Indigestible Markers: Methodology and Applications in Ruminant Nutrition

Animal Scienc

Reactions at Noble Metal Contacts with Methylammonium Lead Triiodide Perovskites: Role of Underpotential Deposition and Electrochemistry

Chemical reactivity of halide perovskites coupled with a low energy of formation makes it a challenge to characterize material properties and achieve long-term device stability. In this study, we elucidate electrochemical reactions occurring at the methylammonium lead triiodide (MAPbI3)/Au interface. X-ray photoemission spectroscopy is used to identify a type of reduction/oxidation reaction termed underpotential deposition (UPD) involving lead, iodine, and hydrogen occurring at interfaces with noble metals. Changes in surface compositions and oxidation states suggest that UPD derived adsorbates at MAPbI3/Au interfaces lower the energy barrier for release of volatile HI and/or I2catalyzing degradation at exposed contacts. Additionally, comparison to PbI2/Au interfaces demonstrates that the presence of methylammonium/methylamine accelerates the formation of a Pb0 adlayer on the Au. Reactions involving UPD Pb0 can transform the typically anodic (hole collecting) Au to a cathode in a photovoltaic measurement. Cyclic voltammetry reveals electrochemical reaction peaks in indium tin oxide (ITO)/MAPbI3/Au devices occurring within voltage ranges commonly used for perovskite characterization. The electrochemical stability window of this device architecture is measured to be between−0.5 V and 0.9 V. Voltage induced interfacial reactions contribute to reversible electrochemical peaks, hysteresis, switchable perovskite diode polarity, and permanent degradation at larger voltages. These types of surface reactions alter the interface/interphase composition beyond ion accumulation, provide a source for the diffusion of defects, and contribute to electrode material dependent current-voltage hysteresis. Moreover, the results imply fundamental limitations to achieving high device stability with noble metals and/or methylammonium containing perovskites

The effect of Zn excess on kesterite solar cells

a b s t r a c t Accuracy in composition control has been one of the top issues for fabricating high-performance kesterite (Cu 2 ZnSn(Se,S) 4 ) solar cells. A detailed understanding of the effect of Zn excess on device performance has not yet been demonstrated. Thus, specific criteria for high-performance devices, in particular discriminating between the effects of Zn-rich features at the front versus the back of the absorber, are desired. In this study, we report that co-evaporated kesterite absorbers can demonstrate high device efficiency despite the presence of large quantities of ZnSe. However, the benign presence of ZnSe is found to be conditional. While large ZnSe grains on the back of the absorbers are not harmful to device performance, the ZnSe grains produced by excess Zn near the end of the deposition degrade the cell efficiency from 8% level to 6% level (without anti-reflection coatings). The other effect related to excess Zn on the front of absorber is the facilitation of breakdown in lower reverse bias. The breakdown indicated here occurs only under the illumination of blue photons, and to our best knowledge has not been reported before. The exact mechanism of the breakdown remains open, but it is demonstrated to be related to the photoconductivity of CdS, and is thus possibly a symptom of lateral defect issues in the absorber, caused by the overdose of Zn. The same type of issue contributing to the breakdown may also be responsible for part of the parasitic loses at the working voltage, and therefore warrants further research

Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry

International audienc

Li2O-Based Cathode Additives Enabling Prelithiation of Si Anodes

Low first-cycle Coulombic efficiency is especially poor for silicon (Si)-based anodes due to the high surface area of the Si-active material and extensive electrolyte decomposition during the initial cycles forming the solid electrolyte interphase (SEI). Therefore, developing successful prelithiation methods will greatly benefit the development of lithium-ion batteries (LiBs) utilizing Si anodes. In pursuit of this goal, in this study, lithium oxide (Li2O) was added to a LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a scalable ball-milling approach to compensate for the initial Li loss at the anode. Different milling conditions were tested to evaluate the impact of particle morphology on the additive performance. In addition, Co3O4, a well-known oxygen evolution reaction catalyst, was introduced to facilitate the activation of Li2O. The Li2O + Co3O4 additives successfully delivered an additional capacity of 1116 mAh/gLi2O when charged up to 4.3 V in half cells and 1035 mAh/gLi2O when charged up to 4.1 V in full cells using Si anodes

Li₂O-Based Cathode Additives Enabling Prelithiation of Si Anodes

Low first-cycle Coulombic efficiency is especially poor for silicon (Si)-based anodes due to the high surface area of the Si-active material and extensive electrolyte decomposition during the initial cycles forming the solid electrolyte interphase (SEI). Therefore, developing successful prelithiation methods will greatly benefit the development of lithium-ion batteries (LiBs) utilizing Si anodes. In pursuit of this goal, in this study, lithium oxide (Li2O) was added to a LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a scalable ball-milling approach to compensate for the initial Li loss at the anode. Different milling conditions were tested to evaluate the impact of particle morphology on the additive performance. In addition, Co3O4, a well-known oxygen evolution reaction catalyst, was introduced to facilitate the activation of Li2O. The Li2O + Co3O4 additives successfully delivered an additional capacity of 1116 mAh/gLi2O when charged up to 4.3 V in half cells and 1035 mAh/gLi2O when charged up to 4.1 V in full cells using Si anodes

Band offsets of n-type electron-selective contacts on cuprous oxide (Cu[subscript 2]O) for photovoltaics

The development of cuprous oxide (Cu [subscript 2]O) photovoltaics (PVs) is limited by low device open-circuit voltages. A strong contributing factor to this underperformance is the conduction-band offset between Cu [subscript 2]O and its n-type heterojunction partner or electron-selective contact. In the present work, a broad range of possible n-type materials is surveyed, including ZnO, ZnS, Zn(O,S), (Mg,Zn)O, TiO[subscript 2], CdS, and Ga[subscript 2]O[subscript 3]. Band offsets are determined through X-ray photoelectron spectroscopy and optical bandgap measurements. A majority of these materials is identified as having a negative conduction-band offset with respect to Cu [subscript 2]O; the detrimental impact of this on open-circuit voltage (V [subscript OC]) is evaluated through 1-D device simulation. These results suggest that doping density of the n-type material is important as well, and that a poorly optimized heterojunction can easily mask changes in bulk minority carrier lifetime. Promising heterojunction candidates identified here include Zn(O,S) with [S]/[Zn] ratios >70%, and Ga[subscript 2]O[subscript 3], which both demonstrate slightly positive conduction-band offsets and high V [subscript OC] potential. This experimental protocol and modeling may be generalized to evaluate the efficiency potential of candidate heterojunction partners for other PV absorbers, and the materials identified herein may be promising for other absorbers with low electron affinities.National Science Foundation (U.S.) (CAREER Award ECCS-1150878)Singapore-MIT Alliance for Research and Technology. Low Energy Electronic Systems Research Program (Singapore. National Research Foundation)National Renewable Energy Laboratory (U.S.) (Non-Proprietary Partnering Program Contract DE-AC36-08-GO28308