A US perspective on closing the carbon cycle to defossilize difficult-to-electrify segments of our economy.

Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.

Role of Surface Acidity in the Surface Stabilization of the High-Voltage Cathode LiNi0.6Mn0.2Co0.2O2.

Metal oxide coatings have been reported to be an effective approach for stabilizing cathode interfaces, but the associated chemistry is unclear. In this work, thin films of TiO2, ZnO, and Cr2O3, which have different surface acidities/basicities, were used to modify the surface chemistry of LiNi0.6Mn0.2Co0.2O2 and study the acidity's role in the cathode/electrolyte interphase composition and impedance under high-voltage cycling (4.5 V vs Li/Li+). Cathodes with more acidic surfaces provided higher initial specific capacity and capacity retention with cycling. More basic surfaces had higher initial impedance and greater impedance growth with cycling. These differences appeared to depend on the degree of LiPF6 salt decomposition at the interface, which was related to acidity, with more neutral surfaces having a LiF/Li x PO y F z ratio close to unity, but basic surfaces had substantially more LiF. This chemistry was more significant than the cathode electrolyte interphase (CEI) thickness as the more acidic surfaces formed a thicker CEI than the basic surface, resulting in better capacity retention. These results suggest that the Brønsted acidity of cathodes directly influences electrolyte degradation, ion transport, and thus, cell lifetime.

Electrolyte Volume Effects on Electrochemical Performance and Solid Electrolyte Interphase in Si-Graphite/NMC Lithium-Ion Pouch Cells.

This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate with 10 wt % fluoroethylene carbonate. Single layer pouch cells (100 mA h) were constructed with 15 wt % Si-graphite/LiNi0.5Mn0.3CO0.2O2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times to the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendrites are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. Solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is nonuniform after cycling.

Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries.

The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M = Ni, Mn, Co: NMC; M = Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1 C/-1 C with respectively 4.35 V and 4.4 V UCV in 2 Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. The ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs.

Correlating cation ordering and voltage fade in a lithium-manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study.

Structure-electrochemical property correlation is presented for lithium-manganese-rich layered-layered nickel manganese cobalt oxide (LMR-NMC) having composition Li1.2Co0.1Mn0.55Ni0.15O2 (TODA HE5050) in order to examine the possible reasons for voltage fade during short-to-mid-term electrochemical cycling. The Li1.2Co0.1Mn0.55Ni0.15O2 based cathodes were cycled at two different upper cutoff voltages (UCV), 4.2 V and 4.8 V, for 1, 10, and 125 cycles; voltage fade was observed after 10 and 125 cycles only when the UCV was 4.8 V. Magnetic susceptibility and selected-area electron diffraction data showed the presence of cation ordering in the pristine material, which remained after 125 cycles when the UCV was 4.2 V. When cycled at 4.8 V, the magnetic susceptibility results showed the suppression of cation ordering after one cycle; the cation ordering diminished upon further cycling and was not observed after 125 cycles. Selected-area electron diffraction data from oxides oriented towards the [0001] zone axis revealed a decrease in the intensity of cation-ordering reflections after one cycle and an introduction of spinel-type reflections after 10 cycles at 4.8 V; after 125 cycles, only the spinel-type reflections and the fundamental O3 layered oxide reflections were observed. A significant decrease in the effective magnetic moment of the compound after one cycle at 4.8 V indicated the presence of lithium and/or oxygen vacancies; analysis showed a reduction of Mn(4+) (high spin/low spin) in the pristine oxide to Mn(3+) (low spin) after one cycle. The effective magnetic moment was higher after 10 and 125 cycles at 4.8 V, suggesting the presence of Mn(3+) in a high spin state, which is believed to originate from distorted spinel (Li2Mn2O4) and/or spinel (LiMn2O4) compounds. The increase in effective magnetic moments was not observed when the oxide was cycled at 4.2 V, indicating the stability of the structure under these conditions. This study shows that structural rearrangements in the LMR-NMC oxide happen only at higher potentials (4.8 V, for example) and provides evidence of a direct correlation between cation ordering and voltage fade.

Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes.

Addition of polyethyleneimine (PEI) to aqueous LiFePO4 nanoparticle suspensions improves stability and reduces agglomerate size, which is beneficial to lithium-ion battery cathode manufacturing. This research examines the effect of both PEI concentration and molecular weight (MW) on dispersing LiFePO4 and Super P C45 in multicomponent aqueous suspensions. It is demonstrated that the optimal conditions for obtaining stable suspensions with minimal agglomerate size are 1.5 wt% PEI with MW=2000 g mol(-1) and 5.0 wt% PEI with MW=10,000 g mol(-1) for LiFePO4 and Super P C45, respectively. The mixing sequence also affects rheological properties of these suspensions. It is found that dispersing the LiFePO4 and Super P C45 separately yielded suspensions with superior properties (Newtonian rheological behavior, smaller agglomerate size, improved settling, etc.). In particular, dispersing the LiFePO4 prior to the Super P C45 when making the final multicomponent suspension is found to be beneficial, which was evidenced by higher half-cell discharge capacity.

Visualizing the chemistry and structure dynamics in lithium-ion batteries by in-situ neutron diffraction.

We report an in-situ neutron diffraction study of a large format pouch battery cell. The succession of Li-Graphite intercalation phases was fully captured under an 1C charge-discharge condition (i.e., charge to full capacity in 1 hour). However, the lithiation and dilithiation pathways are distinctively different and, unlike in slowing charging experiments with which the Li-Graphite phase diagram was established, no LiC24 phase was found during charge at 1C rate. Approximately 75 mol. % of the graphite converts to LiC6 at full charge, and a lattice dilation as large as 4% was observed during a charge-discharge cycle. Our work demonstrates the potential of in-situ, time and spatially resolved neutron diffraction study of the dynamic chemical and structural changes in "real-world" batteries under realistic cycling conditions, which should provide microscopic insights on degradation and the important role of diffusion kinetics in energy storage materials.

Limb amputation for squamous cell carcinoma of the skin: factors involved in this poor evolution.

OBJECTIVE: To analyze retrospectively a series of cases culminating in amputation for advanced squamous cell carcinoma. METHODS: We studied eight patients with histologically confirmed squamous cell carcinoma of the skin that had limbs amputated by tumor invasion at our institution between 2005 and 2008. We evaluated the histological factors and the institutional and psychosocial factors that contributed to this unfavorable outcome. RESULTS: The mean age at diagnosis was 63 years, 37.5% of patients (three patients) had a history of abusive and continuous exposure to sunlight and six (75%) patients had other risk factors for SCC of the skin. Seven patients were diagnosed when the tumor was already larger than 2cm, and it required a large period of time (6.7 years on average) between the onset of the initial lesion and the correct histopathological diagnosis of locally advanced tumor. CONCLUSION: The unfavorable outcome (amputation) in patients with squamous cell carcinoma may be associated with aggressiveness of cancer and related comorbidities, and may also be influenced by factors such as access to public health, quality of care and patient's relationship with the disease.

Local detection of activation energy for ionic transport in lithium cobalt oxide.

Local activation energy for ionic diffusion is probed on the nanometer level in LiCoO(2) thin films using variable temperature electrochemical strain microscopy (ESM). The high spatial resolution of ESM allows one to extract information about ionic activation energies on the level of individual grains and grain facets, thus bridging the lengths scales of atomistic calculations and traditional macroscopic experiments. A series of control experiments have been performed and possible signal generating mechanisms are discussed to explain the temperature-dependent ESM measurements.

Amputação de membros por carcinoma escamocelular da pele: fatores envolvidos nesta evolução desfavorável / Limb amputation for squamous cell carcinoma of the skin: factors involved in this poor evolution

OBJETIVO: Analisar retrospectivamente uma série de casos que culminaram em amputação por carcinoma escamocelular avançado. MÉTODOS: Foram estudados oito pacientes com diagnóstico histológico de carcinoma escamocelular de pele que tiveram membros amputados por invasão tumoral, em nossa Instituição entre 2005 e 2008. Foram avaliados: fatores histológicos, institucionais e psicossociais que contribuíram para este desfecho desfavorável. RESULTADOS: A média de idade ao diagnóstico foi 63 anos; 37,5% dos pacientes (três pacientes) tinham exposição abusiva e contínua aos raios solares, e seis (75%) pacientes tinham outros fatores de risco para CEC de pele. Sete pacientes foram diagnosticados quando o tumor já era maior que 2cm, e foi necessário um período grande de tempo (6,7 anos em média) entre o aparecimento da lesão inicial e o diagnóstico histopatológico correto do tumor localmente avançado. CONCLUSÃO: O desfecho desfavorável (amputação) nos pacientes portadores de carcinoma espinocelular pode estar associado à agressividade da neoplasia e às comorbidades relacionadas, podendo ainda sofrer influência de fatores como acesso à saúde pública, qualidade da assistência médica e relação do paciente com a doença.

OBJECTIVE: To analyze retrospectively a series of cases culminating in amputation for advanced squamous cell carcinoma. METHODS: We studied eight patients with histologically confirmed squamous cell carcinoma of the skin that had limbs amputated by tumor invasion at our institution between 2005 and 2008. We evaluated the histological factors and the institutional and psychosocial factors that contributed to this unfavorable outcome. RESULTS: The mean age at diagnosis was 63 years, 37.5% of patients (three patients) had a history of abusive and continuous exposure to sunlight and six (75%) patients had other risk factors for SCC of the skin. Seven patients were diagnosed when the tumor was already larger than 2cm, and it required a large period of time (6.7 years on average) between the onset of the initial lesion and the correct histopathological diagnosis of locally advanced tumor. CONCLUSION: The unfavorable outcome (amputation) in patients with squamous cell carcinoma may be associated with aggressiveness of cancer and related comorbidities, and may also be influenced by factors such as access to public health, quality of care and patient's relationship with the disease.

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing.

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.

Novel cell design for combined in situ acoustic emission and x-ray diffraction study during electrochemical cycling of batteries.

An in situ acoustic emission (AE) and x-ray diffraction cell for use in the study of battery electrode materials has been designed and tested. This cell uses commercially available coin cell hardware retrofitted with a metalized polyethylene terephthalate (PET) disk, which acts as both an x-ray window and a current collector. In this manner, the use of beryllium and its associated cost and hazards is avoided. An AE sensor may be affixed to the cell face opposite the PET window in order to monitor degradation effects, such as particle fracture, during cell cycling. Silicon particles, which were previously studied by the AE technique, were tested in this cell as a model material. The performance of these cells compared well with unmodified coin cells, while providing information about structural changes in the active material as the cell is repeatedly charged and discharged.

Wetting behaviour of laser synthetic surface microtextures on Ti-6Al-4V for bioapplication.

Wettability at the surface of an implant material plays a key role in its success as it modulates the protein adsorption and thereby influences cell attachment and tissue integration at the interface. Hence, surface engineering of implantable materials to enhance wettability to physiological fluid under in vivo conditions is an area of active research. In light of this, in the present work, laser-based optical interference and direct melting techniques were used to develop synthetic microtextures on Ti-6Al-4V alloys, and their effects on wettability were studied systematically. Improved wettability to simulated body fluid and distilled water was observed for Ca-P coatings obtained by direct melting technique. This superior wettability was attributed to both the appropriate surface chemistry and the three-dimensional surface features obtained using this technique. To assert a better control on surface texture and wettability, a three-dimensional thermal model based on COMSOL's multiphysics was employed to predict the features obtained by laser melting technique. The effect of physical texture and wetting on biocompatibility of laser-processed Ca-P coatings was evaluated in the preliminary efforts on culturing of mouse MC3T3-E1 osteoblast cells.