For investigation of the thermal stability of polycarbonate-based lithium salt-containing electrolytes, polycarbonate–salt mixtures [polyethylene carbonate (PEC) and polypropylene carbonate (PPC) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)] were heated to 100 °C and the conductivity was monitored with electrochemical impedance spectroscopy for at least 24 h. At a constant high temperature, the observed rise in conductivity can be correlated to degradation of long-chain polymer units to small-chain polymer units as the viscosity decreases with a shorter chain length. In both cases, degradation can be observed. With PEC–LiTFSI, it takes ≈9 h until total degradation; with PPC–LiTFSI, the process is slower. Additionally, we repeated the experiments with PEC and other Li salts such as lithium trifluoromethanesulfonate (LiOTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), and lithium difluoro(oxalato)borate (LiDFOB). These experiments resulted in the degradation being dependent on the electrophilic activation by the lithium salt. With different Li-free salts such as sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), potassium bis(trifluoromethanesulfonyl)imide (KTFSI), and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), no degradation of the polymer is observable. As a degradation mechanism, we anticipate a depolymerization of PEC at the α-carbon of the carbonate group in the polymer chain in the presence of a lithium salt with a weakly coordinating anion.
Gd-doped ceria with transition metal oxide co-doping is especially interesting for catalytical applications in the intermediate temperature range between 400-600 • C. Ce 0.9-x Fe x Gd 0.1 O 2-δ samples with x = 0.0 to 0.05 were produced via a sol-gel synthesis route. XRD measurements proved the materials to be single phase with fluorite structure, but electron microscopy investigations showed enrichment of Gd and Fe at the grain boundaries and the existence of small-scale secondary phases for 5 mol% Fe. The effect of Fe co-doping on the ionic and electronic conductivity was monitored using impedance spectroscopy and DC polarizationrelaxation measurements applying ion blocking micro contacts (Hebb-Wagner setup). Already the addition of 1 mol% Fe raised the total conductivity of the material by two decades (about 10 −4 S/cm at 750 • C compared to 5 • 10 −6 S/cm for Ce 0.9 Gd 0.1 O 2-δ ). In addition, already for 1 mol% Fe, but very clearly for 2 and 5 mol% Fe addition, a temperature and oxygen partial pressure dependent maximum in the p-type conductivity has been found, which is attributed to the Fe 2+/3+ redox reaction and a related small polaron hopping process.
Direct observation of the lithiation and de-lithiation in lithium batteries on the component and microstructural scale is still difficult. This work presents recent advances in MeV ion-beam analysis, enabling quantitative contact-free analysis of the spatially-resolved lithium content and state-of-charge (SoC) in all-solid-state lithium batteries via 3 MeV proton-based characteristic x-ray and gamma-ray emission analysis. The analysis is demonstrated on cross-sections of ceramic and polymer all-solid-state cells with LLZO and MEEP/LIBOB solid electrolytes. Different SoC are measured ex-situ and one polymer-based operando cell is charged at 333 K during analysis. The data unambiguously show the migration of lithium upon charging. Quantitative lithium concentrations are obtained by taking the physical and material aspects of the mixed cathodes into account. This quantitative lithium determination as a function of SoC gives insight into irreversible degradation phenomena of all-solid-state batteries during the first cycles and locations of immobile lithium. The determined SoC matches the electrochemical characterization within uncertainties. The presented analysis method thus opens up a completely new access to the state-of-charge of battery cells not depending on electrochemical measurements. Automated beam scanning and data-analysis algorithms enable a 2D quantitative Li and SoC mapping on the µm-scale, not accessible with other methods.
In this study, the possibility to characterize the electrochemical characteristics of the particle-polymer interface in dual-phase electrolytes by measuring the contact potential difference with high local resolution is demonstrated. Two different polymer electrolytes, polyethylene oxide (PEO) and poly[bis-2-(2-methoxyethoxy)-ethoxyphosphazene] (MEEP), were investigated in combination with lithium ion conductive Li7La3Zr2O12 (LLZ) particles and two different mixed ionic-electronic conductive ceramic particles: uncoated and carbon coated LiFePO4 (LFP) as typical cathode material and uncoated Li4Ti5O12 as typical anode material. A distinct Volta potential gradient between the particles and the polymer was observable in all cases, except when no lithium salt was present within the polymer matrix. The measured potential gradients can be explained in terms of a contact potential between the polymer electrolyte and the ceramic electrolyte. A more negatively charged space charge layer around LFP particles in PEO matrix and around LLZ particles in MEEP can be explained by enrichment of salt anions in direct vicinity of the particle. Electrochemical characterization with impedance spectroscopy showed an increased conductivity for addition of LFP for PEO while the addition of various particles in different concentrations showed no effect on the conductivity of MEEP. The lithium transference number was unaffected by particle addition for all samples.
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