Novel redox active porous polymers to use as cathode in batteries

Abstract

[EN]Currently, several organic materials and polymers are under investigationas cathode materials for lithium batteries, for example: organic carbonyl compounds, conductive polymers, radical polymers or organosulfur compounds. Recently, redox-active Conjugated Microporous Polymers (CMPs) have emerged as potential electrode materials for energy storage devices. The aim of this work was to synthesize novel redox-active CMPs through Sonogashira cross-coupling reaction starting from tri-or tetra-functional monomers and differentredox-activedibromine monomers. These monomers have different redox activity andtherefore we envisioned that their redox properties would be different. First, the synthesis of the monomers wascarried out followed by their characterization by 1H and 13C NMR, ATR-FTIR, mass spectrometry and elemental analysis. We found that the synthesis of the tri-and tetra-functional monomers wasmore favorable starting from iodide monomers than from bromine monomers. Afterwards, the obtained monomers were employed for making porous polymers using Sonogashira reaction. The porous polymers were characterizedbysolid13C NMR, FTIR, BET, TGA and elemental analysis. Furthermore, the electrochemical properties of the monomers and polymers were studied through cyclic voltammetries. With this analysisthe effect of the redox activity of each monomer after the polymerizationwas seenand it was possibleto compare the redox activity of the different CMPs. The synthesized CMPs have shown potential as cathode materials, but still more studies are needed to confirm theelectrochemical properties of these materials.

[EU]Azken aldian, zenbait polimero eta material organiko aztertuak izaten ari dira litiozko baterietan katodo bezala erabiltzeko. Adibidez: karbonilodun konposatu organikoak, polimero eroankorrak, polimero erradikalak edo konposatu organosulfuroak. Duela gutxi, erredox aktiboak diren polimero mikroporoso konjugatuek (CMP), energia biltegiratzeko gailuetan elektrodo bezala erabiltzeko material bezala garrantzi handia hartu dute. Lan honen helburu nagusia erredox aktiboak diren CMP berriak sintetizatzea eta haien propietateak aztertzea da. Horretarako, CMP hauek Sonogashira cross-couplingerreakzioaren bidez sintetizatu dira, tri-edo tetra-funtzionalak diren monomeroetatiketa erredox aktiboak diren dibromo monomeroezberdinetatikabiatuz. Monomero hauen erredox aktibitatea ezberdina denez, suposatu da haien erredox propietateak ere ezberdinak izango direla. Hasteko, monomero hauen sintesiak egin dira eta jarraian karakterizatuak izan dira 1H eta 13C EMN, ATR-FTIR, masa espektrometria eta analisis elementalateknikak erabiliz. Gainera, ikusi da monomero ti-eta tetra-funtzionalen sintesia ioduro monomeroetatik abiatuz hobesten dela, bromuroetatik abiatu ordez. Ondoren,monomero hauek erabili dira polimero porotsuak lortzeko Sonogashira erreakzioaren bidez. Polimero porotsu hauen karakterizazioa egin da ondorengo karakterizazio metodoak jarraituz: 13C EMR, FTIR, BET, TGA eta analisis elementala. Honetaz gain, monomeroen eta polimeroen propietate elektrokimikoak boltametria ziklikoen bidez aztertu dira. Analisi honen bitartez polimerizazioaren ondorenmonomero bakoitzaren erredox aktibitateak duen efektua ikusi da eta CMP desberdinen erredox aktibitateakonparatu da. Analisi guztihaueksintetizatutako CMP ak katodoetarako material erabilgarriak izan daitezkeela erakutsi dute.Hala ere, material hauen propietate elektrokimikoak ezagutzeko beharrezkoa da azterketa gehiago egitea.