•Cycle aging of commercial 40Ah pouch cells was studied at different temperatures.•Cycle testing, impedance spectroscopy, and post-mortem analyses were carried out.•Post-mortem study enabled ...attributing the observed aging to different mechanisms.•Capacity fade was related to SEI-layer and at high temperature also to Li plating.•Significant increase in the electrolyte and separator resistances was observed.
Cycle aging of commercial 40Ah pouch-type lithium-ion cells with NMC/graphite chemistry was studied at different cycling temperatures (room temperature, +45°C, and +45°C charge/+65°C discharge). Aging was observed as capacity fade and resistance increase, and the aging mechanisms were characterized by electrochemical impedance spectroscopy and post-mortem analysis, where visual inspection and thickness measurements were employed together with X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses. It was observed that elevated temperatures resulted in accelerated capacity fade, especially for the +45°C/+65°C condition. SEI-layer growth and lithium plating, discovered in cell disassembly, were attributed to be the main mechanisms responsible for capacity loss. In addition to the capacity fade, resistance increase was observed both in ohmic and polarization resistances. The ohmic resistance growth was attributed to lack of electrolyte and increased separator resistance. Polarization resistance evolution during cycling was similar at room temperature and at +45°C, but different at the +45°C/+65°C condition. It was concluded that post-mortem analysis is essential for attributing the cycle testing and impedance spectroscopy results to different components and processes inside the cell. For example, the lithium plating phenomenon could not have been predicted or discovered without disassembling the cells.
The objective of this review is to study the effect of minor alloying and impurity elements, typically present in electronics manufacturing environment, on the interfacial reactions between Sn and ...Cu, which is the base system for Pb-free soldering. Especially, the reasons leading to the observed interfacial reaction layers and their microstructural evolution are analysed. The following conclusions have been reached. Alloying and impurity elements can have three major effects on the reactions between the Sn-based solder and the conductor metal: Firstly, they can increase or decrease the reaction/growth rate. Secondly, additives can change the physical properties of the phases formed (in the case of Cu and Sn, ɛ and η). Thirdly they can form additional reaction layers at the interface or they can displace the binary phases that would normally appear and form other reaction products instead. Further, the alloying and impurity elements can be divided roughly into two major categories: (i) elements (Ni, Au, Sb, In, Co, Pt, Pd, and Zn) that show marked solubility in the intermetallic compound (IMC) layer (generally take part in the interfacial reaction in question) and (ii) elements (Bi, Ag, Fe, Al, P, rare-earth elements, Ti and S) that are not extensively soluble in IMC layer (only change the activities of species taking part in the interfacial reaction and do not usually participate themselves). The elements belonging to category (i) usually have the most pronounced effect on IMC formation. It is also shown that by adding appropriate amounts of certain alloying elements to Sn-based solder, it is possible to tailor the properties of the interfacial compounds to exhibit, for example, better drop test reliability. Further, it is demonstrated that if excess amount of the same alloying elements are used, drastic decrease in reliability can occur. The analysis for this behaviour is based on the so-called thermodynamic–kinetic method.
The objective of this review is to study interfacial reactions between pure Sn or Sn-rich solders, and common base metals used in Pb-free electronics production. In particular, the reasons leading to ...the observed interfacial reactions products and their metallurgical evolution have been analyzed. Results presented in the literature have been critically evaluated with the help of combined thermodynamic–kinetic approach based on the concept of local equilibrium and microstructural knowledge. The following conclusions have been reached: Firstly, the formations of intermetallic compounds in solid/liquid reaction couples are primarily controlled by the dissolution processes of base metals. Other factors that need be considered are the thermodynamic driving force for the formation of intermetallic compounds, their structures and concentration profiles in liquid. Secondly, annealing of solder interconnections in solid state can drastically change the microstructures formed in the solid/liquid reactions, especially if only one of the components in the solder takes part in the interfacial reactions. Thirdly, additional elements can have three major effects on the binary reactions between a base metal and Sn: (i) they can increase or decrease the reaction/growth rates, (ii) the additives can change the physical properties of the phases formed, and (iii) they can form additional reaction products or displace the binary equilibrium phases by forming new reaction products. Finally, if the local stable or metastable equilibrium is established at the interface, stability information together with kinetic considerations can provide a feasible approach to analyze interfacial reactions, which can have significant impact on the reliability of soldered electronics assemblies.
Four years of continuous aerosol number size distribution measurements from the Arctic Climate Observatory in Tiksi, Russia, are analyzed. Tiksi is located in a region where in situ information on ...aerosol particle properties has not been previously available. Particle size distributions were measured with a differential mobility particle sizer (in the diameter range of 7–500 nm) and with an aerodynamic particle sizer (in the diameter range of 0.5–10 μm). Source region effects on particle modal features and number, and mass concentrations are presented for different seasons. The monthly median total aerosol number concentration in Tiksi ranges from 184 cm−3 in November to 724 cm−3 in July, with a local maximum in March of 481 cm−3. The total mass concentration has a distinct maximum in February–March of 1.72–2.38 μg m−3 and two minimums in June (0.42 μg m−3) and in September–October (0.36–0.57 μg m−3). These seasonal cycles in number and mass concentrations are related to isolated processes and phenomena such as Arctic haze in early spring, which increases accumulation and coarse-mode numbers, and secondary particle formation in spring and summer, which affects the nucleation and Aitken mode particle concentrations. Secondary particle formation was frequently observed in Tiksi and was shown to be slightly more common in marine, in comparison to continental, air flows. Particle formation rates were the highest in spring, while the particle growth rates peaked in summer. These results suggest two different origins for secondary particles, anthropogenic pollution being the important source in spring and biogenic emissions being significant in summer. The impact of temperature-dependent natural emissions on aerosol and cloud condensation nuclei numbers was significant: the increase in both the particle mass and the CCN (cloud condensation nuclei) number with temperature was found to be higher than in any previous study done over the boreal forest region. In addition to the precursor emissions of biogenic volatile organic compounds, the frequent Siberian forest fires, although far away, are suggested to play a role in Arctic aerosol composition during the warmest months. Five fire events were isolated based on clustering analysis, and the particle mass and cloud condensation nuclei number were shown to be somewhat affected by these events. In addition, during calm and cold months, aerosol concentrations were occasionally increased by local aerosol sources in trapping inversions. These results provide valuable information on interannual cycles and sources of Arctic aerosols.
We built an automatic chamber system to measure greenhouse gas (GHG) exchange in forested peatland ecosystems. We aimed to build a system robust enough which would work throughout the year and could ...measure through a changing snowpack in addition to producing annual GHG fluxes by integrating the measurements without the need of using models. The system worked rather well throughout the year, but it was not service free. Gap filling of data was still necessary. We observed problems in carbon dioxide (CO2 ) respiration flux estimation during calm summer nights, when a CO2 concentration gradient from soil/moss system to atmosphere builds up. Chambers greatly overestimated the night-time respiration. This was due to the disturbance caused by the chamber to the soil-moss CO2 gradient and consequent initial pulse of CO2 to the chamber headspace. We tested different flux calculation and measurement methods to solve this problem. The estimated flux was strongly dependent on (1) the starting point of the fit after closing the chamber, (2) the length of the fit, (3) the type of the fit (linear and polynomial), (4) the speed of the fan mixing the air inside the chamber, and (5) atmospheric turbulence (friction velocity, u*). The best fitting method (the most robust, least random variation) for respiration measurements on our sites was linear fitting with the period of 120-240 s after chamber closure. Furthermore, the fan should be adjusted to spin at minimum speed to avoid the pulse-effect, but it should be kept on to ensure mixing. If night-time problems cannot be solved, emissions can be estimated using daytime data from opaque chambers.
Drainage for forestry purposes increases the depth of the oxic peat layer and leads to increased growth of shrubs and trees. Concurrently, the production and uptake of the greenhouse gases carbon ...dioxide (CO2), methane (CH4) and nitrous oxide (N2O) change: due to the accelerated decomposition of peat in the presence of oxygen, drained peatlands are generally considered to lose peat carbon (C). We measured CO2 exchange with the eddy covariance (EC) method above a drained nutrient-poor peatland forest in southern Finland for 16 months in 2004–2005. The site, classified as a dwarf-shrub pine bog, had been ditched about 35 years earlier. CH4 and N2O fluxes were measured at 2–5-week intervals with the chamber technique. Drainage had resulted in a relatively little change in the water table level, being on average 40 cm below the ground in 2005. The annual net ecosystem exchange was −870 ± 100 g CO2 m−2 yr−1 in the calendar year 2005, indicating net CO2 uptake from the atmosphere. The site was a small sink of CH4 (−0.12 g CH4 m−2 yr−1) and a small source of N2O (0.10 g N2O m−2 yr−1). Photosynthesis was detected throughout the year when the air temperature exceeded −3 °C. As the annual accumulation of C in the above and below ground tree biomass (175 ± 35 g C m−2) was significantly lower than the accumulation observed by the flux measurement (240 ± 30 g C m−2), about 65 g C m−2 yr−1 was likely to have accumulated as organic matter into the peat soil. This is a higher average accumulation rate than previously reported for natural northern peatlands, and the first time C accumulation has been shown by EC measurements to occur in a forestry-drained peatland. Our results suggest that forestry-drainage may significantly increase the CO2 uptake rate of nutrient-poor peatland ecosystems.
Supercontinuum radiation sources are attractive for spectroscopic applications owing to their broad wavelength coverage, which enables spectral signatures of multiple species to be detected ...simultaneously. Here we report the first use of a supercontinuum radiation source for broadband trace gas detection using a cavity enhanced absorption technique. Spectra were recorded at bandwidths of up to 100 nm, encompassing multiple absorption bands of H(2)O, O(2) and O(2)-O(2). The same instrument was also used to make quantitative measurements of NO(2) and NO(3). For NO(3) a detection limit of 3 parts-per-trillion in 2 s was achieved, which corresponds to an effective 3sigma sensitivity of 2.4 x 10(-9) cm(-1)Hz(-1/2). Our results demonstrate that a conceptually simple and robust instrument is capable of highly sensitive broadband absorption measurements.
We analysed the effect of the 2018 European drought on greenhouse gas (GHG) exchange of five North European mire ecosystems. The low precipitation and high summer temperatures in Fennoscandia led to ...a lowered water table in the majority of these mires. This lowered both carbon dioxide (CO
) uptake and methane (CH
) emission during 2018, turning three out of the five mires from CO
sinks to sources. The calculated radiative forcing showed that the drought-induced changes in GHG fluxes first resulted in a cooling effect lasting 15-50 years, due to the lowered CH
emission, which was followed by warming due to the lower CO
uptake. This article is part of the theme issue 'Impacts of the 2018 severe drought and heatwave in Europe: from site to continental scale'.
The global environment is changing rapidly due to anthropogenic emissions and actions. Such activities modify aerosol and greenhouse gas concentrations in the atmosphere, leading to regional and ...global climate change and affecting, e.g., food and fresh-water security, sustainable use of natural resources and even demography. Here we present a conceptual design of a global, hierarchical observation network that can provide tools and increased understanding to tackle the inter-connected environmental and societal challenges that we will face in the coming decades. The philosophy behind the conceptual design relies on physical conservation laws of mass, energy and momentum, as well as on concentration gradients that act as driving forces for the atmosphere-biosphere exchange. The network is composed of standard, flux and/or advanced and flagship stations, each of which having specific and identified tasks. Each ecosystem type on the globe has its own characteristic features that have to be taken into consideration. The hierarchical network as a whole is able to tackle problems related to large spatial scales, heterogeneity of ecosystems and their complexity. The most comprehensive observations are envisioned to occur in flagship stations, with which the process-level understanding can be expanded to continental and global scales together with advanced data analysis, Earth system modelling and satellite remote sensing. The denser network of the flux and standard stations allows application and up-scaling of the results obtained from flagship stations to the global level.
Abstract
Concentrations of atmospheric carbon dioxide (CO
2
) have continued to increase whereas atmospheric deposition of sulphur and nitrogen has declined in Europe and the USA during recent ...decades. Using time series of flux observations from 23 forests distributed throughout Europe and the USA, and generalised mixed models, we found that forest-level net ecosystem production and gross primary production have increased by 1% annually from 1995 to 2011. Statistical models indicated that increasing atmospheric CO
2
was the most important factor driving the increasing strength of carbon sinks in these forests. We also found that the reduction of sulphur deposition in Europe and the USA lead to higher recovery in ecosystem respiration than in gross primary production, thus limiting the increase of carbon sequestration. By contrast, trends in climate and nitrogen deposition did not significantly contribute to changing carbon fluxes during the studied period. Our findings support the hypothesis of a general CO
2
-fertilization effect on vegetation growth and suggest that, so far unknown, sulphur deposition plays a significant role in the carbon balance of forests in industrialized regions. Our results show the need to include the effects of changing atmospheric composition, beyond CO
2
, to assess future dynamics of carbon-climate feedbacks not currently considered in earth system/climate modelling.
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