3 research outputs found
A nitroxide-containing cathode material for organic radical batteries studied with pulsed EPR spectroscopy
An electron spin echo in a nitroxide-containing polymer cathode film for organic radical batteries is observed for various states of charge at cryogenic temperatures. The EPR-detected state of charge (ESOC), as inferred from the number of paramagnetic centers in the film, is compared to the results of Coulomb counting based on galvanostatic charging. Spin concentration, longitudinal relaxation times T(1 )and phase memory times T-m strongly correlate with the ESOC. In the discharged film, the spin concentration reaches 5 +/- 3x10(20) cm(-3), causing a phase memory time T-m << 100 ns (shorter than the resonator ring-down time) that hinders the detection of the spin echo. In the charged film, the decreased spin concentration results in a longer T-m between 100 ns and 300 ns that enables spin-echo detection, yet limits the length of the microwave pulse sequence. The short, broad-band pulses cause instantaneous diffusion in the unoxidized domains across the oxidized film, affecting the relative peak intensities in the pulsed EPR spectrum. By simulating the spectral distortion caused by instantaneous diffusion, we obtain information on the local spin concentration, which complements the information on the 'bulk' spin concentration determined by electrochemistry and continuous-wave EPR spectroscopy
Spins at work: probing charging and discharging of organic radical batteries by electron paramagnetic resonance spectroscopy
Organic radical batteries (ORBs) are a promising class of electrochemical power sources employing organic radicals as redox-active groups. This article reports on the development of a versatile on-substrate electrode setup for spectroelectrochemical Electron Paramagnetic Resonance (EPR) measurements on redox conductive polymers for ORBs. Quantitative in operando EPR experiments performed on electrochemical cells with a di-TEMPO Ni-Salen polymer as active electrode material demonstrate a strong decrease in the number of paramagnetic centers upon oxidizing the film. The distinct EPR signatures of the TEMPO-containing polymer and its fragments in different molecular environments are used to study its degradation upon repeated cycling. A comparison between the number of EPR-active sites and the number of electrochemically active charges, as measured by cyclic voltammetry, provides information on the nature of the degradation process. Low-temperature ex situ pulse EPR measurements on the oxidized polymer film reveal the spectrum of dilute nitroxide species, which may be associated with electrochemically inactive islands. These experiments pave the way for advanced EPR techniques for accurately determining distances between adjacent paramagnetic centers and thus for identifying performance-limiting loss mechanisms, which can eventually help develop strategies for making ORBs powerful contenders on the path towards sustainable electrochemical power sources
Spins at work: probing charging and discharging of organic radical batteries by electron paramagnetic resonance spectroscopy
Organic radical batteries (ORBs) are a promising class of electrochemical power sources employing organic radicals as redox-active groups. This article reports on the development of a versatile on-substrate electrode setup for spectroelectrochemical Electron Paramagnetic Resonance (EPR) measurements on redox conductive polymers for ORBs. Quantitative in-operando EPR experiments performed on electrochemical cells with a di-TEMPO Ni-Salen polymer as active electrode material demonstrate a strong decrease in the number of paramagnetic centers upon oxidizing the film. The distinct EPR signatures of the TEMPO-containing polymer and its fragments in different molecular environments are used to study its degradation upon repeated cycling. A comparison between the number of EPR-active sites and the number of electrochemically active charges, as measured by cyclic voltammetry, provides information on the nature of the degradation process. Low-temperature ex-situ pulse EPR measurements on the oxidized polymer film reveal the spectrum of dilute nitroxide species, which may be associated with electrochemically inactive islands. These experiments pave the way for advanced EPR techniques for accurately determining distances between adjacent paramagnetic centers and thus for identifying performance-limiting loss mechanisms, which can eventually help develop strategies for making ORBs powerful contenders on the path towards sustainable electrochemical power sources