High Energy Density Capacitors Research Articles

Current development, optimisation strategies and future perspectives for lead-free dielectric ceramics in high field and high energy density capacitors.

To meet the United Nations' sustainable development goal of affordable and clean energy, there has been a growing need for low-cost, green, and safe energy storage technologies. High-field and energy-density capacitors have gained substantial attention from academics and industry, particularly for power electronics, where they will play a key role in optimising the performance of management systems in electric vehicles. The key figure of merit, energy density (Wrec), for high-field applications has dramatically increased year-on-year from 2020 to 2024, as evidenced by over 250 papers, demonstrating ever larger Wrec values. This review briefly introduces the background and principles of high energy density ceramics, but its focus is to provide constructive and comprehensive insight into the evaluation of Wrec, Emax, ΔP, and η, and more importantly, the normalised metrics, Wrec/Emax and Wrec/ΔP in lead-free dielectric ceramics. We also present several optimisation strategies for materials modification and process innovation that have been recently proposed before providing perspectives for the further development of high-field and high-energy density capacitors.

Tailored multilayered films of the PVDF/Ba0.8Sr0.2TiO3 nanocomposites with surface-modified nanoparticles for superior dielectric and energy storage performance

The multilayer thick film (∼40 μm) of polyvinylidene fluoride-Ba0.8Sr0.2TiO3 (PVDF-BST) have been synthesized by a tape-casting technique. The incorporated BST nanoparticles in the PVDF matrix are functionalized by −PO4−3and −OH−group, which are abbreviated as PBST-P and PBST-H multilayer films. The nature of the functional group attached with the BST nanoparticles is found to strongly influence the dielectric properties, breakdown strength and energy storage behavior of the multilayer films. The dielectric constant (at 1 kHz) of PBST-P multilayer film shows a significant increase (∼30) as compared to PBST-H film (∼22), whereas the tangent loss remains the same. The breakdown strength of PBST-P multilayer film is also high (∼381 MV/m) as compared to the PBST-H film (∼318 MV/m). PBST-P film also possesses high discharge energy density (∼7.97 J/cc at 1800 kV) and ultrahigh energy efficiency (∼98 %). Enhanced dielectric and energy storage properties of PBST-P film is attributed to the strong bridging interaction between the PVDF matrix and BST-P nanofiller, which creates additional dipoles and a strong local electric field at the interfaces. The study may lead towards the novel ways of developing polymer-ceramic nanocomposites for high-energy density capacitors, where the incorporation of functionalized nanoparticles in the polymer matrix is accompanied by the architectured structure.

Ultrahigh Energy Storage Performance of BiFeO3-BaTiO3 Flexible Film Capacitor with High-Temperature Stability via Defect Design.

Nanoengineering polar oxide films have attracted great attention in energy storage due to their high energy density. However, most of them are deposited on thick and rigid substrates, which is not conducive to the integration of capacitors and applications in flexible electronics. Here, an alternative strategy using van der Waals epitaxial oxide dielectrics on ultra-thin flexible mica substrates is developed and increased the disorder within the system through high laser flux. The introduction of defects can efficiently weaken or destroy the long-range ferroelectric ordering, ultimately leading to the emergence of a large numbers of weak-coupling regions. Such polarization configuration ensures fast polarization response and significantly improves energy storage characteristics. A flexible BiFeO3-BaTiO3 (BF-BT) capacitor exhibits a total energy density of 43.5 J cm-3 and an efficiency of 66.7% and maintains good energy storage performance over a wide temperature range (20-200 °C) and under large bending deformation (bending radii ≈ 2mm). This study provides a feasible approach to improve the energy storage characteristics of dielectric oxide films and paves the way for their practical application in high-energy density capacitors.

Enhanced energy density in cellulose doped polyimide-based all organic composites for high temperature capacitor applications

Abstract The growing demand for electronic devices has induced a significant requirement for high energy density capacitors. In this investigation, we introduced small groups of cyanoethyl cellulose (CEC) into a polyimide (PI) substrate to create all organic CEC/PI composite films for high energy density capacitor applications. Due to the large dipole moment in C–CN dipoles in CEC groups, the dielectric constant of the CEC/PI-5 (5% CEC) composite increased by 26.3% to 4.31. Compared to the pristine PI film at room temperature, the breakdown field of the CEC/PI-0.5 increased by 4.7% from 502.29 to 526.1 MV m−1 and the energy storage density increased by 95% to 11.70 J cm−3. Furthermore, the CEC/PI-0.5 film exhibited an energy density of 6.39 J cm−3 with the breakdown field of 400 MV m−1 at 150 °C, which is 93.05% higher in energy densities than that of the pristine PI film. Furthermore, simulation results indicate that CEC groups can introduce deep traps in the CEC/PI composite, which can inhibit charge movement in the composite and increase the breakdown field of it. In this study, it was found that by adding small amount of CEC polar group in PI film, the high temperature energy density of CEC/PI composite materials was significantly improved. This study not only makes a significant contribution to the development of high-temperature energy-density capacitors, but also pave a way by using small molecule polar polymers to improve the energy density of dielectric materials at high temperature.

High-energy density cellulose nanofibre supercapacitors enabled by pseudo-solid water molecules

Compared with conventional electrochemical supercapacitors and lithium-ion batteries, the novel amorphous cellulose nanofibre (ACF) supercapacitor demonstrates superior electric storage capacity with a high-power density, owing to its fast-charging capability and high-voltage performance. This study unveils introduces an ACF supercapacitor characterised by a substantial energy density. This is achieved by integrating a singular layer of pseudo-solid water molecules (electrical resistivity of 1.11 × 108 Ω cm) with cellulose nanofibers (CNFs), establishing forming an electric double layer at the electrode interface. The enhanced energy storage in these high-energy density capacitors (8.55 J/m2) is explicated through the polarisation of protons and lone pair electrons on oxygen atoms during water electrolysis, commencing at 1.23 V. Improvements in energy density are attainable through CNF density enhancements and charging-current optimisation. The proposed ACF supercapacitor offers substantial promise for integration into the power sources of flexible and renewable paper-based electronic devices.

High Energy Density in All-Organic Polyimide-Based Composite Film by Doping of Polyvinylidene Fluoride-Based Relaxor Ferroelectrics.

Recently, due to the advantages of superior compatibility, fewer interface defects, and a high electric breakdown field, all-organic dielectric composites have attracted significant research interest. In this investigation, we produced all-organic P(VDF-TrFE-CFE) terpolymer/PI (terp/PI) composite films by incorporating a small amount of terpolymer into PI substrates for high energy density capacitor applications. The resulting terp/PI-5 (5% terpolymer) composite films exhibit a permittivity of 3.81 at 1 kHz, which is 18.7% greater than that of pristine PI (3.21). Furthermore, the terp/PI-5 film exhibited the highest energy density (9.67 J/cm3) and a relatively high charge-discharge efficiency (84.7%) among the terp/PI composite films. The energy density of the terp/PI-5 film was increased by 59.8% compared to that of the pristine PI film. The TSDC results and band structure analysis revealed the presence of deeper traps in the terp/PI composites, contributing to the suppression of leakage current and improved charge-discharge efficiency. Furthermore, durability tests confirm the stability of the composite films under extended high-temperature exposure and cycling, establishing their viability for practical applications.

Ultrahigh efficiency and enhanced discharge energy density at low loading of nanofiller in trilayered polyvinylidene fluoride‐Ba0.8Sr0.2TiO3 nanocomposites

AbstractPoly(vinylidene)fluoride‐Ba0.8Sr0.2TiO3 (PVDF‐BST) trilayered nanocomposites (with different vol% loading of BST nanoparticles, i.e. 0.75%, 1.50%, 2.25% and 3.00%) has been processed by the tape casting technique. The upper and lower layers of the nanocomposites are casted in the same direction, whereas the middle layer is casted in the opposite direction. The trilayered PVDF‐BST nanocomposite consisting of 3.00 vol% of BST nanoparticles exhibited high dielectric permittivity (~25), low tangent loss (~0.03) and moderately high breakdown strength (BDS ~282 MV/m). Moreover, it also possesses a high discharge energy density (~7.8 J/cc at 1400 kV/cm) and efficiency (~93%). A mechanism for the excellent energy storage behavior and dielectric properties has been proposed. Where, moderately high BDS and low tangent loss are associated with the spatial distribution of the local electric field at interlayer interfaces of PVDF‐BST trilayered nanocomposites, which restricts the conduction of charge carriers at high electric field. The ultrahigh efficiency and enhanced discharge energy density is attributed to the formation of interfacial dipoles at various interfaces such as interlayer, intralayer (PVDF/PVDF), and PVDF/BST interfaces. These investigations would be adopted as a futuristic strategy for developing excellently efficient polymer‐ceramic nanocomposites for the high energy density capacitors used in pulsed power applications.Highlights PVDF‐BST trilayered nanocomposites exhibit high ε′ ~25 and low tanδ ~0.03. Nanocomposite shows ultra‐high energy efficiency ~93% and enhanced UD ~ 7.8 J/cc. Mechanism for the excellent energy storage and dielectric properties Relies on the interfacial dipoles and distribution of the local electric field.

Local heterogeneities and order-disorder: An approach to tailor BaTi1-xZrxO3 ceramics properties

Zirconium-doped Barium Titanate with the formula, BaTi1-xZrxO3 (BZT) for 0 ≤ x ≤ 0.08 had been prepared by the modified solid-state reaction route. X-ray diffraction patterns (XRD) and structural refinement showed the formation of single and double phases for pure and Zr-substituted barium titanate, respectively. Pure barium titanate (BT) was found in the tetragonal phase. BZT-3 and BZT-5 had a mixture of tetragonal and orthorhombic phases. A mixture of orthorhombic and rhombohedral phases was present in BZT-8. The Raman analysis confirmed the existence of two oxygen octahedra of Ti and Zr for Zr-doped BT. The FESEM micrograph exhibited an increase in average grain size with Zr content. The temperature-dependent dielectric studies showed single-phase transitions for BT, two-phase transitions for BZT-3 and BZT-5, and three-phase transitions for BZT-8. XPS analysis confirmed the presence of undercoordinated Ti3+ions. The maximum dielectric constant of 5731 was obtained for BZT-3, which decreased linearly afterward. The maximum remanent polarization = 8.287 μC/cm2 was found for BZT-3. The energy storage efficiency ≥ 50.10 % makes all the compositions suitable for high energy density capacitors. Due to the presence of 90.63 % of the orthorhombic phase in BZT-5, the highest d33 = 164 pC/N was obtained. The UV–visible spectroscopy showed the signature of p-d and d-d transitions present in the ceramics due to disordering. The direct optical bandgap increased with the rise in Zr content.

Nanoparticle-Polymer Surface Functionalizations for Capacitive Energy Storage: Experimental Comparison to First Principles Simulations.

Dielectric capacitors present many advantages for large-scale energy storage, but they presently require higher energy density. We demonstrate novel high energy density polymer-nanoparticle composite capacitors utilizing thiol-ene click chemistry surface groups to bond the nanoparticles covalently to the polymer matrix. Interfacial effects in composites cannot be observed directly, and in our previous work, we examined the nanoparticle-polymer interface in silico. In this work, we experimentally examine the five surface functionalizations modeled previously, fabricating high energy density thin film capacitors to test our predictions. Results from this study, in conjunction with properties previously determined in silico, further improve the understanding of the role of surface functionalizations in composites prepared using click chemistry. The coating density of the surface functionalizations is shown to be a key factor in relating our computational results to experimental results. We show how using both coating density and our previous modeling in combination allows for prescreening of surface functionalizations for future composites, reducing experimental cost. We also demonstrate high energy density capacitors with ~20 J/cm3.

Composition design of BNBT-ST relaxor ferroelectric ceramics in superparaelectric state with ultrahigh energy density

BNT-6BT-based lead-free ceramics have gained significant attention due to their relatively large piezoelectric coefficients and tunable morphotropic phase boundary conditions. In this investigation, SrTiO3 (ST) was added to BNT-6BT ceramics to fabricate the BNT-6BT-xST (BNBT-xST) composition. The impact of ST content on the phase structure and dielectric permittivity of the BNBT-xST ceramics was studied. The XRD refinement data show that with increasing ST content, the crystal structure of BNBT-xST ceramics was transformed from the morphotropic phase structure (coexisting tetragonal (P4/mmm) and pseudo-cubic (Pmm) phase) to the pseudo-cubic phase. The dielectric permittivity data of the BNBT-80ST showed that the Tm (the maximum permittivity temperature) moved to −61.9 °C, which caused the room temperature to fall within the range of Tm < T < TB (the Burns temperature). This makes the BNBT-80ST a superparaelectric state in relaxor ferroelectrics (RFE). Furthermore, the maximum energy density and the charge-discharge efficiency of the BNBT-80ST achieved 5.48 J/cm3 and 87% at 495 kV/cm, respectively. The energy density of the BNBT-80ST was improved by 2.97-fold and 49% compared with that of the BNBT-30ST and BNBT-70ST. This is mostly attributed to weakened ferroelectricity and improved paraelectricity in the BNBT-80ST. This investigation demonstrates that BNBT-xST ceramics can be adjusted to a superparaelectric state with an ST content of 80%. This makes the material to possess both a large polarization and a high breakdown field. This material holds great promise for high energy density capacitor applications.

Single material with multiple interfaces: A key one dimensional barium titanate filler for enhancing energy density in polymer nanocomposite

The increasing demand of energy and its storage devices in consumer electronics requires high energy density capacitors. In this context, we proposed a filler of single material with multiple interfaces to enhance the energy density in polymer nanocomposite film. The core-shell polydopamine (PDA) coated BaTiO3 (BT) incorporated in 1D BT architecture filler was prepared by the electrospinning process. In order to investigate the effect of the interfaces, the poly(vinylidene-chlorotrifluoroethylene) (P(VDF-CTFE)) nanocomposite films of a fixed filler (BT, PDA coated BT and 1D core-shell BT) concentration were prepared. The introduction of a ferroelectric filler induces an electroactive phase in P(VDF-CTFE), leading to dielectric constant enhancement by 135% in nanocomposite film. This enhancement in dielectric constant is due to the increased polarizability of nanocomposite film, which was verified by the finite element analysis of electric field distribution. The ferroelectric (polarization vs electric field) loop measurement indicates that the multi-interfaced ferroelectric filler based nanocomposite film exhibits increased maximum polarization of 14.3 μC/cm2, breakdown strength of 5000 kV/cm and improved energy density of 9.9 J/cm3. It implying that an enormous increment (371%) of energy storage as compared to commercial biaxially orientated polypropylene (2.1 J/cm3).

Effects of Post-γ Irradiation on Voltage Maintaining Performance of High Energy Density Capacitors

With the rapid development of the aerospace industry and nuclear technology, metallized film capacitor (MFC), as energy storage unit for pulsed power sources, begin to operate in various high-energy radiation environments. In order to ensure the working reliability of MFC, it is of great significance to study its voltage maintaining performance (VMP) and aging law after irradiation. In this paper, metallized polypropylene (PP) film capacitors (MPPFC) are used as the research object to analyze the irradiation reaction mechanism of polypropylene, and the effect of irradiation dose on the capacitance, dielectric loss and VMP of MPPFC under aerobic conditions is studied. The results show that there is a critical value of 100 kGy for the effect of irradiation dose on MPPFC. When the irradiation dose is less than 100 kGy, the capacitance and dielectric loss of MPPFC remain almost unchanged, and the voltage drop increases with the dose as a power function. When the irradiation dose reached 500 kGy, the macromolecules in PP film were completely cleaved, and the voltage drop of the MPPFC increased from 1.62% to 2.96% without irradiation within 10 s. In order to ensure the energy output efficiency of the power supply, the irradiation dose of MPPFC should be controlled not to exceed 5 kGy. At this time, the voltage drop of the MPPFC within 10 s is 2.30%, and the output efficiency is 95.41%. This paper serves to provide a certain basis for the application of MPPFC in irradiation environment.

Crystal structure, microstructure, and ultra-high energy storage properties of lead-free (x)Bi(Mg0.5Ti0.5O3-(1-x)[0.50Ba(Zr0.2Ti0.8)O3-0.50(Ba0.7Ca0.3)TiO3] ternary ceramics

In recent times, advance electronics demand high energy storage materials that work efficiently for next-generation devices. Herein, a novel ternary lead-free (x)Bi(Mg0.5Ti0.5)O3–(1-x)[0.50Ba(Zr0.2Ti0.8)O3-0.50(Ba0.7Ca0.3)TiO3] solid solution with x ≤ 0.10, ceramic energy storage materials were prepared by high energy ball milling method. The crystal structure, ferroelectric, and energy storage response were investigated in detail. The X-ray diffraction characterization confirms the single-phase perovskite cubic structure for x ≤ 0.10. Dense, pore-free, and homogeneous microstructures were obtained in these samples. The average grain size decreased with increasing ‘x’ due to grain growth inhibition. The developed compositions exhibit significantly improved break-down strength with strong frequency dispersion in εr and tanδ. Slim polarization (P)-Electric field (E) hysteresis loops were obtained for x ≤ 0.10. The composition x = 0.075 exhibits ultra-high energy storage efficiency (ɳ) (∼81 %) and large recoverable energy density (Wrec) (0.276 J/cm3) which makes it a potential candidate for various applications that require high energy density capacitors.

Investigation on Dielectric Permittivity of PVDF/BaTiO3 Nanocomposites Materials by Response Surface Methodology

It is well known that the size and loading of nanoparticles affect the dielectric permittivity of nanodielectric materials. In this study, poly(vinylidene fluoride) (PVDF) based nanodielectric for high energy density capacitor were prepared by mixing PVDF with barium titanate, BaTiO3 (BT) using ball milling process. A response surface methodology (RSM) based Box–Behnken Design (BBD) was systematically used to design and analyze the experiments. Interaction effect of independent factors such as BT size, BT volume fraction and milling time on effective dielectric permittivity was examined. The result showed the effective dielectric permittivity is sensitive to BT size and BT volume fraction. Also, RSM optimization approach was applied to generate optimum conditions corresponding to a combination of BT size of 69.92 nm, BT volume fraction of 29.95% and milling time of 44.07 min. At these conditions, the optimum dielectric response is 21.87.

Ultralow contents of AgNbO3 fibers induced high energy storage density in ferroelectric polymer nanocomposites

Polymer dielectric films have been widely used in electronic and power systems due to their unique dielectric properties, processing properties, and excellent cost performance. Although the dielectric constant of dielectric polymers can be improved by adding high contents of ceramic fillers, this approach comes at the expense of the breakdown strength (Eb). This work is inspired by the idea that high-aspect-ratio fibers can induce a larger electric dipole moment without sacrificing too much Eb compared to zero-dimensional nanoparticles, thereby effectively improving the energy storage performance of the composites. We synthesized antiferroelectric AgNbO3 (ANO) fibers by using an in situ topotactic transition reaction which were then introduced into the polyvinylidene fluoride (PVDF) matrix for energy storage applications. The results show that the nanocomposite film with an ultralow loading of 0.4 wt. % ANO fibers achieves a high discharge energy density of 12.97 J cm−3 at 490 MV m−1. Nanocomposites based on ultralow content ANO fibers show great promise as one-dimensional antiferroelectric fillers for high energy density capacitor applications.

Realizing enhanced energy density in ternary polymer blends by intermolecular structure design

Polymer nanocomposites have been extensively studied for dielectric energy storage applications, however, the relatively low breakdown strength due to inevitable defects and voids limits themselves in the development of the high energy density capacitors while large-scale manufacturing. Herein, we propose a facile strategy to improve the breakdown strength and thus energy density by synergistically designing the intermolecular structure in a ternary polymer blend composed of poly(methyl methacrylate), poly(vinylidene fluoride), and poly(vinylidene fluoride-hexafluoropropylene). We show that the appropriate quenching temperature can decrease crystal size and increase the fraction of the amorphous phase. Meanwhile, by designing the mass ratio of the ferroelectric poly(vinylidene fluoride) and poly(vinylidene fluoride-hexafluoropropylene), it will successfully introduce the intermolecular interaction, which stabilizes the γ-phase in ferroelectric polymers and leads to dense chain packing. All the phenomena contribute to the ultrahigh breakdown strength (850 MV/m), and the optimized blend exhibits a record high discharged energy density of 30 J/cm3. Of particular importance is that a large-area dielectric film with high property uniformity can be fabricated, demonstrating that the proposed design approach can be used as a general technology for mass production.

Boosting capacitive energy density of conjugated molecule modified porous graphene film as high-performance electrode materials

The increasing demand for the electronic market has put forward large requirements for electrochemical capacitors with high energy and power density. Herein, the 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) modified flame reduced graphene oxide (FRGO) film (N/FRGO) is fabricated by π−π noncovalent interactions, which has abundant wavy wrinkles and fluffy pores to improve the interfacial contact performance, thus achieving large efficient ions storage areas. And the combined NTCDA molecules provide large numbers of additional redox-active sites. The N/FRGO based symmetric supercapacitor (SSC) exhibits a high capacitance value of 246.4 F g−1 at 0.2 A g−1, excellent rate capability of 65.5% capacitance retention at the increased current density of 50 A g−1, and the outstanding cyclability of 90% capacitance retention after 40,000 cycles. Moreover, by combining Zn deposition/stripping battery behavior, the N/FRGO film can achieve a high specific capacity of 217.0 mAh g−1. The N/FRGO based zinc ion capacitor (ZIC) has the maximum energy and power density of 166.5 Wh kg−1 and 29.0 kW kg−1, and can realize the prominent capacity retention under different bending angles and 800 bending cycles. Therefore, the N/FRGO shows a promising application in high energy density capacitors.

A review of ferroelectric materials for high power devices

Compact autonomous ultrahigh power density energy storage and power generation devices that exploit the spontaneous polarization of ferroelectric materials are capable of producing hundreds of kilovolt voltages, multi-kiloampere currents, and megawatt power levels for brief interval of time. The storage life of these devices is four orders of magnitude longer than that for electrochemical batteries and electrochemical capacitors. Herein is an up to date survey of ferroelectric materials used for these high power devices. Several types of ferroelectric ceramics possess the ability to be depolarized under adiabatic compression and can be successfully used for high power applications. In addition to bulk ferroelectric ceramics, multilayer ferroelectric films are very efficient materials for high power systems. Of particular importance is the ability of relaxor ferroelectric single crystals to produce significantly higher electric charge density and energy density than ceramics, making them promising materials for high power applications. Also provided is a brief survey of recent developments of ferroelectric materials for high energy density and power density dielectric capacitors. Numerous ceramics have been developed, including antiferroelectric and relaxor antiferroelectric solid solutions, providing high energy density and efficiency simultaneously.

Synthesis conditions induced disorder and its role in affecting structural, dielectric, piezoelectric, optical behavior and enhancing energy storage efficiency in (Ba1-xCax)TiO3 ceramics

We examined the effect of Ca2+ substitution on the structural, dielectric, ferroelectric, piezoelectric, and optical properties of Barium Titanate (BT) prepared via the solid-state reaction route assisted with a heating cycle. X-ray diffraction (XRD) patterns confirmed the formation of single-phase perovskite structures for Ba1-xCaxTiO3, 0 ≤ x ≤ 0.08. Raman spectroscopy of the Ca2+ doped BT was in good agreement with the XRD data. Structural analysis revealed an increase in average grain size with the increase in Ca2+ concentration in BT except for BCT-5 (x = 0.05) whose average grain size decreased. The Curie temperature shifted towards a higher temperature with the increase in Ca2+ concentration in BT, which is consistent with the literature when Ca2+ goes into the Ba2+ site. For BCT-5, the decrease in average grain size and the increase in diffuseness parameter to 1.51 confirmed partial substitution of Ca2+ at Ti4+-site, generating oxygen vacancies that inhibited grain growth during the synthesis procedure. The recoverable energy density calculated from the PE hysteresis loop showed maximum value for BCT-3 = 224.3 mJ/cm3 with a storage efficiency of 85%. The energy storage efficiency was greater than 80% for all the compositions, making them suitable for high energy density capacitors. The piezoelectric charge coefficient increased linearly with Ca2+ concentration except for BCT-5, due to partial substitution of Ca2+ at the Ti4+ site. The indirect optical bandgap varied from 1.97 eV to 2.24 eV with Ca2+ concentration associated with the combined effect of lattice disorder and defects, which can have applications in optoelectronics. Partial substitution of Ca2+ at the Ti4+ site decreased the optical bandgap of BCT-5.

Research Advances in Hierarchically Structured PVDF-Based All-Organic Composites for High-Energy Density Capacitors.

Polymer film capacitors have been widely applied in many pulsed power fields owing to their fastest energy-released rates. The development of ferroelectric polyvinylidene fluoride (PVDF)-based composites has become one of the hot research directions in the field of high-energy storage capacitors. Recently, hierarchically-structured all-organic composites have been shown to possess excellent comprehensive energy storage performance and great potential for application. In this review, most research advances of hierarchically-structured all-organic composites for the energy storage application are systematically classified and summarized. The regulating strategies of hierarchically structured all-organic composites are highlighted from the perspective of preparation approaches, tailored material choices, layer thicknesses, and interfaces. Systematic comparisons of energy storage abilities are presented, including electric displacement, breakdown strength, energy storage density, and efficiency. Finally, we present the remaining problems of hierarchically structured all-organic composites and provide an outlook for future energy storage applications.