基于电化学-热-力耦合模型的锂离子电池热失控研究

为提升锂离子电池的安全性能,减少由热失控导致的安全事故,分析电池温升的原因并有效降低其温度,依据电化学反应中浓度、电势与热模型中温度的相互影响关系,建立电化学-热-力耦合模型。通过模拟单电池和电池组温度分布的实时情况,分析单电池温度不均匀分布和电池组温度正态分布情况的原因,探讨换热面积和流通量对散热量的影响,研究电池组中单体电池的位置分布及不同传热介质的散热情况。研究结果显示:低温和相对高温环境下,欧姆热、极化热及电化学反应热产热占比不同,但产热最高温度未达到电极材料与电解液分解反应的临界温度420 K;高温环境下,电池温度持续升高接近临界温度,出现热失控趋势,对流换热系数对电池影响较大。电池组间隙为10 mm和20 mm时,整体温度比间隙为0时分别降低了1.1%和1.8%;与无间隙电池组相比,以铜板和铝板为传热介质的电池组温度分别降低了2.0%和1.6%。

锂离子电池电化学-热-力耦合数值模拟及分析

建立了锂离子电池电化学-热-力耦合模型,并使用COMSOL Multiphysics软件进行了数值求解。研究了电化学-热-力耦合模型与电化学-力耦合模型的差异,对比了温度场以及电极粒子内部浓度场的变化,同时分析了隔膜孔隙度变化时外载对电池电压及容量的影响。研究发现:引入温度场后电池容量和电压平台会有所升高,模型温度会变低,粒子内部浓度相比电化学-力耦合更加均匀;当加入外载后,会导致电池电压和容量的降低,且同等外载对低放电速率下电池性能的影响更明显。此外还发现了电池在外载作用下会引起隔膜孔隙度变化进而影响电池放电性能。

Effects of precipitation strengthening heat treatment for Al-Mg alloy

The corrosions resulting from defects in painting layers frequently occur in Al alloys, so the application of corrosion preventing systems is also very important. Optimum conditions in terms of electrochemistry in relation to solution treatment, quenching and artificial aging treatment were established in order to optimize precipitation strengthening conditions intended to enhance the strength of Al alloys. Slow strain rate tests （SSRT） at various applied potentials were conducted in potential range from -1.8 to 0.5 V. The results show that the maximum tensile strengths, elongations and time-to-fracture are shown to be high values. After precipitation strengthening heat treatment, a tendency appear that time-to-fracture increases as elongation increases. In the potential range from -1.3 V to -0.7 V, the specimens show excellent mechanical properties, and thus this range is considered to be a corrosion prevention range.

Thermodynamic Analysis of Methane-fueled Solid Oxide Fuel Cells Considering CO Electrochemical Oxidation

Thermodynamic analyses in the literature have shown that solid oxide fuel cells(SOFCs) with proton conducting electrolyte(H-SOFC) exhibited higher performance than SOFC with oxygen ion conducting electrolyte(O-SOFC).However, these studies only consider H2 electrochemical oxidation and totally neglect the contribution of CO electrochemical oxidation in O-SOFC. In this short communication, a thermodynamic model is developed to compare the theoretically maximum efficiencies of H-SOFC and O-SOFC, considering the electrochemical oxidation of CO in O-SOFC anode. It is found that O-SOFC exhibits a higher maximum efficiency than H-SOFC due to the contribution from CO electrochemical oxidation, which is contrary to the common understanding of electrolyte effect on SOFC performance. The effects of operating temperature and fuel utilization factor on the theoretical efficiency of SOFC are also analyzed and discussed.

Thermo-Magneto-Electric Currents with Dynamical Magnetization Inhomogeneities

We study the effect of potential and thermal gradient induced non-equilibrium magnetization in quasi1-d itinerant magnets.A semi-phenomenological theory is employed in conjunction with the drift-diffusion model forthis study.Using the methods of non-equilibrium thermodynamics,we derive the transport currents correspondingto charge,heat,and magnetization flows in the presence of non-equilibrium magnetization textures.It is shown howtime-dependent magnetic textures give rise to charge and thermal currents even in the absence of external potential andthermal gradients through spin pumping.The presence of dynamical textures also affect the thermodynamic parametersof the system.As an application,we consider the case of a helimagnet.

锂离子电池不可逆膨胀模型及应用

针对锂离子电池多次充放电循环后容量衰减量的快速估算问题,文中基于锂离子电池(Lithium-Ion Battery,LIB)容量衰减模型提出了一种利用电池外部膨胀位移快速估算其内部容量衰减的方法。在锂离子电池容量衰减模型的基础上推导其径向不可逆膨胀模型,通过COMSOL Multiphysics对圆柱形锂离子电池Sanyo UR18650E进行建模和求解,并对比数值结果与实验数据,从而对所提模型进行验证。基于上述模型,分析了电池在充放电循环过程中由于副反应参与而造成的容量衰减和不可逆膨胀行为的原因。结果表明,副反应速率变化造成了副反应产物浓度在负极的梯度分布,副反应产物堆积使电池膨胀位移随循环线性增长。文中还利用副反应产物作为桥梁得到电池容量衰减与其径向位移的函数计算式,为容量衰减量的快速估算提供了新方法。

锂离子电池多物理场耦合模型中的粒径分析

为深入理解锂离子电池(Lithium-Ion Battery,LIB)内部的多物理场耦合行为,更好地为锂离子电池的生产制造及优化等工作提供参考,文中通过数值模拟方式,在有限元仿真软件COMSOL Multiphysics中建立了更符合物理实际的锂离子电池电化学-热-力(Electrochemical-Thermal-Mechanical,ETM)耦合模型,并进行求解。该模型考虑了电池工作时电极与颗粒两个尺度中的应力生成,解决了以往模型中电极层面应力难以计算的问题。同时通过考虑应力对锂离子扩散及过电位的修正,更好地关联了应力与电化学间的关系。基于该模型,文中讨论了不同正极粒径对电池性能的影响。数值结果表明,当正极粒径小时,锂离子电池放电过程中各物理场的性能指标较好,电池能量密度增大,证明采用较小的正极粒径可提升锂离子电池性能。

锂离子电池极耳分布对电极应力的影响

为了研究极耳分布对电极应力的影响,建立了软包锂离子电池三维电化学-热-力多物理场耦合模型。使用COMSOL Multiphysics进行多物理场数值模拟,分析了极耳排布方式对电极电化学场、温度场和应力场的影响。结果发现极耳结构处于居中且对侧排布时电极内部电化学反应将更均匀,极耳结构的存在会使电极最大von Mises应力值增加。利用该模型对锂离子电池极耳的尺寸和材料属性(杨氏模量和泊松比)进行了参数分析。该研究有助于深入认识电池极耳结构对电极应力的影响,同时为极耳结构的优化和选材提供一定的参考。

Electrochemical hydrogen compression and purification versus competing technologies: Part Ⅰ. Pros and cons

It is undisputed that hydrogen will play a great role in our future energetic mix, because it enables the storage of renewable electricity(power-to-H2) and the reversible conversion into electricity in fuel cell, not to speak of its wide use in the(petro)chemical industry. Whereas in these applications, pure hydrogen is required, today’s hydrogen production is still largely based on fossil fuels and can therefore not be considered pure. Therefore, purification of hydrogen is mandatory, at a large scale. In addition, hydrogen being the lightest gas, its volumetric energy content is well-below its competing fuels, unless it is compressed at high pressures(typically 70 MPa), making compression unavoidable as well. This contribution will detail the means available today for both purification and for compression of hydrogen. It will show that among the available technologies, the electrochemical hydrogen compressor(EHC), which also enables hydrogen purification, has numerous advantages compared to the classical technologies currently used at the industrial scale. EHC has their thermodynamic and operational advantages, but also their ease of use. However, the deployment of EHCs will be viable only if they reach sufficient performances, which implies some specifications that their base materials should stick to. The present contribution will detail these specifications.

A new measurement method of crack propagation rate for brittle rock under THMC coupling condition

A new electrical method of conductive carbon-film(with waterproof and anticorrosion ability)was proposed to continuously measure crack propagation rate of brittle rock under THMC coupling condition.A self-designed coupling testing system was used to conduct THMC coupling fracture tests of the pre-cracked red sandstone specimens(where the temperature is only changed)by this new electrical method of conductive carbon-film.Calculation results obtained by the energy method coincide well with the test results.And the higher the temperature is,the earlier the crack is initiated and the larger the crack propagation rate and accelerated velocity are,which can prove the validity of the new electrical method.This new electrical method has advantages of continuously measuring crack propagation rate over the conventional electrical,optical and acoustic methods,and can provide important basis for safety assessment and cracking-arrest design of deep rock mass engineering.

Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction

Broadly,the oxygen evolution reaction(OER)has been deeply understood as a significant part of energy conversion and storage.Nevertheless,the anions in the OER catalysts have been neglected for various reasons such as inactive sites,dissolution,and oxidation,amongst others.Herein,we applied a model catalyst s-Ni(OH)2 to track the anionic behavior in the catalyst during the electrochemical process to fill this gap.The advanced operando synchrotron radiation Fourier transform infrared(SR-FTIR)spectroscopy,synchrotron radiation photoelectron spectroscopy(SRPES)depth detection and differential X-ray absorption fine structure(D-XAFS)spectrum jointly point out that some oxidized sulfur species(SO_(4)^(2-))will selfoptimize new Ni–S bonds during OER process.Such amazing anionic self-optimization(ASO)behavior has never been observed in the OER process.Subsequently,the optimization-derived component shows a significantly improved electrocatalytic performance(activity,stability,etc.)compared to reference catalyst Ni(OH)_(2).Theoretical calculation further suggests that the ASO process indeed derives a thermodynamically stable structure of the OER catalyst,and then gives its superb catalytic performance by optimizing the thermodynamic and kinetic processes in the OER,respectively.This work demonstrates the vital role of anions in the electrochemical process,which will open up new perspectives for understanding OER and provide some new ideas in related fields(especially catalysis and chemistry).

Electromotive Force for Solid Oxide Fuel Cells Using Biomass Produced Gas as Fuel

The electromotive force （e.m.f.） of solid oxide fuel cells using biomass produced gas （BPG） as the fuels is calculated at 700-1,200 K using an in-house computer program, based on thermodynamic equilibrium analysis. Tour program also predicts the concentration of oxygen in the fuel chamber as well as the concentration of equilibrium species such as H2, CO, CO2 and CH4. Compared with using hydrogen as a fuel, the e.m.f. for cells using BPG as the fuels is relative low and strongly influenced by carbon deposition. To remove carbon deposition, the optimum amount of H2O to add is determined at various operating temperatures. Further the e.m.f, for cells based on yttria stabilized zirconia and doped ceria as electrolytes are compared. The study reveals that when using BPG as fuel, the depression of e.m.f, for a SOFC using doped ceria as electrolyte is relatively small when compared with that using Yttria stabilized zirconia.

Targeted design of advanced electrocatalysts by machine learning

Exploring the production and application of clean energy has always been the core of sustainable development.As a clean and sustainable technology,electrocatalysis has been receiving widespread attention.It is crucial to achieve efficient,stable and cheap electrocatalysts.However,the traditional“trial and error”method is time-consuming,laborious and costly.In recent years,with the significant increase in computing power,computations have played an important role in electrocatalyst design.Nevertheless,it is still difficult to search for advanced electrocatalysts in the vast chemical space through traditional density functional theory(DFT)computations.Fortunately,the development of machine learning and interdisciplinary integration will inject new impetus into targeted design of electrocatalysts.Machine learning is able to predict electrochemical performances with an accuracy close to DFT.Here we provide an overview of the application of machine learning in electrocatalyst design,including the prediction of structure,thermodynamic properties and kinetic barriers.We also discuss the potential of explicit solvent model combined with machine learning molecular dynamics in this field.Finally,the favorable circumstances and challenges are outlined for the future development of machine learning in electrocatalysis.The studies on electrochemical processes by machine learning will further realize targeted design of high-efficiency electrocatalysts.

In-situ interaction of nano-PbS with gelatin

Water-soluble gelatin-PbS bionanocomposites （BNCs） were synthesized via a facile one-pot chemical reaction method at pH 7.40. The samples were characterized by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, UV-vis absorption spectra （UV-vis）, Fourier transform infrared spectra （FT-IR） and circular dichroism （CD）. FT-IR data were used to envis- age the binding of PbS particles with oxygen atoms of carbonyl groups of gelatin molecule. The possible integration mechanism between gelatin and PbS was discussed in detail. The effect of Pb2＋ and PbS on the conformations of gelatin has also been analyzed by means of UV-vis, CD and FT-IR spectra, resulting in less c^-helix content and more open structures （[3-sheet, r-turn, or expanded）. A new formula to calculate the association constant was proposed according to the relationship between the absorbance of gelatin-PbS BNCs and the free concentration of PbS, and apparent association constants K （298/303/308 K： 3.11/2.00/1.60 × 10^6 tool/L） at three different temperatures were calculated based on this formula. Thermodynamic parameters such as AG^θ, △Hθ and △S^θ were also determined. The results of the thermodynamic investigations indicated that the reaction was spontaneous （AG^θ 〈 0）, and enthalpy-driven （△H^8 〈 0）.

Cationic-potential tuned biphasic layered cathodes for stable desodiation/sodiation

Sodium layered oxides generally suffer from deep-desodiation instability in P2 structure and sluggish kinetics in O3 structure.It will be great to design P2/O3 biphasic materials that bring the complementary merits of both structures.However,such exploration is hindered by the ambiguous mechanism of material formation.Herein,supported by theoretical simulations and various spectroscopies,we prove that P2/O3 biphasic structures essentially originate from the internal heterogeneity of cationic potential,which can be realized by constraining the temperature-driven ion diffusion during solid-state reactions.Consequently,P2/O3 biphasic Na_(0.7)Ni_(0.2)Cu_(0.1)Fe_(0.2)Mn_(0.5)O_(2)-δ with well-designed quaternary composition is successfully obtained,exhibiting much-improved rate capabilities(62 mAh g^(-1)at 2.4 A g^(-1)) and cycling stabilities(84%capacity retention after 500 cycles)than its single-phase analogues.Furthermore,synchrotron-based diffraction and X-ray absorption spectroscopy are employed to unravel the underlying sodium-storage mechanism of the P2/O3 biphasic structure.This work presents new insights toward the rational design of advanced layered cathodes for sodium-ion batteries.

The Chemical Principle of Green Coal Power

Coal is still a major source of energy, also a major source of SO_2, NOx and CO_2 emission though. Removal of SO_2 and NOx doubled the cost of power generation, and capture of CO_2 is equivalent to double the market price of power coal. The GCP （green coal power） is the power generated in coal-combustion with zero emission. The author indicates that it is possible to make coal-fired power plants emission free based on thermodynamic analysis and purposely designed experiments using SFG （simulated flue gases）. It is concluded in the study that all SO_2 and NOx in the post-combustion flue gas are reduced to inoffensive substances at temperature lower than 750 ℃ when contacting carbon and elemental sulfur is separated in succeeded cooling of flue gas at temperatures 200-400 ℃, and the ultrafine dusts are trapped in condensed water at temperature blow 100 ℃. Based on chemical engineering expertise the author is sure that the cost for removing acid gases is much lower than any clean coal technologies known to today. Instead of capture, the remained CO_2 is converted to CO in the second time contact with carbon at 900-950 ℃. CO is the raw material of chemical synthesis and, thus, CO_2 is stored in chemical products such as methanol, fertilizer, plastics, etc. The simple and low-cost processing allows GCP utilized in practice easily.

Fuel Cells as Energy Systems： Efficiency, Power Limits and Thermodynamic Behavior

Steady-state model of a high-temperature solid oxide fuel cell （SOFC） is considered, which refers to constant chemical potentials of incoming hydrogen fuel and oxidant. Lowering of the cell voltage below its reversible value is attributed to polarizations and imperfect conversions of reactions. An imperfect power formula summarizes the effect of transport laws, irreversible polarizations and efficiency of power yield. Reversible electrochemical theory is extended to the case with dissipative chemical reactions; this case includes systems with incomplete conversions, characterized by ＂reduced affinities＂ and an idle run voltage. Efficiency drop is linked with thermodynamic and electrochemical irreversibilities expressed in terms of polarizations （activation, concentration and ohmic）. Effect of incomplete conversions is modeled by assuming that substrates can be remained after the reaction and that side reactions may occur. Optimum and feasibility conditions are discussed for basic input parameters of the cell. Calculations of maximum power show that the data differ for power generated and consumed and depend on current intensity, number of mass transfer units, polarizations, electrode surface area, average chemical rate, etc.. These data provide bounds for SOFC energy generators, which are more exact and informative than reversible bounds for electrochemical transformation.

A Comparative Study on the Separating Methods of Al,Ca and Mg Based on Theoretical Energy Consumption

Based on thermodynamics and physical chemistry theory,the theoretical energy consumption (TEC) of the typical separating processes of Al,Ca and Mg has been calculated and analyzed.This paper attempts to prove that the thermal method is more reasonable than the electrolytic methods to separate Al,Ca and Mg under the domestic circumstances of the low efficiency of coal-firing power plant at present.