Voltage Polarity Research Articles

3D structured lithiophilic current collector with lithiation nucleation overpotential near 0 V for dendrite-free lithium metal anode

The poor lithium affinity of most metal skeletons leads to uneven electric field distribution, resulting in the notorious Li dendrite growth. Herein, a 3D structured Cu mesh@Ag current collector is introduced using a simple chemical plating method to enable dendrite-free Li anode. The high electronic conductivity and matrix pore structure of Cu mesh can alleviate the local current density and provide buffer space for lithium deposition. The lithiophilic Ag can form infinite solid solution with Li while reducing the initial lithiation nucleation overpotential to about 0 V, achieving homogenous Li deposition. As a result, the symmetric cell can maintain a low polarization voltage (20 mV) after cycling at 0.5 mA cm-2 for 1300 h Full cells assembled with LiFePO4 cathode present a long-term cycling stability of 500 cycles at 1C with a capacity retention of 80.3%. This work provides a reliable approach to create stable Li-metal batteries.

Additive Manufacturing of Grid Reservoir-Integrated Anodes for Dendrite-Free, Safe, and Ultra-Low Voltage Zinc-Ion Batteries.

This work reports a novel 3D printed grid reservoir-integrated mesoporous carbon coordinatedsilicon oxycarbide hybrid composite (3DP-MPC-SiOC) to establish the zincophile interphase for controlling the dendrite formation. The customized 3D printed grid patterned structure inhibits Zn dendrite growth and achieves long-term stability with reduced voltage polarization due to homogeneous electric field distribution. The hybrid composite consisting of SiOC interpenetrated within carbon constructs a high zinc nucleation interphase, hence promoting uniform Zn2+ deposition and enhancing ionic diffusion with dendrite-free growth and a reduced nucleation energy barrier. As a result, the 3DP-MPC-SiOC@Zn symmetrical cell affords a highly reversible Zn plating/stripping and dendrite-free structure over 198h with an ultra-low voltage polarization. These inspiring performances endow the 3DP anode with a 3DP-VO cathode as a full battery, which shows a retention capacity of 78.8mAhg-1 (Coulombic efficiency: 94.04%) at 0.1Ag-1 and a large energy density of 41Whkg-1 at a power density of 1.2Wkg-1 (based on the total mass of electrode) after 120 cycles. This newly developed 3D printing of hybrid composite as an electrode is straightforward and scalable and provides a novel concept for realizing dendrite-free and stable rechargeable Zn-ion batteries.

Investigation of Partial Discharge Transformation Characteristics in Polyimide (PI) Insulations under High-Frequency Electric Stress.

This research delves into the primary issue of polyimide (PI) insulation failures in high-frequency power transformers (HFPTs) by scrutinizing partial discharge development under high-frequency electrical stress. This study employs an experimental approach coupled with a plasma simulation model for a ball-sphere electrode structure. The simulation model integrates the particle transport equation, Poisson equation, and complex chemical reactions to ascertain microscopic parameters, including plasma distribution, electric field, electron density, electron temperature, surface, and space charge distribution. The effect of the voltage polarity and electrical energy on the PD process is also discussed. The contact point plays a pivotal role in triggering partial discharges and culminating in the breakdown of PI insulation. Asymmetry phenomena were found between positive and negative half-cycles by analyzing the PD data stage by stage. A significant number of PDs increased at every stage and the PD amplitude was higher during the negative cycle at the initial stage, but in later stages, the PD amplitude was found to be higher in the positive half-cycle, and scanning electron microscopy (SEM) revealed that the maximum damage occurred near the contact point junction. The simulation results show that the plasma initially accumulates the electron density near the contact point junction. Under the action of the electric field, plasma starts traveling at the PI surface outward from the contact point. Before the PD activity, all parameters have higher values in the plasma head. The microscopic parameters reveal maximum values near the contact point junction, during PD activities where significant damage takes place. These parameter distributions exhibit a decreasing trend over time as when the PD activity ends. The model's predictions are consistent with the experimental data. The paper lays the foundation for future research in polymer insulation design under high-frequency electrical stress.

The interaction between filaments in dielectric barrier discharge excited by bipolar/unipolar nanosecond pulse powers

This study investigates the behavior of discharge filaments in dielectric barrier discharges with a focus on the effects of nanosecond pulse voltage polarity. We observed significant repulsion between discharge filaments when the pin electrode was grounded in bipolar nanosecond pulse discharge. The tilt angle of the filaments was directly proportional to the peak current, which is indicative of charge density. When the bare pin electrode acted as an H.V. electrode, the repulsion phenomenon was diminished. Surface charges released through the bare pin electrode instead of accumulated on the dielectric surface accounts for this phenomenon. The study also highlights the impact of bipolar versus unipolar nanosecond pulse powers. The addition of a water resistor (WR) results in a slower falling edge of the pulse voltage and the absence of subsequent reverse discharges. The repulsion between filaments disappears both in pin-to-ground discharge and pin-to-H.V. discharge. The introduction of WR leads to a reduction of the current pulse’s duration and a premature termination of the discharge process, resulting the influence of surface charges on filament positioning negligible. It is hypothesized that the spatial distribution of ions does not exhibit significant repulsion, attributed to their substantial mass and sparse distribution in space.

Low-Power Driving Waveform Design for Improving the Display Effect of Electrophoretic Electronic Paper.

To address the high power consumption associated with image refresh operations in EPDs, this paper proposes a low-power driving waveform that reduces the refresh power of EPDs by lowering the system's peak power. Compared to traditional waveforms, this waveform first activates the particles before erasing them, thus reducing voltage polarity changes. Additionally, it introduces a specific duration of 0 V voltage during the activation phase based on the physical characteristics of the electrophoretic particles to reduce the voltage span. Finally, a particular duration of 0 V voltage is introduced during the erasure phase to minimize the voltage span while ensuring the stability and consistency of the reference gray scale. The experimental results demonstrate that, in standard power tests, the new driving waveform reduces the power fluctuation value by 1.33% and the energy fluctuation value by 37.24% compared to the traditional driving waveform. This reduction in refresh power also mitigates screen flicker and ghosting phenomena.

Hollow nickel sources for improving nickel utilization in Zebra batteries

The Zebra (Na-NiCl2) batteries are regarded as a promising option for large-scale electrical energy storage due to their plentiful electrode material resources, high energy density, and safety features. In the cathode of Zebra battery, the nickel powders serve as both an active material and a conductive agent. In practice, its amount is significantly greater than its theoretical usage, often exceeding three times the theoretical amount. Hence, the presence of ultra-excessive nickel results in high material costs, posing obstacles to the wider implementation of Zebra batteries. To address this problem, we introduce hollow nickel source as active material to improve the nickel utilization in Zebra battery. In this work, we assemble Zebra batteries using nickel hollow spheres (NHS) with sizes of ∼200 nm, ∼500 nm, ∼1 μm and ∼ 5 μm as nickel source. The battery using NHSs with a size of 1 μm exhibits the best cycling performance and the lowest polarization voltage. By reducing the Ni(NHS, ∼1 μm)/NaCl mass ratio to 1.0, 60% theoretical capacity can be achieved after 170 cycles at 260 °C, which surpasses the traditional batteries using solid nickel source at the same Ni/NaCl ratio. This performance is comparable to that of traditional solid nickel sources with a mass ratio of 1.5 to NaCl. Therefore, using NHS as the nickel source in Zebra batteries reduces nickel usage by 33% without compromising performance.

Study on the Relationship between Electron Transfer and Electrical Properties of XLPE/Modification SR under Polarity Reversal.

The insulation of high-voltage direct-current (HVDC) cables experiences a short period of voltage polarity reversal when the power flow is adjusted, leading to sever field distortion in this situation. Consequently, improving the insulation performance of the composite insulation structure in these cables has become an urgent challenge. In this paper, SiC-SR (silicone rubber) and TiO2-SR nanocomposites were chosen for fabricating HVDC cable accessories. These nanocomposites were prepared using the solution blending method, and an electro-acoustic pulse (PEA) space charge test platform was established to explore the electron transfer mechanism. The space charge characteristics and field strength distribution of a double-layer dielectric composed of cross-linked polyethylene (XLPE) and nano-composite SR at different concentrations were studied during voltage polarity reversal. Additionally, a self-built breakdown platform for flake samples was established to explore the effect of the nanoparticle doping concentration on the breakdown field strength of double-layer composite media under polarity reversal. Therefore, a correlation was established between the micro electron transfer process and the macro electrical properties of polymers (XLPE/SR). The results show that optimal concentrations of nano-SiC and TiO2 particles introduce deep traps in the SR matrix, significantly inhibiting charge accumulation and electric field distortion at the interface, thereby effectively improving the dielectric strength of the double-layer polymers (XLPE/SR).

Development of Reconfigurable High-Frequency Devices Using Liquid Crystal in Substrate-Integrated Gap Waveguide Technology

This article presents the theoretical study, numerical simulation and fabrication of a phase shifter and a stub resonator for use in microstrip ridge gap waveguide (MRGW) technology, using a liquid crystal (LC) in the substrate as a reconfigurable material. The phase shifter and the stub resonator are filled with LC, and thanks to the LC’s dielectric anisotropy properties, the phase shift and the resonance response can be easily controlled using an external electric or magnetic bias field. The phase shifter was designed to operate in the range of 10 to 20 GHz, and the resonator was designed to operate in the range of 7.8 to 8.8 GHz. The phase shifter’s responses (including both phase shift and insertion losses), associated with both the parallel and perpendicular permittivity values of the LC, were computed and measured, and then the corresponding figure of merit (FoM) was extracted. The resonator’s frequency responses, associated with both the LC’s parallel and perpendicular permittivity, were computed. The resonator’s frequency responses, which provided different polarization voltages, were measured and compared to the simulation results. All technological issues related to both prototypes are also discussed here. The good agreement between the simulation and measurement results confirm this technology as a viable approach to the practical implementation of these microwave reconfigurable devices.

The development and evaluation of a parameter-free circuit-based model of bipolar membrane electrodialysis for process design and optimisation

Bipolar membrane electrodialysis (BPMED) is an emerging electromembrane technology which has the potential to replace existing pH manipulation process units among others and take advantage of the benefits posed by process electrification. The development of robust and flexible process models of BPMED for design and optimisation is paramount in derisking potential instillations and improving commercial viability. Herein, a circuit-based model of BPMED is presented which avoids reliance on empirical fitting parameters and training data. The resulting model is flexible enough that extension to account for added complexities may be readily adopted. The mass transfer and electrical resistance of six different domains (three membranes and three streams) were computed by applying fundamental laws such as Ohm’s law and Faraday’s first law. Acid-base reactions and their effect releasing current within the membranes were also considered. Furthermore, the stack model can be readily embedded in a broader process model. To this end, the stack model is applied to a recirculating-batch experiment using a delayed differential material balance to account for dead-time within the tubing and measurement flow-cells. Two orthogonal methods of experimental validation were conducted to assess the performance of the model over a range of concentrations and applied voltages. These involved running a recirculating-batch experiment and collecting current–voltage polarisation data, respectively, and both showed good agreement with the model predictions. Overall, a robust model of BPMED has been produced which is able to accurately predict system performance and will prove useful for the design and optimisation of industrial systems.

Quasi-Gel Polymer Electrolyte Interfaced with Electrodes through Solvent-Swollen Poly(ethylene oxide) for High-Performance Lithium/Lithium-Ion Batteries.

Solid polymer electrolytes (SPEs) are regarded as a superior alternative to traditional liquid electrolytes of lithium-ion batteries (LIBs) due to their improved safety features. The practical implementation of SPEs faces challenges, such as low ionic conductivity at room temperature (RT) and inadequate interfacial contact, leading to high interfacial resistance across the electrode and electrolyte interfaces. In this study, we addressed these issues by designing a quasi-gel polymer electrolyte (QGPE), a blend of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide) (PEO), and succinonitrile (SN), with the desired mechanical strength, ionic conductivity, and interfacial stability through a simple solution casting technique. The QGPE features a thin solvated PEO layer on its surface, which wets the electrode, reducing the interfacial resistance and ensuring a homogeneous Li-ion flux across the interface. The optimized QGPE exhibits a good lithium-ion conductivity of 1.14 × 10-3 S cm-1 with a superior lithium-ion transference number of 0.7 at 25 °C. The Li/QGPE/Li symmetric cell exhibits a highly reversible lithium plating/stripping process for over 1300 h with minimal voltage polarization of ∼20 mV. The Li/QGPE/LiFePO4 full cell demonstrates good rate capability and excellent long-term cycling performance at a 0.1 C rate at 25 °C, maintaining a specific discharge capacity of 148 mAh g-1 over 200 cycles. The effectiveness of QGPE for LIBs is proven using a graphite/QGPE/LiFePO4 4 × 4 cm pouch cell, showcasing outstanding flexibility and tolerance against intentional abuse.

Percolative Metal Microweb-Based Flexible Lithium-Ion Battery with Fast Charging and High Energy Density.

Flexible and high-performance lithium-ion batteries (LIBs) encounter challenges due to the inherent trade-offs in conventional electrode designs, particularly concerning mechanical flexibility and high energy density. Here, a novel percolative metal microweb-based electrode, fabricated via electrohydrodynamic processes, yielding a three-dimensional (3D) network structure with exceptional electrical properties and mechanical durability is introduced. This lightweight electrode design addresses the need for improved energy density by reducing the weight of the current collector, which typically accounts for more than 10% of the battery's weight. The 3D architecture of the electrode enhances the contact area with the electrolyte, thereby minimizing polarization voltage and improving lithium-ion diffusion. Furthermore, the low coating thickness-to-weight ratio promotes electron transfer and mitigates capacity fade at high current densities. The microweb-based full cell exhibits energy and power densities of 110 and 1,048Wkg⁻¹ at 10 C, respectively, which are the highest reported values among LIBs utilizing similar materials. The design of the electrode proposed in this study is expected to significantly contribute to the development of wearable and flexible electronics.

Iodine-induced self-depassivation strategy to improve reversible kinetics in Na-Cl2 battery

Rechargeable sodium-chlorine (Na-Cl2) batteries show high theoretical specific energy density and excellent adaptability for extreme environmental applications. However, the reported cycle life is mostly less than 500 cycles, and the understanding of battery failure mechanisms is quite limited. In this work, we demonstrate that the substantially increased voltage polarization plays a critical role in the battery failure. Typically, the passivation on the porous cathode caused by the deposition of insulated sodium chloride (NaCl) is a crucial factor, significantly influencing the three-phase chlorine (NaCl/Na+, Cl-/Cl2) conversion kinetics. Here, a self-depassivation strategy enabled by iodine anion (I-)-tuned NaCl deposition was implemented to enhance the chlorine reversibility. The nucleation and growth of NaCl crystals are well balanced through strong coordination of the NaI deposition-dissolution process, achieving depassivation on the cathode and improving the reoxidation efficiency of solid NaCl. Consequently, the resultant Na-Cl2 battery delivers a super-long cycle life up to 2000 cycles.

PGM-Free Oxygen Evolution Reaction Catalyst for PEM Water Electrolysis – a Mechanistic Study on Activity and Durability for Practical Applications

Low temperature proton exchange membrane water electrolyzer (PEMWE) represents a critical technology for green hydrogen production. It offers the advantages of significantly higher current density and higher H2 purity, rendering it a preferred technology when high energy efficiency and low footprint are essential. Working in the oxidative and acidic environment under high polarization voltage, however, adds substantial demand to the electrode catalyst and the support. This is particularly the case at anode where the oxygen evolution reaction (OER) takes place. At present, the platinum group metal (PGM) materials such as Ir black or Ir oxide are catalysts of choice. Their high cost and limited reserve add a significant cost barrier to PEM electrolyzer, which contributes to the overall expense of hydrogen production next only to the cost of electricity. Replacing Ir with earth-abundant transition metal oxides could help to reduce the electrolyzer system cost.For PEMWE application, a PGM-free anodic catalyst must be highly active to match the performance of Ir. Furthermore, it must be stable against oxidative acid corrosion. At Argonne National Laboratory, we recently developed a new PGM-free OER of a nanofibrous cobalt spinel catalyst co-doped with lanthanum and manganese (LMCF). [1] The catalyst was synthesized from the precursor of cobalt zeolitic methyl-imidazolate framework (Co-ZIF) doped with manganese and lanthanum. The Co-ZIF was mixed with a polymer solution and electrospun into nanofiber before being converted to fibrous cobalt spinel under low temperature oxidation to remove all the organics and carbon. The new PGM-free catalyst demonstrated a low overpotential of 353 mV (RHE) at 10 mA/cm2 and a low OER degradation over 360 hours in acidic electrolyte. A PEMWE containing this catalyst at its anode at ~2.0 mg/cm2 demonstrated a current density of 2000 mA/cm2 at 2.47 volts (Nafion® 115 membrane) or 4000 mA/cm2 at 3.00 volt (Nafion® 212 membrane). The membrane electrode was also subjected to accelerated-stress-test (AST) in both voltage cycling and galvanostatic run at different current densities. Low degradation rates under both ASTs were observed.In addition to catalyst design and synthesis, we also conducted extensive structural characterizations, stability measurement, as well as computational modeling. Our in situ study found that the OER process involves significant lattice oxygen movement, leading to lowering instead of raising the cobalt oxidation state during the electrolysis. The measurement of the stability number, combined with computational Pourbaix diagram, elucidated the importance of the operating potential in reducing catalyst dissolution. These findings offer in-depth understanding and direction of future development for PGM-free OER catalyst in PEM water electrolyzer. Acknowledgement: This work is supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewal Energy, Hydrogen and Fuel Cell Technologies Office, and by Laboratory Directed Research and Development funding of Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DEAC02-06CH11357. Work performed at the Center for Nanoscale Materials and Advanced Photon Source, both U.S. Department of Energy Office of Science User Facilities, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.[1] “La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis” Lina Chong, Guoping Gao, Jianguo Wen, Haixia Li, Haiping Xu, Zach Green, Joshua D. Sugar, A. Jeremy Kropf, Wenqian Xu, Xiao-Min Lin, Hui Xu, Lin-Wang Wang, Di-Jia Liu, Science 380, 609–616 (2023)

A 3D conducting scaffold with lithiophilic carbon nanoparticles for stable lithium metal battery anodes

Li metal anode with high capacity, negative potential and low density is regarded as the most promising anode material. Unfortunately, its commercialization is greatly limited by Li dendrites. Here, a 3D carbon paper scaffold with lithiophilic carbon nanoparticles is synthesized as a Li host via the carbonization of metal-organic framework and the doping of oxygen atom. Carbon nanoparticles effectively improve the specific surface area of carbon paper that can low the local current density and provide rich internal spaces for Li reservoir. In addition, the rich lithiophilic groups (such as ZnO, nitrogen atom and oxygen atom) can regulate a uniform Li+ flux and achieve a controllable Li deposition. Based on these structural advantages, uniform nucleation and growth of Li metal have been realized. Especially, the symmetric cell renders an outstanding cyclic stability for 750 h with an ultra-low polarization voltage of 14 mV at 1 mA/cm2. Additionally, the full cell partied with a LiFePO4 cathode displays an initial specific capacity of 138.1 mAh/g, and even maintains 97.7 % capacity retention after 120 cycles at 0.5C. Therefore, this strategy presents a universal approach to construct porous hosts with abundant lithiophilic sites for long-lifespan Li metal batteries.

Supramolecular Metal-Organic Framework for the High Stability of Aqueous Rechargeable Zinc Batteries.

Aqueous rechargeable Zn batteries (AZBs) are considered to be promising next-generation battery systems. However, the growth of Zn dendrites and water-induced side reactions have hindered their practical application, especially with regard to long-term cyclability. To address these challenges, we introduce a supramolecular metal-organic framework (SMOF) coating layer using an α-cyclodextrin-based MOF (α-CD-MOF-K) and a polymeric binder. The plate-like α-CD-MOF-K particles, combined with the polymeric binder create dense and homogeneous Zn2+ ion conductive pore channels that can vertically transport Zn2+ ions through the cavity while restricting the contact of water molecules. Molecular dynamics (MD) simulation verifies that Zn2+ ions can reversibly migrate through the pores of α-CD-MOF-K by partial dehydration. The uniform Zn deposition/dissolution promotes a smooth solid-electrolyte interface layer on the Zn metal anode and effectively suppresses side reactions with free water molecules. The α-CD-MOF-K@Zn symmetric cell exhibits stable cycling and a small polarization voltage of 70 mV for 800 h at 5 mA cm-2, and the α-CD-MOF-K@Zn|α-MnO2 full cell shows only 0.12% capacity decay per cycle at a rate of 1 A g-1.

Diffusion of Carbon Quantum Dots on Lithium Liquid Metal for Artificial SEI

AbstractThe unstable solid electrolyte interface (SEI) formed on the surface of Li metal can induce dendrite growth, resulting in capacity fading, battery short circuit, and other problems, thus hindering the practical application of Li metal battery. In order to obtain stable and effective SEI, it is an effective strategy to construct an ideal artificial SEI (ASEI) by regulating the composition and structure of the interface. Among the inorganic materials used in the construction of ASEI, carbon quantum dots (CQDs) stand out as promising material due to their small size and abundant active sites. Herein, benefiting from the fluidity, surface smoothness, and high reactivity of liquid metal, combined with the use of N‐doped CQDs as dispersing particles, a surface modification method to achieve uniform dispersion of particles within the liquid metal is proposed. This technique offers a low‐cost solution for achieving uniform dispersion of little quantities of N‐doped CQDs (single dose < 0.1 mg cm−2) while ensuring enhanced interface adhesion to realize the construction of dense, strong and uniform ASEI. The corresponding symmetrical cells show lower voltage polarization and outstanding cycling stability than the bare Li electrode.

Studying of Filamentation Mechanism for Nanosecond Surface Dielectric Barrier Discharge. Part 1. Local Field Approximation

The goal of this work is to check numerically whether or not the previously proposed mechanism for surface barrier discharge filamentation in nitrogen in the case of positive polarity nanosecond voltage pulse is applicable for similar process in nitrogen and air in the case of negative voltage polarity pulse. The results have shown, that in this case some signs of successful filamentation modeling are present both in nitrogen and air, but the whole dynamics of discharge development is qualitatively different from that one observed in experiment. It is assumed, that the failure of simulation is due to the usage of local field approximation, which is too rough inside a region with steep electron density gradient relevant to filamentation zone.

Effect of the repetition frequency and polarity of square wave voltage on the partial discharge of electric machine insulation for more electrical aircraft

Effect of the repetition frequency and polarity of square wave voltage on the partial discharge of electric machine insulation for more electrical aircraft

Electron-phonon interaction, magnetic phase transition, charge density waves, and resistive switching in VS2 and VSe2 revealed by Yanson point-contact spectroscopy

VS2 and VSe2 have attracted particular attention among the transition metals dichalcogenides because of their promising physical properties concerning magnetic ordering, charge density wave (CDW), emergent superconductivity, etc., which are very sensitive to stoichiometry and dimensionality reduction. Yanson point-contact (PC) spectroscopic study reveals metallic and nonmetallic states in VS2 PCs, as well as a magnetic phase transition, was detected near 20 K. The rare PC spectra, where the magnetic phase transition was not visible, show a broad maximum of around 20 mV, likely connected with electron-phonon interaction (EPI). The PC spectra of VSe2 demonstrate metallic behavior, which allowed us to detect features associated with EPI and CDW transition. The Kondo effect appeared for both compounds, apparently due to interlayer vanadium ions. Besides, the resistive switching was observed in PCs on VSe2 between a low resistive, mainly metallic-type state, and a high resistive nonmetallic-type state by applying bias voltage (about 0.4 V). Reverse switching occurs by applying a voltage of opposite polarity (about 0.4 V). The reason may be the alteration of stoichiometry in the PC core due to the displacement of V ions to interlayer under a high electric field. The observed resistive switching characterizes VSe2 as a potential material, e.g., for non-volatile resistive RAM, neuromorphic engineering, and other nanoelectronic applications. Per contra, VS2 attracts attention as a rare layered van der Waals compound with magnetic transition.

Self‐Selective Crossbar Synapse Array with n‐ZnO/p‐NiOx/n‐ZnO Structure for Neuromorphic Computing

AbstractArtificial synapse devices are essential elements for highly energy‐efficient neuromorphic computing. They are implemented as crossbar array architecture, where highly selective synaptic weight updates for training and sneak leakage‐free inference operations are required. In this study, self‐selective bipolar artificial synapse device is proposed with n‐ZnO/p‐NiOx/n‐ZnO heterojunction, and its analog synapse operation with high selectivity is demonstrated in 32 × 32 crossbar array architecture without the aid of selector devices. The built‐in potential barrier at p‐NiOx/n‐ZnO junction and the Zener tunneling effect provided nonlinear current–voltage characteristics at both voltage polarities for self‐selecting function for synaptic potentiation and depression operations. Voltage‐driven redistribution of oxygen ions inside n–p–n oxide structure, evidenced by x‐ray photoelectron spectroscopy, modulated the distribution of oxygen vacancies in the layers and consequent conductance in an analog manner for the synaptic weight update operation. It demonstrates that the proposed n–p–n oxide device is a promising artificial synapse device implementing self‐selectivity and analog synaptic weight update in a crossbar array architecture for neuromorphic computing.