High Frequency Thermal Energy Harvesting Using Magnetic Shape Memory Films

A new method for thermal energy harvesting at small temperature difference and high cycling frequency is presented that exploits the unique magnetic properties and actuation capability of magnetic shape memory alloy (MSMA) films. Polycrystalline films of the Ni_50.4Co_3.7Mn_32.8In_13.1 alloy are tailored, showing a large abrupt change of magnetization and low thermal hysteresis well above room temperature. Based on this material, a free‐standing film device is designed that exhibits thermomagnetically induced actuation between a heat source and sink with short heat transfer times. The cycling frequency of the device is tuned by mechanical frequency up‐conversion to over 200 Hz. An integrated pick‐up coil converts the thermally induced change of magnetization as well as the kinetic energy to electricity. For a temperature change of 10 K, the maximum peak power density is in the order of 5 mW cm^‐3.     

Toward a Carbon Dioxide Neutral Industrial Park

The industrial park of Herdersbrug (Brugge, Flanders, Belgium) comprises 92 small and medium‐sized enterprises, a waste‐to‐energy incinerator, and a power plant (not included in the study) on its site. To study the carbon dioxide (CO₂) neutrality of the park, we made a park‐wide inventory for 2007 of the CO₂ emissions due to energy consumption (electricity and fossil fuel) and waste incineration, as well as an inventory of the existing renewable electricity and heat generation. The definition of CO₂ neutrality in Flanders only considers CO₂ released as a consequence of consumption or generation of electricity, not the CO₂ emitted when fossil fuel is consumed for heat generation. To further decrease or avoid CO₂ emissions, we project and evaluate measures to increase renewable energy generation. The 21 kilotons (kt) of CO₂ emitted due to electricity consumption are more than compensated by the 25 kt of CO₂ avoided by generation of renewable electricity. Herdersbrug Industrial Park is thus CO₂ neutral, according to the definition of the Flemish government. Only a small fraction (6.6%) of the CO₂ emitted as a consequence of fossil fuel consumption (heat generation) and waste incineration is compensated by existing and projected measures for renewable heat generation. Of the total CO₂ emission (149 kt) due to energy consumption (electricity + heat generation) and waste incineration on the Herdersbrug Industrial Park in 2007, 70.5% is compensated by existing and projected renewable energy generated in the park. Forty‐seven percent of the yearly avoided CO₂ corresponds to renewable energy generated from waste incineration and biomass fermentation.     

Dynamics of the First‐Order Metamagnetic Transition in Magnetocaloric La(Fe,Si)13: Reducing Hysteresis

The influence of dynamics and sample shape on the magnetic hysteresis in first‐order magnetocaloric metamagnetic LaFe_13–xSi_x with x = 1.4 is studied. In solid‐state magnetic cooling, reducing magnetic and thermal hysteresis is critical for refrigeration cycle efficiency. From magnetization measurements, it is found that the fast field‐rate dependence of the hysteresis can be attributed to extrinsic heating directly related to the thickness of the sample and the thermal contact with the bath. If the field is paused partway through the transition, the subsequent relaxation is strongly dependent on shape due to both demagnetizing fields and thermal equilibration; magnetic coupling between adjacent sample fragments can also be significant. Judicious shaping of the sample can both increase the onset field of the ferromagnetic–paramagnetic (FM–PM) transition but have little effect on the PM–FM onset, suggesting a route to engineer the hysteresis width by appropriate design. In the field‐paused state, the relaxation from one phase to the other slows with increasing temperature, implying that the process is neither thermally activated or athermal; comparison with the temperature dependence of the latent heat strongly suggests that the dynamics reflect the intrinsic free energy difference between the two phases.     

High Performance Thermoelectricity in Earth‐Abundant Compounds Based on Natural Mineral Tetrahedrites

Thermoelectric materials can convert waste heat into electricity, potentially improving the efficiency of energy usage in both industry and everyday life. Unfortunately, known good thermoelectric materials often are comprised of elements that are in low abundance and require careful doping and complex synthesis procedures. Here, we report dimensionless thermoelectric figure of merit near unity in compounds of the form Cu_12‐xM_xSb₄S₁₃, where M is a transition metal such as Zn or Fe, for wide ranges of x. The compounds investigated here span the range of compositions of the natural mineral family of tetrahedrites, the most widespread sulfosalts on Earth, and we further show that the natural mineral itself can be used directly as an inexpensive source thermoelectric material. Thermoelectrics comprised of earth‐abundant elements will pave the way to many new, low cost thermoelectric energy generation opportunities.     

Realizing High‐Ranged Out‐of‐Plane ZTs in N‐Type SnSe Crystals through Promoting Continuous Phase Transition

Thermoelectric technology enables direct conversion between heat and electricity. The conversion efficiency of a thermoelectric device is determined by the average dimensionless figure of merit ZT_ave. Here, a record high ZT_ave of ≈1.34 in the range of 300–723 K in n‐type SnSe based crystals is reported. The remarkable thermoelectric performance derives from the high power factor and the reduced thermal conductivity in the whole temperature range. The high power factor is realized by promoting the continuous phase transition in SnSe crystals through alloying PbSe, which results in a higher symmetry of the crystal structure and the correspondingly modified electronic band structure. Moreover, PbSe alloying induces mass and strain fluctuations, which enables the suppression of thermal transport. These findings provide a new strategy to enhance the thermoelectric performance for the continuous phase transition materials.     

能源活动CO2排放不同核算方法比较和减排策略选择

能源活动CO₂排放是温室气体排放的最重要部分,这部分CO₂排放量的核算是温室气体清单编制和减排方案制定的关键和基础。采用直接法、电热终端法和隐含终端法核算了2009年中国能源消费的CO₂排放量,对不同核算法的CO₂排放部门分布、部门排放强度进行了比较,明确不同核算方法的差异和适用范围。采用电热终端法的核算结果定量分析了各产业部门和工业行业的经济增长和排放强度变化对中国能源活动CO₂排放增长的影响。结果表明,中国2009年隐含终端CO₂排放量为65.6亿t,略高于直接和电热终端CO₂排放量62.2亿t。3种核算方法的CO₂排放部门分布和排放强度有明显的差异:电、热力生产与供应业的直接排放占比为45.2%,而电热终端CO₂排放仅占4.5%;制造业的直接法、电热终端法和隐含终端法核算的CO₂排放占比分别为35.3% 、61.1%和65.5%,是终端能源消费CO₂排放最主要的部门;制造业、电热力生产与供应业和交通运输业的电热终端CO₂排放强度分别为2.166、1.72和1.622 t CO₂/万元GDP,是排放强度较高的部门。在产业部门中,制造业的色金属冶炼及压延加工业、非金属矿物制品业等5个行业以9.8%的经济增长贡献,排放了52.4%的CO₂,是产业结构调整、技术和工程减排的重点;服务业以7.2%的CO₂排放,贡献了38.4%的经济增长,应作为中国低碳经济优先发展的产业。     

Interpreting diel hysteresis between soil respiration and temperature

Increasing use of automated soil respiration chambers in recent years has demonstrated complex diel relationships between soil respiration and temperature that are not apparent from less frequent measurements. Soil surface flux is often lagged from soil temperature by several hours, which results in semielliptical hysteresis loops when surface flux is plotted as a function of soil temperature. Both biological and physical explanations have been suggested for hysteresis patterns, and there is currently no consensus on their causes or how such data should be analyzed to interpret the sensitivity of respiration to temperature. We used a one‐dimensional soil CO₂ and heat transport model based on physical first principles to demonstrate a theoretical basis for lags between surface flux and soil temperatures. Using numerical simulations, we demonstrated that diel phase lags between surface flux and soil temperature can result from heat and CO₂ transport processes alone. While factors other than temperature that vary on a diel basis, such as carbon substrate supply and atmospheric CO₂ concentration, can additionally alter lag times and hysteresis patterns to varying degrees, physical transport processes alone are sufficient to create hysteresis. Therefore, the existence of hysteresis does not necessarily indicate soil respiration is influenced by photosynthetic carbon supply. We also demonstrated how lags can cause errors in Q₁₀ values calculated from regressions of surface flux and soil temperature measured at a single depth. Furthermore, synchronizing surface flux and soil temperature to account for transport‐related lags generally does not improve Q₁₀ estimation. In order to calculate the sensitivity of soil respiration to temperature, we suggest using approaches that account for the gradients in temperature and production existing within the soil. We conclude that consideration of heat and CO₂ transport processes is a requirement to correctly interpret diel soil respiration patterns.     

Life Cycle Assessment of Biomass‐based Combined Heat and Power Plants

Norway, like many countries, has realized the need to extensively plan its renewable energy future sooner rather than later. Combined heat and power (CHP) through gasification of forest residues is one technology that is expected to aid Norway in achieving a desired doubling of bioenergy production by 2020. To assess the environmental impacts to determine the most suitable CHP size, we performed a unit process‐based attributional life cycle assessment (LCA), in which we compared three scales of CHP over ten environmental impact categories—micro (0.1 megawatts electricity [MWe]), small (1 MWe), and medium (50 MWe) scale. The functional units used were 1 megajoule (MJ) of electricity and 1 MJ of district heating delivered to the end user (two functional units), and therefore, the environmental impacts from distribution of electricity and hot water to the consumer were also considered. This study focuses on a regional perspective situated in middle‐Norway's Nord‐ and Sør‐Trøndelag counties. Overall, the unit‐based environmental impacts between the scales of CHP were quite mixed and within the same magnitude. The results indicated that energy distribution from CHP plant to end user creates from less than 1% to nearly 90% of the total system impacts, depending on impact category and energy product. Also, an optimal small‐scale CHP plant may be the best environmental option. The CHP systems had a global warming potential ranging from 2.4 to 2.8 grams of carbon dioxide equivalent per megajoule of thermal (g CO₂‐eq/MJ_th) district heating and from 8.8 to 10.5 grams carbon dioxide equivalent per megajoule of electricity (g CO₂‐eq/MJ_el) to the end user.     

Thermal–Electric Nanogenerator Based on the Electrokinetic Effect in Porous Carbon Film

Converting low‐grade thermal energy with small temperature gradient into electricity is challenging due to the low efficiency and high cost. Here, a new type of thermal–electric nanogenerator is reported that utilizes electrokinetic effect for effective harvesting thermal energy. The nanogenerator is based on an evaporation‐driven water flow in porous medium with small temperature gradient. With a piece of porous carbon film and deionized water, a maximum open‐circuit voltage of 0.89 V under a temperature difference of 4.2 °C is obtained, having a corresponding pseudo‐Seebeck coefficient of 210 mV K^?1. The large pseudo‐Seebeck coefficient endows the nanogenerator sufficient power output for powering existing electronics directly. Furthermore, a wearable bracelet nanogenerator utilizing body heat is also demonstrated. The unique properties of such conversion process offer great potential for ultra‐low temperature‐gradient thermal energy recovery, wearable electronics, and self‐powered sensor systems.     

Unassisted Water Splitting Using a GaSbxP(1−x) Photoanode

Here, unbiased water splitting with 2% solar‐to‐hydrogen efficiency under AM 1.5 G illumination using new materials based on GaSb_0.03P_0.97 alloy is reported. Freestanding GaSb_xP_1?x is grown using halide vapor phase epitaxy. The native conductivity type of the alloy is modified by silicon doping, resulting in an open‐circuit potential (OCP) of 750 mV, photocurrents of 7 mA cm^?2 at 10 sun illumination, and corrosion resistance in an aqueous acidic environment. Alloying GaP with Sb at 3 at% improves the absorption of high‐energy photons above 2.68 eV compared to pure GaP material. Electrochemical Impedance Spectroscopy and illuminated OCP measurements show that the conduction band of GaSb_xP_1?x is at ?0.55 V versus RHE irrespective of the Sb concentration, while photocurrent spectroscopy indicates that only radiation with photon energies greater than 2.68 eV generate mobile and extractable charges, thus suggesting that the higher‐laying conduction bands in the Γ 1 valley of the alloys are responsible for exciton generation.     

High‐Performance Thermomagnetic Generators Based on Heusler Alloy Films

Recent developments on Heusler alloys including Ni–Mn–X and Ni–Co–Mn–X (X = Ga, In, Sn,…) demonstrate multiferroic phase transformations with large abrupt changes in lattice parameters of several percent and corresponding abrupt changes in ferromagnetic ordering near the transition temperatures. These materials enable a new generation of thermomagnetic generators that convert heat to electricity within a small temperature difference below 5 K. While thermodynamic calculations on this energy conversion method predict a power density normalized to material volume of up to 300 mW cm^?3, experimental results have been in the range of µW cm^?3. Challenges are related to the development of materials with bulk‐like single‐crystal properties as well as geometries with large surface‐to‐volume ratio for rapid heat exchange. This study demonstrates efficient thermomagnetic generation via resonant actuation of freely movable thin‐film devices of the Heusler alloy Ni–Mn–Ga with unprecedented power density of 118 mW cm^?3 that compares favorably with the best thermoelectric generators. Due to the large temperature‐dependent change of magnetization of the films, a periodic temperature change of only 3 K is required for operation. The duration of thermomagnetic duty cycle is only about 12 ms, which matches with the period of oscillatory motion.     

Effect of Change of Forest Carbon Storage on Net Carbon Dioxide Balance of Wood Use for Energy in Japan

This study analyzed the net carbon dioxide (CO₂) emission reductions between 2005 and 2050 by using wood for energy under various scenarios of forest management and energy conversion technology in Japan, considering both CO₂ emission reductions from replacement of fossil fuels and changes in carbon storage in forests. According to our model, wood production for energy results in a significant reduction of carbon storage levels in forests (by 46% to 77% in 2050 from the 2005 level). Thus, the net CO₂ emission reduction when wood is used for energy becomes drastically smaller. Conventional tree production for energy increases net CO₂ emissions relative to preserving forests, but fast‐growing tree production may reduce net CO₂ emissions more than preserving forests does. When wood from fast‐growing trees is used to generate electricity with gas turbines, displacing natural gas, the net CO₂ emission reduction from the combination of fast‐growing trees and electricity generation with gas turbines is about 58% of the CO₂ emission reduction from electricity generation from gas turbines alone in 2050, and an energy conversion efficiency of around 20% or more is required to obtain net reductions over the entire period until 2050. When wood is used to produce bioethanol, displacing gasoline, net reductions are realized after 2030, provided that heat energy is recovered from residues from ethanol production. These results show the importance of considering the change in carbon storage when estimating the net CO₂ emission reduction effect of the wood use for energy.     

Back Contact Engineering for Increased Performance in Kesterite Solar Cells

The thin‐film photovoltaic absorber Cu₂ZnSn(S,Se)₄ (CZTSSe) holds considerable promise for large scale conversion of sunlight into electricity. CZTSSe is composed of Earth‐abundant elements that exhibit low‐toxicities, but improvements in device efficiency have been hampered by difficulties in increasing open circuit voltages (V_OC) due, at least in part, to disorder induced band tailing. We present a method to increase V_OC through direct modification of the back contact; our approach involves the separation of fully functioning devices from their Mo/glass substrate to reveal the back CZTSSe surface. Formation of a new back contact consisting of a thermally deposited high work function material (MoO₃), together with a higly reflective (Au) capping layer, creates an electrostatic field that drives electrons to the front p‐n junction and leads to a decrease in electron‐hole recombination. Model simulations indicating an increase in V_OC with decreasing absorber thickness are borne out by experiments with devices of varying thicknesses (0.7–2.0 μm). We report V_OC increases of up to 49 mV for a 1 μm thick absorber, with even greater increases up to 61 mV when the back CZTSSe surface is etched with bromine‐methanol.     

Alternatives for natural‐gas‐based heating systems: A quantitative GIS‐based analysis of climate impacts and financial feasibility

The heating of buildings currently produces 6% of global greenhouse gas emissions. Sustainable heating technologies can reduce heating‐related CO₂ emissions by up to 90%. We present a Python‐based GIS model to analyze the environmental and financial impact of strategies to reduce heating‐related CO₂ emissions of residential buildings. The city‐wide implementation of three alternatives to natural gas are evaluated: high‐temperature heating networks, low‐temperature heating networks, and heat pumps. We find that both lowering the demand for heat and providing more sustainable sources of heat will be necessary to achieve significant CO₂‐emission reductions. Of the studied alternatives, only low‐temperature heating networks and heat pumps have the potential to reduce CO₂ emissions by 90%. A CO₂ tax and an increase in tax on the use of natural gas are potent policy tools to accelerate the adoption of low‐carbon heating technologies.     

Achieving High Open‐Circuit Voltages up to 1.57 V in Hole‐Transport‐Material‐Free MAPbBr3 Solar Cells with Carbon Electrodes

An open‐circuit voltage (V_oc) of 1.57 V under simulated AM1.5 sunlight in planar MAPbBr₃ solar cells with carbon (graphite) electrodes is obtained. The hole‐transport‐material‐free MAPbBr₃ solar cells with the normal architecture (FTO/TiO₂/MAPbBr₃/carbon) show little hysteresis during current–voltage sweep under simulated AM1.5 sunlight. A solar‐to‐electricity power conversion efficiency of 8.70% is achieved with the champion device. Accordingly, it is proposed that the carbon electrodes are effective to extract photogenerated holes in MAPbBr₃ solar cells, and the industry‐applicable carbon electrodes will not limit the performance of bromide‐based perovskite solar cells. Based on the analysis of the band alignment, it is found that the voltage (energy) loss across the interface between MAPbBr₃ and carbon is very small compared to the offset between the valence band maximum of MAPbBr₃ and the work function of graphite. This finding implies either Fermi level pinning or highly doped region inside MAPbBr₃ layer exists. The band‐edge electroluminescence spectra of MAPbBr₃ from the solar cells further support no back‐transfer pathways of electrons across the MAPbBr₃/TiO₂ interface.     

Fundamental Understanding of Photocurrent Hysteresis in Perovskite Solar Cells

Organic–inorganic hybrid perovskite solar cells (PSCs) have become a promising candidate in the photovoltaic field due to their high power conversion efficiency and low material cost. However, the development of PSCs is limited by their poor stability under practical conditions in the presence of oxygen, moisture, sunlight, heat, and the current–voltage (I–V) hysteresis. In particular, the hysteretic I–V issue casts doubt on the validity of the photovoltaic performance results that are achieved, making it difficult to evaluate the authentic performance of PSCs. This review article focuses on understanding the I–V hysteresis behavior in PSCs and on exploring the possible reasons leading to this hysteresis phenomenon. The various strategies attempted to suppress the I–V hysteresis in PSCs are summarized, and a brief future recommendation is provided.     

Energy Use and Greenhouse Gas Emissions of Air‐Source Heat Pump and Innovative Ground‐Source Air Heat Pump in a Cold Climate

This article compares climate impacts of two heat‐pump systems for domestic heating, that is, energy consumption for space heating of a residential building. Using a life cycle approach, the study compared the energy use and greenhouse gas (GHG) emissions of direct electric heating, a conventional air‐source heat pump, and a novel ground‐source air heat pump innovated by a citizen user, to assess whether such user innovation holds benefit. The energy use of the heat pumps was modeled at six temperature intervals based on duration curves of outdoor temperature. Additionally, two heat pump end‐of‐life scenarios were analyzed. Probabilistic uncertainty analysis was applied using a Monte Carlo simulation. The results indicated that, in ideal conditions, that is, assuming perfect air mixing, the conventional air‐source heat pump's emissions were over 40% lower and the ground‐air heat pump's emissions over 70% lower than in the case of direct electric heating. Although proper handling of the refrigerant is important, total leakage from the retirement of the heat‐pump appliance would increase GHG emissions by just 10%. According to the sensitivity analysis, the most influential input parameters are the emission factor related to electricity and the amount of electricity used for heating.     

Melting, glass transition, and apparent heat capacity of α-d-glucose by thermal analysis

The thermal behaviors of α-d-glucose in the melting and glass transition regions were examined utilizing the calorimetric methods of standard differential scanning calorimetry (DSC), standard temperature-modulated differential scanning calorimetry (TMDSC), quasi-isothermal temperature-modulated differential scanning calorimetry (quasi-TMDSC), and thermogravimetric analysis (TGA). The quantitative thermal analyses of experimental data of crystalline and amorphous α-d-glucose were performed based on heat capacities. The total, apparent and reversing heat capacities, and phase transitions were evaluated on heating and cooling. The melting temperature (T_m) of a crystalline carbohydrate such as α-d-glucose, shows a heating rate dependence, with the melting peak shifted to lower temperature for a lower heating rate, and with superheating of around 25 K. The superheating of crystalline α-d-glucose is observed as shifting the melting peak for higher heating rates, above the equilibrium melting temperature due to of the slow melting process. The equilibrium melting temperature and heat of fusion of crystalline α-d-glucose were estimated. Changes of reversing heat capacity evaluated by TMDSC at glass transition (T_g) of amorphous and melting process at T_m of fully crystalline α-d-glucose are similar. In both, the amorphous and crystalline phases, the same origin of heat capacity changes, in the T_g and T_m area, are attributable to molecular rotational motion. Degradation occurs simultaneously with the melting process of the crystalline phase. The stability of crystalline α-d-glucose was examined by TGA and TMDSC in the melting region, with the degradation shown to be resulting from changes of mass with temperature and time. The experimental heat capacities of fully crystalline and amorphous α-d-glucose were analyzed in reference to the solid, vibrational, and liquid heat capacities, which were approximated based on the ATHAS scheme and Data Bank.     

HSP12, a new small heat shock gene of Saccharomyces cerevisiae: Analysis of structure, regulation and function

Summary We have isolated a new small heat shock gene, HSP12, from Saccharomyces cerevisiae. It encodes a polypeptide of predicted Mr 12 kDa, with structural similarity to other small heat shock proteins. HSP12 gene expression is induced several hundred-fold by heat shock and on entry into stationary phase. HSP12 mRNA is undetectable during exponential growth in rich medium, but low levels are present when cells are grown in minimal medium. Analysis of HSP12 expression in mutants affected in cAMP-dependent protein phosphorylation suggests that the gene is regulated by cAMP as well as heat shock. A disruption of the HSP12 coding region results in the loss of an abundant 14.4 kDa protein present in heat shocked and stationary phase cells. It also leads to the induction of the heat shock response under conditions normally associated with low-level HSP12 expression. The HSP12 disruption has no observable effect on growth at various temperatures, nor on the ability to acquire thermotolerance.     

Two forms of sustained xanthophyll cycle-dependent energy dissipation in overwintering Euonymus kiautschovicus

Seasonal differences in PSII efficiency (F_v/F_m), the conversion state of the xanthophyll cycle (Z + A)/ (V + A + Z), and leaf adenylate status were investigated in Euonymus kiautschovicus. On very cold days in winter, F_v/F_m assessed directly in the field remained low and Z + A high throughout day and night in both sun and shade leaves. Pre-dawn transfer of leaves from subfreezing temperatures in the field to room temperature revealed that recovery (increases in F_v/F_m and conversion of Z + A to violaxanthin) consisted of one, rapid phase in shade leaves, whereas in sun leaves a rapid phase was followed by a slow phase requiring days. The pre-dawn ATP/ADP ratio, as well as that determined at midday, was similar when comparing overwintering leaves with those sampled in the summer, although pre-dawn levels of ATP + ADP were elevated in all leaves during winter relative to summer. After a natural transition to warmer days during the winter, pre-dawn F_v/F_m and Z + A in shade leaves had returned to values typical for summer, whereas in sun leaves F_v/F_m and Z + A levels remained intermediate between the cold day in winter and the summer day. Thus two distinct forms of sustained (Z + A)-dependent energy dissipation were identified based upon their differing characteristics. The form that was sustained on cold days but relaxed rapidly upon warming occurred in all leaves and may result from maintenance of a low lumenal pH responsible for the nocturnal engagement of (Z + A)-dependent thermal dissipation exclusively on very cold days in the winter. The form that was sustained even upon warming and correlated with slow Z + A to violaxanthin conversion occurred only in sun leaves and may represent a sustained engagement of (Z + A)-dependent energy dissipation associated with an altered PSII protein composition. In the latter, warm-sustained form, uncoupler or cycloheximide infiltration had no effect on the slow phase of recovery, but lincomycin infiltration inhibited the slow increase in F_v/F_m and the conversion of Z + A to violaxanthin.