A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating condition...A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating conditions.Electrochemical impedance spectra(EIS) of PCCs were first acquired under a variety of opera ting conditions to provide a dataset containing 36 sets of EIS spectra for the model.An artificial neural network(ANN) was then trained to model the relationship between the cell operating condition and EIS response.Finally,ANN model-predicted EIS spectra were analyzed by the distribution of relaxation times(DRT) and compared to DRT spectra obtained from the experimental EIS data,enabling an assessment of the accumulative errors from the predicted EIS data vs the predicted DRT.We show that in certain cases,although the R^(2)of the predicted EIS curve may be> 0.98,the R^(2)of the predicted DRT may be as low as~0.3.This can lead to an inaccurate ANN prediction of the underlying time-resolved electrochemical response,although the apparent accuracy as evaluated from the EIS prediction may seem acceptable.After adjustment of the parameters of the ANN framework,the average R^(2)of the DRTs derived from the predicted EIS can be improved to 0.9667.Thus,we demonstrate that a properly tuned ANN model can be used as an effective tool to predict not only the EIS,but also the DRT of complex electrochemical systems.展开更多
The classical power law relaxation, i.e. relaxation of current with inverse of power of time for a step-voltage excitation to dielectric—as popularly known as Curie-von Schweidler law is empirically derived and is ob...The classical power law relaxation, i.e. relaxation of current with inverse of power of time for a step-voltage excitation to dielectric—as popularly known as Curie-von Schweidler law is empirically derived and is observed in several relaxation experiments on various dielectrics studies since late 19th Century. This relaxation law is also regarded as “universal-law” for dielectric relaxations;and is also termed as power law. This empirical Curie-von Schewidler relaxation law is then used to derive fractional differential equations describing constituent expression for capacitor. In this paper, we give simple mathematical treatment to derive the distribution of relaxation rates of this Curie-von Schweidler law, and show that the relaxation rate follows Zipf’s power law distribution. We also show the method developed here give Zipfian power law distribution for relaxing time constants. Then we will show however mathematically correct this may be, but physical interpretation from the obtained time constants distribution are contradictory to the Zipfian rate relaxation distribution. In this paper, we develop possible explanation that as to why Zipfian distribution of relaxation rates appears for Curie-von Schweidler Law, and relate this law to time variant rate of relaxation. In this paper, we derive appearance of fractional derivative while using Zipfian power law distribution that gives notion of scale dependent relaxation rate function for Curie-von Schweidler relaxation phenomena. This paper gives analytical approach to get insight of a non-Debye relaxation and gives a new treatment to especially much used empirical Curie-von Schweidler (universal) relaxation law.展开更多
Human mesenchymal stem cells(hMSCs)were labeled with Dotarem or(Gd-DOTA)2-EM7(EM7Gd2)via electroporation(EP).Cellular transmission electron microscopy(TEM)reveals free distribution of Gd agents and formation of EM7Gd...Human mesenchymal stem cells(hMSCs)were labeled with Dotarem or(Gd-DOTA)2-EM7(EM7Gd2)via electroporation(EP).Cellular transmission electron microscopy(TEM)reveals free distribution of Gd agents and formation of EM7Gd2 clusters in the cytosol.Cellular magnetic resonance imaging(MRI)reveals that the free Gd agents induce MRI signal enhancement effect due to its fast exocytosis and subsequent interaction with intercellular water molecules.The EM7Gd2 clusters exhibits a longer intracellular retention time and induce a persistent MRI signal reduction effect.The cellular MRI results are interpreted by taking into account both T1 and T2 relaxation rates and their correlation with cellular binding structures of Dotarem and EM7Gd2.展开更多
随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完...随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完善有十分重要的意义。基于此,该文通过容量增量曲线对电池容量衰减的内因展开分析;在不同影响因素下自放电过程中电池阻抗谱变化规律的基础上,利用弛豫时间分布法进行理论原理分析;最后,在电池自放电老化过程的原理推导的基础上总结电池容量衰减量随时间的变化规律,并结合实验数据建立不同影响因素下电池容量衰减模型。结果表明,在存储过程中,电池的固体电解质界面(solid electrolyte interface,SEI)膜内阻增大,且存储温度越高、初始充电状态(state of charge,SOC)越大,相应的阻抗增加幅度越大。自放电过程电池老化主要原因是可循环活性锂离子的消耗和SEI膜的生长。同时该文推导出电池容量损失与时间近似呈0.5次方关系,并利用实验数据拟合得到电池在不同初始SOC和不同存储温度影响下的容量变化模型,为锂电池寿命模型预测提供更进一步的参考。展开更多
退役电池在进行梯次利用之前需要对其参数进行测试与评估,以保证后续依据电池的性能为其选择适合的应用场景。健康状态(state of health,SOH)的准确评估是退役动力电池是否有梯次利用价值的前提。针对目前退役动力电池SOH评估准确性低...退役电池在进行梯次利用之前需要对其参数进行测试与评估,以保证后续依据电池的性能为其选择适合的应用场景。健康状态(state of health,SOH)的准确评估是退役动力电池是否有梯次利用价值的前提。针对目前退役动力电池SOH评估准确性低的问题。本工作首先利用弛豫时间分布法对电化学阻抗谱进行分析,用以得到其中能准确反应电池健康状态的特征频率,将特征频率对应的阻抗数据作为特征输入参量,输入麻雀算法优化的极限学习机模型以实现退役动力电池SOH的评估。为了验证评估方法的有效性,针对7只方形磷酸铁锂退役电池进行循环老化实验,并在每个循环周期后进行电化学阻抗测试。使用退役动力电池的实际的电化学阻抗谱用于分析与建模实现SOH评估,并将结果与实际的SOH数据进行对比,并与传统的SOH评估方法进行了对比。评估结果表明,相较于其他方法采用弛豫时间分布法进行分析的均方误差(mean square error,MSE)与平均绝对百分比误差(mean absolute percentage error,MAPE)更低。相较于使用未优化的极限学习机模型,MSE和MAPE分别降低了47.1%和60.5%,表明本文的SOH评估方法具有更小的误差和更高的准确性,在实际的梯次利用中很有应用价值。展开更多
All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid...All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs,which is challenging to investigate quantitatively by experimental approach.This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs.With the assistance of an equivalent circuit model and distribution of relaxation times,it is discovered that as the number of voids and the sharpness of cracks increase,the contact resistance Rcgrows and ultimately dominates the battery impedance.Through accurate fitting,inverse proportional relations between contact resistance Rcand(1-porosity)as well as crack angle was disclosed.This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.展开更多
In this study,low-field nuclear magnetic resonance(LF-NMR)was used to collect the transverse relaxation signals of camphor seeds that had been dried at different temperatures and for different durations.The transverse...In this study,low-field nuclear magnetic resonance(LF-NMR)was used to collect the transverse relaxation signals of camphor seeds that had been dried at different temperatures and for different durations.The transverse relaxation time of the hydrogen nucleus was obtained by SIRT(Simultaneous Iterative Reconstruction Technique)inversion,and the correlation between the moisture content on dry basis and the amplitude of NMR signal of camphor seeds sampled at different drying stages was analyzed.The results showed that water existed in three main forms strongly bound water,weakly bound water and free water in camphor seeds.During the drying process,the peak position of strongly bound water remained unchanged,but the peak positions of weakly bound water and free water fluctuated.Drying rate increased with drying temperature increasing.In addition,there was a very significant linear relationship between the total NMR signal amplitude and moisture content on dry basis,and the correlation coefficient reached 0.984 4.展开更多
基金funding from the National Natural Science Foundation of China,China(12172104,52102226)the Shenzhen Science and Technology Innovation Commission,China(JCYJ20200109113439837)the Stable Supporting Fund of Shenzhen,China(GXWD2020123015542700320200728114835006)。
文摘A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating conditions.Electrochemical impedance spectra(EIS) of PCCs were first acquired under a variety of opera ting conditions to provide a dataset containing 36 sets of EIS spectra for the model.An artificial neural network(ANN) was then trained to model the relationship between the cell operating condition and EIS response.Finally,ANN model-predicted EIS spectra were analyzed by the distribution of relaxation times(DRT) and compared to DRT spectra obtained from the experimental EIS data,enabling an assessment of the accumulative errors from the predicted EIS data vs the predicted DRT.We show that in certain cases,although the R^(2)of the predicted EIS curve may be> 0.98,the R^(2)of the predicted DRT may be as low as~0.3.This can lead to an inaccurate ANN prediction of the underlying time-resolved electrochemical response,although the apparent accuracy as evaluated from the EIS prediction may seem acceptable.After adjustment of the parameters of the ANN framework,the average R^(2)of the DRTs derived from the predicted EIS can be improved to 0.9667.Thus,we demonstrate that a properly tuned ANN model can be used as an effective tool to predict not only the EIS,but also the DRT of complex electrochemical systems.
文摘The classical power law relaxation, i.e. relaxation of current with inverse of power of time for a step-voltage excitation to dielectric—as popularly known as Curie-von Schweidler law is empirically derived and is observed in several relaxation experiments on various dielectrics studies since late 19th Century. This relaxation law is also regarded as “universal-law” for dielectric relaxations;and is also termed as power law. This empirical Curie-von Schewidler relaxation law is then used to derive fractional differential equations describing constituent expression for capacitor. In this paper, we give simple mathematical treatment to derive the distribution of relaxation rates of this Curie-von Schweidler law, and show that the relaxation rate follows Zipf’s power law distribution. We also show the method developed here give Zipfian power law distribution for relaxing time constants. Then we will show however mathematically correct this may be, but physical interpretation from the obtained time constants distribution are contradictory to the Zipfian rate relaxation distribution. In this paper, we develop possible explanation that as to why Zipfian distribution of relaxation rates appears for Curie-von Schweidler Law, and relate this law to time variant rate of relaxation. In this paper, we derive appearance of fractional derivative while using Zipfian power law distribution that gives notion of scale dependent relaxation rate function for Curie-von Schweidler relaxation phenomena. This paper gives analytical approach to get insight of a non-Debye relaxation and gives a new treatment to especially much used empirical Curie-von Schweidler (universal) relaxation law.
基金the Natural Science Foundation of China(21673281,31870982)a National Key R&D Program from MOST of China(2017YFA0104301).
文摘Human mesenchymal stem cells(hMSCs)were labeled with Dotarem or(Gd-DOTA)2-EM7(EM7Gd2)via electroporation(EP).Cellular transmission electron microscopy(TEM)reveals free distribution of Gd agents and formation of EM7Gd2 clusters in the cytosol.Cellular magnetic resonance imaging(MRI)reveals that the free Gd agents induce MRI signal enhancement effect due to its fast exocytosis and subsequent interaction with intercellular water molecules.The EM7Gd2 clusters exhibits a longer intracellular retention time and induce a persistent MRI signal reduction effect.The cellular MRI results are interpreted by taking into account both T1 and T2 relaxation rates and their correlation with cellular binding structures of Dotarem and EM7Gd2.
文摘随着锂电池在动力和储能等领域得到广泛应用,锂电池的寿命问题成为限制其发展的重要桎梏。电池处于存储状态时也会发生性能衰退而影响寿命,因此,研究电池自放电过程中的阻抗变化以表征内部电化学反应与结构相变过程,对于电池寿命模型完善有十分重要的意义。基于此,该文通过容量增量曲线对电池容量衰减的内因展开分析;在不同影响因素下自放电过程中电池阻抗谱变化规律的基础上,利用弛豫时间分布法进行理论原理分析;最后,在电池自放电老化过程的原理推导的基础上总结电池容量衰减量随时间的变化规律,并结合实验数据建立不同影响因素下电池容量衰减模型。结果表明,在存储过程中,电池的固体电解质界面(solid electrolyte interface,SEI)膜内阻增大,且存储温度越高、初始充电状态(state of charge,SOC)越大,相应的阻抗增加幅度越大。自放电过程电池老化主要原因是可循环活性锂离子的消耗和SEI膜的生长。同时该文推导出电池容量损失与时间近似呈0.5次方关系,并利用实验数据拟合得到电池在不同初始SOC和不同存储温度影响下的容量变化模型,为锂电池寿命模型预测提供更进一步的参考。
基金supported by the Beijing Natural Science Foundation(Z200011,L233004)the National Key Research and Development Program(2021YFB2500300)+3 种基金the National Natural Science Foundation of China(52394170,52394171,22109011,22393900,and 22108151)the Tsinghua-Jiangyin Innovation Special Fund(TJISF)(2022JYTH0101)the S&T Program of Hebei(22344402D)the Tsinghua University Initiative Scientific Research Program.
文摘All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs,which is challenging to investigate quantitatively by experimental approach.This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs.With the assistance of an equivalent circuit model and distribution of relaxation times,it is discovered that as the number of voids and the sharpness of cracks increase,the contact resistance Rcgrows and ultimately dominates the battery impedance.Through accurate fitting,inverse proportional relations between contact resistance Rcand(1-porosity)as well as crack angle was disclosed.This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.
文摘In this study,low-field nuclear magnetic resonance(LF-NMR)was used to collect the transverse relaxation signals of camphor seeds that had been dried at different temperatures and for different durations.The transverse relaxation time of the hydrogen nucleus was obtained by SIRT(Simultaneous Iterative Reconstruction Technique)inversion,and the correlation between the moisture content on dry basis and the amplitude of NMR signal of camphor seeds sampled at different drying stages was analyzed.The results showed that water existed in three main forms strongly bound water,weakly bound water and free water in camphor seeds.During the drying process,the peak position of strongly bound water remained unchanged,but the peak positions of weakly bound water and free water fluctuated.Drying rate increased with drying temperature increasing.In addition,there was a very significant linear relationship between the total NMR signal amplitude and moisture content on dry basis,and the correlation coefficient reached 0.984 4.
