High Energy Density Research Articles

Synergistic coupling of optical field and built-in electric field for lithium-sulfur batteries with high cyclabilities and energy densities

Photo-assisted lithium sulfur batteries (PA-LSBs) provide vital and sustainable protocols for promoting sulfur redox reactions via powerful photoinduced effects. However, precise control of the stepwise adsorption, diffusion and photocatalytic conversion of polysulfides at the surface of photocatalysts is required to accelerate the photo-assisted process. Herein, optical field and built-in electric field synergistically-assisted LSBs are developed with a p-n junction of Co3O4-TiO2 on the carbon cloth, possessing a spontaneously generated built-in electric field and a well-matched energy band structure with sulfur redox reactions. Under light irradiation, the directional migration of soluble polysulfides and the space separation of photogenerated carriers are achieved with the synergistical coupling of the optical field and built-in electric field to precisely regulate the selective deposition of Li2S and inhibit the shuttle effect via an effective photocatalytic-promoted process, leading to a maximum capacity of 1087 mAh g−1 at 2 C and a low capacity attenuation of 0.068% per cycle at 5 C. A high areal capacity of 9.6 mAh cm−2 and a great potential photo-charge process can be realized with light irradiation. Furthermore, the stability of lithium metal anodes is improved accordingly. This work demonstrates a new insight to develop high-performance LSBs with a multifield synergistical coupling protocol.

Improved electro-kinetics of new electrolyte composition for realizing high-performance zinc-bromine redox flow battery

Aqueous Redox Flow Batteries (ARFB) are the most prominent technology for large-scale energy storage applications. The energy density of the ARFBs is mainly determined by the electrolyte components, which highly influence the flow battery performance. In the present work, we acutely investigated the various electrolyte compositions and optimized the best electrolyte for realizing the high performance of Zn-Br2 ARFBs. The electrode kinetics, such as rate constant, exchange current density, conductivity, and diffusion coefficient, were analyzed using electrochemical techniques, cyclic voltammetry, and electrochemical impedance analysis. It was observed that zinc bromide (ZnBr2) + perchloric acid (HClO4) + 1-Ethyl-1-methylmorpholinium bromide (MEM) + N-ethyl-N-methylpyrrolidinium bromide (MEP) and ZnBr2 + zinc chloride (ZnCl2) + MEM + MEP electrolytes showed improved performance, where the redox kinetics of 2Br-/Br2 redox couple is greatly enhanced. The presence of perchloric acid unlocks the capacity of full electro-oxidation of bromide (Br-) to bromine (Br2) as it involves 1e- per Br-, which would be highly beneficial to attain high energy density. Further, Zn-Br2 RFB adopted with optimized electrolyte formulation ZnBr2 + HClO4 + MEM+ MEP shows a better round-trip efficiency and displays a stable long cycling performance over 200 cycles with an energy (EE) and coulombic efficiency (CE) of > 68% and > 92%, respectively.

Measurement of Si pixel sensor alignment for the ALICE ITS detector

Abstract A Large Ion Collider Experiment (ALICE) experiment is one of the four experiments at the Large Hadron Collider (LHC) designed to investigate the status of matter under very high energy densities produced during heavy-ion collisions. The ALICE inner tracking system (ITS) consists of seven concentric cylindrical layers of monolithic silicon pixel sensors known as ALICE pixel detector (ALPIDE). The sensors are used to reconstruct the paths of charged particles generated in the collisions. The sensor alignment of the detector must be adjusted to a high precision standard. The adjustment objective is to obtain a detector that can undertake high-resolution measurements. This paper introduces a method for measuring the reference markers utilized in sensor alignment determination. Markers engraved at the chip corners have been detected using the Hough transform, Canny edge detection, and template matching techniques. The distances between two markers are measured to determine the accuracy of the pixel sensor alignment before and after assembly. The proposed methods exhibit an accuracy exceeding 99% and demonstrate high speed analysis. The average processing times for detecting the circle and cross markers are 105.9 ms/image and 113.8 ms/image, respectively. The sensor alignment of the detector must be adjusted to a high precision standard. However, recent studies have shown deviations of up to 5 μ m above the desired value in the measured sensor position. Such deviations do not represent a major issue, nevertheless it is important to measure them in order to speed-up and make more accurate the recursive track-based alignment procedure used to reconstruct the position of each pixel sensor in the tracking detector. The proposed method offers a promising solution to deliver precise and rapid measurements for a large number of examined objects.

Self‐Supporting Solid Electrolyte Based on Supramolecular Interaction for Stable Li Metal Batteries

AbstractLi metal batteries based on solid polymer electrolytes offer the benefits of high energy density and safety, as well as extended cycling life, making them an excellent candidate for the next‐generation battery system. However, current solid polymer electrolytes still suffer from low ion conductivity and Li+ transfer number, which seriously restricts its practical application. Herein, a self‐supporting composite solid polymer electrolyte was prepared, where phenolic resin rich in hydroxyl groups (BR) and polyethylene oxide (PEO) are mixed evenly and poured onto a cellulose membrane in one step. In such an electrolyte, PEO and BR combine to form intermolecular hydrogen bonds, lowering the crystallinity of PEO and increasing the Li+ transfer number. Lastly, the obtained solid electrolytes exhibited a high ion conductivity (1.1×10−4 S cm−1) and Li+ transfer number (0.53), as well as improved electrochemical window. Consequently, Li || Li symmetrical cells can run stably for more than 700 h at 0.1 mA cm−2/0.25 mAh cm−2. And full cells with LiFePO4 cathode can also demonstrate high discharge capacity of 152.12 mAh g−1 and rate performance. We believe that such a design based on supramolecular interaction offer a new avenue to advanced solid polymer electrolytes.

Competing CO and HCOOH Pathways in CO2 Electroreduction

AbstractHuman activities have significantly contributed to the increase in global carbon emissions, leading to adverse environmental effects such as global warming. Electrochemical reduction of carbon dioxide (CO2RR) presents a promising approach to mitigate carbon emissions. This process not only stores the low energy density renewable energies into high energy density chemical bonds, but also produces a variety of valuable products, including one‐carbon products like HCOOH and CO, as well as multi‐carbon products like CH3CH2OH and C2H4. Among them, HCOOH and CO can be produced with over 90 % selectivity on various catalysts, indicating their potential for large‐scale applications. However, the precise reaction pathways toward CO and HCOOH remain unclear, and the competition between these pathways often leads to low product selectivity. This review offers a comprehensive examination of the latest research on the selective reduction of CO2 to CO and/or HCOOH, focusing on the development of the reaction mechanisms based on theoretical simulations and experimental investigations, and the application of catalysts designed to fine‐tune CO/HCOOH selectivity. Additionally, this review highlights the challenges and prospects for the further development and understanding of selective catalysts for CO and HCOOH production, aiming to provide valuable insights for future studies in this intriguing and significant research field.

Pendant Group Functionalization of Cyclic Olefin for High Temperature and High-Density Energy Storage.

High-temperature flexible polymer dielectrics are critical for high-power-density energy storage and conversion under harsh operating conditions. These types of dielectrics will need to simultaneously possess a high bandgap, dielectric constant and glass transition temperature - a substantial challenge when designing novel dielectric polymers. In this work, by varying halogen substituents of an aromatic pendant hanging off a bicyclic mainchain polymer, a class of high-temperature olefins with adjustable thermal stability are obtained, all with uncompromised large bandgaps. Halogens substitution of the pendant groups at para or ortho position of polyoxanorborneneimides (PONB) imparts it with tunable high glass transition temperature from ∼220 to 245°C, while with also moderate dielectric constant of ∼ 2.8-3.0 and high breakdown strength of ∼625-800MV/m. A high energy density of 7.1 J/cc at 200°C is achieved with p-POClNB, representing the highest reported energy density among all-organic homo-polymer dielectrics. Molecular dynamic simulations and ultrafast infrared spectroscopy were used to probe the free volume element distribution and chain relaxations of the polymers to provide insights to the dielectric thermal properties. An increase in free volume element is observed with the change in the pendant group from fluorine to bromine at the para position; however, a decrease in free volume element is observed as we change the pendant group from fluorine to chlorine at the ortho position because of the steric hindrance. Overall, the dielectric constant and band gap remain stable while the glass transition temperature changes more obviously. Consequently, by proper designing the pendant groups, the thermal stability of PONB can be improved for harsh condition electrification. This article is protected by copyright. All rights reserved.

Iron as recyclable metal fuel: Unraveling oxidation behavior and cyclization effects through thermogravimetric analysis, wide-angle X-ray scattering and Mössbauer spectroscopy.

The carbon-free chemical storage and release of renewable energy is an important task to drastically reduce CO2 emissions. The high specific energy density of iron and its recyclability makes it a promising storage material. Energy release by oxidation with air can be realized by the combustion of micron-sized iron powders in retro-fitted coal fired power plants and in fixed-bed reactors under milder conditions. An experimental parameter study of iron powder oxidation with air was conducted based on thermogravimetric analysis in combination with wide-angle X-ray scattering and Mössbauer spectroscopy. In agreement with literature the oxidation was found to consist of a very fast initial oxidation of the outer particle layer followed by much slower oxidation due to diffusion of iron ions through the Fe2O3/Fe3O4 layer being the ratelimiting step. Scanning electron microscopy analysis of the iron particle before and after oxidation reveal a strong particle morphology transformation. This impact on the reaction was studied by cyclization experiments. Up to 10 oxidation-reduction cycles show that both, oxidation and reduction rates, increase strongly with cycling due to increased porosity.

Aqueous Electrolyte with Weak Hydrogen Bonds for Four-Electron Zinc-Iodine Battery Operates in a Wide Temperature Range.

In the pursuit of high-performance energy storage systems, four-electron zinc-iodine aqueous batteries (4eZIBs) with successive I-/I2/I+ redox couples are appealing for their potential to deliver high energy density and resource abundance. However, the susceptibility of positive valence I+ to hydrolysis and the instability of Zn plating/stripping in conventional aqueous electrolyte pose significant challenges. In response, we introduce polyethylene glycol (PEG 200) as a co-solvent in 2 m ZnCl2 aqueous solution to design a wide temperature electrolyte. Through a comprehensive investigation combining spectroscopic characterizations and theoretical simulations, we elucidate that PEG disrupts the intrinsic strong H-bonds of water by global weak PEG-H2O interaction, which strengthens the O-H covalent bond of water and intensifies the coordination with Zn2+. This synergistic effect substantially reduces water activity to restrain the I+ hydrolysis, facilitating I-/I2/I+ redox kinetics, mitigating I3 - formation, and smoothening Zn deposition. The 4eZIBs in the optimized hybrid electrolyte not only deliver superior cyclability with a low fading rate of 0.0009% per cycle over 20000 cycles and a close-to-unit coulombic efficiency, but also exhibit stable performance in a wide temperature range from 40°C to -40°C. This study offers valuable insights into the rational design of electrolytes for 4eZIBs. This article is protected by copyright. All rights reserved.

A Cu/MnOx Composite with Copper-Doping-Induced Oxygen Vacancies as a Cathode for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries are anticipated to be the next generation of important energy storage devices to replace lithium-ion batteries due to the ongoing use of lithium resources and the safety hazards associated with organic electrolytes in lithium-ion batteries. Manganese-based compounds, including MnOx materials, have prominent places among the many zinc-ion battery cathode materials. Additionally, Cu doping can cause the creation of an oxygen vacancy, which increases the material's internal electric field and enhances cycle stability. MnOx also has great cyclic stability and promotes ion transport. At a current density of 0.2 A g-1, the Cu/MnOx nanocomposite obtained a high specific capacitance of 304.4 mAh g-1. In addition, Cu/MnOx nanocomposites showed A high specific capacity of 198.9 mAh g-1 after 1000 cycles at a current density of 0.5 A g-1. Therefore, Cu/MnOx nanocomposites are expected to be a strong contender for the next generation of zinc-ion battery cathode materials in high energy density storage systems.

Reaction Center Shifting in Partially Fluorinated Electrolytes for Robust Lithium Metal Battery.

The strategic formulation of a compatible electrolyte plays a pivotal role in extending the longevity of lithium-metal batteries (LMBs). Here, we present findings on a partially fluorinated electrolyte distinguished by a subdued solvation affinity towards Li+ ions and a concentrated anion presence within the primary solvation layer. This distinctive solvation arrangement redirects the focal points of reactions from solvent molecules to anions, facilitating the predominant involvement of anions in the creation of a LiF-enriched solid-electrolyte interphase (SEI). Electrochemical assessments showcase effective Li+ transport kinetics, diminished overpotential polarization for Li nucleation, and prolonged cycling durability in Li||Li cells employing the partially fluorinated electrolyte. When tested in Li||NCM811 cells, the designed electrolyte delivers a capacity retention of 89.30% and exhibits a high average Coulombic efficiency of 99.80% over 100 cycles with a charge-potential cut-off of 4.6 V vs. Li/Li+ under the current density of 0.4 C. Furthermore, even at a current density of 1C, the cells maintain 81.90% capacity retention and a high average Coulombic efficiency of 99.40% after 180 cycles. This work underscores the significance of weak-solvation interaction in partially fluorinated electrolytes and highlights the crucial role of solvent structure in enabling the long-term stability and high-energy density of LMBs.

High-Voltage Catholyte for High-Energy-Density Nonaqueous Redox Flow Battery.

Redox flow batteries (RFBs) with high energy densities are essential for efficient and sustainable long-term energy storage on a grid scale. To advance the development of nonaqueous RFBs with high energy densities, a new organic RFB system employing a molecularly engineered tetrathiafulvalene derivative ((PEG3/PerF)-TTF) as a high energy density catholyte was developed.When paired with a lithium metal anode, the two-electron-active (PEG3/PerF)-TTF catholyte produced a cell voltage of 3.56 V for the first reduction and 3.92 V for the second reduction process. In cyclic voltammetry and flow cell tests, the redox chemistry exhibited excellent cycling stability. The Li|(PEG3/PerF)-TTF batteries, with concentrations of 0.1 M and 0.5 M, demonstrated capacity retention rates of ~94% (99.87% per cycle, 97.52% per day) and 90% (99.93% per cycle, 99.16% per day), and the average Coulombic efficiencies of 99.38% and 98.35%, respectively. The flow cell achieved a high power density of 129 mW/cm2. Furthermore, owing to the high redox potential and solubility of (PEG3/PerF)-TTF, the flow cell attained a high operational energy density of 72 Wh/L (100 Wh/L theoretical). A 0.75 M flow cell exhibited an even higher operational energy density of 96 Wh/L (150 Wh/L theoretical).

Chitin-derived hierarchical meso- and microporous carbon enables high-rate sulfur cathode of sodium-sulfur batteries.

Room temperature Na-S batteries are considered as a promising alternative energy storage system because of their abundant material resources and high theoretical energy density. However, the severe polysulfide shuttle effect and slow reaction kinetics hinder their practical application. Herein, a hierarchical meso- and microporous carbon with nitrogen self-doping (NSPC) is prepared using chitin as the carbon precursor and serves as a novel host to confine the sulfur (S⊂NSPC). An optimized structure of NSPC, including abundant graphite nanocrystals, large pore volume of 1.76 cm3 g-1, and large specific surface area of 2073 m2 g-1 is obtained at the carbonization temperature of 1000 °C. These merits contribute to significantly enhanced charge transfer and ion diffusion of the as-prepared S⊂NSPC-1000 cathode, which exhibits the outstanding sodium storage performance, including high reversible capacities of 1207 mAh g-1 at 0.1 C and 891 mAh g-1 at 2 C and stable cycling with a low capacity decay for 400 cycles at 1 C, among other S⊂NSPC cathodes and previously reported cathodes for Na-S batteries. This cathode can also afford stable cycling at a high sulfur loading.

Chemical-based Hydrogen Storage Systems: Recent Developments, Challenges, and Prospectives.

Hydrogen (H2) is being acknowledged as the future energy carrier due to its high energy density and potential to mitigate the intermittency of other renewable energy sources. H2 also ensures a clean, carbon-neutral, and sustainable environment for current and forthcoming generations by contributing to the global missions of decarbonization in the transportation, industrial, and building sectors. Several H2 storage technologies are available and have been employed for its secure and economical transport. The existing H2 storage and transportation technologies like liquid-state, cryogenic, or compressed hydrogen are in use but still suffer from significant challenges regarding successful realization at the commercial level. These factors affect the overall operational cost of technology. Therefore, H2 storage demands novel technologies that are safe for mobility, transportation, long-term storage, and yet it is cost-effective. This review article presents potential opportunities for H2 storage technologies, such as physical and chemical storage. The prime characteristics and requirements of H2 storage are briefly explained. A detailed discussion of chemical-based hydrogen storage systems such as metal hydrides, chemical hydrides (CH3OH, NH3, and HCOOH), and liquid organic hydrogen carriers (LOHCs) is presented. Furthermore, the recent developments and challenges regarding hydrogen storage, their real-world applications, and prospects have also been debated.

Isomer‐Dependent Melting Behavior of Low Molar Mass Azobenzene Derivatives: Observation of a Higher Melting Z‐Isomer

AbstractAzobenzene compounds are putative solar thermal fuels (STF) due to the excellent photostability and structural control of isomerization rates. Azobenzenes, in which both Z‐ and E‐isomers are liquid at room temperature, are promising candidates for STF flow technology. A literature survey of melting points led to the synthesis and isomer separation of ortho‐ and meta‐monosubstituted azobenzenes with fluoro, methyl, ethyl, trifluoromethyl and methoxy substituents and several dimethyl substituted azobenzenes. Four of the compounds are liquid azobenzenes with higher specific energy than literature work with higher molar mass, liquid compounds. Eight of the compounds unexpectedly displayed a higher melting point for the Z‐isomer which is rarely observed. Intermolecular close contacts in the crystal lattice of the Z‐isomer are the main factor responsible for the higher melting temperatures.

Elevating Discharge Voltage of Li₂CO₃-routine Li-CO₂Battery over 2.9 V at an Ultra-wide Temperature Window.

The Li-CO₂ batteries utilizing greenhouse gas CO₂ possess advantages of high energy density and environmental friendliness. However, these batteries following Li₂CO₃-product route typically exhibit low work voltage (<2.5 V) and energy efficiency. Herein, we have demonstrated for the first time that cobalt phthalocyanine (CoPc) as homogeneous catalyst can elevate the work plateau towards 2.98 V, which is higher than its theoretical discharge voltage without changing the Li₂CO₃-product route. This unprecedented discharge voltage is illustrated by mass spectrum and electrochemical analyses that CoPc has powerful adsorption capability with CO₂(-7.484 kJ/mol) and forms discharge intermediate of C₃₃H₁₆CoN₈O₂. Besides high discharge capacity of 18724 mAh/g and robust cyclability over 1600 hours (1000 mAh/gcut-off) at a current density of 100 mA/g, the batteries show high temperature adaptability (-30~80 ⁰C). Our work is paving a promising avenue for the progress of high-efficiency Li-CO₂ batteries.

Monolithic Layered Silicon Composed of a Crystalline-Amorphous Network for Sustainable Lithium-Ion Battery Anodes.

While nanostructural engineering holds promise for improving the stability of high-capacity silicon (Si) anodes in lithium-ion batteries (LIBs), challenges like complex synthesis and the high cost of nano-Si impede its commercial application. In this study, we present a local reduction technique to synthesize micron-scale monolithic layered Si (10-20 μm) with a high tap density of 0.9-1.0 g cm-3 from cost-effective montmorillonite, a natural layered silicate mineral. The created mesoporous structure within each layer, combined with the void spaces between interlayers, effectively mitigates both lateral and vertical expansion throughout repeated lithiation/delithiation cycles. Furthermore, the remaining SiO2 network fortifies the layered structure, preventing it from collapsing during cycling. Half-cell tests reveal a capacity retention of 92% with a reversible capacity of 1130 mAh g-1 over 500 cycles. Moreover, the pouch cell integrated with this Si anode (with a mass loading of 3.0 mg cm-2) and a commercial NCM811 cathode delivers a high energy density of 655 Wh kg-1 (based on the total mass of the cathode and anode) and maintains 82% capacity after 200 cycles. This work demonstrates a cost-efficient and scalable strategy to manufacture high-performance micron Si anodes for the ever-growing demand for high-energy LIBs.

Interfacially Ordered NiCoMoS Nanosheets Arrays on Hierarchical Ti3C2Tx MXene for High-energy-density Fiber-Shaped Supercapacitors with Accelerated Pseudocapacitive Kinetics.

Balancing electrochemical activity and structural reversibility of fibrous electrodes with accelerated Faradaic charge transfer kinetics and pseudocapacitive storage are highly crucial for fiber-shaped supercapacitors (FSCs). Herein, we report novel core-shell hierarchical fibers for high-performance FSCs, in which the ordered NiCoMoS nanosheets arrays are chemically anchored on Ti3C2Tx fiber. Beneficial from architecting stable polymetallic sulfide arrays and conductive networks, the NiCoMoS-Ti3C2Tx fiber maintains fast charge transfer, low diffusion and OH- adsorption barrier, and stabilized multi-electronic reaction kinetics of polymetallic sulfide. Consequently, the NiCoMoS-Ti3C2Tx fiber exhibits a large volumetric capacitance (2472.3 F cm-3) and reversible cycling performance (20,000 cycles). In addition, the solid-state symmetric FSCs deliver a high energy density of 50.6 mWh cm-3 and bending stability, which can significantly power electronic devices and offer sensitive detection for dopamine.

Large-Scale Fabrication of Stable Silicon Anode in Air for Sulfide Solid State Batteries via Ionic-Electronic Dual Conductive Binder.

The construction of a continuous ionic/electronic pathway is critical for Si-based sulfide all-solid-state batteries (ASSBs) with the advantages of high-energy density and high-cycle stability. However, a significant impediment arises from the parasitic reaction occurring between the ionic sulfide solid-state electrolyte and electronic carbon additive, posing a formidable challenge. Additionally, the fabrication of electrodes necessitates stringent operational conditions, further limiting practical applicability. Herein, an ionic-electronic dual conductive binder for the fabrication of robust silicon anode under ambient air conditions in the absence of high-cost and air-sensitive sulfide solid-state electrolyte for ASSBs is reported. This binder incorporates in situ reduced silver nanoparticles into a high-strength polymer rich in ether bonds, establishing a conductive pathway for lithium ions and electrons. With the binder-composited Si anode, the half-cell exhibits a remarkable capacity of 1906.9mAhg-1 and stable cycling for 500 cycles at a current density of 2C (4.4mAcm-2) under a low stack pressure of 5MPa. The full cell using Ni0.9Co0.075Mn0.025O2 (NCM90) exhibits a remark cycling stability within 2000 cycles at 5C (8mAcm-2). This work presents an inspired design of functional binders for large-scale manufacture and mild operation in a low-cost way for Si anodes in ASSBs.

Impact of Potassium in Layered Cobalt Oxide Cathodes on Electrochemical Performance in Sodium‐Ion Batteries

AbstractRechargeable sodium‐ion batteries are promising sustainable energy storage systems, owing to their low cost and high energy density. However, the existing cathode chemistries, particularly layered sodium transition metal oxides, exhibit restricted electrochemical performance, which hinders their extensive applications. To overcome challenges, originating from kinetically limited structural transformations, various cation substitutions are reported in the literature. Especially the partial Na–K replacement is discussed recently, which can increase bulk Na‐diffusivity and suppress undesirable phase transitions. Here, a critical study of potassium doping in different layered materials P3‐K0.5Co0.33Mn0.67O2 and P3‐K0.5Co0.33Mn0.67O2*0.5H2O with redox‐active Co (and Mn), and P2‐Na0.7Co0.8Ti0.2O2 and P2‐K0.1Na0.7Co0.8Ti0.2O2 with Co activity is presented. It is found that the presence of K significantly enhances the moisture sensitivity: P3‐K0.5Co0.33Mn0.67O2*0.5H2O is quickly formed in the air from K0.5Co0.33Mn0.67O2, while Na0.7Co0.8Ti0.2O2 remains stable under the same conditions. In electrochemical Na‐cells, a partial K–Na cation exchange in P3‐K0.5Co0.33Mn0.67O2 and P3‐K0.5Co0.33Mn0.67O2*0.5H2O occurs without applying current. The electrochemical performance of P3‐K0.5Co0.33Mn0.67O2 is slightly increased in comparison to K‐free P2‐Na0.67Co0.33MnO.67O2 from the literature, staying, however, behind the performance of Na0.7Co0.8Ti0.2O2. K0.1Na0.7Co0.8Ti0.2O2 shows weaker rate capability than isostructural Na0.7Co0.8Ti0.2O2, reflecting a negative impact of K on Na‐diffusivity. Therefore, effect of K‐incorporation in layered structures on the battery performance strongly depends on the cathode composition.

High energy storage properties for dielectric composite by asymmetric three-layer films design

Polymer dielectrics are extensively studied for applications in electronics pulsed power systems owing to their excellent processability, high breakdown strength and low energy loss. To synergistically achieve high energy density and high discharge efficiency, we report an asymmetric three-layer all-polymer composite, which consists of a mixture of P(VDF-HFP) and P(St-MMA) as an intermediate layer sandwiched between a linear polymer P(St-MMA) dielectric layer and a nonlinear polymer P(VDF-HFP) dielectric layer. The results of the study showed that a high efficiency of 94.14 % and a high energy discharge density of 14.86 J/cm3 were achieved concurrently. In this case, the linear dielectric layer provides high energy efficiency, and the high energy density is provided by the nonlinear layer dielectric layer. In particular, the middle layer can effectively balance the electric field distribution, which improves the breakdown strength and increases the energy density. The structural design of asymmetric three-layer all-polymer films provides an effective way to realize high-performance dielectric energy storage materials.