JPS63160154A - Battery - Google Patents
BatteryInfo
- Publication number
- JPS63160154A JPS63160154A JP61306538A JP30653886A JPS63160154A JP S63160154 A JPS63160154 A JP S63160154A JP 61306538 A JP61306538 A JP 61306538A JP 30653886 A JP30653886 A JP 30653886A JP S63160154 A JPS63160154 A JP S63160154A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- battery
- polymer
- poly
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 18
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 15
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 abstract description 12
- 150000001450 anions Chemical class 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229920000128 polypyrrole Polymers 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 abstract 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- KOBVMCLMUHZDRD-UHFFFAOYSA-N 2,4-dioxa-3$l^{4}-thiabicyclo[3.2.2]nona-1(7),5,8-triene 3-oxide Chemical compound O1S(=O)OC2=CC=C1C=C2 KOBVMCLMUHZDRD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000908115 Bolivar Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002863 poly(1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 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
-
- 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〕 本発明は、新規な電池に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel battery.
従来、正極（′電池の放電（二より活物質が還元される
極）活物質として導電性高分子を用いた電池としては、
合成金属国際会議予稿集、Ｐ−ｇθ、１９Ｉｌｌ″乙
に示される電池が挙げられる。該電池における導磁性高
分子（正極活物質）はボリビａ−ルであり、負極活物質
はリチウムである。該ポリピロールは酸化還元により支
持電解質の陰イオンの収り込み放出を行うので、電池の
放電が進行する（＝つれて、両極間に支持電解質が蓄積
する。Conventionally, batteries using conductive polymers as the positive electrode (the electrode where the active material is reduced)
Proceedings of the International Conference on Synthetic Metals, P-gθ, 19Ill″B
Examples include the batteries shown in . The magnetically conductive polymer (positive electrode active material) in this battery is Bolivar, and the negative electrode active material is lithium. Since the polypyrrole traps and releases anions of the supporting electrolyte through redox, the discharge of the battery progresses (as the supporting electrolyte accumulates between the two electrodes).
該支持電解質を溶解させるためには、多量の有機溶媒が
必要となる。ところが一般に有機溶媒は電解質を溶解す
る力が弱く、たとえ溶けても十分な導電性が得られにく
い。このため重負荷に耐える電池を得るためには、液層
をきわめて薄くするなど特別の工夫が必要となり、従っ
て多量の溶媒を使用できず前記要求とは相反する。以上
の理由から、該電池のシステムで大容量でしかも重負荷
に耐える電池を得ることは困難である。A large amount of organic solvent is required to dissolve the supporting electrolyte. However, organic solvents generally have a weak ability to dissolve electrolytes, and even if they do dissolve, it is difficult to obtain sufficient conductivity. Therefore, in order to obtain a battery that can withstand heavy loads, special measures such as making the liquid layer extremely thin are required, and therefore a large amount of solvent cannot be used, which is contrary to the above requirements. For the reasons mentioned above, it is difficult to obtain a battery that has a large capacity and can withstand heavy loads using the battery system.
本発明者らは、この様な従来技術が持つ問題点を解決す
べく鋭意研究を行った結果、導磁性高分子とアニオン性
高分子電解質よりなる複合体が、酸化還元に伴いカチオ
ンの放出取込を行う性質に着目し、該複合体を多隙性導
電体に担持せしめて電池の正極として用いると、放電に
よって負極活物質より生じるカチオンが該複合体中に収
り込まれ電解液中に蓄積せず、したがって少量の溶媒で
電池を構成でき、しかも該正極は内部抵抗が低いために
大電流が取り出せ、さらに正極活物質の脱落が少ないこ
とを見い出し本発明を完成するに至つた。The inventors of the present invention have conducted extensive research to solve the problems of the conventional technology, and have discovered that a composite consisting of a magnetically conductive polymer and an anionic polymer electrolyte is capable of releasing and removing cations during redox. When this composite is supported on a porous conductor and used as a positive electrode of a battery, the cations generated from the negative electrode active material during discharge are trapped in the composite and released into the electrolyte. The present inventors have discovered that the positive electrode does not accumulate, so a battery can be constructed with a small amount of solvent, and that a large current can be extracted because the positive electrode has a low internal resistance, and that the positive electrode active material is less likely to fall off, leading to the completion of the present invention.
体を、電池の正極としてなる特徴とする電池である。 This is a battery characterized by the body serving as the positive electrode of the battery.
本発明において導電性高分子とは、その主鎖がπ共役系
から成り立つことにより導電性を発現する高分子である
。例を挙げると、ポリアセチレン、ポリ（／、乙−へブ
タジイン）、ポリジアセチレン、ポリピロール、ポリ（
Ｎ−アルキルピロール）、ポリ（Ｎ−アリールピロール
）、ポリ（３−アルキルピロール）、ポリ（３，グージ
アルキルピロール）、ポリチオフェン、ポリ（３−アル
キルチオフェン）、ポリ（３，クージアルキルチオフェ
ン）、ボ！ｊ（ｐ−フェニレン）、ポリ（ｍ−フェニレ
ン）、ポリ（ｐ−フェニレンビニレン）、ボ！Ｉ（ｐ−
フェニレンスルフィト）、ポリ（ｍ−フェニレンスルノ
イド）、ポリ（ｐ−フェニレンオキシド）、ポリアニリ
ン、ポリ（Ｎ−アルキルアニリン）、ポリ（０−アルキ
ルアニリン）、ポリ（ｍ−アルキルアニリン）などが挙
げられる。この中でも特にポリピロール、ポリ（Ｎ−ア
ルキルピロール）、ポリ（Ｎ−アリールピロール）、ポ
リ（３，クージアルキルピロール）、ポリアニリン、ポ
リ（Ｎ−アルキルアニリン）、ポリ（０−アルキルアニ
リン）、ポリ（ｍ−アルキルアニリン）が好ましい。In the present invention, a conductive polymer is a polymer that exhibits conductivity because its main chain is composed of a π-conjugated system. Examples include polyacetylene, poly(/, hebutadiyne), polydiacetylene, polypyrrole, poly(
N-alkylpyrrole), poly(N-arylpyrrole), poly(3-alkylpyrrole), poly(3,gudialkylpyrrole), polythiophene, poly(3-alkylthiophene), poly(3,gudialkylthiophene), Bo! j (p-phenylene), poly (m-phenylene), poly (p-phenylene vinylene), bo! I(p-
phenylene sulfite), poly(m-phenylenesulnoid), poly(p-phenylene oxide), polyaniline, poly(N-alkylaniline), poly(0-alkylaniline), poly(m-alkylaniline), etc. It will be done. Among these, polypyrrole, poly(N-alkylpyrrole), poly(N-arylpyrrole), poly(3,cudialkylpyrrole), polyaniline, poly(N-alkylaniline), poly(0-alkylaniline), poly( m-alkylaniline) is preferred.
本発明においてアニオン性高分子電解質とは、イオン解
離により陰イオンとなる高分子である。In the present invention, an anionic polymer electrolyte is a polymer that becomes an anion through ionic dissociation.
例を挙げると、ポリアクリル酸アニオン、ポリメタクリ
ル酸アニオン、ポリスチレンスルホン酸アニオン、ポリ
エチレンスルホン酸アニオン、ポリビニル硫酸アニオン
、フルオロカーボンスルホン酸アニオン等が挙げられる
。この中でも特に、ポリスチレンスルホン酸アニオン、
ポリエチレンスルホン酸アニオン、ポリビニル硫酸アニ
オンおよびこれらのポリマーの水素原子がフッ素原子と
置換したポリマーが好ましい。Examples include polyacrylate anion, polymethacrylate anion, polystyrene sulfonate anion, polyethylene sulfonate anion, polyvinyl sulfate anion, fluorocarbon sulfonate anion, and the like. Among these, in particular, polystyrene sulfonate anion,
Polyethylene sulfonate anions, polyvinyl sulfate anions, and polymers in which the hydrogen atoms of these polymers are substituted with fluorine atoms are preferred.
本発明において、導電性高分子とアニオン性高分子電解
質よりなる複合体とは、導電性高分子とアニオン性高分
子電解質がイオン対を形成して混合しているか、物理的
に混合しているが、あるいは化学結合による混合してい
る相をいう。両者の混合の状態は互いに細かくあるいは
一方が他方の中に細かく分散していることが好ましく、
分子レベルで混合していることが特に好ましい。該複合
体では酸化状態（カチオン状態）の導電性高分子は、ア
ニオン性高分子電解質とイオン対を形成している。但し
このとき、導電性高分子とイオン対を形成していない高
分子電解質の解離基は他の適当なカチオンと対を形成し
ていてもよい。この状態の該複合体が還元を受けた場合
、該複合体中の導電性高分子は中性となり、高分子電解
質は、低分子電解質と異り、その大きさの為に該複合体
の外に拡散できず、該高分子電解質の電気的中性を保つ
ために外部よりカチオンが進入し、導電性高分子と高分
子電解質のイオン対は解消される。引きつづいて該複合
体が酸化を受けた場合、先に進入したカチオンは該複合
体の外部に放出され、導電性高分子と高分子電解質のイ
オン対が再び生成する。この様な該複合体の酸化還元に
伴うカチオンの放出、取り込みは可逆的に行われるので
、該複合体は一次電池のみならず二次電池の正極活物質
としても有効である。In the present invention, a complex consisting of a conductive polymer and an anionic polymer electrolyte refers to a complex in which the conductive polymer and anionic polymer electrolyte form an ion pair and are mixed, or are physically mixed. However, it refers to a phase in which the phase is mixed due to chemical bonds. It is preferable that the two be mixed finely with each other or one finely dispersed in the other.
It is particularly preferred that they are mixed at the molecular level. In the composite, the conductive polymer in an oxidized state (cationic state) forms an ion pair with the anionic polymer electrolyte. However, at this time, the dissociative group of the polymer electrolyte that does not form an ion pair with the conductive polymer may form a pair with another appropriate cation. When the complex in this state undergoes reduction, the conductive polymer in the complex becomes neutral, and unlike low molecular electrolytes, polyelectrolytes, due to their size, are external to the complex. In order to maintain the electrical neutrality of the polymer electrolyte, cations enter from the outside, and the ion pair between the conductive polymer and the polymer electrolyte is dissolved. When the complex is subsequently oxidized, the cations that entered earlier are released from the complex, and ion pairs of the conductive polymer and the polyelectrolyte are regenerated. Since the release and uptake of cations accompanying redox of the composite is performed reversibly, the composite is effective as a positive electrode active material not only for primary batteries but also for secondary batteries.
本発明において多隙性導電体とは、その表面および又は
内部に多数の間隙又は空孔な有し、このために表面積が
非常に大であり、かつ導電性を有するものである。例を
挙げると、炭素繊維、炭素クイスカー、金属繊維、金属
ウィスカー等よりなる編織布、紙、不織体、フェルト等
のシート状あるいは塊状成形体、炭素粉末、金属粉末よ
りなるシート状、板状、あるいは塊状成形体等である。In the present invention, a porous conductor is one that has a large number of gaps or holes on its surface and/or inside, and therefore has a very large surface area and is electrically conductive. Examples include woven fabrics made of carbon fibers, carbon quiskers, metal fibers, metal whiskers, etc., sheet-like or lump-like molded products such as paper, non-woven materials, and felt, sheet-like or plate-like products made of carbon powder, metal powder, etc. , or a block-like molded body.
この中でも炭素繊維、炭素ウィスカー、炭素粉末よりな
る多隙性導電体が好ましく、気相法炭素繊維よりなる多
隙性導電体は特に好ましい。Among these, porous conductors made of carbon fibers, carbon whiskers, and carbon powder are preferred, and porous conductors made of vapor-grown carbon fibers are particularly preferred.
該多隙性導゛庖体を作成するには、例えば、繊維状素材
を用いた場合はその素材の機械的な絡み合いを利用して
、上に述べた形状に成形すればよく、またこの時必要に
応じて結着剤を用いてもよい。To create the porous conductive body, for example, if a fibrous material is used, it may be formed into the above-mentioned shape by utilizing the mechanical entanglement of the material. A binder may be used if necessary.
また粉末状素材を用いた場合は、通常粉末電池活−乙
−
物質を成形する方法、例えば結着剤を用いて圧縮成形す
る方法等をとればよい。In addition, when powdered materials are used, it is usually necessary to use powder batteries.
- A method of molding the substance, such as compression molding using a binder, may be used.
導電性高分子とアニオン性高分子電解質とからなる複合
体を多隙性導電体に担持することによって得られる電池
正極は、酸化還元によってカチオンを可逆的に放出取込
みし、しかも、内部抵抗が低い特徴を持つ。また担持さ
れた該複合体の脱落が少ない。A battery positive electrode obtained by supporting a composite consisting of a conductive polymer and an anionic polymer electrolyte on a porous conductor can reversibly release and incorporate cations through redox, and has low internal resistance. have characteristics. Furthermore, the supported composite is less likely to fall off.
該正極を作成するには例えば電解酸化重合法を用いるこ
とが可能である。代表的な方法は、水（′″−導屯性高
分子のモノマーと、アニオン性高分子電電体の多隙構造
乃至表面に仮着せしめて複合体を担持させることにより
作成することができる。For example, an electrolytic oxidation polymerization method can be used to create the positive electrode. A typical method is to temporarily attach water ('''-conductive polymer monomer to the porous structure or surface of an anionic polymer electrolyte to support the composite).
本発明の電池において用いることのでさる負極活物質と
しては、その標準電極電位がθ、θＶ（対ＳＨＥ ）以
下のものが好ましい。例を挙げれば、Ｌｉ 、 Ｋ
、 Ｃａ、 Ｍｇ、 ＡＩ 、 Ｚｎ 、
Ｃｒ ％ Ｆｅ、Ｃｄ。The negative electrode active material used in the battery of the present invention preferably has a standard electrode potential of θ, θV (vs. SHE) or less. For example, Li, K
, Ca, Mg, AI, Zn,
Cr% Fe, Cd.
Ｎｉ 、 Ｓｎ、 Ｐｂまたはこれらの金属の付合等が
挙げられる。この中でも特にリチウムおよびリチウム合
金が好ましい。Examples include Ni, Sn, Pb, and combinations of these metals. Among these, lithium and lithium alloys are particularly preferred.
本発明において用いることのできる溶媒は、負極活物質
によって異るので一概に規定できないが、水、無機系固
体電解質、有機溶媒、有機系固体電解質である。有機溶
媒としては、例えばアセトニトリル、プロピレンカーボ
ネート、ジメチルホルムアミド、ジメチルスルホキシド
、テトラヒドロフラン、スルホラン、／、２−ジメトキ
シエタン、γ−ブチロラクトン等が挙げられる。溶媒中
には溶媒の導電率を上げるために支持塩を溶解させても
よい。支持塩の例を挙げると、陽イオンとしては、Ｌｉ
＋、Ｎａ＋、戸、Ｃａ２＋、その他金属イオン、ＮＨ４
＋、テトラアルキルアンモニクムイオンなどが挙げられ
、陰イオンとしては、ＥＦ４７、ＣｔＯ４−１Ｃ４−１
ＳＯと、ＮＯ３−５Ｆ−１Ｂｒ−５■−１ＰＦ６−１Ａ
ｓＦ６−１Ｒ−ＣＯＯ−（Ｒはアルキル基又はアリール
基）、Ｒ−８０３−（Ｒはアルキル基又はアリール基）
などが挙げられる。Solvents that can be used in the present invention vary depending on the negative electrode active material and cannot be unconditionally defined, but include water, inorganic solid electrolytes, organic solvents, and organic solid electrolytes. Examples of the organic solvent include acetonitrile, propylene carbonate, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, sulfolane, 2-dimethoxyethane, and γ-butyrolactone. A supporting salt may be dissolved in the solvent in order to increase the conductivity of the solvent. To give an example of a supporting salt, as a cation, Li
+, Na+, door, Ca2+, other metal ions, NH4
+, tetraalkylammonicum ions, etc., and anions include EF47, CtO4-1C4-1
SO and NO3-5F-1Br-5■-1PF6-1A
sF6-1R-COO- (R is an alkyl group or an aryl group), R-803- (R is an alkyl group or an aryl group)
Examples include.
本発明は、正極活物質として、カチオンの放出取り込み
を行う、導電性高分子とアニオン性高分子電解質よりな
る複合体を用いているので、放電により負極から発生し
た陽イオンを該正極が収り込むために、溶媒中に該陽イ
オンよりなる塩が蓄積することがなく、シたがって多量
の溶媒は不必要なため軽量であり、しかも多隙性導電体
を用いているので正極の内部抵抗が低くまた活物質の脱
落の少ない一次電池もしくは二次電池である。The present invention uses a composite of a conductive polymer and an anionic polymer electrolyte, which releases and takes in cations, as the positive electrode active material, so the positive electrode collects the cations generated from the negative electrode during discharge. Since salts made of the cations do not accumulate in the solvent, a large amount of solvent is not required, making it lightweight, and since a porous conductor is used, the internal resistance of the positive electrode is low. It is a primary battery or a secondary battery that has a low active material and less shedding of the active material.
以下に実施例を挙げ本発明をさらに詳しく説明する。 The present invention will be explained in more detail with reference to Examples below.
実施例／
陽極として気相法炭素繊維よりなるフェルト状成形体７
０．３可を用い、陰極として白金板を用い、３．３係の
ポリスチレンスルホン酸ナトリウムと、θ、６７係のビ
ロールを含む水溶液を７θｍＡ、Ｊ時間電解し、該陽極
上にポリピロールとポリスチレンスルホン酸アニオンよ
りなる複合体を担持させた。これを／ｌＯ℃３時間、真
空乾燥を行い屯−タ −
池正極とした。該複合体の担持量はにθ、Ｊ’岬であっ
た。Example/ Felt-like molded body 7 made of vapor-grown carbon fiber as anode
Using a platinum plate as a cathode, an aqueous solution containing sodium polystyrene sulfonate with a coefficient of 3.3 and virol with a coefficient of θ of 67 was electrolyzed at 7θ mA for J hours, and polypyrrole and polystyrene sulfone were placed on the anode. A complex consisting of acid anions was supported. This was vacuum-dried for 3 hours at 10°C and used as a tonta-ike positive electrode. The amount of the complex supported was θ, J'.
該正極と、８ＵＳネツト上にリチウムのプロピレンカー
ボネート溶液に入れ、乾燥窒素下で電池を組み立てた。The positive electrode was placed in a propylene carbonate solution of lithium on an 8US net and a cell was assembled under dry nitrogen.
該電池の開路電圧は３．４ｔ Ｖであり１，２ｍＡで充
放電を繰り返したところ良好な特性を示した。The open circuit voltage of the battery was 3.4 tV, and it showed good characteristics when repeatedly charged and discharged at 1.2 mA.
実施側御
陽極として気相法炭素繊維よりなるフェルト状成形体！
、に■を用い、陰極として白金板を用い、３．３％のポ
リエチレンスルホン酸ナトリウムと、０、ｔ ７％のピ
ロールを含む水溶液を／θｍｋ２時間電解し、該陽極上
にポリピロールとポリエチレンスルホン酸アニオンより
なる複合体を担持させた。これを／♂θ℃３時間、真空
乾燥を行い電池正極とした。該複合体の担持量は３３．
θ〜であった。A felt-like molded body made of vapor grown carbon fiber as the active anode!
, using a platinum plate as a cathode, electrolyzed an aqueous solution containing 3.3% sodium polyethylene sulfonate and 7% pyrrole /θmk for 2 hours, and deposited polypyrrole and polyethylene sulfonic acid on the anode. A complex consisting of anions was supported. This was vacuum-dried for 3 hours at /♂θ°C and used as a battery positive electrode. The amount of the complex supported is 33.
It was θ~.
該正極と、８ＵＳネツト上にリチウムを圧看した負極を
、７Ｍの過塩素酸リチウムのプロピレンカーボネ−ト溶
液に入れ、乾燥窒素下で電池を組み立てた。The positive electrode and the negative electrode containing lithium on an 8US net were placed in a 7M solution of lithium perchlorate in propylene carbonate, and a battery was assembled under dry nitrogen.
該電池の開路電圧は３．３ｖであり、２ｍＡで充放電を
繰り返したところ良好な特性を示した。The open circuit voltage of the battery was 3.3 V, and when it was repeatedly charged and discharged at 2 mA, it showed good characteristics.
第７図は実施例／による電池の、ｊｍＡでの充放電特性
を示し、第一図は実施例２による電池の２ｍＡでの放電
特性を示す。FIG. 7 shows the charge/discharge characteristics at jmA of the battery according to Example 2, and FIG. 1 shows the discharge characteristics at 2 mA of the battery according to Example 2.
Claims (1)
とからなる複合体が被着した担持体を電池の正極として
なる特徴とする電池。A battery characterized in that the positive electrode of the battery is a carrier in which a composite consisting of a conductive polymer and an anionic polymer electrolyte is adhered to a porous conductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61306538A JPS63160154A (en) | 1986-12-24 | 1986-12-24 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61306538A JPS63160154A (en) | 1986-12-24 | 1986-12-24 | Battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63160154A true JPS63160154A (en) | 1988-07-02 |
Family
ID=17958240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61306538A Pending JPS63160154A (en) | 1986-12-24 | 1986-12-24 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63160154A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999066572A1 (en) * | 1998-06-19 | 1999-12-23 | Adven Polymers, Inc. | Polymeric thin-film reversible electrochemical charge storage devices |
-
1986
- 1986-12-24 JP JP61306538A patent/JPS63160154A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999066572A1 (en) * | 1998-06-19 | 1999-12-23 | Adven Polymers, Inc. | Polymeric thin-film reversible electrochemical charge storage devices |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10727531B2 (en) | Lithium metal secondary battery featuring an anode-protecting layer | |
| Zeng et al. | High performance lithium–sulfur batteries with a permselective sulfonated acetylene black modified separator | |
| CN105637677B (en) | Barrier film and the lithium-sulfur cell for including it | |
| KR101997074B1 (en) | Polyethyleneimine carbon-based material attached and separator for lithium-sulfur battery comprising the same | |
| JP3594895B2 (en) | Proton conductive polymer secondary battery | |
| US20160172667A1 (en) | Multilayered Sulfur Composite Cathodes for Lithium Sulfur Batteries | |
| KR20040081186A (en) | Redox active reversible electrode and novel cell using it | |
| Novák et al. | Composite polymer positive electrodes in solid‐state lithium secondary batteries | |
| CN111740177A (en) | Positive electrode material, positive electrode, battery, and battery pack | |
| JPH1050345A (en) | Polymer electrolyte and lithium polymer battery using the same | |
| WO2019246474A1 (en) | Lithium metal secondary battery featuring an anode-protecting layer | |
| JPS63160154A (en) | Battery | |
| CN105336956A (en) | Battery | |
| JP3089707B2 (en) | Solid electrode composition | |
| JPS63285864A (en) | Electrode for battery | |
| JPS6293861A (en) | Secondary batter | |
| JPH05314964A (en) | Lithium secondary battery | |
| KR100573098B1 (en) | Surface-treating composition of electrode current collector for lithium secondary battery and surface-treating method using the same | |
| JP3349191B2 (en) | Battery electrode | |
| JPS63152867A (en) | Polyaniline | |
| JPS6380473A (en) | Cell | |
| JPS622468A (en) | Polymer secondary cell | |
| JPS62115663A (en) | Organic electrolyte secondary battery | |
| JPS622469A (en) | High-molecular secondary cell | |
| JP2001257133A (en) | Conductive polymer composite electrode and electrochemical capacitor |