JP4179746B2 - Electrically responsive complex - Google Patents
Electrically responsive complex Download PDFInfo
- Publication number
- JP4179746B2 JP4179746B2 JP2000380981A JP2000380981A JP4179746B2 JP 4179746 B2 JP4179746 B2 JP 4179746B2 JP 2000380981 A JP2000380981 A JP 2000380981A JP 2000380981 A JP2000380981 A JP 2000380981A JP 4179746 B2 JP4179746 B2 JP 4179746B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- complex
- halide
- phenylazomethine
- phenyl
- 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.)
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- -1 vanadium halide Chemical class 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 9
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 125000004957 naphthylene group Chemical group 0.000 claims description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 125000006267 biphenyl group Chemical group 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000004043 responsiveness Effects 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 230000009918 complex formation Effects 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- NPENBPVOAXERED-UHFFFAOYSA-N (4-benzoylphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 NPENBPVOAXERED-UHFFFAOYSA-N 0.000 description 2
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GSEZYWGNEACOIW-UHFFFAOYSA-N bis(2-aminophenyl)methanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1N GSEZYWGNEACOIW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- DDFCAIWQSXAFHH-UHFFFAOYSA-N [Ni].[Cd].[Ni] Chemical compound [Ni].[Cd].[Ni] DDFCAIWQSXAFHH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development 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
- 238000000921 elemental analysis Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、電気応答性錯体に関するものである。さらに詳しくは、この出願の発明は、二次電池の正極材料や錯体触媒として有効に作用するフェニルアゾメチン錯体およびフェニレンジアミン錯体に関するものである。
【０００２】
【従来の技術とその課題】
近年、ノート型パソコンや携帯電話の普及、あるいは電気自動車の開発、実用化に伴って、二次電池の軽量化、長寿命化、高性能化が望まれている。
【０００３】
従来の二次電池は、電極材料としてニッケル、水素吸蔵合金などを用いたニッケル水素電池やニッケルカドミウム（ニカド）電池などが一般的であったが、最近では、より高いエネルギー密度を有するリチウム二次電池が注目されており、携帯端末用の小型電池としてのみならず、自動車用、宇宙用の大型電池としても期待され、研究が盛んに行われている。
【０００４】
このようなリチウム二次電池では、主に正極材料としてコバルト酸リチウムが用いられているが、コバルトの埋蔵量が僅か８４０万トンと極めて少ないため、材料のコストが高く、価格も変動しやすいという問題があった。そこで、低コスト化を図るために、ニッケル、マンガン、バナジウムなどの他の金属酸化物を用いた正極材料が開発され、一部で採用されている。
【０００５】
しかし、これらの金属材料を主体とする二次電池は重く、携帯電子機器等の小型用途ではもちろんのこと、自動車用、宇宙用等の大型用途においては、二次電池の重量が大きくなるために実現可能な大きさが制限されるという問題があった。
【０００６】
また、二次電池の性能という面では、リチウム二次電池の移動イオンが金属イオンであるため、移動速度が遅く、充放電できる電流量はあまり大きくなく、応答性も低いという問題があった。さらに、リチウム二次電池では、充放電の際にリチウムイオンが電極材料（結晶）に繰り返し挿入（充電）、放出（放電）されるため、電極材料の構造変化が大きく、劣化が生じ易かった。これにより、電池の繰り返し寿命が短くなってしまうという問題があった。さらに、以上のとおりのリチウム二次電池を含む一般の電池では、正極と負極を隔離するために、液体の電解質が使用されている。したがって、電解質溶液の漏洩が起こる可能性があり、薄型化も困難であった。
【０００７】
そこで、ポリマーと電解質塩のみから構成されるポリマー電解質やこれらを有機溶媒でゲル化したゲル状ポリマー電解質が開発され、実用化されている。しかし、このようなポリマー電解質を用いたポリマー二次電池においても、大きなイオン種が移動するため内部抵抗が高く、応答性が悪いという問題があった。また、これらのポリマー電池は、リチウム二次電池と同様に、電極材料の主体がコバルト酸リチウム等の金属材料であるため、上記の種々の問題も解決されずに残っていたのである。
【０００８】
これらの問題に対応する有効な解決するために、適当な電極材料として導電性高分子が考慮される。しかし、現在のところ、そのような導電性高分子材料は実用化には至っておらず、高性能の高分子電極材料が望まれていたのが実情である。
【０００９】
一方、従来より化学反応用の金属触媒としては種々のものが報告、提供されているが、工業レベルでの使用において有用な金属触媒として、安定な酸化還元を示し、かつ多電子の移動が可能なものが求められている。また、金属触媒が工業的に使用されるためには、触媒効率の更なる向上とともに、熱安定性も求められているが、そのような金属触媒はこれまでにあまり多く知られていないのが実情である。
【００１０】
そこで、この出願の発明は、以上のとおりの事情に鑑みてなされたものであり、従来技術の問題点を解消し、二次電池の小型化、軽量化が可能で、長い寿命と高速応答性を示す高性能な二次電池用の電極材料を提供することを課題としている。また、この出願の発明は、合わせて、多電子を移動でき、安定な酸化還元を示す、熱安定性の高い金属触媒を提供することを課題としている。
【００１１】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、まず第１には、電気応答性を有する錯体であって、次の一般式（Ｉ）
【００１２】
【化４】
（ただし、Ａｒはフェニレン基、ビフェニレン基、またはナフチレン基を示し、Ｒ1およびＲ2は各々同一または別異にフェニル基、ビフェニル基、またはナフチル基を示し、ＲおよびＲaは各々同一または別異にフェニル基またはナフチル基を示し、Ｍは希土類金属、ハロゲン化錫（ II ）、ハロゲン化バナジウム、またはハロゲン化リチウムを示す。）で表されるフェニルアゾメチン錯体を提供する。
【００１４】
第２には、この出願の発明は、電気応答性を有する錯体であって、次の一般式（II）
【００１５】
【化５】
（ただし、Ａｒはフェニレン基、ビフェニレン基、またはナフチレン基を示し、Ｒ3およびＲ4は各々同一または別異にフェニル基、ビフェニル基、またはナフチル基を示し、Ｒbは各々同一または別異にフェニレン基、ビフェニレン基、ジフェニレンスルフィド基、またはナフチレン基を示し、Ｍは希土類金属、ハロゲン化錫（ II ）、ハロゲン化バナジウム、またはハロゲン化リチウムを示し、ｎは重合度を示す１以上の整数である。）で表されるポリフェニルアゾメチン錯体を提供する。
【００２２】
【発明の実施の形態】
発明者等は、前記の課題を解決すべく、鋭意研究を重ね、これまでにプロトン電極の正極材料として有用なポリフェニルアゾメチン誘導体を報告している（特願平２０００−２７０７１２）。その後、希土類金属イオンがこれらのフェニルアゾメチン誘導体やフェニレンジアミン誘導体類に対して高い配位能を有することを見出した。そして、希土類金属イオンとフェニルアゾメチン誘導体やフェニレンジアミン誘導体が、錯形成することにより電気活性となることを見出し、この出願の発明に至ったものである。
【００２３】
この出願の発明のフェニルアゾメチン錯体やフェニレンジアミン錯体は、イオン移動を伴わずに酸化還元されるため、従来の導電性高分子類に比べ、格段に高いエネルギー密度を持つ正極材料として有用なものである。また、触媒能を有する金属イオンと効率よく錯形成できるため、π共役系を介した円滑な電子移動に基づく触媒効率の向上も期待できる。
【００２４】
したがって、この出願の発明は、電気応答性錯体としてフェニルアゾメチン錯体やフェニレンジアミン錯体を提供するものである。
【００２５】
フェニルアゾメチン錯体としては、次の一般式（IV）
【００２６】
【化７】
（ただし、Ａｒはフェニレン基、ビフェニレン基、またはナフチレン基を示し、Ｒ1およびＲ2は各々同一または別異にフェニル基、ビフェニル基、またはナフチル基を示し、ＲおよびＲaは各々同一または別異にフェニル基またはナフチル基を示す。）で表されるフェニルアゾメチン誘導体のＮに希土類金属、またはハロゲン化金属が配位し、錯形成したものが提供される。
【００２８】
配位するＭは、希土類金属またはハロゲン化金属から選択される。希土類金属としては、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、ランタン（Ｌａ）、アクチニウム（Ａｃ）から選択されるスカンジウム族やセリウム（Ｃｅ）、ユウロピウム（Ｅｕ）、テルビウム（Ｔｂ）、イッテルビウム（Ｙｂ）等のランタノイド（Ｌｎ）系の金属が挙げられる。中でもＬａ、Ｃｅ、Ｅｕ、Ｔｂが好ましい。一方、ハロゲン化金属としては、ＳｎＣｌ2、ＳｎＢｒ2等のハロゲン化錫（II）、ＶＣｌ3等のハロゲン化バナジウム、ＬｉＣｌやＬｉＢｒ等のハロゲン化リチウムが挙げられる。
【００２９】
上記一般式（IV）に示されるようなフェニルアゾメチン誘導体は、どのような方法で合成されるものであってもよい。種々の公知の方法が例示されるが、具体的には、四塩化チタンやパラトルエンスルホン酸などの酸存在下、ジアミンとジケトン、もしくはアミノフェニルケトンを脱水反応して得る方法が考えられる。このようにして得られたフェニルアゾメチン誘導体への希土類金属やハロゲン化金属（Ｍ）の配位は、どのような方法で行われてもよいが、実際には、フェニルアゾメチン誘導体とＭを溶液中で共存させることにより容易に錯形成が起こる。また、溶液中で共存させた後、溶媒を除去すれば、フェニルアゾメチン錯体が単離できる。
【００３０】
この出願の発明では、さらに、次の一般式（V）
【００３１】
【化８】
（ただし、Ａｒはフェニレン基、ビフェニレン基、またはナフチレン基を示し、Ｒ3およびＲ4は各々同一または別異にフェニル基、ビフェニル基、またはナフチル基を示し、Ｒbは各々同一または別異にフェニレン基、ビフェニレン基、ジフェニレンスルフィド基、またはナフチレン基を示し、ｎは重合度を示す１以上の整数である。）で表されるポリフェニルアゾメチン誘導体のＮ部位に上記のとおりのＭが配位したポリフェニルアゾメチン錯体が提供される。
【００３４】
一般式（V）のポリフェニルアゾメチン誘導体は、どのような方法で合成されるものであってもよく、種々の公知の合成法が適用できる。例えば、四塩化チタン、パラトルエンスルホン酸などの酸存在下における、ジアミンとジケトン、もしくはアミノフェニルケトンの脱水反応が考慮される。このようにして得られたポリフェニルアゾメチン誘導体への希土類金属やハロゲン化金属（Ｍ）の配位は、どのような方法で行われてもよいが、実際には、ポリフェニルアゾメチン誘導体とＭを溶液中で共存させることにより容易に錯形成が起こる。また、溶液中で両者を共存させた後、溶媒を除去すれば、ポリフェニルアゾメチン錯体が単離される。
【００４１】
以上のとおりの各錯体は、高い電気応答性と安定な酸化還元電位を示す化合物であり、これらは高エネルギー密度二次電池の正極材料や安定性の高い金属触媒として有用である。
【００４２】
以下、実施例を示し、この発明の実施の形態についてさらに詳しく説明する。もちろん、この発明は以下の例に限定されるものではなく、細部については様々な態様が可能であることは言うまでもない。
【００４３】
【実施例】
＜実施例１＞ ビス［（α−フェニル）フェニルアゾメチン］ベンゼン（ｉ）の合成
以下の化学式（Ａ）に従って、ビス［（α−フェニル）フェニルアゾメチン］ベンゼン（i）を合成した。
【００４４】
【化１０】
１００ｍＬの三口フラスコに、１，４−ジベンゾイルベンゼン（１．４３ｇ、５．０ｍｍｏｌ）、アニリン（１．８ｍＬ、２０ｍｍｏｌ）、ジアザビシクロ［２，２，２］オクタン（３０．０ｍｍｏｌ）を加え、窒素雰囲気下とした後、溶媒としてクロロベンゼン（５０ｍＬ）を加えた。四塩化チタン（０．８ｍＬ、７．５ｍｍｏｌ）を滴下し、１２５℃で１２時間加熱還流した。反応終了後、沈殿物を濾過し、濾液を濃縮し、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル＝１／１０）により目的物を収率９７％で単離した。
【００４６】
得られた目的物を、赤外吸収スペクトル、質量分析、および元素分析により同定した。結果を表１に示した。
【００４７】
【表１】
＜実施例２＞ ビス［（α−フェニル）フェニルアゾメチン］ベンゼンと塩化錫（II）の錯形成と電気化学測定
０．２Ｍ ＴＢＡＢＦ4を含むアセトニトリル溶液中において、２ｍＭのビス［（α−フェニル）フェニルアゾメチン］ベンゼンのサイクリックボルタンメトリー測定（作用電極：炭素電極、対極：白金電極、参照電極：Ａｇ／Ａｇ+、掃引速度：０．１Ｖ／ｓｅｃ）を行った。
【００４９】
系中に４ｍＭの塩化錫（II）を加えたところ、錯形成に基づく極めて良好な酸化還元波（Ｅ1/2＝０．６５Ｖｖｓ．Ａｇ／Ａｇ+）が観測された。
＜実施例３＞ ビス［（α−フェニル）フェニルアゾメチン］ベンゼンと塩化リチウムの錯形成と電気化学測定
０．２Ｍ ＴＢＡＢＦ4を含むアセトニトリル溶液中において、２ｍＭのビス［（α−フェニル）フェニルアゾメチン］ベンゼンのサイクリックボルタンメトリー測定（作用電極：炭素電極、対極：白金電極、参照電極：Ａｇ／Ａｇ+、掃引速度：０．１Ｖ／ｓｅｃ）を行った。
【００５０】
系中に４ｍＭの塩化リチウムを加えたところ、錯形成に基づく極めて良好な酸化還元波（Ｅ1/2＝０．６５Ｖｖｓ．Ａｇ／Ａｇ+）が観測された。
＜実施例４＞ ビス［（α−フェニル）フェニルアゾメチン］とランタン（III）イオンの錯形成と電気化学測定
０．２Ｍ ＴＢＡＢＦ4を含むアセトニトリル溶液中において、２ｍＭのビス［（α−フェニル）フェニルアゾメチン］ベンゼンのサイクリックボルタンメトリー測定（作用電極：炭素電極、対極：白金電極、参照電極：Ａｇ／Ａｇ+、掃引速度：０．１Ｖ／ｓｅｃ）を行った。
【００５１】
系中に４ｍＭのＬａ（ＯＳＯ2ＣＦ3）3を加えたところ、錯形成に基づく極めて良好な酸化還元波（Ｅ1/2＝−０．５５Ｖｖｓ．Ａｇ／Ａｇ+）が観測された。＜実施例５＞ ポリ［（α−フェニル）フェニルアゾメチン］（ii）の合成
次の化学式（Ｂ）に従ってポリ［（α−フェニル）フェニルアゾメチン］（ii）を合成した。
【００５２】
【化１１】
５０ｍＬの三口フラスコに、１，４−ジベンゾイルベンゼン（０．２８６ｇ、１．０ｍｍｏｌ）、４，４’−チオジアミン（０．２１６ｇ、１．０ｍｍｏｌ）、ジアザビシクロ［２，２，２］オクタン（８．０ｍｍｏｌ）を加え、窒素雰囲気下とした後、クロロベンゼン（２０ｍＬ）を加え、四塩化チタン（２．０ｍｍｏｌ）を滴下した。１２５℃で２４時間加熱還流した。反応終了後、沈殿物を濾過し、濾液を濃縮した後、メタノール中で再沈殿して、目的物を黄色粉体として収率９６％で得た。
【００５４】
生成物の同定結果を表２に示した。
【００５５】
【表２】
【発明の効果】
以上詳しく説明したとおり、この発明によって、高エネルギー密度を有する二次電池の正極材料や、安定な錯体触媒として有用なフェニルアゾメチン錯体およびポリフェニルアゾメチン錯体が提供される。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to an electroresponsive complex. More specifically, the invention of this application relates to a phenylazomethine complex and a phenylenediamine complex that effectively act as a positive electrode material or a complex catalyst of a secondary battery.
[0002]
[Prior art and its problems]
In recent years, with the widespread use of notebook personal computers and mobile phones, or the development and commercialization of electric vehicles, there is a demand for lighter, longer life and higher performance secondary batteries.
[0003]
Conventional secondary batteries are generally nickel-metal hydride batteries and nickel-cadmium (nickel) batteries using nickel, hydrogen storage alloy, etc. as electrode materials, but recently, lithium secondary batteries having higher energy density. Batteries have attracted attention, and are expected not only as small batteries for portable terminals but also as large batteries for automobiles and space, and research is being actively conducted.
[0004]
In such a lithium secondary battery, lithium cobaltate is mainly used as a positive electrode material. However, since the reserve of cobalt is as small as only 8.4 million tons, the cost of the material is high and the price is likely to fluctuate. There was a problem. Thus, in order to reduce the cost, positive electrode materials using other metal oxides such as nickel, manganese, vanadium, etc. have been developed and partially adopted.
[0005]
However, secondary batteries mainly composed of these metal materials are heavy, and not only for small applications such as portable electronic devices, but also for large applications such as automobiles and space use, the weight of the secondary battery increases. There was a problem that the realizable size was limited.
[0006]
Further, in terms of the performance of the secondary battery, since the mobile ion of the lithium secondary battery is a metal ion, there is a problem that the moving speed is slow, the amount of current that can be charged and discharged is not so large, and the response is low. Furthermore, in the lithium secondary battery, since lithium ions are repeatedly inserted (charged) and released (discharged) into and from the electrode material (crystal) during charge and discharge, the structure of the electrode material is greatly changed and easily deteriorated. As a result, there is a problem that the repeated life of the battery is shortened. Furthermore, in a general battery including the lithium secondary battery as described above, a liquid electrolyte is used to separate the positive electrode and the negative electrode. Therefore, leakage of the electrolyte solution may occur, and it is difficult to reduce the thickness.
[0007]
Therefore, a polymer electrolyte composed only of a polymer and an electrolyte salt and a gel polymer electrolyte obtained by gelling these with an organic solvent have been developed and put into practical use. However, even in the polymer secondary battery using such a polymer electrolyte, there is a problem in that the internal resistance is high and the response is poor because large ionic species move. Further, in these polymer batteries, as in the case of the lithium secondary battery, since the main material of the electrode material is a metal material such as lithium cobaltate, the various problems described above remain unsolved.
[0008]
In order to effectively solve these problems, conductive polymers are considered as suitable electrode materials. However, at present, such a conductive polymer material has not been put into practical use, and a high-performance polymer electrode material has been desired.
[0009]
On the other hand, various types of metal catalysts for chemical reactions have been reported and provided. However, as metal catalysts useful for industrial use, they exhibit stable redox and can move many electrons. There is a need for something. In addition, in order to use metal catalysts industrially, there is a need for further improvement in catalyst efficiency and thermal stability, but such metal catalysts are not well known so far. It is a fact.
[0010]
Therefore, the invention of this application has been made in view of the circumstances as described above, solves the problems of the prior art, enables the secondary battery to be reduced in size and weight, and has a long life and high-speed response. It is an object to provide a high performance electrode material for a secondary battery. Another object of the invention of this application is to provide a highly heat-stable metal catalyst that can move many electrons and exhibits stable redox.
[0011]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention of this application is firstly a complex having electrical responsiveness, which has the following general formula (I):
[0012]
[Formula 4]
(However, Ar represents a phenylene group, a biphenylene group, or a naphthylene group , R 1 and R 2 are the same or different, and each represents a phenyl group, a biphenyl group, or a naphthyl group, and R and Ra are the same or different. different from a phenyl group or a naphthyl group, M provides a rare earth metal, tin halide (II), vanadium halide or phenyl azomethine complex represented by halogenated showing the lithium.).
[0014]
Secondly, the invention of this application is a complex having electrical responsiveness, which has the following general formula (II):
[0015]
[Chemical formula 5]
(However, Ar represents a phenylene group, a biphenylene group, or a naphthylene group , R 3 and R 4 are the same or different, and each represents a phenyl group, a biphenyl group, or a naphthyl group, and R b is the same or different. Represents a phenylene group, a biphenylene group, a diphenylene sulfide group, or a naphthylene group , M represents a rare earth metal , tin ( II ) halide, vanadium halide, or lithium halide, and n represents an integer of 1 or more indicating the degree of polymerization. providing polyphenyl azomethine complex represented by it.) in.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The inventors have made extensive studies to solve the above-mentioned problems, and have so far reported polyphenylazomethine derivatives that are useful as positive electrode materials for proton electrodes (Japanese Patent Application No. 2000-270712). Subsequently, it was found that rare earth metal ions have a high coordination ability with respect to these phenylazomethine derivatives and phenylenediamine derivatives. The inventors have found that a rare earth metal ion and a phenylazomethine derivative or a phenylenediamine derivative become electroactive by complex formation, leading to the invention of this application.
[0023]
The phenylazomethine complex and phenylenediamine complex of the invention of this application are useful as positive electrode materials having a much higher energy density than conventional conductive polymers because they are oxidized and reduced without ion transfer. is there. Moreover, since it can be efficiently complexed with metal ions having catalytic ability, an improvement in catalytic efficiency based on smooth electron transfer via a π-conjugated system can be expected.
[0024]
Therefore, the invention of this application provides a phenylazomethine complex or a phenylenediamine complex as an electroresponsive complex.
[0025]
As the phenylazomethine complex, the following general formula (IV)
[0026]
[Chemical 7]
(However, Ar represents a phenylene group, a biphenylene group, or a naphthylene group , R 1 and R 2 are the same or different, and each represents a phenyl group, a biphenyl group, or a naphthyl group, and R and Ra are the same or different. A phenyl group or a naphthyl group is also provided ) and a complex formed by coordination of a rare earth metal or a metal halide with N of the phenylazomethine derivative represented by
[0028]
The coordinated M is selected from rare earth metals or metal halides. Examples of rare earth metals include scandium (Sc), yttrium (Y), lanthanum (La), actinium (Ac), scandium group, cerium (Ce), europium (Eu), terbium (Tb), ytterbium (Yb). And lanthanoid (Ln) -based metals. Of these, La, Ce, Eu, and Tb are preferable. On the other hand, as the metal halides, SnCl 2, SnBr 2 halogens, such as tin (II), vanadium halides such as VCl 3, and halogenated lithium such as LiCl or LiBr.
[0029]
The phenylazomethine derivative represented by the general formula (IV) may be synthesized by any method. Various known methods are exemplified, and specifically, a method obtained by dehydrating diamine and diketone or aminophenylketone in the presence of an acid such as titanium tetrachloride or paratoluenesulfonic acid can be considered. Coordination of the rare earth metal or metal halide (M) to the phenylazomethine derivative thus obtained may be carried out by any method. In practice, however, the phenylazomethine derivative and M are dissolved in a solution. Coexistence is easily caused by the coexistence of. In addition, the phenylazomethine complex can be isolated by removing the solvent after coexistence in the solution.
[0030]
In the invention of this application, the following general formula (V)
[0031]
[Chemical 8]
(However, Ar represents a phenylene group, a biphenylene group, or a naphthylene group , R 3 and R 4 are the same or different, and each represents a phenyl group, a biphenyl group, or a naphthyl group, and R b is the same or different. A phenylene group, a biphenylene group, a diphenylene sulfide group, or a naphthylene group , and n is an integer of 1 or more indicating the degree of polymerization.) M is arranged at the N site of the polyphenylazomethine derivative represented by Coordinated polyphenylazomethine complexes are provided.
[0034]
The polyphenylazomethine derivative of the general formula (V) may be synthesized by any method, and various known synthesis methods can be applied. For example, a dehydration reaction between a diamine and a diketone or aminophenyl ketone in the presence of an acid such as titanium tetrachloride or paratoluenesulfonic acid is considered. Coordination of the rare earth metal or metal halide (M) to the polyphenylazomethine derivative thus obtained may be carried out by any method. In practice, however, the polyphenylazomethine derivative and M may be combined with each other. Complex formation easily occurs when they coexist in a solution. Moreover, if both are made to coexist in a solution and a solvent is removed, a polyphenylazomethine complex will be isolated.
[0041]
Each complex as described above is a compound that exhibits high electrical responsiveness and a stable redox potential, and these are useful as positive electrode materials for high energy density secondary batteries and highly stable metal catalysts.
[0042]
Hereinafter, examples will be shown, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail.
[0043]
【Example】
<Example 1> Synthesis of bis [(α-phenyl) phenylazomethine] benzene (i) According to the following chemical formula (A), bis [(α-phenyl) phenylazomethine] benzene (i) was synthesized.
[0044]
Embedded image
To a 100 mL three-necked flask, 1,4-dibenzoylbenzene (1.43 g, 5.0 mmol), aniline (1.8 mL, 20 mmol), diazabicyclo [2,2,2] octane (30.0 mmol) are added, and nitrogen is added. After the atmosphere, chlorobenzene (50 mL) was added as a solvent. Titanium tetrachloride (0.8 mL, 7.5 mmol) was added dropwise, and the mixture was heated to reflux at 125 ° C. for 12 hours. After completion of the reaction, the precipitate was filtered, the filtrate was concentrated, and the target product was isolated with a yield of 97% by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/10).
[0046]
The obtained object was identified by infrared absorption spectrum, mass spectrometry, and elemental analysis. The results are shown in Table 1.
[0047]
[Table 1]
Example 2 Complex formation and electrochemical measurement of bis [(α-phenyl) phenylazomethine] benzene and tin (II) chloride 2 mM bis [(α-phenyl) in acetonitrile solution containing 0.2 M TBABF 4 Phenylazomethine] benzene was measured by cyclic voltammetry (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: Ag / Ag + , sweep rate: 0.1 V / sec).
[0049]
When 4 mM tin (II) chloride was added to the system, a very good oxidation-reduction wave (E 1/2 = 0.65 V vs. Ag / Ag + ) based on complex formation was observed.
Example 3 Complex formation and electrochemical measurement of bis [(α-phenyl) phenylazomethine] benzene and lithium chloride In an acetonitrile solution containing 0.2 M TBABF 4 , 2 mM bis [(α-phenyl) phenylazomethine] Cyclic voltammetry measurement of benzene (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: Ag / Ag + , sweep rate: 0.1 V / sec) was performed.
[0050]
When 4 mM lithium chloride was added to the system, a very good redox wave (E 1/2 = 0.65 Vvs. Ag / Ag + ) based on complex formation was observed.
Example 4 Complex formation and electrochemical measurement of bis [(α-phenyl) phenylazomethine] and lanthanum (III) ion 2 mM bis [(α-phenyl) phenyl in acetonitrile solution containing 0.2 M TBABF 4 Azomethine] benzene was measured by cyclic voltammetry (working electrode: carbon electrode, counter electrode: platinum electrode, reference electrode: Ag / Ag + , sweep rate: 0.1 V / sec).
[0051]
When 4 mM of La (OSO 2 CF 3 ) 3 was added to the system, a very good redox wave (E 1/2 = −0.55 V vs. Ag / Ag + ) based on complex formation was observed. <Example 5> Synthesis of poly [(α-phenyl) phenylazomethine] (ii) Poly [(α-phenyl) phenylazomethine] (ii) was synthesized according to the following chemical formula (B).
[0052]
Embedded image
To a 50 mL three-necked flask, 1,4-dibenzoylbenzene (0.286 g, 1.0 mmol), 4,4′-thiodiamine (0.216 g, 1.0 mmol), diazabicyclo [2,2,2] octane (8 0.0 mmol) was added to form a nitrogen atmosphere, chlorobenzene (20 mL) was added, and titanium tetrachloride (2.0 mmol) was added dropwise. The mixture was heated to reflux at 125 ° C. for 24 hours. After completion of the reaction, the precipitate was filtered, and the filtrate was concentrated and then reprecipitated in methanol to obtain the desired product as a yellow powder with a yield of 96%.
[0054]
The product identification results are shown in Table 2.
[0055]
[Table 2]
【The invention's effect】
As described in detail above, the present invention provides a positive electrode material for a secondary battery having a high energy density, and a phenylazomethine complex and a polyphenylazomethine complex useful as a stable complex catalyst.
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