μV Rms Research Articles

Development, characterization and validation of a novel physics-informed equivalent circuit model for silicon–graphite battery cells

The widespread deployment of electric vehicles (EVs), as well as the growing requirements both from manufacturers and consumers, necessitate an increase in energy density with regard to current lithium-ion batteries (LIBs). In this regard, one of the most promising alternatives is the addition of silicon to conventional graphite anodes, thus giving rise to energy-dense LIBs. However, this entails a significant increment in modeling, parameterization and computational complexities due to the interactions between both negative electrode materials. In this article, we present a novel physics-informed equivalent circuit model for cells with blended electrodes, which is able to provide accurate results with respect to a state-of-the-art electrochemical model, not only for the output voltage (≤25 mV RMS), but also internal states, namely active material particle surface concentrations (≤1.2 %) and current distribution (≤2.6 %) at a much lower computational cost. Furthermore, this formulation also allows for a notable simplification of model parameterization. Hence, we describe thorough static and dynamic parameterization processes from half-cell experimental data and impedance measurements. Finally, we validate the proposed model in constant-current as well as dynamic operation, highlighting the influence that the choice of hysteresis model has on the latter. We understand that the presented model is an interesting alternative for the modeling of cells with blended electrodes, and is also suitable for its implementation in Battery Management Systems (BMSs) in EVs.

Comparison of Approaches for Assessing Linearity of Impedance Measurements

There are two experimental methods available to assess the linearity of electrochemical impedance measurements. Observation of current as a function of potential, known as Lissajous plots, provides an instantaneous visual representation of the data.1 Deviation from an elliptical shape suggests a perturbation amplitude that is too large, resulting in nonlinear impedance data. A second approach is to measure, along with the fundamental, the higher harmonics of the measurement signal. Under potentiostatic control, the harmonics of current that exceed the noise level suggest nonlinear behavior. These harmonics may be expressed in terms of a frequency-dependent total harmonic distortion, THD, written as the ratio between the sum of the root mean square of the harmonic magnitude and fundamental frequency magnitude for electrochemical applications.The impedance was measured for a model system consisting of a Pt disk immersed in an electrolyte containing 0.01 M potassium ferricyanide, 0.01 M potassium ferrocyanide, and 1 M KCl. Measurements were performed using a Gamry Reference 3000 with THD measurement enabled and disabled. Low-frequency (10 mHz) Lissajous plots were recorded to facilitate comparison of the two methods for assessing linearity. The impedance measurements with THD enabled or disabled were in good agreement, including the frequency-dependent stochastic error structure, the shapes of Lissajous curves, and the values of the impedance. Both the low-frequency THD and the low-frequency Lissajous plots gave similar sensitivity to nonlinear behavior. Perturbation amplitudes of 1, 5, and 10 mV rms yielded elliptical Lissajous plots with THD values on the order of the background noise. Interestingly, the THD for the 10 mV perturbation was slightly above the background noise with a value of 0.01 (or 1 % of the fundamental). Perturbation amplitudes of 20, 60, and 100 mV rms yielded both non-elliptical Lissajous plots and low-frequency THD values much larger than the background noise.The regression of the measurement model 2 to the imaginary part of the impedance was applied to assess the consistency of the measured data to the Kramers-Kronig relations.3 Data measured at amplitudes of 1, 5, 10, and 20 mV rms were found to be consistent with the Kramers-Kronig relations, and data collected with amplitudes of 60 or 100 mV rms were found to be inconsistent with the Kramers-Kronig relations. As the measurement with a 20 mV rms amplitude was found to be nonlinear by observation of non-elliptical Lissajous plots and a THD of 4.2% at a frequency of 10 mHz, the post-measurement analysis of consistency with the Kramers-Kronig relations was found to be less sensitive than experimental observation of Lissajous plots and calculation of THD. Comparison of Lissajous plots to THD values suggests that experiments with THD less than 1% of the fundamental may be considered to be linear.

Quantification of pitting corrosion resistance in stainless steel with hyperspectral imaging in the Vis/NIR range

The impact of 316L stainless steel discolouration on chloride induced pitting corrosion was quantified. Several degrees of discolouration were produces by chemical passivation, simulated rouging or anodic polarization. Discolouration was characterized by spectral analysis in the visible and NIR range (400-1000 nm). Pitting corrosion resistance was quantified by pitting potential measurements. The spectra were used to indicate whether pitting or transpassive behaviour would occur using chemometric classification techniques with 88% accuracy. In addition, pitting potentials were predicted combining chemometrics and survival analysis techniques with a 90 mV RMS error in cross-validation. XPS analysis linked pitting resistance with the Cr/Fe balance.

A 10.5 ppm/°C Modified Sub-1 V Bandgap in 28 nm CMOS Technology with Only Two Operating Points

Reference voltage/current generation is essential to the Analog circuit design. There have been several ways to generate quality reference voltage using bandgap reference (BGR) and there are mainly two types: current mode and voltage mode. The current-mode bandgap reference (CBGR) is widely accepted in industry due to having an output voltage which is below 1 V. However, its drawbacks include a lack of proportional to absolute temperature (PTAT) current availability, a large silicon area, multiple operating points, and a large temperature coefficient (TC). In this paper, various operating points are explained in detail with diagrams. Similar to the conventional voltage mode bandgap reference (VBGR) circuits, modifications of the existing circuits with only two operating points have also been proposed. Moreover, the proposed BGR occupies a much smaller area due to eliminating the complimentary to absolute temperature (CTAT) current-generating resistor. A new self-biased opamp was introduced to operate from a 1.05 V supply, reducing systematic offset and TC of the BGR. The proposed solution has been implemented in 28 nm CMOS TSMC technology, and extraction simulations were performed to prove the robustness of the proposed circuit. The targeted mean BGR output is 500 mV, and across the industrial temperature range (−40 to 125 °C), the simulated TC is approximately 10.5 ppm/°C. The integrated output noise within the observable frequency band is 19.6 µV (rms). A 200-point Monte Carlo simulation displays a histogram with a 2.6 mV accuracy of 1.2% (±3-sigma). The proposed BGR circuit consumes 32.8 µW of power from a 1.05 V supply in a fast process and hot (125 °C) corner. It occupies a silicon area of 81 × 42 µm (including capacitors). This design can aim for use in biomedical and sensor applications.

Oxidation of Alloy 690 in Simulated Pressurized Water Reactor Primary Coolant – Experiments and Modeling

During normal operation of the primary loop of a water cooled-water moderated energy reactor (WWER), the associated water chemistry evolves from an initially high-boron high-potassium (beginning-of-cycle, 1200 ppm B and 8 ppm K) to significantly lower concentrations (ca. 400 ppm B and 3.5 ppm K) at the end of the respective campaign. In addition to that, the concentration of Li produced by transmutation of B reaches ca. 0.7 – 0.9 ppm. To the best of our knowledge, the effect of such water chemistry changes on pressurized water reactor (PWR) internals such as Alloy 690 have not been studied yet. Such a study appears relevant also within the frames of a discussion for a possible transition from B-Li to B-K water chemistry in PWRs.In the present paper, the effect of evolution of primary water chemistry during operation on the corrosion rate and conduction mechanism of oxide films on Alloy 690 is studied by in-situ impedance spectroscopy at 280 °C / 8 MPa during 1-week exposures in an autoclave connected to a re-circulation loop. Impedance measurements were performed in three-electrode mode featuring a Pt sheet counter electrode and a Pd electrode negatively polarized with a current of -10 µA vs. another Pt to approximate the reversible hydrogen electrode (RHE). Spectra were recorded at the corrosion potential in a frequency range 10 kHz – 0.1 mHz using an ac amplitude of 50 mV (rms). At the end of exposure, the samples were polarized in the range of potentials -0.1 to 0.5 V vs. RHE to evaluate the stability of the passive oxide. Separate samples of Alloy 690 were simultaneously exposed in the autoclave and subsequently analyzed by Glow-Discharge Optical Emission Spectroscopy (GDOES) in order to estimate the thickness and the in-depth composition of the formed oxides.Impedance data were quantitatively interpreted using the Mixed-Conduction Model for Oxide Films (MCM) to estimate the rates of metal oxidation at the alloy/oxide interface, oxide dissolution and restructuring at the film/coolant interface and ion transport in the protective layer. The effect of water chemistry evolution on corrosion rate and conduction mechanism in the oxide on Alloy 690 in primary coolant is discussed on the basis of the obtained parameters.Acknowledgments: This study is funded by the European Union-NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria, project № BG-RRP-2.004-0002 (BiOrgaMCT).

A High-Precision Current-Mode Bandgap Reference With Low-Frequency Noise/Offset Elimination

This brief presents a low-noise, low-offset bandgap reference for the biomedical electronic systems application. In order to reduce the low-frequency noise and increase the accuracy, the low-frequency noise/offset elimination technique based on current-mode bandgap reference (BGR) is proposed. Besides, this BGR utilizes a proportional to absolute temperature (PTAT) resistor feedback technique to minimize the low-frequency noise and offset from the current mirror. The proposed BGR is implemented in a 180 nm deep n-well CMOS process occupying an active area of 0.0725 mm2. The measured results indicate that the BGR outputs 0.6 V voltage and consumes 69 μA current under 1.2 V supply voltage. It can achieve 3.5 μV(rms) noise from 0.1 to 10 Hz and a 0.21% DC accuracy.

TDCpix pixel detector ASIC with 100 ps time stamping

The TDCpix pixel read-out ASIC contains 1800 pixels arranged in 40 columns and 45 rows with the dimension of 300μm x 300μm. Each pixel contains a preamplifier and shaper circuit with a dynamic range of 0.8 to 10 fC and a rise time of 5 ns, followed by a Leading-Edge discriminator with Time-over-Threshold correction. The discriminator outputs of each pixel are connected to time-to-digital converters (TDC) measuring the time when the input signal has exceeded the threshold and the pulse width with a binning of 97 ps. The electronics noise of pre-amplifier/shaper is 170 e− or 2.7 mV rms with a gain of 65 mV/fC. The jitter of the entire processing chain for an electrical input signal of 2.4 fC is lower than 60 ps rms. The ASIC has been designed to work in radiated environments of 6 * 104 Gray per year and 2 x 1014 1 MeV neutron equivalent cm−2.

A high-speed transient waveform sampling SCA ASIC prototype in 180 nm CMOS technology

Switched capacitor array (SCA) is an important method of waveform digitization in high-energy physics experiments. This paper presents the design and test results of an eight-channel SCA ASIC for high-speed waveform sampling. The ASIC is designed and fabricated in 180 nm CMOS technology. The sampling rate of up to 14.25 Gsps is achieved by adopting the proposed dual-chain interpolating delay cell in DLL. The ASIC can be configured to operate in two modes: long-chain mode for deeper sampling depth and ping-pong mode for recording two waveforms in a short time. The bandwidth is over 1.1 GHz. By optimizing the sampling order, the distortion caused by the bandwidth discontinuity is reduced. Deep N-well is adopted to isolate the interference between digital and analog signals. The test results show that the random noise is approximately 0.87 mV RMS after the fixed-pattern noise correction. The time resolution is better than 5 ps RMS over the time measurement range of approximately 73μs.

An Experimentally Parameterized Equivalent Circuit Model of a Solid-State Lithium-Sulfur Battery

This paper presents and parameterizes an equivalent circuit model of an all-solid-state lithium-sulfur battery cell, filling a gap in the literature associated with low computational intensity models suitable for embedded battery management applications. The paper addresses this gap by parameterizing a three-state equivalent circuit model using experimental pulse power characterization data from a laboratory-fabricated lithium-sulfur cell. The cell is mechanically loaded during electrical cycling to achieve maximum ionic conductivity and consistent capacity. A nested combination of linear and nonlinear least squares regression is used to estimate the model parameters. The model captures slow cycling and fast pulse charge/discharge dynamics within 34 mV RMS error. The series resistance changes significantly at high/low states of charge and low C-rates. A sensitivity analysis determines that accurately modeling the dependence of resistance on C-rate and state of charge is important for model fidelity.

RF Josephson Arbitrary Waveform Synthesizer With Integrated Superconducting Diplexers

We present the design and characterization of a broadband RF Josephson arbitrary waveform synthesizer (RF-JAWS) with a series array of 4500 Josephson junctions (JJs) and integrated low-pass/high-pass five-pole superconducting diplexers. The integrated diplexers enable broadband filtering of the feedthrough signal components in the drive-current pulses with decade-wide instantaneous bandwidth. The diplexers have at least 30 GHz passband with less than 0.8 dB insertion loss. The JJ array is driven with a delta-sigma pulse sequence that encodes 10 kHz and 1.005 GHz tones, and generates an open-circuit voltage of 22 mV rms (−26.18 dBm available power assuming a 50 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"><tex-math notation="LaTeX">$\mathrm{\Omega }$</tex-math></inline-formula> Thevenin equivalent source) at 1.005 GHz—a 25% increase compared to the state of the art. The drive current pulses undergo a three-step equalization to compensate for the linear distortion of the room-temperature electronics, the on-chip diplexers, and the remaining on- and off-chip components. The measured parasitic feedthrough voltages at 1.005 GHz are around −33 dBc, and their effect on the quantum locking ranges (QLRs) is quantified by measurements. The results demonstrated in this article show a significant step toward a broadband, integrated, quantum-based microwave voltage source with useful power above −30 dBm.

Design and Simulation of a Low Power 384-channel Actively Multiplexed Neural Interface.

Brain computer interfaces (BCIs) provide clinical benefits including partial restoration of lost motor control, vision, speech, and hearing. A fundamental limitation of existing BCIs is their inability to span several areas (> cm2) of the cortex with fine (<100 μm) resolution. One challenge of scaling neural interfaces is output wiring and connector sizes as each channel must be independently routed out of the brain. Time division multiplexing (TDM) overcomes this by enabling several channels to share the same output wire at the cost of added noise. This work leverages a 130-nm CMOS process and transfer printing to design and simulate a 384-channel actively multiplexed array, which minimizes noise by adding front end filtering and amplification to every electrode site (pixel). The pixels are 50 μm × 50 μm and enable recording of all 384 channels at 30 kHz with a gain of 22.3 dB, noise of 9.57 μV rms, bandwidth of 0.1 Hz - 10 kHz, while only consuming 0.63 μW/channel. This work can be applied broadly across neural interfaces to create high channel-count arrays and ultimately improve BCIs.

ECG Arrhythmia Classification on an Ultra-Low-Power Microcontroller.

Wearable biomedical systems allow doctors to continuously monitor their patients over longer periods, which is especially useful to detect rarely occurring events such as cardiac arrhythmias. Recent monitoring systems often embed signal processing capabilities to directly identify events and reduce the amount of data. This work is the first to document a complete beat-to-beat arrhythmia classification system implemented on a custom ultra-low-power microcontroller. It includes a single-channel analog front-end (AFE) circuit for electrocardiogram (ECG) signal acquisition, and a digital back-end (DBE) processor to execute the support vector machine (SVM) classification software with a Cortex-M4 CPU. The low-noise instrumentation amplifier in the AFE consumes 1.4 μW and has an input-referred noise of 0.9 μV RMS. The all-digital time-based ADC achieves 10-bit effective resolution over a 250-Hz bandwidth with an area of only 900 μm 2. The classification software reaches a sensitivity of 82.6% and 88.9% for supraventricular and ventricular arrhythmias respectively on the MIT-BIH arrhythmia database. The proposed system has been prototyped on the SleepRider SoC, a 28-nm fully-depleted silicon on insulator (FD-SOI) 3.1-mm 2 chip. It consumes 13.1 μW on average from a 1.8-V supply.

Optics-Free Chip-Scale Intraoperative Imaging Using NIR-Excited Upconverting Nanoparticles.

We present an optics-free CMOS image sensor that incorporates a novel time-gated dual-photodiode pixel design to allow filter- and lens-less image acquisition of near-infrared-excited (NIR-excited) upconverting nanoparticles. Recent biomedical advances have highlighted the benefits of NIR excitation, but NIR interaction with silicon has remained a challenge, even with high-performance optical blocking filters. Using a secondary diode and a dual-photodiode design, this sensor is able to remove the 100s of mV of NIR background on pixels and bring it down to single-digit mV level, nearing its noise floor of 2.2 mV rms, not achievable with any optical filter. Non-linear effects of background cancellation using the diode pair has been mitigated using an initial one-time pixel-level curve fitting and calibration in a post-processing setting. This imager comprises a highly linear 11 fF metal-oxide-metal (MOM) capacitor and includes integrated angle-selective gratings to reject oblique light and enhance sharpness. Each pixel also includes two distinct correlated double sampling schemes, to remove low frequency flicker noise and systematic offset in the datapath. We demonstrate the performance of this imager using pulsed NIR-excited upconverting nanoparticles on standard United-States-Air-Force (USAF) resolution targets and achieve an SNR of 15 dB, while keeping NIR background below 6 mV. This 36-by-80-pixel array measures only 2.3 mm by 4.8 mm and can be thinned down to 25 µm, allowing it to become surgically compatible with intraoperative instruments and equipment, while remaining optics-free.

Physics-Based Equivalent Circuit Model for Lithium-Ion Cells via Reduction and Approximation of Electrochemical Model

&lt;div class="section abstract"&gt;&lt;div class="htmlview paragraph"&gt;Physics-based electrochemical models and empirical Equivalent Circuit Models (ECMs) are well-established and widely used modeling techniques to predict the voltage behavior of lithium-ion cells. Electrochemical models are typically very accurate and require relatively little experimental data to calibrate, but present high mathematical and computational complexity. Conversely, ECMs are more computationally efficient and mathematically simpler, making them well-suited for applications in controls, diagnosis, and state estimation of lithium-ion battery packs. However, the calibration process requires extensive testing to calibrate the parameters of the model over a wide range of operating conditions.&lt;/div&gt;&lt;div class="htmlview paragraph"&gt;This paper bridges the gap between these two classes of models by developing a method to analytically define the ECM parameters starting from an already-calibrated Extended Single-Particle Model (ESPM). The governing equations of the ESPM were reduced via model order reduction, linearization and by introducing approximations to yield the mathematical structure of a second order ECM. This allowed for analytically defining the parameters of the resulting ECM, without resorting to complex lookup tables and related extensive testing for calibration. The newly defined electrochemistry-based ECM (E-ECM) saw less than 1 mV RMS error increase compared to the ESPM voltage prediction across several test profiles.&lt;/div&gt;&lt;/div&gt;

Simulation and experimental characterisation of a 3D-printed electromagnetic vibration sensor

Additive manufacturing, also known as 3D printing has already transformed from a rapid prototyping tool to a final end-product manufacturing technique. 3D printing can be used to develop various types of sensors. This paper investigates the ability to use the electromagnetic induction properties of 3D printed carbon-based filament for developing sensors. The paper presents a novel prototype vibration sensor which is 3D-printable, except for an included NdFeB magnet. Motion is detected from the voltage induced by the relative motion of the magnet. The devised vibration sensor is simulated using ANSYS, and a novel prototype is 3D-printed for physical testing to characterise and understand its electromagnetic properties. Simulation helped establish constraints for the design. Two types of experimental setups were physically tested, one setup with a magnet freely sliding inside a cylindrical cavity within an oscillating coil, and the other setup with a stationary coil and oscillating magnet. At a frequency of 10 Hz and a motion travel of about 12 mm, the induced voltage for the moving coil case varied from 5.4 mV RMS for pure sliding motion of the internal magnet to 22.1 mV RMS. The findings of this paper suggest that future sensors can be developed using the electromagnetic induction properties of the carbon-based filament.

Numerical study of POD-Galerkin-DEIM reduced order modeling of cardiac monodomain formulation

The three-dimensional cardiac monodomain model with inhomogeneous and anisotropic conductivity characterizes a complicated system that contains spatial and temporal approximation coefficients along with a nonlinear ionic current term. These complexities make its numerical modeling computationally challenging, and therefore, the formation of an efficient computational approximation is important for studying cardiac propagation. In this paper, a reduced order modeling approach has been developed for the simplified cardiac monodomain model, which yields a significant reduction of the full order dynamics of the cardiac tissue, reducing the required computational resources. Additionally, the discrete empirical interpolation technique has been implemented to accurately estimate the nonlinearity of the ionic current of the cardiac monodomain scheme. The proper orthogonal decomposition technique has been utilized, which transforms a given dataset called ‘snapshots’ to a new coordinate system. The snapshots are computed first from the original system, and they encapsulate all the information observed over both time and parameter variations. Next, the proper orthogonal decomposition provides a reduced order basis for projecting the original solution onto a low-dimensional orthonormal subspace. Finally, a reduced set of unknowns of the forward problem is obtained for which the solution involves significant computational savings compared to that for the original system of unknowns. The efficiency of the model order reduction technique for finite difference solution of cardiac electrophysiology is examined concerning simulation time, error potential, activation time, maximum temporal derivative, and conduction velocity. Numerical results for the monodomain show that its solution time can be reduced by a significant factor, with only 0.474 mV RMS error between the full order and reduced dimensions solution.

A Microwave Quantum-Defined Millivolt Source

We demonstrate a tenfold increase in the amplitude of microwave-frequency waveforms generated by a quantum-defined superconducting voltage source, with an open-circuit signal of 17.56 mV rms at 1.005 GHz. The voltage source is an RF Josephson arbitrary waveform synthesizer (RF-JAWS) that utilizes a circuit that is cooled to 4 K and is composed of an array of 4500 Josephson junctions. These junctions are connected in series along the center conductor of a 50- <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\Omega $ </tex-math></inline-formula> superconducting coplanar waveguide transmission line. We introduce a new zero-forcing equalization technique for reducing distortion in drive current pulse patterns. This technique allows an increase in the amplitude of the quantum-based voltage waveforms while suppressing parasitic feedthrough signals to −75 dBc. Synthesizing a two-tone delta–sigma waveform, we monitor an audio-frequency 10-kHz tone of less than 100- <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\mu \text{V}$ </tex-math></inline-formula> rms amplitude while simultaneously measuring the 1.005-GHz tone of −28.12-dBm power in a 50- <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\Omega $ </tex-math></inline-formula> environment. The two-tone synthesis allows simultaneous verification of correct operation of the voltage source using time-efficient low-frequency measurement techniques as well as slower microwave measurements.

Development of a front-end electronics for thin-gap resistive plate chamber

To cope with the challenge of high hit rates in some applications, the new-generation large-area Resistive Plate Chamber (RPC) with 1 mm thin gap was proposed. Compared to the RPC generation presently, the signal of the thin-gap RPC is much weaker (of the order of hundreds of μV) and faster (pulse width of about 5 ns). Hence a new-generation Front-End (FE) electronics needs to be developed for the thin-gap RPC. The FE board contains 8 independent electronic channels, each with an amplifier, a discriminator, and a Low-Voltage Differential Signaling (LVDS) transmitter. The amplifier is made of discrete components, with particular emphasis on SiGe:C transistors. A simplified but stable power system is designed for the FE board, and its status can be monitored in real-time. The test results show that the overall charge gain of the FE amplifier reaches 0.4 mV/fC, with very low noise (lower than 700 μV RMS with up to 10 pF input detector capacitance), and good linearity when the amplitude of the input amplitude is lower than 3 mV. The -3-dB bandwidth of the amplifier reaches 154 MHz. The jitter caused by the electronics (including amplifier, discriminator and LVDS transmitter) is around 10 ps when the threshold voltage is higher than 20 mV. The maximum event rate per channel exceeds 20 MHz. The cosmic ray test was conducted with two FE boards mounted on a 1 mm thin-gap RPC of 1.4 × 0.4 m2 area. The efficiency of the detector system reaches 95% when the threshold voltage is 20 mV, with almost no accidental coincidence event. The overall time resolution of the detector system is 484 ps. The performance of our FE electronics satisfies the requirement of the thin-gap RPC.

In-situ Analysis of the Solid-Electrolyte Interphase Formed in Li[N(CF3SO2)2] and Li[N(FSO2)2] Tetraglyme Solvate Ionic Liquids

Li metal has attracted attention as the negative electrode for secondary batteries due to its low density and negative redox potential. However, its negative operating potential also leads to the decomposition of electrolytes, resulting in the formation of some interfacial phase on the anode, i.e., solid-electrolyte interphase (SEI). The decomposition of the electrolyte causes the low coulombic efficiency of the Li anode. Therefore, the characterization of SEI is necessary in order to utilize the Li anode.Solvate ionic liquids (SILs) composed of 1:1 equimolar mixture of lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) or bis(fluorosulfonyl)amide (LiFSA) and glyme have been investigated as the alternative electrolytes for lithium secondary batteries because of their high Li+ concentration [1, 2]. The deposition and dissolution of Li were reported to be possible in the SILs, although the cathodic decomposition of the electrolyte also proceeded at the potential more positive than that of Li(I)/Li. We have already reported the improvement of the morphology of Li deposits and the cyclability of the Li anode in LiTFSA-triglyme (G3) by the formation of SEI on a Cu electrode at 0 V vs. Li|Li(I) prior to the deposition of Li [3]. The cyclability of the Li anode in LiFSA-tetraglyme (G4) was found to be superior to that in LiTFSA-G4. However, the difference in the stability of Li deposits in these SILs has not been elucidated. In the present study, the formation of SEI on a Cu electrode and the interfacial reaction of the Li deposits were investigated in LiTFSA-G4 and LiFSA-G4 using electrochemical impedance spectroscopy (EIS) combined with electrochemical quartz crystal microbalance (EQCM).The solvate ionic liquids were prepared by mixing the equimolar quantities of G4 and LiTFSA or LiFSA. EIS and EQCM measurement were conducted on the same Cu-coated EQCM electrode (fundamental frequency: 9 MHz) using an impedance-type EQCM system (SEIKO EG&G, QCM922A) and a computerized electrochemical system (Hokuto Denko, HZ-7000). Li foil was used as a reference and counter electrode, respectively. SEI was formed at 0 V vs. Li|Li(I) on the Cu-coated EQCM electrode prior to the galvanostatic deposition of Li. EIS was performed at the open circuit potential (OCP) in the frequency range from 20 kHz to 1.0 Hz with an amplitude of 5 mV rms during SEI formation and after Li deposition.The resonance frequency (f) of a Cu-coated EQCM electrode gradually decreased with keeping the potential of the electrode at 0 V. A semicircle corresponding to the parallel circuit of the resistance and capacitance of SEI was observed in the Nyquist plots of the Cu electrode after keeping the potential at 0 V. The resistance of SEI, R SEI, increased with the lapse of time over 24 hours, indicating the formation and growth of SEI on the Cu electrode at 0 V in LiTFSA-G4 and LiFSA-G4. The changes in f and R SEI in LiFSA-G4 were smaller than those in LiTFSA-G4, suggesting the SEI formed in LiFSA-G4 was lighter and more conductive.The larger change in f of the Cu-EQCM electrode than that calculated from the passed electric charge implied that SEI was also formed on Li deposits during the galvanostatic cathodic reduction at 0.01 mA cm–2, as observed during cyclic voltammetry in LiTFSA-G3 [4]. Δf in LiFSA-G4 was smaller while the changes in the resonance resistance mainly reflecting the surface roughness of the electrode were close in the SILs, suggesting the reactivity against Li was low in LiFSA-G4. The electrode potential of the Cu-EQCM electrode changed over from that of Li(I)/Li after few tens of hours, suggesting the SEI formed in SILs did not suppress completely the reaction between Li and the electrolyte at the OCP. The transition time of the potential in LiFSA-G4 was longer than that in LiTFSA-G4, indicating Li deposits were more stable in LiFSA-G4.References H. Moon, et al., J. Phys. Chem. C, 118, 20246 (2014).S. Terada, et al., Aust. J. Chem., 72, 70 (2019).N. Serizawa, et al., J. Electrochem. Soc., 167, 110560 (2020).N. Serizawa, et al., J. Electrochem. Soc., 160, A1529 (2013). AcknowledgementThis study was supported in part by the JSPS KAKENHI (Grant No. 19K15682) and Advanced Low Carbon Technology Research and Development Program (ALCA, JPMJAL1301).

Experimental Study of Parylene Based Capacitive Humidity Sensor for Integrated Thermal Comfort Sensing Application

In this letter, we report the temperature effect and noise characterization of the Parylene-based capacitive humidity sensor which can be used for integrated CMOS compatible thermal comfort sensing. The sensor is comprised of a pair of interdigitated Pt electrodes deposited on a silicon substrate and a parylene hygroscopic layer coated on the electrodes using room temperature chemical vapor deposition process. The sensor was characterized at different relative humidity (RH) values and working temperatures in a testing setup. The capacitance of the sensor increases with the RH due to the absorption of water molecules on the surface of the sensing film. The capacitance of the sensor also increases with temperature, which is due to the stronger thermal movement of the molecules that helps increase the polarization at increased temperature levels. Besides, a readout circuit was done on a printed circuit board using capacitance to voltage converter for the sensor. The sensor achieved a maximum sensitivity of 76.2 mV/%RH and response and recovery times of about 31.5 and 29.2 s, respectively. Besides, the sensor shows a noise level of 1.399 mV rms within 25 Hz bandwidth in the output voltage response. The experimental results also indicated a resolution of about 0.072-2% within the ASHRAE standard approved RH range (25-95%) for the fabricated sensor.