCCOC(=O)C=C QUASZQPLPKGIJY-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SWUVABDWGGGJQY-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO.OCCOCCOCCO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO.OCCOCCOCCO SWUVABDWGGGJQY-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、負極に金属リチウムまたはリチウム合金を活
物質として用いた電池において、結着材として固体電解
質を用いたことを特徴とする正極体の製造法に関するも
のである。さらに詳しくは、負極に金属リチウムまたは
リチウム合金を活物質として用いた電池において、アク
リロイル変性ポリアルキレンオキシドとリチウムイオン
塩とポリアルキレングリコールとから成る組成物を結着
材として用いたことを特徴とする電池用正極体の製造法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a positive electrode body in a battery using metallic lithium or a lithium alloy as an active material in the negative electrode, characterized in that a solid electrolyte is used as a binder. . More specifically, a battery using metallic lithium or a lithium alloy as an active material in the negative electrode is characterized in that a composition comprising an acryloyl-modified polyalkylene oxide, a lithium ion salt, and a polyalkylene glycol is used as a binder. The present invention relates to a method for manufacturing a positive electrode body for batteries.
［産業上の利用分野］
本発明は、高分子化合物を主成分とする固体電解質を正
極体の結着材として用いたリチウム電池に関する。[Industrial Application Field] The present invention relates to a lithium battery using a solid electrolyte mainly composed of a polymer compound as a binder for a positive electrode body.
［従来の技術およびその問題点］
リチウム電池の正極体は、種々の形状に加工するために
、結着材を使用する。しかし、よく用いられるポリテト
ラフルオロエチレンなどは、イオン伝導性が小さく、多
量に使用すると正極体活物質が結着材で被覆され、正極
の内部抵抗が増大して電池特性が低下する。そのため、
多量に結着材を含有することができず、加工性が悪いと
いう欠点がある。[Prior Art and its Problems] A binder is used to process the positive electrode body of a lithium battery into various shapes. However, commonly used materials such as polytetrafluoroethylene have low ionic conductivity, and when used in large quantities, the positive electrode active material is coated with a binder, increasing the internal resistance of the positive electrode and deteriorating battery characteristics. Therefore,
It has the disadvantage that it cannot contain a large amount of binder and has poor processability.
この問題を解決するため、例えば、特開昭５８−８５２
６９号では、高分子固体電解質組成物に有機溶媒を添加
して、見かけ上、固体状を保ったままイオン導電性を有
する組成物を正極体の結着材として用いる方法が提案さ
れている。しかし、。In order to solve this problem, for example, Japanese Patent Laid-Open No. 58-852
No. 69 proposes a method in which an organic solvent is added to a solid polymer electrolyte composition, and the composition has ionic conductivity while maintaining an apparent solid state, and is used as a binder for a positive electrode body. but,.
有機溶媒含有量の調整、脱溶媒等の工程が複雑であり、
用いられている有機溶媒の沸点がさほど高くないことか
ら、有機溶媒が使用中に組成物から徐々に気化してイオ
ン伝導性が低下したり、有機溶媒が組成物からにじみだ
したりするなど、長期信頼性に問題があった。Processes such as adjusting organic solvent content and removing solvent are complicated;
Since the boiling point of the organic solvent used is not very high, the organic solvent may gradually vaporize from the composition during use, resulting in a decrease in ionic conductivity, or the organic solvent may ooze out of the composition. There were reliability issues.
［問題を解決するための手段］
本発明は、負極に金属リチウムまたはリチウム合金を活
物質として用いた電池において、■下記の一般式（Ｉ）
ＣＨ２−Ｃ−Ｃ−０−（Ｉ）
（但し、Ｒは水素または低級アルキル基を示す）で表さ
れるアクリロイル基構造と、
下記の一般式（ＩＩ ）
（ＣＨ２ＣＨＲＯ）ｒｌ （ＩＩ ）（但
し、ｎは１〜３０の整数、
・Ｒは水素または低級アルキル基を示す）で表されるポ
リアルキレンオキシド構造を、含有するアクリロイル変
性ポリアルキレンオキシドと、
■リチウムイオン塩と、
■−一般式ｍ）
ＲＯ（ＣＨ２ＣＨＲＯ）ｎ−Ｒ（ＤＩ）（但し、Ｒは水
素または低級アルキル基、ｎは３〜３０の整数を示す）
で表されるポリアルキレングリコールと、から成る組成
物を硬化して、結着させることを特徴とする正極体の製
造法を提供することにより、前記目的を達成したもので
ある。[Means for solving the problem] The present invention provides a battery using metallic lithium or a lithium alloy as an active material in the negative electrode, which has the following general formula (I) CH2-C-C-0-(I) (however, , R represents hydrogen or a lower alkyl group), and the following general formula (II) (CH2CHRO) rl (II) (where n is an integer from 1 to 30, ・R is hydrogen or an acryloyl-modified polyalkylene oxide containing a polyalkylene oxide structure represented by (representing a lower alkyl group); ■ a lithium ion salt; and ■ - general formula m) RO(CH2CHRO)n-R(DI) (however, R is hydrogen or a lower alkyl group, and n is an integer of 3 to 30. By providing this, the above objective has been achieved.
本発明の組成物を構成するの成分である、前記一般式（
Ｉ）及び（Ｉりで表される構造を含有するアクリロイル
変性ポリアルキレンオキシドとしては、例えば、トリエ
チレングリコールモノアクリレート、テトラエチレング
リコールモノアクリレート、ポリエチレングリコールモ
ノアクリレート、メトキシテトラエチレングリコールモ
ノアクリレート、フェノキシテトラエチレングリコール
モノアクリレート、メトキシポリエチレングリコールモ
ノアクリレート、トリエチレングリコールモノメタクリ
レート、ポリエチレングリコールモノメタクリレート、
メトキシポリエチレングリコールモノメタクリレート、
ポリエチレングリコールジアクリレート、ポリエチレン
グリコールジメタクリレート、トリエチレングリコール
トリメチロールプロパントリアクリレート、および上記
の化合物のエチレングリコール構造をプロピレングリコ
ール構造に代えた化合物などを挙げることができる。The above general formula (
Examples of acryloyl-modified polyalkylene oxides containing structures represented by I) and (I) include triethylene glycol monoacrylate, tetraethylene glycol monoacrylate, polyethylene glycol monoacrylate, methoxytetraethylene glycol monoacrylate, and phenoxytetra Ethylene glycol monoacrylate, methoxypolyethylene glycol monoacrylate, triethylene glycol monomethacrylate, polyethylene glycol monomethacrylate,
methoxypolyethylene glycol monomethacrylate,
Examples include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol trimethylol propane triacrylate, and compounds obtained by replacing the ethylene glycol structure of the above compounds with a propylene glycol structure.
上記アクリロイル変性ポリアリキレンオキシドの分子量
は特に制限はなく、通常２００〜３００００、好ましく
は２５０〜３０００のものが用いられる。The molecular weight of the above-mentioned acryloyl-modified polyalkylene oxide is not particularly limited, and a molecular weight of usually 200 to 30,000, preferably 250 to 3,000 is used.
また、上記アクリロイル変性ポリアリキレンオキシドは
、２種以上併用することもできる。Furthermore, two or more of the above acryloyl-modified polyalkylene oxides can be used in combination.
また、本発明の組成物を構成する■成分であるリチウム
イオン塩としては、特に制限はないが、例えば、ＬｉＣ
見０４ 、Ｌｉｌ、Ｌｉ５ＣＮ。Furthermore, there is no particular restriction on the lithium ion salt which is component (1) constituting the composition of the present invention, but for example, LiC
See04, Lil, Li5CN.
ＬｉＢＦａ 、ＬｉＡｓＦ６ 、ＬｉＣＦ３ＳＯ３。LiBFa, LiAsF6, LiCF3SO3.
ＬｉＰＦ６などを使用することができる。LiPF6 or the like can be used.
上記リチウムイオン塩の含有量は、アクリロイル変性ポ
リアルキレンオキシド及びポリアルキレンゲリコールの
アルキレンオキシドユニット（以下ＥＯと略称する）に
対して（リチウムイオン塩／ＥＯ）Ｘ１００ （モル％
）が、好ましくは０．０５〜５０モル％、より好ましく
は０．１〜３０モル％となる量である。The content of the above lithium ion salt is (lithium ion salt/EO) x 100 (mol%) with respect to the alkylene oxide unit (hereinafter abbreviated as EO) of the acryloyl-modified polyalkylene oxide and polyalkylene gellicol.
) is preferably 0.05 to 50 mol%, more preferably 0.1 to 30 mol%.
上記リチウムイオン塩の含有量が多すぎると。If the content of the lithium ion salt is too high.
過剰のリチウムイオン塩が解離せず、単に混在するのみ
になり、このため電池性能が逆に低下する。また、含有
量が少なすぎても、解離するイオンの数が小さくなり、
電池性能が低下する。Excess lithium ion salts do not dissociate and simply coexist, resulting in a decrease in battery performance. Also, if the content is too low, the number of dissociated ions will be small,
Battery performance deteriorates.
また、上記リチウムイオン塩は、２種以上併用すること
ができる。Further, two or more of the above lithium ion salts can be used in combination.
本発明の組成物を構成する■成分である、前記一般式（
ＩＩＩ）で表されるポリアルキレングリコールとしては
、例えば、テトラエチレングリコール、ヘキサエチレン
グリコール、オクタエチレングリコール、及びそれらの
モノあるいはジメチルエーテル、並びに上記の化合物の
エチレングリコール構造をプロピレングリコール構造に
代えた化合物などを挙げることができる。また、上記ポ
リアルキレングリコールは、２種以上併用することがで
きる。Component (2) constituting the composition of the present invention is the general formula
Examples of the polyalkylene glycol represented by III) include tetraethylene glycol, hexaethylene glycol, octaethylene glycol, their mono- or dimethyl ethers, and compounds in which the ethylene glycol structure of the above compounds is replaced with a propylene glycol structure. can be mentioned. Moreover, two or more kinds of the above polyalkylene glycols can be used in combination.
上記ポリアルキレングリコールは、分子量が１００〜２
０００のものが好ましい０分子量が高すぎるとイオン伝
導性が低下し、８電池性能が低下する。また、分子量が
低すぎると沸点が低くなり、組成物から徐々に気化する
問題がある。The above polyalkylene glycol has a molecular weight of 100 to 2
If the molecular weight is too high, the ionic conductivity will decrease and the battery performance will decrease. Furthermore, if the molecular weight is too low, the boiling point will be low, causing the problem of gradual vaporization from the composition.
上記ポリアルキレングリコールの含有量は、前記アクリ
ロイル変性ポリアルキレンオキシドに対して、好ましく
は１〜５００重量％、特に好ましくは２５〜４００重量
％の範囲である。上記ポリアルキレングリコールの含有
量が多すぎると硬化物の機械的性質が低下し、実用上好
ましくない。The content of the polyalkylene glycol is preferably in the range of 1 to 500% by weight, particularly preferably 25 to 400% by weight, based on the acryloyl-modified polyalkylene oxide. If the content of the polyalkylene glycol is too large, the mechanical properties of the cured product will deteriorate, which is not preferred in practice.
また、少なすぎるとイオン伝導度が低下し、電池性能が
低下する。On the other hand, if the amount is too small, ionic conductivity decreases and battery performance deteriorates.
前記■成分、前記■成分及び前記■成分から成る本発明
の組成物を硬化させる手段としては、好ましくは加熱す
る方法が用いられる。加熱する方法による場合、必要な
らば、組成物に開始剤として、過酸化物、例えば、ベン
ゾイルパーオキサイド、メチルエチルケトンパーオキサ
イド、ｔ−プチルバーオキシビパレート、ジイソプロピ
ルパーオキシカーボネートなどを添加しておくのが好ま
しい。Preferably, heating is used as a means for curing the composition of the present invention comprising the component (1), the component (2), and the component (2). When using the heating method, if necessary, a peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxy biparate, diisopropyl peroxy carbonate, etc. may be added to the composition as an initiator. is preferred.
また正極体の活物質としては、例えば、二酸化マンガン
、三酸化モリブテン、五酸化バナジウムなどの金属酸化
物、また、チタンあるいはニオブの硫化物などを用いる
ことができる。Further, as the active material of the positive electrode body, for example, metal oxides such as manganese dioxide, molybdenum trioxide, vanadium pentoxide, and sulfides of titanium or niobium can be used.
正極体はこれらの活物質に、さらに導電剤、及び上記組
成物を混合し、加圧成形あるいは集電板に塗布乾燥して
加熱硬化させて作製される。The positive electrode body is produced by mixing these active materials, a conductive agent, and the above-mentioned composition, and press-molding the mixture or coating the mixture on a current collector plate, drying it, and curing it by heating.
［本発明の効果］
本発明は、高分子化合物を主成分とする固体電解質を正
極体の結着材に使用しているので、正極体の加工性２機
械的性質が良好であり、これを使用した電池容量は大き
く、長期使用において、液漏れ等の欠点のないものが得
られる。[Effects of the present invention] Since the present invention uses a solid electrolyte mainly composed of a polymer compound as a binder for the positive electrode body, the workability and mechanical properties of the positive electrode body are good. The capacity of the battery used is large, and it can be used for a long period of time without any defects such as leakage.
［本発明の実施例］
（実施例１）
負極として、直径１６ ｍ ｍ 、厚さ７０ＩＬｍの金
属リチウム円板を用いる。正極体は次の様に作製する。[Example of the present invention] (Example 1) A metal lithium disk having a diameter of 16 mm and a thickness of 70 ILm is used as a negative electrode. The positive electrode body is produced as follows.
二酸化マンガン５１．９ｍｇ、アセチレンブラック９．
７ｍｇの混合物に、メトキシポリエチレンゲルコールモ
ノアクリレート（新中村化学製ＡＭ−９０Ｇ）を４．９
ｍｇ、ポリエチレングリコールジメタクリレート（新中
村化学製９Ｇ）１．ａｍｇ、ベンゾイルパーオキサイＩ
ＳＯ，０６５ｍｇを混合し、これを７．５ｔｏｎ／ｃｒ
ｒｆの圧力で加圧成形し、直径１３ｍｍ、厚さ３００ｐ
ｍの円板状にする。さらに、ジメトキシポリエチレング
リコール（旭電化製ＬＸ−５２１）に過塩素酸リチウム
を溶解させた（濃度０．７５ｍ ｍｏｌ）溶液１０ＩＬ
ｆＬを上記の正極体用の円板に含浸させ、１００℃〒３
時１ｉｆｔ加熱処理して、厚み３００γｍの正極体を作
製した。成形性及び機械的強度も良好であった。また、
電解質用の組成物として、ＡＭ−９０Ｇを０．７５ｇ、
Ｍ−９Ｇを０．２５ｇ、過塩素酸’）ｆ’）ム１ｃＬＸ
−５２１に溶解した溶液（濃度０ 、７５ ｍｏｌ／Ｉ
Ｌ）、及び光増感剤として、２．２−ジメトキシアセト
フェノン０．０１ｇ／ｆＬの混合液を１ｍＪｌ準備した
。この電解質溶液を８ｇｆＬｔ−前記リチウム金属円板
に塗布し、２５０Ｗの超高圧水銀灯を用い、５ｍＷ／
ｃ ｍの照度で３分間照射して、厚み５０ｐｍの硬化フ
ィルムを形成した。これに前記正極板を積層して、電池
を作り、４３ｐＡで定電流放電試験を行ない、７．３ｍ
Ａｈの電池容量を得た。Manganese dioxide 51.9 mg, acetylene black 9.
Add 4.9 mg of methoxypolyethylene gelcol monoacrylate (AM-90G manufactured by Shin Nakamura Chemical) to 7 mg of the mixture.
mg, polyethylene glycol dimethacrylate (Shin Nakamura Chemical 9G) 1. amg, benzoyl peroxyl I
Mix 065mg of SO, and add 7.5ton/cr
Pressure molded with RF pressure, diameter 13mm, thickness 300p
Make into a disk shape of m. Furthermore, 10 IL of a solution (concentration 0.75 mmol) of lithium perchlorate dissolved in dimethoxypolyethylene glycol (Asahi Denka LX-521) was added.
Impregnate fL into the disk for the positive electrode body and heat at 100℃〒3
A positive electrode body having a thickness of 300 γm was produced by heat treatment for 1 ift. The moldability and mechanical strength were also good. Also,
As a composition for electrolyte, 0.75g of AM-90G,
0.25g of M-9G, perchloric acid')f')mu1cLX
-521 solution (concentration 0, 75 mol/I
1 mJl of a mixed solution containing 0.01 g/fL of 2.2-dimethoxyacetophenone as a photosensitizer was prepared. This electrolyte solution was applied to 8gfLt-the above lithium metal disk, and using a 250W ultra-high pressure mercury lamp, 5mW/
A cured film with a thickness of 50 pm was formed by irradiation for 3 minutes at an illumination intensity of cm. The above-mentioned positive electrode plate was laminated on this to make a battery, and a constant current discharge test was performed at 43 pA.
A battery capacity of Ah was obtained.
（比較例１）
実施例１において、結着材としてポリテトラフルオロエ
チレンを用いた以外は実施例１と同様にして電池を作り
、同様の放電試験を行なったところ、電池容量は３．５
ｍＡｈであった。(Comparative Example 1) A battery was made in the same manner as in Example 1 except that polytetrafluoroethylene was used as the binder, and a similar discharge test was conducted. As a result, the battery capacity was 3.5.
It was mAh.
Claims (1)
用いた電池において、 （１）下記の一般式（ I ） ▲数式、化学式、表等があります▼（ I ）
（但し、Ｒは水素または低級アルキル基を示す）で表さ
れるアクリロイル基構造と、 下記の一般式（II） −（ＣＨ＿２−ＣＨＲＯ）＿ｎ（II） （但し、ｎは１〜３０の整数、 Ｒは水素または低級アルキル基を示す） で表されるポリアルキレンオキシド構造を、含有するア
クリロイル変性ポリアルキレンオキシドと、 （２）リチウムイオン塩と、 （３）一般式（III） ＲＯ（ＣＨ＿２ＣＨＲＯ）＿ｎ−Ｒ（III） （但し、Ｒは水素または低級アルキル基、 ｎは３〜３０の整数を示す） で表されるポリアルキレングリコールと、 から成る組成物を硬化して、結着させることを特徴とす
る電池用正極体の製造法。[Claims] In a battery using metallic lithium or lithium alloy as an active material in the negative electrode, (1) the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
(However, R represents hydrogen or a lower alkyl group) and the following general formula (II) -(CH_2-CHRO)_n(II) (However, n is an integer from 1 to 30, (R represents hydrogen or a lower alkyl group) An acryloyl-modified polyalkylene oxide containing a polyalkylene oxide structure represented by (2) a lithium ion salt, (3) general formula (III) RO(CH_2CHRO)_n -R(III) (wherein R is hydrogen or a lower alkyl group, and n is an integer of 3 to 30) A composition consisting of a polyalkylene glycol represented by the following is cured and bonded. A method for manufacturing a positive electrode body for a battery.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62012273A JPS63181259A (en) | 1987-01-23 | 1987-01-23 | Manufacture of positive electrode body for cell |
| US07/342,122 US4908283A (en) | 1986-10-09 | 1989-04-24 | Preparation of ion conductive solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62012273A JPS63181259A (en) | 1987-01-23 | 1987-01-23 | Manufacture of positive electrode body for cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63181259A true JPS63181259A (en) | 1988-07-26 |
| JPH0563905B2 JPH0563905B2 (en) | 1993-09-13 |
Family
ID=11800757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62012273A Granted JPS63181259A (en) | 1986-10-09 | 1987-01-23 | Manufacture of positive electrode body for cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63181259A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580865A1 (en) * | 1992-01-17 | 1994-02-02 | Yuasa Corporation | Secondary battery |
| EP0576686A4 (en) * | 1992-01-21 | 1995-04-26 | Dai Ichi Kogyo Seiyaku Co Ltd | Cell. |
| JP2001256980A (en) * | 2000-03-09 | 2001-09-21 | Nippon Zeon Co Ltd | Binder for lithium ion secondary battery electrode and its utlization |
-
1987
- 1987-01-23 JP JP62012273A patent/JPS63181259A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580865A1 (en) * | 1992-01-17 | 1994-02-02 | Yuasa Corporation | Secondary battery |
| EP0580865A4 (en) * | 1992-01-17 | 1994-07-27 | Yuasa Battery Co Ltd | Secondary battery |
| EP0576686A4 (en) * | 1992-01-21 | 1995-04-26 | Dai Ichi Kogyo Seiyaku Co Ltd | Cell. |
| JP2001256980A (en) * | 2000-03-09 | 2001-09-21 | Nippon Zeon Co Ltd | Binder for lithium ion secondary battery electrode and its utlization |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0563905B2 (en) | 1993-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3202216B2 (en) | High performance solid electrochemical stacked cell | |
| US6235433B1 (en) | High molecular gel electrolyte and secondary battery using the same | |
| KR20030042288A (en) | Lithium polymer secondary battery having crosslinked polymer protective thin film and method for manufacturing the same | |
| JPH10116516A (en) | Polymeric solid electrolyte and lithium secondary battery adopting the same | |
| EP1229603A1 (en) | Lithium cell | |
| JP4404322B2 (en) | Secondary battery and electrolyte and electrode active material used for the secondary battery | |
| KR20210048493A (en) | Binder composition for all-solid secondary battery, slurry composition for all-solid secondary battery electrode mixture layer, slurry composition for solid electrolyte layer for all-solid secondary battery, electrode for all-solid secondary battery, solid electrolyte layer for all-solid secondary battery, and all-solid secondary battery | |
| JPS63181259A (en) | Manufacture of positive electrode body for cell | |
| JPH01169873A (en) | Cell | |
| JP3698259B2 (en) | Ion conductive polymer electrolyte | |
| JPH01169875A (en) | Cell | |
| CN114464880B (en) | Self-repairing composite solid lithium ion battery electrolyte and preparation method thereof | |
| CN114050315B (en) | High room temperature ionic conductivity solid polymer composite electrolyte for metal lithium battery and preparation method thereof | |
| JPH01169807A (en) | Macromolecular solid polyelectrolyte | |
| JPS6394563A (en) | Solid electrolyte battery | |
| JPH05114419A (en) | Solid electrolyte secondary battery | |
| CN112993396A (en) | Polymer solid electrolyte membrane, preparation method thereof and all-solid-state battery | |
| KR100400215B1 (en) | Polymer matrix, polymer solid electrolyte containing the matrix, and lithium secondary battery employing the electrolyte | |
| JP4669980B2 (en) | Thin lithium secondary battery | |
| KR100400211B1 (en) | Solid polymer electrolyte and lithium secondary battery containing the electrolyte | |
| JPH01169874A (en) | Lithium cell | |
| JPH0324162A (en) | Solid polyelectrolyte | |
| KR100389896B1 (en) | Solid polymer electrolyte composition, preparation method, and lithium secondary battery employing the electrolyte | |
| JP3942232B2 (en) | Gel-like solid electrolyte and battery | |
| US11811065B2 (en) | Method of producing slurry composition for secondary battery positive electrode, method of producing positive electrode for secondary battery, and method of producing secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |