Enhancing capacitive deionization performance and cyclic stability of nitrogen-doped activated carbon by the electro-oxidation of anode materials

Electrode materials with high desalination capacity and long-term cyclic stability are the focus of capacitive deionization(CDI) community. Understanding the causes of performance decay in traditional carbons is crucial to design a high-performance material. Based on this, here, nitrogen-doped activated carbon(NAC) was prepared by pyrolyzing the blend of activated carbon powder(ACP) and melamine for the positive electrode of asymmetric CDI. By comparing the indicators changes such as conductivity, salt adsorption capacity, pH, and charge efficiency of the symmetrical ACP-ACP device to the asymmetric ACP-NAC device under different CDI cycles, as well as the changes of the electrochemical properties of anode and cathode materials after long-term operation, the reasons for the decline of the stability of the CDI performance were revealed. It was found that the carboxyl functional groups generated by the electro-oxidation of anode carbon materials make the anode zero-charge potential(E_(pzc)) shift positively,which results in the uneven distribution of potential windows of CDI units and affects the adsorption capacity. Furthermore, by understanding the electron density on C atoms surrounding the N atoms, we attribute the increased cyclic stability to the enhanced negativity of the charge of carbon atoms adjacent to quaternary-N and pyridinic-oxide-N.

Flexible capacitive pressure sensor based on interdigital electrodes with porous microneedle arrays for physiological signal monitoring

Flexible pressure sensors have many potential applications in the monitoring of physiological signals because of their good biocompatibil-ity and wearability.However,their relatively low sensitivity,linearity,and stability have hindered their large-scale commercial application.Herein,aflexible capacitive pressure sensor based on an interdigital electrode structure with two porous microneedle arrays(MNAs)is pro-posed.The porous substrate that constitutes the MNA is a mixed product of polydimethylsiloxane and NaHCO3.Due to its porous and interdigital structure,the maximum sensitivity(0.07 kPa-1)of a porous MNA-based pressure sensor was found to be seven times higher than that of an imporous MNA pressure sensor,and it was much greater than that of aflat pressure sensor without a porous MNA structure.Finite-element analysis showed that the interdigital MNA structure can greatly increase the strain and improve the sensitivity of the sen-sor.In addition,the porous MNA-based pressure sensor was found to have good stability over 1500 loading cycles as a result of its bilayer parylene-enhanced conductive electrode structure.Most importantly,it was found that the sensor could accurately monitor the motion of afinger,wrist joint,arm,face,abdomen,eye,and Adam’s apple.Furthermore,preliminary semantic recognition was achieved by monitoring the movement of the Adam’s apple.Finally,multiple pressure sensors were integrated into a 33 array to detect a spatial pressure distribu-×tion.Compared to the sensors reported in previous works,the interdigital electrode structure presented in this work improves sensitivity and stability by modifying the electrode layer rather than the dielectric layer.

Customized modulation on plasma uniformity by non-uniform magnetic field in capacitively coupled plasma

A two-dimensional fluid model based on COMSOL Multiphysics is developed to investigate the modulation of static magnetic field on plasma homogeneity in a capacitively coupled plasma(CCP)chamber. To generate a static magnetic field, direct current is applied to a circular coil located at the top of the chamber. By adjusting the magnetic field's configuration, which is done by altering the coil current and position, both the plasma uniformity and density can be significantly modulated. In the absence of the magnetic field, the plasma density exhibits an inhomogeneous distribution characterized by higher values at the plasma edge and lower values at the center. The introduction of a magnetic field generated by coils results in a significant increase in electron density near the coils. Furthermore, an increase in the sets of coils improves the uniformity of the plasma. By flexibly adjusting the positions of the coils and the applied current,a substantial enhancement in overall uniformity can be achieved. These findings demonstrate the feasibility of using this method for achieving uniform plasma densities in industrial applications.

Abnormal transition of the electron energy distribution with excitation of the second harmonic in low-pressure radio-frequency capacitively coupled plasmas

The self-excited second harmonic in radio-frequency capacitively coupled plasma was significantly enhanced by adjusting the external variable capacitor.At a lower pressure of 3 Pa,the excitation of the second harmonic caused an abnormal transition of the electron energy probability function,resulting in abrupt changes in the electron density and temperature.Such changes in the electron energy probability function as well as the electron density and temperature were not observed at the higher pressure of 16 Pa under similar harmonic changes.The phenomena are related to the influence of the second harmonic on stochastic heating,which is determined by both amplitude and the relative phase of the harmonics.The results suggest that the self-excited high-order harmonics must be considered in practical applications of lowpressure radio-frequency capacitively coupled plasmas.

Effect of a negative DC bias on a capacitively coupled Ar plasma operated at different radiofrequency voltages and gas pressures

The effect of a negative DC bias,|V_(dc)|,on the electrical parameters and discharge mode is investigated experimentally in a radiofrequency(RF)capacitively coupled Ar plasma operated at different RF voltage amplitudes and gas pressures.The electron density is measured using a hairpin probe and the spatio-temporal distribution of the electron-impact excitation rate is determined by phase-resolved optical emission spectroscopy.The electrical parameters are obtained based on the waveforms of the electrode voltage and plasma current measured by a voltage probe and a current probe.It was found that at a low|V_(dc)|,i.e.inα-mode,the electron density and RF current decline with increasing|V_(dc)|;meanwhile,the plasma impedance becomes more capacitive due to a widened sheath.Therefore,RF power deposition is suppressed.When|V_(dc)|exceeds a certain value,the plasma changes toα–γhybrid mode(or the discharge becomes dominated by theγ-mode),manifesting a drastically growing electron density and a moderately increasing RF current.Meanwhile,the plasma impedance becomes more resistive,so RF power deposition is enhanced with|V_(dc)|.We also found that the electrical parameters show similar dependence on|V_(dc)|at different RF voltages,andα–γmode transition occurs at a lower|V_(dc)|at a higher RF voltage.By increasing the pressure,plasma impedance becomes more resistive,so RF power deposition and electron density are enhanced.In particular,theα–γmode transition tends to occur at a lower|V_(dc)|with increase in pressure.

Boosting Capacitive Deionization Performance of Commercial Carbon Fibers Cloth via Structural Regulation Based on Catalytic-Etching Effect

Monolithic carbon electrodes with robust mechanical integrity and porous architecture are highly desired for capacitive deionization but remain challenging.Owing to the excellent mechanical strength and electroconductivity,commercial carbon fibers cloth demonstrates great potential as high-performance electrodes for ions storage.Despite this,its direct application on capacitive deionization is rarely reported in terms of limited pore structure and natural hydrophobicity.Herein,a powerful metal-organic framework-engaged structural regulation strategy is developed to boost the desalination properties of carbon fibers.The obtained porous carbon fibers features hierarchical porous structure and hydrophilic surface providing abundant ions-accessible sites,and continuous graphitized carbon core ensuring rapid electrons transport.The catalytic-etching mechanism involving oxidation of Co and subsequent carbonthermal reduction is proposed and highly relies on annealing temperature and holding time.When directly evaluated as a current collector-free capacitive deionization electrode,the porous carbon fibers demonstrates much superior desalination capability than pristine carbon fibers,and remarkable cyclic stability up to 20 h with negligible degeneration.Particularly,the PCF-1000 showcases the highest areal salt adsorption capacity of 0.037 mg cm^(−2) among carbon microfibers.Moreover,monolithic porous carbon fibers-carbon nanotubes with increased active sites and good structural integrity by in-situ growth of carbon nanotubes are further fabricated to enhance the desalination performance(0.051 mg cm^(−2)).This work demonstrates the great potential of carbon fibers in constructing high-efficient and robust monolithic electrode for capacitive deionization.

Exploration of the Exceptional Capacitive Deionization Performance of CoMn_(2)O_(4) Microspheres Electrode

The“battery type”inorganic electrode has been demonstrated the highly efficient sodium ion intercalation capacity for capacitive deionization.In this work,the CoMn_(2)O_(4)(CMO)microspheres with porous core-shell structure are prepared via co-precipitation and followed by annealing.The effects of annealing temperatures on the morphology,pore structure,valence state,and electrochemical behavior of CMO are explored.As electrode for capacitive deionization,the salt removal capacity and current efficiency of optimized AC||CMO device reaches up to 60.7 mg g^(−1) and 97.6%,respectively,and the capacity retention rate is 74.1%after 50 cycles.Remarkably,both the in-situ X-ray diffraction and ex-situ X-ray diffraction analysis features that the intercalation/de-intercalation of sodium ions are governed by(103)and(221)crystal planes of CMO.Accordingly,the density functional theory calculations realize that the adsorption energies of Na+onto(103)and(221)crystal planes are higher than that of any other crystal planes,manifesting the priorities in adsorption of sodium atoms.Furthermore,the X-ray photoelectron spectra of pristine and post-CMO electrode highlights that the reversible conversion of Mn^(3+)/Mn^(4+)couple is resulted from the intercalation/de-intercalation of Na^(+),while this is irreversible for Co^(3+)/Co^(2+)couple.Beyond that,the CMO electrode has been proven the selectivity removal of Na^(+) over K^(+)and Mg^(2+)in a multi-cation stream.

Nano-single-crystal-constructed submicron MnCO_(3) hollow spindles enabled by solid precursor transition combined Ostwald ripening in situ on graphene toward exceptional interfacial and capacitive lithium storage

Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ardent pursuing on the synthetic approaches of hollow materials.Herein,an intriguing route,combining solid precursor transition and Ostwald ripening(SPTOR),is developed to craft nano single-crystal(SC)-constructed MnCO_(3) submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix(MnCO_(3) SMHSs/rGO).It is noteworthy that the H-bonding interaction between Mn_(3)O_(4) nanoparticles(NPs)and oxygen-containing groups on GO promotes uniform anchoring of Mn_(3)O_(4) NPs on GO,mild reductant ascorbic acid triggers the progressive solid-to-solid transition from Mn_(3)O_(4) NPs to MnCO_(3) submicron solid spindles(SMSSs)in situ on GO,and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO_(3) SMSSs and subsequent recrystallization on surface SCs of MnCO_(3) SMHSs.Remarkably,MnCO_(3) SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g^(-1) at 1000 mAg^(-1),which is 10 times higher than that of MnCO_(3) microspheres/rGO fabricated from a conventional Mn^(2+)salt precursor(202 mAh g^(-1)).The ultrahigh capacity and ultralong lifespan of MnCO_(3) SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability,enabled by the fast ion/electron transfer,large specific surface area,and robust electrode pulverization inhibition efficacy.Moreover,fascinating in-depth lithium storage reactions of MnCO_(3) are observed such as the oxidation of Mn^(2+)in MnCO_(3) to Mn^(3+)in charge process after long-term cycles and the further lithiation of Li_(2)CO_(3) in discharge process.As such,the Carbon Energy.SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.

Capacitive energy storage from single pore to porous electrode identified by frequency response analysis

Rate capability,peak power,and energy density are of vital importance for the capacitive energy storage(CES)of electrochemical energy devices.The frequency response analysis(FRA)is regarded as an efficient tool in studying the CES.In the present work,a bi-scale impedance transmission line model(TLM)is firstly developed for a single pore to a porous electrode.Not only the TLM of the single pore is reparameterized but also the particle packing compactness is defined in the bi-scale.Subsequently,the CES properties are identified by FRA,focused on rate capability vs.characteristic frequency,peak power vs.equivalent series resistance,and energy density vs.low frequency limiting capacitance for a single pore to a porous electrode.Based on these relationships,the CES properties are numerically simulated and theoretically predicted for a single pore to a porous electrode in terms of intra-particle pore length,intra-particle pore diameter,inter-particle pore diameter,electrolyte conductivity,interfacial capacitance&exponent factor,electrode thickness,electrode apparent surface area,and particle packing compactness.Finally,the experimental diagnosis of four supercapacitors(SCs)with different electrode thicknesses is conducted for validating the bi-scale TLM and gaining an insight into the CES properties for a porous electrode to a single pore.The calculating results suggest,to some extent,the inter-particle pore plays a more critical role than the intra-particle pore in the CES properties such as the rate capability and the peak power density for a single pore to a porous electrode.Hence,in order to design a better porous electrode,more attention should be given to the inter-particle pore.

Recent progress in flexible capacitive sensors:Structures and properties

The future intelligent era that will be brought about by 5G technology can be well predicted.For example,the connection between humans and smart wearable devices will become increasingly more intimate.Flexible wearable pressure sensors have received much attention as a part of this process.Nevertheless,there is a lack of complete and detailed discussion on the recent research status of capacitive pressure sensors composed of polymer composites.Therefore,this article will mainly discuss the key concepts,preparation methods and main performance of flexible wearable capacitive sensors.The concept of a processing“toolbox”is used to review the developmental status of the dielectric layer as revealed in highly cited literature from the past five years.The preparation methods are categorized into types of processing:primary and secondary.Using these categories,the preparation methods and structure of the dielectric layer are discussed.Their influence on the final capacitive sensing behavior is also addressed.Recent developments in the electrode layer are also systematically reviewed.Finally,the results of the above discussion are summarized and future development trends are discussed.

Effect of parallel resonance on the electron energy distribution function in a 60 MHz capacitively coupled plasma

In general,as the radio frequency(RF)power increases in a capacitively coupled plasma(CCP),the power transfer efficiency decreases because the resistance of the CCP decreases.In this work,a parallel resonance circuit is applied to improve the power transfer efficiency at high RF power,and the effect of the parallel resonance on the electron energy distribution function(EEDF)is investigated in a 60 MHz CCP.The CCP consists of a power feed line,the electrodes,and plasma.The reactance of the CCP is positive at 60 MHz and acts like an inductive load.A vacuum variable capacitor(VVC)is connected in parallel with the inductive load,and then the parallel resonance between the VVC and the inductive load can be achieved.As the capacitance of the VVC approaches the parallel resonance condition,the equivalent resistance of the parallel circuit is considerably larger than that without the VVC,and the current flowing through the matching network is greatly reduced.Therefore,the power transfer efficiency of the discharge is improved from 76%,70%,and 68%to 81%,77%,and 76%at RF powers of 100 W,150 W,and 200 W,respectively.At parallel resonance conditions,the electron heating in bulk plasma is enhanced,which cannot be achieved without the VVC even at the higher RF powers.This enhancement of electron heating results in the evolution of the shape of the EEDF from a biMaxwellian distribution to a distribution with the smaller temperature difference between high-energy electrons and low-energy electrons.Due to the parallel resonance effect,the electron density increases by approximately 4%,18%,and 21%at RF powers of 100 W,150 W,and 200 W,respectively.

Global simulation of plasma series resonance effect in radio frequency capacitively coupled Ar/O_(2) plasma

Radio frequency capacitively coupled plasmas(RF CCPs)play a pivotal role in various applications in etching and deposition processes on a microscopic scale in semiconductor manufacturing.In the discharge process,the plasma series resonance(PSR)effect is easily observed in electrically asymmetric and geometrically asymmetric discharges,which could largely influence the power absorption,ionization rate,etc.In this work,the PSR effect arising from geometrically and electrically asymmetric discharge in argon-oxygen mixture gas is mainly investigated by using a plasma equivalent circuit model coupled with a global model.At relatively low pressures,as Ar content(α)increases,the inductance of the bulk is weakened,which leads to a more obvious PSR phenomenon and a higher resonance frequency(ω_(psr)).When the Ar content is fixed,varying the pressure and gap distance could also have different effects on the PSR effect.With the increase of the pressure,the PSR frequency shifts towards the higher order,but in the case of much higher pressure,the PSR oscillation would be strongly damped by frequent electron-neutral collisions.With the increase of the gap distance,the PSR frequency becomes lower.In addition,electrically asymmetric waveforms applied to a geometrically asymmetric chamber may weaken or enhance the asymmetry of the discharge and regulate the PSR effect.In this work,the Ar/O_(2) electronegative mixture gas is introduced in a capacitive discharge to study the PSR effect under geometric asymmetry effect and electrical asymmetry effect,which can provide necessary guidance in laboratory research and current applications.

Enhancing surface adhesion of polytetrafluoroethylene induced by two-step in-situ treatment with radiofrequency capacitively coupled Ar/Ar+CH_(4)+NH_(3) plasma

Although some progress in plasma modification of the polytetrafluoroethylene(PTFE) surface has been made recently,its adhesion strength still needs to be further improved.In this work,the surface of a PTFE sample was treated with a two-step in-situ method.Firstly,the PTFE surface was treated with capacitively coupled Ar plasma to improve its mechanical interlocking performance;then,Ar+NH_(3)+CH_(4) plasma was used to deposit an a-CNx:H cross-linking layer on the PTFE surface to improve the molecular bonding ability.After treatment,a high specific surface area of 2.20 and a low F/C ratio of 0.32 were achieved on the PTFE surface.Its surface free energy was increased significantly and its maximum adhesion strength reached77.1 N·10 mm^(-1),which is 56% higher than that of the single-step Ar plasma-treated sample and32% higher than that of the single-step Ar+CH_(4)+NH_(3) plasma-treated sample.

A Novel Capacitive Pressure Sensor

A novel capacitive pressure sensor is presented, whose sensing structure is a solid-state capacitor consisting of three square membranes with Al/SiO2/n-type silicon. It was fabricated using pn junction self-stop etching combined with adhesive bonding,and only three masks were used during the process. Sensors with side lengths of 1000,1200,and 1400μm were fabricated,showing sensitivity of 1.8,2.3, and 3.6fF/hPa over the range of 410～ 1010hPa, respectively. The sensi- tivity of the sensor with a side length of 1500μm is 4. 6fF/hPa,the nonlinearity is 6. 4% ,and the max hysteresis is 3.6%. The results show that permittivity change plays an important part in the capacitance change.

A Novel Capacitive Biaxial Microaccelerometer Based on the Slide-Film Damping Effect

A novel capacitive biaxial microaccelerometer with a highly symmetrical microstructure is developed. The sensor is composed of a single seismic mass, grid strip, supporting beam, joint beam, and damping adjusting combs. The sensing method of changing capacitance area is used in the design,which depresses the requirement of the DRIE process, and de- creases electronic noise by increasing sensing voltage to improve the resolution. The parameters and characteristics of the biaxial microaccelerometer are discussed with the FEM tool ANSYS. The simulated results show that the transverse sensitivity of the sensor is equal to zero. The testing devices based on the slide-film damping effect are fabricated, and the testing quality factor is 514, which shows that the designed structure can improve the resolution and proves the feasibility of the designed process.

Capacitive Microwave MEMS Switch

A novel capacitive microwave MEMS switch with a silicon/metal/dielectric as a membrane is fabricated successfully by bonding and etching-stop process. Its principal, design, and fabricating process are described in detail. A patterned dielectric layer, Ta2O5, with dielectric constant of 24 is reached. Experiment results show this novel structure,where the switch＇s dielectric layer is not prepared on the transmission line, features very low insertion loss. The insertion loss is 0.06dB at 2GHz and lower than 0.5dB in the wider range from De up to 20GHz,especially when the transmission line metal is only 0. 5μm thick.

CAPACITIVE DROP ANALYSER FOR MEASURING PHYSICAL PROPERTIES OF LIQUIDS

A new instrument called capacitive drop analyser (CDA) for measuring the physical properties of liquid is developed.A delivery head with a specialized wetting design was constructed for forming drops.The capacitive transducer uses the delivery head as one of its plates and a cylindrical ring plate.Excellent linearity is achieved by optimising the design,with an accuracy of drop volume measurement of approximately 2 μL.It is suitable for measuring both drops in equilibrium and those in the process of growing.Its capability of real time measurement makes it particularly useful for volatile liquids,in which instance the measurement of drop volume using a flowmeter or a pump is no longer reliable.The CDA can also be used to determine concentration.It is found that concentration curve is linear for aqueous glycerol solutions although not so for aqueous ethanol solution.The CDAs capability of measuring surface tension is also explored and experimental results are presented.

Insights into Enhanced Capacitive Behavior of Carbon Cathode for Lithium Ion Capacitors: The Coupling of Pore Size and Graphitization Engineering

The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.

Capacitive charge storage enables an ultrahigh cathode capacity in aluminum-graphene battery

Aluminum^-graphene battery is promising for its abundant raw materials,high power density,ultralong cycle life and superior safety.However,the development of aluminum^-graphene battery is currently restricted by its insufficient cathode capacity,calling for a newly developed working mechanism.In addition,an irregular constant increase of the cathode capacity was always observed during cycling,but cannot be explained based on the current understanding.Here,we observed an increase of specific capacity by 60%with stable Coulombic efficiency of 98%during 7000 cycles life of Al-graphene batteries employing AlCl3/ET3NHCl electrolyte.We demonstrated this growing cathode capacity is attributed to an increasing contribution of capacitive charge storage during cycling,because a gradually enlarged surface area as capacitive active sites is enabled by the exfoliation of graphitic cathode during the periodic intercalation process.Moreover,the graphene cathode was exfoliated more significantly in AlCl3/ET3NHCl than 1-ethyl-3-methylimidazolium chloride-based electrolyte,which results from the heavier stress on the graphene layers caused by the larger intercalants in AlCl3/ET3NHCl.The common intercalation of cations with AlCl4-clusters was therefore supposed to occur during charging.This new proposed mechanism can offer the new thought for future design on high-capacity cathode of Al-ion battery.

A Three-Stage Operational Amplifier for a Wide Range of Capacitive Loads

This paper presents a three-stage CMOS operational amplifier （opamp） that combines accuracy with stability for a wide range of capacitive loads. A so-called quenching capacitor is added to a multipath nested Miller compensation （MNMC） topology to obtain stability for a wide range of capacitive loads. Theoretical analysis and mathematical formulas are provided to prove the improvement in stability. A prototype of this frequency compen- sation scheme is implemented in a 0.7μm CMOS process. Measurement′s show that the amplifier can drive capaci- tive loads ranging from 100pF to 100/μF with a gain of 90dB and a minimum phase margin of 26°. The amplifier has a unity-gain bandwidth of 1MHz for a 100pF capacitive load. It employs a quenching capacitance of 18pF.