JPH04136195A - Novel composite material - Google Patents
Novel composite materialInfo
- Publication number
- JPH04136195A JPH04136195A JP2255256A JP25525690A JPH04136195A JP H04136195 A JPH04136195 A JP H04136195A JP 2255256 A JP2255256 A JP 2255256A JP 25525690 A JP25525690 A JP 25525690A JP H04136195 A JPH04136195 A JP H04136195A
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- composite material
- oxide particles
- type
- containing oxide
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 61
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 59
- 239000011572 manganese Substances 0.000 claims abstract description 59
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 27
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- -1 alkali metal cations Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000128 polypyrrole Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 150000002696 manganese Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はマンガン含有酸化物粒子と導電性高分子とを含
んでなる複合材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composite material comprising manganese-containing oxide particles and a conductive polymer.
このような材料は、例えば電池正極用材料として用いる
ことができる。Such a material can be used, for example, as a battery positive electrode material.
［従来の技術］
近年、導電性高分子材料と無機正極材料のひとつである
マンガン含有酸化物粒子との複合材料の研究がなされて
おり、これら複合材料は電池正極用材料として応用が期
待されている。このような複合材料を従来の技術で製造
するには、マンガン含有酸化物粒子を懸濁させた電解質
中で電解重合を行なう方法が考えられる。しかしながら
、この方法ではマンガン含有酸化物粒子は導電性高分子
中に分散せず、複合材料は得られないという問題がある
。すなわち、上記方法においては複合材料ではなく、複
合材料と比較して導電性′や電気化学活性の不十分な導
電性高分子のみしか得られない。[Prior art] In recent years, research has been conducted on composite materials of conductive polymer materials and manganese-containing oxide particles, which is an inorganic positive electrode material, and these composite materials are expected to be applied as battery positive electrode materials. There is. A possible method for producing such a composite material using conventional techniques is to carry out electrolytic polymerization in an electrolyte in which manganese-containing oxide particles are suspended. However, this method has a problem in that the manganese-containing oxide particles are not dispersed in the conductive polymer and a composite material cannot be obtained. That is, in the above method, only a conductive polymer, which is not a composite material but has insufficient conductivity and electrochemical activity compared to a composite material, is obtained.
また、特開昭６３−２５０４８２号においては、マンガ
ン塩と導電性高分子前駆体からなる電解質を用いて電解
し、上記複合体を作製する方法が開示されているが、こ
の方法で得られる複合材料中に含まれるマンガン酸化物
粒子の結晶構造はアモルファス状であり、このことが複
合材料の電気化学的活性を低下せしめる原因となり、こ
れを例えば電池用正極材料として用いた場合、十分な機
能を果たさないという問題があった。Furthermore, JP-A No. 63-250482 discloses a method for producing the above composite by electrolyzing using an electrolyte consisting of a manganese salt and a conductive polymer precursor. The crystal structure of the manganese oxide particles contained in the material is amorphous, which causes a decrease in the electrochemical activity of the composite material, and when used as a positive electrode material for batteries, for example, it may not have sufficient functionality. The problem was that it didn't work.
［問題点を解決するための手段］
本発明の目的は、電気化学的に十分に活性であり、電池
用正極材料として用いることのできるマンガン含有酸化
物粒子と導電性高分子とを含んでなる複合材料及びその
製造方法を提供することにある。[Means for Solving the Problems] The object of the present invention is to provide a material comprising manganese-containing oxide particles and a conductive polymer that are sufficiently electrochemically active and can be used as a positive electrode material for batteries. An object of the present invention is to provide a composite material and a method for manufacturing the same.
［課題を解決するための手段］
本発明者は、上記課題を解決するためにマンガン含有酸
化物粒子と導電性高分子とを含んでなる複合材料につい
て検討を行なった結果、複合材料中のマンガン含有酸化
物粒子の結晶構造を制御することにより、複合材料に電
気化学的活性を十分に与えられることを見出し、本発明
を完成するに至った。すなわち本発明は、マンガン酸化
物粒子、マンガンとアルカリ金属との複合酸化物粒子及
びマンガンとアルカリ土類金属との複合酸化物粒子から
選ばれた少なくとも一種以上のマンガン含有酸化物粒子
と少なくとも一種以上の導電性高分子とを含んでなる複
合材料において、複合材料中のマンガン含有酸化物の結
晶構造がアモルファス以外の結晶構造であることを特徴
とする複合材料及びその製造方法並びに用途である。以
下、本発明を具体的に説明する。[Means for Solving the Problems] In order to solve the above problems, the present inventor investigated a composite material containing manganese-containing oxide particles and a conductive polymer, and found that manganese in the composite material The present inventors have discovered that sufficient electrochemical activity can be imparted to a composite material by controlling the crystal structure of the oxide particles contained therein, and have completed the present invention. That is, the present invention provides at least one manganese-containing oxide particle selected from manganese oxide particles, composite oxide particles of manganese and an alkali metal, and composite oxide particles of manganese and an alkaline earth metal, and at least one or more manganese-containing oxide particles. A composite material comprising a conductive polymer and a manganese-containing oxide in the composite material has a crystal structure other than an amorphous crystal structure, a method for manufacturing the same, and uses thereof. The present invention will be explained in detail below.
本発明の複合材料はマンガン含有酸化物粒子と導電性高
分子を含んでなるが、本発明において述べる複合材料と
は、上記マンガン含有酸化物粒子と導電性高分子が複合
体中で実質的に均一に存在し、複合体の導電性の制御、
電気化学特性が実用上何ら問題のない状態で複合化され
ているものをいう。このような複合材料は、例えば第２
図のように、マンガン含有酸化物及び導電性高分子に起
因する特徴的なサイクリックポルタモグラムを示すもの
となる。なお、第２図は本発明の複合材料の一例である
、β型のＭｎ Ｏ２とポリピロールとを含んでなる複合
材料のサイクリックポルタモグラムを示すが、ポリピロ
ールによる酸化還元ピークに加えて、Ｍ ｎ ０２に特
有なブロードな酸化還元ピークが認められる。The composite material of the present invention comprises manganese-containing oxide particles and a conductive polymer, and the composite material described in the present invention is such that the manganese-containing oxide particles and conductive polymer are substantially Uniform presence and control of conductivity of the composite,
It refers to a compound whose electrochemical properties are combined without causing any practical problems. Such a composite material can be used, for example, in a second
As shown in the figure, a characteristic cyclic portamogram caused by the manganese-containing oxide and the conductive polymer is shown. FIG. 2 shows a cyclic portamogram of a composite material containing β-type MnO2 and polypyrrole, which is an example of the composite material of the present invention. A broad redox peak unique to n 02 is observed.
本発明の複合材料を構成するマンガン含有酸化物粒子の
結晶構造はアモルファスでなければ特に限定されないが
、マンガン含有酸化物粒子の結晶構造が得られる複合材
料の電気化学的活性に影響を及ぼし、アモルファスであ
る場合、複合材料の電気化学的活性は不十分となる。従
って、本発明の複合材料に含まれるマンガン含有酸化物
粒子の結晶構造は、アモルファス以外の結晶構造がその
用途によって適宜選択される。例えば複合材料をリチウ
ム電池正極用材料として用いる場合、複合材料にはリチ
ウムイオンの侵入、脱離反応が伴ない、この反応がスム
ーズに行なわれることが好ましい。そのためには、複合
材料に含まれるマンガン含有酸化物は、リチウムイオン
の侵入、脱離反応に適した構造のものが選ばれ、このよ
うな構造を有するマンガン含有酸化物としては、β型ま
たはγ型のＭｎＯ□、７．β型のＭｎＯ２、Ｌｉ２Ｍ
ｎ Ｏ、とγ、β型のＭ ｎ Ｏ２との複合酸化物ある
いはスピネル型の構造を有するＬｉＭｎ２Ｏ４などが選
択される。更に、本発明の複合材料を構成する導電性高
分子とは電気化学的に活性で、充放電が可能な高分子で
あり、例えばポリアニリン、ポリピロールなど一般に導
電性を有するとされる有機高分子などが挙げられる。The crystal structure of the manganese-containing oxide particles constituting the composite material of the present invention is not particularly limited as long as it is amorphous, but the crystal structure of the manganese-containing oxide particles affects the electrochemical activity of the resulting composite material, , the electrochemical activity of the composite material will be insufficient. Therefore, as the crystal structure of the manganese-containing oxide particles contained in the composite material of the present invention, a crystal structure other than amorphous is appropriately selected depending on the intended use. For example, when a composite material is used as a material for a positive electrode of a lithium battery, the composite material undergoes an intrusion and desorption reaction of lithium ions, and it is preferable that this reaction occurs smoothly. For this purpose, the manganese-containing oxide contained in the composite material is selected to have a structure suitable for lithium ion penetration and elimination reactions. type MnO□, 7. β-type MnO2, Li2M
A composite oxide of n O, and γ- and β-type M n O2, or LiMn2O4 having a spinel structure is selected. Furthermore, the conductive polymer constituting the composite material of the present invention is a polymer that is electrochemically active and capable of being charged and discharged, such as organic polymers that are generally considered to have conductivity, such as polyaniline and polypyrrole. can be mentioned.
本発明の複合材料は、以上述べたようにマンガン含有酸
化物粒子と導電性高分子が実質的に均一分散して構成さ
れ、また含まれるマンガン含有酸化物粒子の結晶構造が
アモルファス以外であるので、十分な導電性及び電気化
学的活性を有するものとなる。また、本発明の複合材料
はこれら特性に伴ない、マンガン含有酸化物粒子と導電
性高分子を含んでなることから、高い体積当りのエネル
ギー密度を有し、なおかつ高出力で十分高性能を示すと
いう特性を併せもつため、例えば電池正極用材料として
好ましく用いることができる。As described above, the composite material of the present invention is composed of substantially uniformly dispersed manganese-containing oxide particles and conductive polymer, and the crystal structure of the manganese-containing oxide particles is other than amorphous. , it has sufficient electrical conductivity and electrochemical activity. In addition to these properties, the composite material of the present invention also has a high energy density per volume because it contains manganese-containing oxide particles and a conductive polymer, and also exhibits sufficient performance with high output. Because of these characteristics, it can be preferably used as a material for battery positive electrodes, for example.
次に本発明の複合体の製造方法の一例を説明する。本発
明の複合材料は、例えばアモルファス以外の結晶構造を
有するマンガン酸化物粒子、マンガンとアルカリ金属と
の複合酸化物粒子及びマンガンとアルカリ土類金属との
複合酸化物粒子から選ばれた少なくとも一種以上のマン
ガン含有酸化物粒子、該マンガン含有酸化物粒子に吸着
可能なアニオン種の少なくとも一種及び少なくとも一種
以上の導電性高分子前駆体を含む電解液中にて電解重合
を行なうことにより製造することができる。Next, an example of the method for manufacturing the composite of the present invention will be explained. The composite material of the present invention includes at least one selected from manganese oxide particles having a crystal structure other than amorphous, composite oxide particles of manganese and an alkali metal, and composite oxide particles of manganese and an alkaline earth metal. manganese-containing oxide particles, at least one kind of anion species that can be adsorbed to the manganese-containing oxide particles, and at least one conductive polymer precursor. can.
この製造方法において、導電性高分子前駆体とは、重合
することにより導電性高分子となり得る低分子有機材料
であり、複合体中を構成する導電性高分子により適宜選
択される。また、アモルファス以外の結晶構造を有する
マンガン含有酸化物は、複合材料の中に含まれる所望の
マンガン含有酸化物粒子と同じ結晶構造のものが用いら
れる。更に、マンガン含有酸化物粒子に吸着可能なアニ
オン種とは、電解液中において、通常単独であれば無電
荷又はカチオン種としての挙動を示すマンガン含有酸化
物と吸着し、マンガン含有酸化物をアニオンとしての挙
動をさせることが可能なものを示す。In this manufacturing method, the conductive polymer precursor is a low-molecular organic material that can be polymerized to become a conductive polymer, and is appropriately selected depending on the conductive polymer constituting the composite. Further, as the manganese-containing oxide having a crystal structure other than amorphous, one having the same crystal structure as the desired manganese-containing oxide particles contained in the composite material is used. Furthermore, anionic species that can be adsorbed to manganese-containing oxide particles are adsorbed with manganese-containing oxides that normally behave as uncharged or cationic species when used alone in the electrolytic solution, and convert the manganese-containing oxide into anionic species. Indicates something that can behave as follows.
このようなアニオン種は用いる電解液やマンガン含有酸
化物によっても異なるが、Ｉ−ＣｌＳＯ４２−などが挙
げられる。なお、添加するアニオン種の電荷補償のため
、同時に電解液中にカチオン種を添加してもよい。この
ようなカチオン種はＮａ、Ｌｉ等のアルカリ金属カチオ
ン、Ｃａ。Such anion species vary depending on the electrolytic solution and manganese-containing oxide used, but include I-ClSO42- and the like. Note that, in order to compensate for the charge of the added anion species, a cation species may be added to the electrolytic solution at the same time. Such cation species include alkali metal cations such as Na and Li, and Ca.
Ｍｇ等のアルカリ土類金属カチオン、遷移金属カチオン
、プロトン、アンモニウムイオンなどの無機カチオン、
カチオン種を有する有機イオンあるいはカチオン性有機
高分子など電解液中でアニオンと十分な解離度を示し、
添加するアニオン種の吸着特性を妨げないものであれば
特に限定されない。上記方法はこれらのマンガン含有酸
化物粒子、該マンガン含有酸化物粒子に吸着可能なアニ
オン種の少なくとも一種及び少なくとも一種以上の導電
性高分子前駆体を含む電解液中にて電解重合を行なうこ
とであるが、このことにより、アモルファス以外の結晶
構造を有するマンガン含有酸化物粒子は、電解液中に含
まれるアニオン種と共に導電性高分子が析出する正極に
誘導され、その結晶構造を保持したまま導電性高分子中
に実質的に均一に分散して、本発明の複合材料が得られ
る。なお、上記方法において用いられるマンガン含有酸
化物の量は、所望の複合材料の特性により適宜調整し得
るが、電解液に対して ０．１ｇ／ｊ〜５０ｇ／ｌの範
囲で用いることが好ましい。この範囲未満では得られる
複合材料の電気化学的活性は満足できないものとなるお
それがあり、越える量を用いてもマンガン含有酸化物の
導電性高分子中に分散する量は増えず、あまり意味がな
い。特に好ましくは５ｇ７１〜３０ｇ／ｌである。また
、添加するマンガン含有酸化物粒子に吸着可能なアニオ
ンの量は、特異吸着能を発揮し得る量を添加すれば如何
なる量でも良いが、好ましくは電解液に対して０．１〜
１．０１ｍａｌ／Ｉ−特に好ましくは０．３〜０．８曽
−〇１／１の範囲で用いられる。更に電解重合の条件は
、従来知られている導電性高分子前駆体から電解重合に
より導電性高分子を製造できるあらゆる条件が適用可能
である。Alkaline earth metal cations such as Mg, transition metal cations, protons, inorganic cations such as ammonium ions,
Organic ions with cationic species or cationic organic polymers exhibit a sufficient degree of dissociation with anions in the electrolyte,
It is not particularly limited as long as it does not interfere with the adsorption properties of the anionic species to be added. The above method involves performing electrolytic polymerization in an electrolytic solution containing these manganese-containing oxide particles, at least one type of anion species that can be adsorbed to the manganese-containing oxide particles, and at least one conductive polymer precursor. However, due to this, the manganese-containing oxide particles having a crystal structure other than amorphous are guided to the positive electrode where the conductive polymer is deposited together with the anion species contained in the electrolyte, and they become conductive while maintaining their crystal structure. The composite material of the present invention is obtained by being substantially uniformly dispersed in the organic polymer. The amount of the manganese-containing oxide used in the above method can be adjusted as appropriate depending on the properties of the desired composite material, but it is preferably used in the range of 0.1 g/j to 50 g/l relative to the electrolytic solution. If the amount is less than this range, the electrochemical activity of the resulting composite material may be unsatisfactory, and if the amount exceeds this range, the amount of manganese-containing oxide dispersed in the conductive polymer will not increase and is of little significance. do not have. Particularly preferred is 5g/71 to 30g/l. Further, the amount of anions that can be adsorbed to the manganese-containing oxide particles to be added may be any amount as long as the amount can exhibit specific adsorption ability, but it is preferably 0.1 to 0.1 to the electrolytic solution.
1.01 mal/I, particularly preferably 0.3 to 0.8 so, is used in the range of 1/1. Further, as the conditions for electrolytic polymerization, any conditions that can produce a conductive polymer by electrolytic polymerization from a conventionally known conductive polymer precursor can be applied.
上述の方法によれば、導電性高分子とマンガン含有酸化
物粒子を容易に均一に複合化でき、また複合化されるマ
ンガン酸化物粒子の結晶構造も保持されるので、本発明
の複合体を製造することができる。According to the above method, the conductive polymer and the manganese-containing oxide particles can be easily and uniformly composited, and the crystal structure of the composited manganese oxide particles is also maintained, so that the composite of the present invention can be easily and uniformly composited. can be manufactured.
［実施例］
以下、本発明を実施例に基づき説明するが、本発明は以
下の実施例に何ら限定されない。[Examples] The present invention will be described below based on Examples, but the present invention is not limited to the following Examples.
参照例１
５ｍＭのＮａｌ水溶液に、β型のＭ ｎ ０２粒子を２
ｇ／ｆ１分散させて電気泳動実験を行なったところ、Ｍ
ｎ ０２粒子は正極側に移動した。このことから、ｌ
−は本発明において述べるマンガン含有酸化物粒子に特
異吸着するアニオンであることが確認された。Reference Example 1 Two β-type M n 02 particles were added to a 5 mM Nal aqueous solution.
When an electrophoresis experiment was conducted with g/f1 dispersion, M
The n 02 particles moved to the positive electrode side. From this, l
It was confirmed that - is an anion that specifically adsorbs to the manganese-containing oxide particles described in the present invention.
実施例１
０．１ｍＭのピロール水溶液に、０．５ｍＭのＮａｌを
添加し、更にこれにβ型のＭ ｎ ０２粒子を２ｇ／ｉ
ｔ分散させた。その後、この水溶液を０．３ｍＡ／ｃシ
の電流密度で２００１Ｃ／ｃ−電解を行ったところ、陽
極にポリピロール膜が形成された。Example 1 0.5 mM Nal was added to a 0.1 mM pyrrole aqueous solution, and 2 g/i of β-type M n 02 particles were added to this.
t dispersed. Thereafter, when this aqueous solution was subjected to 2001C/c-electrolysis at a current density of 0.3 mA/c, a polypyrrole film was formed on the anode.
得られたポリピロール膜は、４５０”Ｃで一晩焼成した
後、過ヨウ素酸カリウム酸化吸光光度法により測定した
ところ、１９重量％のＭ ｎ Ｏ２を含む複合材料であ
ることが確認された。また、元素分析の結果、この複合
材料中には０．０６％のヨウ素がドープされていること
がわかった。更に、この複合材料から第１図に示すＸ線
回折パターン（実線）が得られた。なお、β型のＭ ｎ
Ｏ２は第１図のうち、破線により示されるＸ線回折パ
ターンを示すことから、複合材料中のＭ ｎ Ｏ２の結
晶型は、原料として用いたＭ ｎ ０２と同一のβ型の
構造を保持していることが確認された。The obtained polypyrrole film was baked at 450"C overnight and then measured by potassium periodate oxidation spectrophotometry, and it was confirmed that it was a composite material containing 19% by weight of MnO2. As a result of elemental analysis, it was found that this composite material was doped with 0.06% iodine.Furthermore, the X-ray diffraction pattern (solid line) shown in Figure 1 was obtained from this composite material. .In addition, β-type M n
Since O2 shows the X-ray diffraction pattern indicated by the broken line in Figure 1, the crystal type of M n O2 in the composite material maintains the same β-type structure as M n 02 used as the raw material. It was confirmed that
次に、上記により得られた複合材料のサイクッリクボル
タモグラムをＩＭのＬ ｉ Ｃ（１０４を溶解したプロ
ピレンカーボネート（以下、ＰＣと略す）と１，２−ジ
メトキシエタン（以下、ＤＭＥと略す）の等量混合溶液
中で測定した。その結果を第２図に示す。第２図から、
得られた複合材料のサイクッリクボルタモグラムには０
．５Ｖ付近のポリピロールによる酸化還元ピークに加え
て、１．９ｖと１．１ｖ付近ニＭ ｎ Ｏ２ニ特有ノフ
ロードな酸化還元ピークが現れることが確認され、この
ことから複合材料中のＭ ｎ Ｏ２は有効に酸化還元反
応を行っていることがわかった。Next, the cyclic voltammogram of the composite material obtained above was plotted using IM L i C (propylene carbonate (hereinafter abbreviated as PC) in which 104 was dissolved and 1,2-dimethoxyethane (hereinafter abbreviated as DME), etc. The amount was measured in a mixed solution.The results are shown in Figure 2.From Figure 2,
The cyclic voltammogram of the obtained composite material shows 0
．． In addition to the redox peak due to polypyrrole around 5V, it was confirmed that low-load redox peaks unique to MnO2 appeared around 1.9v and 1.1v, and this indicates that MnO2 in the composite material is effective. It was found that an oxidation-reduction reaction took place.
実施例２
重合電流密度を０．１ｍＡ／ｃ−とし、重合電気量を２
００ｍＣ／ｃｄとした以外は実施例１と同様の方法で複
合材料を得た。Example 2 The polymerization current density was 0.1 mA/c-, and the amount of polymerization electricity was 2.
A composite material was obtained in the same manner as in Example 1 except that the temperature was 00 mC/cd.
その後、得られた複合材料の充放電特性を、ＰＣとＤＭ
Ｅの等量混合溶液中にＬｉＣｌｌＯ４を０．１Ｍ溶解し
た溶液中で行なった。その結果を第３図（実線）に示す
。また、このときの放電電気量は、８ ｍｃ／ ｃ−で
あった。Afterwards, the charge-discharge characteristics of the obtained composite material were evaluated using PC and DM.
The experiment was carried out in a solution in which 0.1 M of LiClO4 was dissolved in a mixed solution of equal amounts of E. The results are shown in Figure 3 (solid line). Further, the amount of discharged electricity at this time was 8 mc/c-.
実施例３
電解電流密度を１．０ｍＡ／ｃ−とした以外は、実施例
１と同様の方法で複合材料を得た。Example 3 A composite material was obtained in the same manner as in Example 1, except that the electrolytic current density was 1.0 mA/c-.
なお、得られた複合材料のＸ線パターンより、複合材料
中のＭ ｎ Ｏ２の結晶型は、原料として用いたβ型の
Ｍ ｎ Ｏ２と同一であることが確認された。In addition, from the X-ray pattern of the obtained composite material, it was confirmed that the crystal type of M n O2 in the composite material was the same as the β-type M n O2 used as a raw material.
更に得られた複合材料の充放電特性を実施例２と同様に
測定した。その結果を第３図（破線）に示す。また、こ
のときの放電電気量は１５ Ｉｌｃ／ ｃｄであった。Furthermore, the charge/discharge characteristics of the obtained composite material were measured in the same manner as in Example 2. The results are shown in Figure 3 (dashed line). Further, the amount of discharged electricity at this time was 15 Ilc/cd.
比較例ｌ
ＭｎＯ２を分散させなかった以外は、実施例２と同様の
方法で電解を行なった結果、ポリピローを得た。Comparative Example 1 Polypillows were obtained as a result of electrolysis performed in the same manner as in Example 2 except that MnO2 was not dispersed.
さらに実施例２と同様に電池テストを行った結果を第三
図（点線）に示す。また、このときの放電電気量は４ｍ
Ｃ／ｃｄであった。Furthermore, the results of a battery test conducted in the same manner as in Example 2 are shown in Figure 3 (dotted line). Also, the amount of electricity discharged at this time was 4 m
It was C/cd.
参照例２
５ｍＭの塩化テトラエチルアンモニウム（以下ＴＥＡＣ
Ｊと略す）を含むＰＣ溶液中にβ型のＭ ｎ ０２粒子
を２ｇ／ＩＩ分散させて電気泳動実験を行なったところ
、Ｍ ｎ ０２粒子は正極側に移動した。このことから
、Ｃｊ７−は本発明で述べる、マンガン含有酸化物粒子
に特異吸着するアニオンであることが確認された。Reference example 2 5mM tetraethylammonium chloride (hereinafter referred to as TEAC)
When an electrophoresis experiment was conducted by dispersing β-type M n 02 particles at 2 g/II in a PC solution containing PC, the M n 02 particles moved to the positive electrode side. From this, it was confirmed that Cj7- is an anion specifically adsorbed to the manganese-containing oxide particles described in the present invention.
実施例４
０．１ｍＭのピロールを溶解したＰＣ溶液に、０．５ｍ
ＭのＴ Ｅ Ａ ＣＩＩを添加し、更にこれにβ型のＭ
ｎ ０２粒子を１０ｇ／Ｎ分散させた。その後、この
ＰＣ溶液を攪拌しながら０．１ｍＡ／ｃ−の電流密度で
２００ｍＣ／ｃｄ電解を行なったところ、陽極に５０重
量％のＭ ｎ Ｏ２とポリピロールとの複合材料が形成
された。更に、この複合材料のＸ線回折パターンから、
複合材料中のＭ ｎ Ｏ２の結晶型は、原料として用い
たＭ ｎ Ｏ２と同一のβ型の構造を保持していること
が確認された。Example 4 Add 0.5mM to a PC solution containing 0.1mM pyrrole
M TEA CII is added, and β-type M is added to this.
n 02 particles were dispersed at 10 g/N. Thereafter, electrolysis was performed at 200 mC/cd at a current density of 0.1 mA/c- while stirring this PC solution, and a composite material of 50% by weight MnO2 and polypyrrole was formed on the anode. Furthermore, from the X-ray diffraction pattern of this composite material,
It was confirmed that the crystal type of M n O2 in the composite material maintained the same β-type structure as the M n O2 used as the raw material.
次に、得られた複合材料の充放電特性を実施例２と同様
の方法で測定した結果、その放電容量は３７ｓＣ／ｃ−
であった。Next, the charge/discharge characteristics of the obtained composite material were measured in the same manner as in Example 2, and as a result, the discharge capacity was 37 sC/c-
Met.
実施例５
ＭｎＯ２を１０ ｇ／ｉｔ分散させた以外は実施例４と
同様の方法で複合材料を得た。なお、得られた複合材料
中のＭ ｎ ０２の結晶型は、この複合材料のＸ線回折
パターンから。原料として用いたＭ ｎ Ｏ２と同一の
β型の構造を保持していることが確認された。また、複
合材料中のＭ ｎ Ｏ２含有量は５０重量％であった。Example 5 A composite material was obtained in the same manner as in Example 4 except that 10 g/it of MnO2 was dispersed. The crystal type of M n 02 in the obtained composite material was determined from the X-ray diffraction pattern of this composite material. It was confirmed that the same β-type structure as M n O2 used as a raw material was maintained. Moreover, the M n O2 content in the composite material was 50% by weight.
次に、得られた複合材料の充放電特性を実施例２と同様
の方法で測定した結果、その放電容量は４８ｓＣ／ｃ−
であった。Next, the charge and discharge characteristics of the obtained composite material were measured in the same manner as in Example 2, and the discharge capacity was 48 sC/c-
Met.
比較例２
Ｍ ｎ ０２を分散させなかった以外は、実施例４と同
様の方法で電解を行なった。その結果、ポリピールが得
られた。得られたポリピロールの充放電特性を実施例２
と同様の方法で測定した結果、その放電容量は２７１Ｃ
／ｃ−であった。Comparative Example 2 Electrolysis was performed in the same manner as in Example 4, except that M n 02 was not dispersed. As a result, a polypeel was obtained. Example 2 shows the charge-discharge characteristics of the obtained polypyrrole.
As a result of measurement using the same method, the discharge capacity was 271C.
/c-.
第１図は本発明の実施例１において得られた複合材料の
Ｘ線回折パターン及びβ型のＭ ｎ Ｏ２のＸ線回折パ
ターンを示す図である。図中、実線は複合材料、破線は
β型のＭ ｎ Ｏ２のパターンを各々示す。
第２図は本発明の複合材料のサイクリックポルタモグラ
ムの一例を示す図である。
第３図は本発明の複合材料の充放電特性の一例を示す図
である。
強度FIG. 1 is a diagram showing the X-ray diffraction pattern of the composite material and the X-ray diffraction pattern of β-type M n O2 obtained in Example 1 of the present invention. In the figure, the solid line shows the pattern of the composite material, and the broken line shows the pattern of β-type M n O2. FIG. 2 is a diagram showing an example of a cyclic portamogram of the composite material of the present invention. FIG. 3 is a diagram showing an example of charge/discharge characteristics of the composite material of the present invention. Strength
Claims (6)
の複合酸化物粒子及びマンガンとアルカリ土類金属との
複合酸化物粒子から選ばれた少なくとも一種以上のマン
ガン含有酸化物粒子と少なくとも一種以上の導電性高分
子とを含んでなる複合材料において、複合材料中のマン
ガン含有酸化物の結晶構造がアモルファス以外の結晶構
造であることを特徴とする複合材料。(1) At least one manganese-containing oxide particle selected from manganese oxide particles, composite oxide particles of manganese and alkali metals, and composite oxide particles of manganese and alkaline earth metals, and at least one conductive particle. 1. A composite material comprising: a manganese-containing oxide having a crystalline structure other than an amorphous crystalline structure;
γ、β型またはスピネル型である請求項第（１）項に記
載の複合材料。(2) The crystal structure of the manganese-containing oxide is β type, γ type,
The composite material according to claim 1, which is of γ, β type or spinel type.
化物粒子、マンガンとアルカリ金属との複合酸化物粒子
及びマンガンとアルカリ土類金属との複合酸化物粒子か
ら選ばれた少なくとも一種以上のマンガン含有酸化物粒
子、該マンガン含有酸化物粒子に吸着可能なアニオン種
の少なくとも一種及び少なくとも一種以上の導電性高分
子前駆体を含む電解液中にて電解重合を行なうことを特
徴とするマンガン含有酸化物粒子と導電性高分子とを含
む複合材料の製造方法。(3) At least one manganese-containing oxide selected from manganese oxide particles having a crystal structure other than amorphous, composite oxide particles of manganese and alkali metals, and composite oxide particles of manganese and alkaline earth metals. Manganese-containing oxide particles, characterized in that electrolytic polymerization is carried out in an electrolytic solution containing particles, at least one kind of anion species that can be adsorbed to the manganese-containing oxide particles, and at least one conductive polymer precursor. A method for producing a composite material containing a conductive polymer.
γ、β型またはスピネル型である請求項第（３）項に記
載の複合材料の製造方法。(4) The crystal structure of the manganese-containing oxide is β type, γ type,
The method for producing a composite material according to claim 3, wherein the composite material is of γ, β type, or spinel type.
がＣｌ−及び／又はＩ＾−である請求項第（３）項に記
載の複合材料の製造方法。(5) The method for producing a composite material according to claim (3), wherein the anion species that can be adsorbed to the manganese-containing oxide particles are Cl- and/or I^-.
の複合酸化物粒子及びマンガンとアルカリ土類金属との
複合酸化物粒子から選ばれた少なくとも一種以上のマン
ガン含有酸化物粒子と少なくとも一種以上の導電性高分
子とを含んでなる複合材料において、複合材料中のマン
ガン含有酸化物の結晶構造がアモルファス以外の結晶構
造である複合材料を含んでなる電池正極用材料。(6) At least one kind of manganese-containing oxide particle selected from manganese oxide particles, composite oxide particles of manganese and alkali metals, and composite oxide particles of manganese and alkaline earth metals and at least one kind of conductive material. 1. A material for a battery positive electrode, which comprises a composite material comprising a polymorphous polymer, in which the crystal structure of the manganese-containing oxide in the composite material is other than amorphous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255256A JPH04136195A (en) | 1990-09-27 | 1990-09-27 | Novel composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255256A JPH04136195A (en) | 1990-09-27 | 1990-09-27 | Novel composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04136195A true JPH04136195A (en) | 1992-05-11 |
Family
ID=17276218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255256A Pending JPH04136195A (en) | 1990-09-27 | 1990-09-27 | Novel composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04136195A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0589294A1 (en) * | 1992-09-25 | 1994-03-30 | Sanyo Electric Co., Ltd. | Nonaqueous secondary battery |
| JP2001273900A (en) * | 2000-01-21 | 2001-10-05 | Showa Denko Kk | Positive active material, method of manufacturing same, and nonaqueous secondary battery using the active material |
| JP2006076865A (en) * | 2004-09-13 | 2006-03-23 | Yamaguchi Univ | Method for manufacturing layered manganese oxide |
| WO2013115335A1 (en) * | 2012-02-03 | 2013-08-08 | 東ソー株式会社 | Electrolytic manganese dioxide, method for producing same, and use of same |
| US8950019B2 (en) | 2007-09-20 | 2015-02-10 | Bradley Fixtures Corporation | Lavatory system |
| US8997271B2 (en) | 2009-10-07 | 2015-04-07 | Bradley Corporation | Lavatory system with hand dryer |
| US9758953B2 (en) | 2012-03-21 | 2017-09-12 | Bradley Fixtures Corporation | Basin and hand drying system |
| US10041236B2 (en) | 2016-06-08 | 2018-08-07 | Bradley Corporation | Multi-function fixture for a lavatory system |
| US10100501B2 (en) | 2012-08-24 | 2018-10-16 | Bradley Fixtures Corporation | Multi-purpose hand washing station |
| US11015329B2 (en) | 2016-06-08 | 2021-05-25 | Bradley Corporation | Lavatory drain system |
-
1990
- 1990-09-27 JP JP2255256A patent/JPH04136195A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0589294A1 (en) * | 1992-09-25 | 1994-03-30 | Sanyo Electric Co., Ltd. | Nonaqueous secondary battery |
| JP2001273900A (en) * | 2000-01-21 | 2001-10-05 | Showa Denko Kk | Positive active material, method of manufacturing same, and nonaqueous secondary battery using the active material |
| JP2006076865A (en) * | 2004-09-13 | 2006-03-23 | Yamaguchi Univ | Method for manufacturing layered manganese oxide |
| JP4547495B2 (en) * | 2004-09-13 | 2010-09-22 | 国立大学法人山口大学 | Method for producing layered manganese oxide thin film |
| US8950019B2 (en) | 2007-09-20 | 2015-02-10 | Bradley Fixtures Corporation | Lavatory system |
| US8997271B2 (en) | 2009-10-07 | 2015-04-07 | Bradley Corporation | Lavatory system with hand dryer |
| WO2013115335A1 (en) * | 2012-02-03 | 2013-08-08 | 東ソー株式会社 | Electrolytic manganese dioxide, method for producing same, and use of same |
| US9758953B2 (en) | 2012-03-21 | 2017-09-12 | Bradley Fixtures Corporation | Basin and hand drying system |
| US10100501B2 (en) | 2012-08-24 | 2018-10-16 | Bradley Fixtures Corporation | Multi-purpose hand washing station |
| US10041236B2 (en) | 2016-06-08 | 2018-08-07 | Bradley Corporation | Multi-function fixture for a lavatory system |
| US11015329B2 (en) | 2016-06-08 | 2021-05-25 | Bradley Corporation | Lavatory drain system |
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