High Volumetric Energy Density Research Articles

Pressure‐Induced Dense and Robust Ge Architecture for Superior Volumetric Lithium Storage

AbstractThe germanium (Ge) anode attains wide attention in lithium‐ion batteries because of its high theoretical volumetric capacity (8646 mAh cm−3). However, the huge volume expansion (≈230%) results in its poor electrochemical performances. The strategies reported in the literature to solve the issue often cause a low packing density, lowering the volumetric capacity. Here, a pressure‐induced route is proposed to fabricate a Ge architecture, in which nano‐sized Ge (≈15 nm) is encapsulated by robust TiO2 and highly conductive carbon, which offer the advantages of a low stress–strain characteristic, low volume expansion in thickness change, high electrical conductivity (463.2 S m−1), high Li‐ion diffusion coefficient (9.55 × 10−9–8.51 × 10−12 cm2 s−1), and high tapping density (1.79 g cm−3). As a result, the dense architecture obtains outstanding volumetric capacities of 3559.8 mAh cm−3 at 0.1 A g−1 and 2628.2 mAh cm−3 at 20 A g−1, along with excellent cycling life over 5000 cycles at 10 A g−1. Remarkably, the full cell achieves a high volumetric energy density of 1760.1 Wh L−1, along with impressive fast‐charging performances and long cycling life. This work provides a new synthesis strategy and deep insight into the design of high‐volumetric capacity alloy‐based lithium‐ion‐battery anodes.

Hydrogen storage methods by lithium borohydride

This paper addresses the urgent need for efficient hydrogen storage methods in the context of combating climate change and transitioning to sustainable energy sources. Among various storage options, LiBH4 is highlighted for its high volumetric and gravimetric energy densities, critical factors in determining its suitability for energy applications. However, challenges arise due to its high thermolysis temperature, which poses difficulties, especially in applications like automotive use where high temperatures are required. The commercial viability of LiBH4 remains a significant obstacle due to the nascent stage of chemical hydride technology and the absence of large-scale production facilities. Environmental concerns also loom large, as the production of LiBH4 relies on extensive mining of lithium and boron, known for their environmental impact. Furthermore, the economic feasibility of LiBH4 as a hydrogen storage medium is questioned, given the substantial portion of total expenses attributed to hydrogen costs, affecting all methods except those based on fossil fuels or electricity. Nevertheless, there is optimism that with technological advancements and improved infrastructure, the costs associated with LiBH4 and hydrogen storage overall may decrease over time.In conclusion, while LiBH4 presents promising energy density characteristics, its practical implementation faces challenges such as high production costs, environmental concerns, and technological limitations. Overcoming these obstacles is crucial for realizing a sustainable and carbon-free energy landscape driven by hydrogen.

2.5 μm‐Thick Ultrastrong Asymmetric Separator for Stable Lithium Metal Batteries

Lithium metal batteries (LMBs) are considered the ideal choice for high volumetric energy density lithium‐ion batteries, but uncontrolled lithium deposition poses a significant challenge to the stability of such devices. In this paper, we introduce a 2.5 μm‐thick asymmetric and ultrastrong separator, which can induce tissue‐like lithium deposits. The asymmetric separator, denoted by utPE@Cu2O, was prepared by selective synthesis of Cu2O nanoparticles on one of the outer surfaces of a nanofibrous (diameter ~10 nm) ultrastrong ultrahigh molecular weight polyethylene (UHMWPE) membrane. Microscopic analysis shows that the lithium deposits have tissue‐like morphology, resulting in the symmetric lithium cells assembled using utPE@Cu2O with symmetric Cu2O coating exhibiting stable performance for over 2000 h of cycling. This work demonstrates the feasibility of a facile approach ultrathin separators for the deployment of lithium metal batteries, providing a pathway towards enhanced battery performance and safety.

Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes.

Multivalent-ion battery technologies are increasingly attractive options for meeting diverse energy storage needs. Calcium ion batteries (CIB) are particularly appealing candidates for their earthly abundance, high theoretical volumetric energy density, and relative safety advantages. At present, only a few Ca-ion electrolyte systems are reported to reversibly plate at room temperature: for example, aluminates and borates, including Ca[TPFA]2, where [TPFA]- = [Al(OC(CF3)3)4]- and Ca[B(hfip)4]2, [B(hfip)4]2- = [B(OCH(CF3)2)4]-. Analyzing the structure of these salts reveals a common theme: the prevalent use of a weakly coordinating anion (WCA) consisting of a tetracoordinate aluminum/boron (Al/B) center with fluorinated alkoxides. Leveraging the concept of theory-aided design, we report an innovative, one-pot synthesis of two new calcium-ion electrolyte salts (Ca[Al(tftb)4]2, Ca[Al(hftb)4]2) and two reported salts (Ca[Al(hfip)4]2 and Ca[TPFA]2) where hfip = (-OCH(CF3)2), tftb = (-OC(CF3)(Me)2), hftb = (-OC(CF3)2(Me)), [TPFA]- = [Al(OC(CF3)3)4]-. We also reveal the dependence of Coulombic efficiency on their inherent propensity for cation-anion coordination.

Potential of Aluminum as a Metal Fuel for Supporting EU Long‐Term Energy Storage Needs

AbstractThe EU's energy transition necessitates availability of green energy carriers with high volumetric energy densities for long‐term energy storage (ES) needs. A fully decarbonized scenario considering renewable energy availability is analyzed underpinning the need for such carriers. Considering the shortcomings of Power‐to‐X technologies in terms of efficiency and low volumetric density, Aluminum (Al) is identified as a potential alternative showing significantly high volumetric energy densities (23.5 kWh L−1). In this paper, an Al‐based long‐term ES concept is investigated, taking advantage of the inherent recycling of the active species (i.e., Al2O3 to Al) coupling decarbonized Hall–Héroult process with an Al‐steam oxidation for simultaneous hydrogen (H2) and heat generation. This work demonstrates an innovative lab‐scale fine Al powder‐steam oxidation process at ≈900 °C without use of catalysts or additives, exploiting alumina as inert material. Conducted SEM‐EDX analysis on oxidized Al provides supporting evidence in favor of employed oxidation pathway, hindering tendency of aluminum oxide (Al2O3) clumping and enabling direct use of oxides in the smelting process for fully recyclability. Moreover, outcomes of XRD analyses are presented to validate the measured total H2 yields.

Creep-type all-solid-state cathode achieving long life

Electrochemical-mechanical coupling poses enormous challenges to the interfacial and structural stability but create new opportunities to design innovative all-solid-state batteries from scratch. Relying on the solid-solid constraint in the space-limited domain structure, we propose to exploit the lithiation-induced stress to drive the active materials creep, thereby improving the structural integrity. For demonstration, we fabricate the creep-type all-solid-state cathode using creepable Se material and an all-in-one rigid ionic/electronic conducting Mo6Se8 framework. As indicated by the in-situ experiment and numerical simulation, this cathode presents unique capabilities in improving interparticle contact and avoiding particle fracture, leading to its superior electrochemical performance, including a superior long-cycle life of more than 3000 cycles at 0.5 C and a high volumetric energy density of 2460 Wh/L at the cathode level. We believe this innovative strategy to utilize mechanics to boost the electrochemical performance could shed light on the future design of all-solid-state batteries for practical applications.

In-situ growth of 3D amorphous Ni-Co-Mn phosphate on 2D Ti3C2Tx nanocomposite for commercial-level hybrid energy storage application

To overcome the limited electronic conductivity and capacity of single and binary transition metal phosphates (TMPs), highly electrochemical active materials and rational structural design of ternary TMPs composite are urgently required. In this study, we successfully synthesized an amorphous 3D Ni-Co-Mn phosphate@2D Ti3C2Tx (MXene) nanocomposite (NCMP series) through the electrodeposition method. The amorphous Ni-Co-Mn phosphate effectively restricts the self-accumulation of MXene nanosheets, resulting in the development of a porous nanostructure. This structure exposes more active sites, expands the ion transport path, and enhances the conductivity of the Ni-Co-Mn phosphate@Ti3C2Tx material. Owing to the synergistic effect offered by Ni-Co-Mn phosphate and MXene nanocomposite, the anchored Ni-Co-Mn phosphate@Ti3C2Tx (NCMP-5) electrode delivers an elevated capacity of 342 mAh/g (1230 C/g) at 5.0 A/g, surpassing the pristine Ni-Co-Mn phosphate (NCMP-4, 260 mAh/g) and MXene (33.3 mAh/g). Moreover, a hybrid solid-state supercapacitor (HSSC) device is assembled with NCMP-5 as a cathode and reduced graphene oxide (rGO) as an anode within a polymer gel (PVA-KOH) electrolyte. Notably, the fabricated HSSC device displays a supreme specific capacity of 27.5 mAh/g (99 C/g) and a high (volumetric) energy density of 22 Wh/kg (3.6 Wh/cm3) at a power density of 0.80 kW/kg (0.13 kW/cm3) for 1.0 A/g. Moreover, the HSSC device retains 95.4 % of its initial capacity even after 10,000 cycles. Importantly, the operational potential window of two serially connected HSSC devices approaches +3.2 V, enabling different colored commercial light-emitting diodes (LEDs) to be efficiently illuminated. Eventually, the remarkable supercapacitive characteristics of the 3D@2D amorphous Ni-Co-Mn phosphate@MXene nanocomposite make it an attractive choice for advanced electroactive materials in upcoming hybrid energy storage technologies.

Cellulose-based high-loading flexible electrode for lithium-ion battery with high volumetric energy density

Thick electrodes with high loading are attractive for high-energy storage devices, but they face major challenges of slow ion transfer and poor mechanical stability. Carbon templates such as reduced graphene oxide and carbon nanotube can promote the electrons transfer of thick electrodes and enhance their strength, but they still exhibit a complex producing process, slow Li+ transfer and high cost. Herein, a nanofiber network with double fast Li+ and electrons transfer pathways by the self-assembly of carbon nanoparticles on the negatively charged natural cellulose fibers was designed. The abundant oxygen-containing functional groups from the cellulose fibers enabled the electrode with abundant negative charge which can adsorb the neutral particles with strong electrostatic interaction. And the Density Functional Theory calculation demonstrates that oxygen-containing functional groups also has stronger adsorption energy for PF6− anions in electrolyte which can promote the desolvation of the solvated Li salts, thus promote Li+ transfer. After integration with lithium iron phosphate, this network achieves a robust high-loaded electrode with good electrical conductivity and shortened ion transfer pathways without traditional current collector and binder. Based on the robust electrode structure and fast transfer kinetics of electrons and Li+, the batteries exhibit excellent cycle stability with capacity retention of 98 % after long 400 cycles and high volumetric energy density of 740 Wh/L, which greatly surpass the conventional batteries with coating LiFePO4 (LFP) cathode. Given the low-cost raw materials and convenient operation, the design of self-standing flexible electrodes with high loading will offer a promising and effective strategy for other storage devices with high energy.

Preparation, characterization, and combustion properties of NGO/GF/B composite system

Boron is a potential fuel for energetic materials due to its high volumetric and gravimetric energy density. However, its application has long been constrained by ignition difficulties and insufficient combustion. In this study, a mixture of NGO and GF was introduced as an additive to boron particles. We prepared NGO/GF-coated B complexes and performed several characterizations, showing that NGO combined with GF had a good coating effect on B. The combustion heat was measured by an oxygen bomb calorimeter, while the combustion mechanism was proposed. Its effect on the thermal decomposition behavior of AP was also analyzed. The results showed that the combustion efficiency of NGO/GF-modified B was significantly improved, which was 14.34% higher than that of pure B. This enhancement was attributed to the synergistic effect of NGO and GF, which promoted ignition and combustion by releasing heat, gases, and fluorocarbon radicals. In addition, both boron and NGO/GF-modified boron accelerated the decomposition of AP, especially, in the presence of NGO/GF, the decomposition temperature of AP was advanced by 73.2 °C compared to that in the presence of boron alone. These findings may provide valuable theoretical guidance for the design and potential application of NGO/GF modified boron in energetic materials.

Solvothermal Guided V2O5 Microspherical Nanoparticles Constructing High-Performance Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries have attracted a lot of attention owing to their cost effectiveness and plentiful resources, but less research has been conducted on the aspect of high volumetric energy density, which is crucial to the space available for the batteries in practical applications. In this work, highly crystalline V2O5 microspheres were self-assembled from one-dimensional V2O5 nanorod structures by a template-free solvothermal method, which were used as cathode materials for zinc-ion batteries with high performance, enabling fast ion transport, outstanding cycle stability and excellent rate capability, as well as a significant increase in tap density. Specifically, the V2O5 microspheres achieve a reversible specific capacity of 414.7 mAh g-1 at 0.1 A g-1, and show a long-term cycling stability retaining 76.5% after 3000 cycles at 2 A g-1. This work provides an efficient route for the synthesis of three-dimensional materials with stable structures, excellent electrochemical performance and high tap density.

Tailored Yolk-Shell Design to Silicon Microparticles via Scalable and Template-Free Synthesis for Superior Lithium Storage.

Micrometer-sized Si particles are beneficial to practical lithium-ion batteries in regard to low cost and high volumetric energy density in comparison with nanostructured Si anodes. However, both the issues of electrical contact loss and overgrowth of solid electrolyte interface for microscale Si induced by colossal volume change still remain to be addressed. Herein, a scalable and template-free method is introduced to fabricate yolk-shell structured Si anode from commercially available Si microparticles. The void is created via a one-step alkali etching process with the remaining silicon core as the yolk, and a double-walled shell is formed from simultaneous in situ growth of the conformal native oxide layer and subsequent carbon coating. In this configuration, the well-defined void spaces allow the Si core to expand without compromising structural integrity, while the double-walled shell acts as a static capsule to confine silicon fragments despite likely particle fracture. Therefore, electrical connectivity is maintained on both the particle and electrode level during deep galvanostatic cycling, and the solid-electrolyte interface is stabilized on the shell surface. Owing to the benefits of tailored design, excellent cycling stability (capacity retention of 95% after 100 cycles) and high coulombic efficiency (99.5%) are realized in a practical full-cell demonstration.

TiH2-based anode: In situ formation of solid electrolyte for high volumetric energy density with minimal content of conducting agent

Herein, we report the fabrication of an electrode composite with an ultra-high active material content (90 wt%). This composite was possible because of the utilization of TiH2 as an anode active material that forms a solid electrolyte (LiH) in situ and functions as an electronic conductor, enabling a substantial reduction of the amount of conductor additive in the electrodes. The electrochemical performance of the TiH2-based electrodes with a high active material content was comparable to that of electrode composites that include a solid electrolyte because of sufficient Li+-ion conduction pathways provided by the LiH formed in situ. To further increase the capacity of the TiH2-based electrode, MgH2 (theoretical capacity: 2036 mAh/g) was mixed with TiH2 to function as an active material. TiH2, which is known to exhibit high electron conductivity and a high density, is expected to be used as a partial substitute for low-density carbon additives to increase the volumetric energy density of batteries and their active material content. Hence, the xMgH2-(1 − x)TiH2-AB (AB: acetylene black) electrode composite exhibited a high active material content (90 wt%) and improved volumetric energy density (1687 Wh/L, based on the anode) compared with a MgH2-AB (70:30 wt%) electrode composite (1157 Wh/L), even when the AB content of the xMgH2-(1 − x)TiH2-AB composite was 10 wt%. In addition, a MgH2-TiH2-VGCF (VGCF: vapor-grown carbon fiber) based electrode composite exhibited the highest volumetric and gravimetric energy density (2154 Wh/L, 1888 Wh/kg) among the investigated composites, facilitated by sufficient electron pathways provided by VGCF.

Three-Dimensional Vanadium and Nitrogen Dual-Doped Ti3C2 Film with Ultra-High Specific Capacitance and High Volumetric Energy Density for Zinc-Ion Hybrid Capacitors.

Zinc-ion hybrid capacitors (ZICs) can achieve high energy and power density, ultralong cycle life, and a wide operating voltage window, and they are widely used in wearable devices, portable electronics devices, and other energy storage fields. The design of advanced ZICs with high specific capacity and energy density remains a challenge. In this work, a novel kind of V, N dual-doped Ti3C2 film with a three-dimensional (3D) porous structure (3D V-, N-Ti3C2) based on Zn-ion pre-intercalation can be fabricated via a simple synthetic process. The stable 3D structure and heteroatom doping provide abundant ion transport channels and numerous surface active sites. The prepared 3D V-, N-Ti3C2 film can deliver unexpectedly high specific capacitance of 855 F g-1 (309 mAh g-1) and demonstrates 95.26% capacitance retention after 5000 charge/discharge cycles. In addition, the energy storage mechanism of 3D V-, N-Ti3C2 electrodes is the chemical adsorption of H+/Zn2+, which is confirmed by ex situ XRD and ex situ XPS. ZIC full cells with a competitive energy density (103 Wh kg-1) consist of a 3D V-, N-Ti3C2 cathode and a zinc foil anode. The impressive results provide a feasible strategy for developing high-performance MXene-based energy storage devices in various energy-related fields.

Zinc ion Batteries: Bridging the Gap from Academia to Industry for Grid-Scale Energy Storage.

Zinc ion batteries (ZIBs) exhibit significant promise in the next generation of grid-scale energy storage systems owing to their safety, relatively high volumetric energy density, and low production cost. Despite substantial advancements in ZIBs, a comprehensive evaluation of critical parameters impacting their practical energy density (Epractical) and calendar life is lacking. Hence, we suggest using formulation-based study as a scientific tool to accurately calculate the cell-level energy density and predict the cycling life of ZIBs. By combining all key battery parameters, such as the capacity ratio of negative to positive electrode (N/P), into one formula, we assess their impact on Epractical. When all parameters are optimized, we urge to achieve the theoretical capacity for a high Epractical. Furthermore, we propose a formulation that correlates the N/P and Coulombic efficiency of ZIBs for predicting their calendar life. Finally, we offer a comprehensive overview of current advancements in ZIBs, covering cathode and anode, along with practical evaluations. This Minireview outlines specific goals, suggests future research directions, and sketches prospects for designing efficient and high-performing ZIBs. It aims at bridging the gap from academia to industry for grid-scale energy storage.

Zinc ion Batteries: Bridging the Gap from Academia to Industry for Grid‐Scale Energy Storage

AbstractZinc ion batteries (ZIBs) exhibit significant promise in the next generation of grid‐scale energy storage systems owing to their safety, relatively high volumetric energy density, and low production cost. Despite substantial advancements in ZIBs, a comprehensive evaluation of critical parameters impacting their practical energy density (Epractical) and calendar life is lacking. Hence, we suggest using formulation‐based study as a scientific tool to accurately calculate the cell‐level energy density and predict the cycling life of ZIBs. By combining all key battery parameters, such as the capacity ratio of negative to positive electrode (N/P), into one formula, we assess their impact on Epractical. When all parameters are optimized, we urge to achieve the theoretical capacity for a high Epractical. Furthermore, we propose a formulation that correlates the N/P and Coulombic efficiency of ZIBs for predicting their calendar life. Finally, we offer a comprehensive overview of current advancements in ZIBs, covering cathode and anode, along with practical evaluations. This Minireview outlines specific goals, suggests future research directions, and sketches prospects for designing efficient and high‐performing ZIBs. It aims at bridging the gap from academia to industry for grid‐scale energy storage.

Three-dimensional Ordered Macroporous Flexible Electrode Design toward High-Performance Zinc-Ion Batteries.

Flexible zinc-ion batteries (ZIBs) have been considered to have huge potential in portable and wearable electronics due to their high safety, cost efficiency, and considerable energy density. Therein, the design and construction of flexible electrodes significantly determine the performance and lifespan of flexible battery devices. In this work, an ultrathin flexible three-dimensional ordered macroporous (3DOM) Sn@Zn anode (60 μm in thickness) is presented to relieve dendrite growth and expand the lifespan of flexible ZIBs. The 3DOM structure can ensure uniform electric field distribution, guide oriented zinc plating/stripping, and extend the lifespan of anodes. The rich zincophilic Sn sites on the electrode surface significantly facilitate Zn nucleation. Accordingly, a lowered nucleation overpotential of 8.9 mV and an ultralong cycling performance of 2400 h at 0.1 mA cm-2 and 0.1 mAh cm-2 are achieved in symmetric cells, and the 3DOM Sn@Zn anode can also operate in deep cycling for over 200 h at 10 mA cm-2 and 5 mAh cm-2. A flexible 3DOM MnO2/Ni cathode with a high structural stability and a high mass-specific capacity is fabricated to match with the anode to form a flexible ZIB with a total thickness of 200 μm. The flexible device delivers a high volumetric energy density of 11.76 mWh cm-3 at 100 mA gMnO2-1 and a high average open-circuit voltage of 1.5 V and exhibits high-performance power supply under deformation in practical application scenarios. This work may shed some light on the design and fabrication of flexible energy-storage devices.

Mitigation of charge heterogeneity by uniform in situ coating enables stable cycling of LiCoO2 at 4.6V

LiCoO2 is a predominant cathode for lithium-ion batteries of portable electronics owing to its merit of high volumetric energy density. Nevertheless, it experiences rapid capacity deterioration under high voltages, concomitant with structural degradation and numerous intragranular cracks. Coating has been recognized as an efficacious strategy to ameliorate the decline in cycling performance of LiCoO2 at high voltages. Hence, a systematic elucidation of the precise mechanisms underlying the mitigation of structural degradation via coating layers assumes paramount importance in the context of advancing the next generation of high-voltage LiCoO2. In this work, the intricate interrelation among lithium-ion diffusion coefficients, charge heterogeneity, and crack distribution is explicated through techniques inclusive of galvanostatic intermittent titration technique (GITT), finite element analysis (FEA), and X-ray computed tomography (XCT). A robustly stable lithium-ion-conducting coating material serves the function of curtailing the occurrence of surface passivation layers, achieved by diminishing side reactions between the LiCoO2 and the electrolyte; while a uniform coating ensures a homogeneous lithium-ion flux, thereby mitigating charge heterogeneity and the resultant mechanical strain as well as intragranular cracks. Both are important elements that collectively allow the coating to effectively protect the surface from structural degradation, thus achieving superior performances upon high-voltage charging.

Recent Approaches for Cleaving the C─C Bond During Ethanol Electro-Oxidation Reaction.

Direct ethanol fuel cells (DEFCs) play an indispensable role in the cyclic utilization of carbon resources due to its high volumetric energy density, high efficiency, and environmental benign character. However, owing to the chemically stable carbon-carbon (C─C) bond of ethanol, its incomplete electrooxidation at the anode severely inhibits the energy and power density output of DEFCs. The efficiency of C─C bond cleaving on the state-of-the-art Pt or Pd catalysts is reported as low as 7.5%. Recently, tremendous efforts are devoted to this field, and some effective strategies are put forward to facilitate the cleavage of the C─C bond. It is the right time to summarize the major breakthroughs in ethanol electrooxidation reaction. In this review, some optimization strategies including constructing core-shell nanostructure with alloying effect, doping other metal atoms in Pt and Pd catalysts, engineering composite catalyst with interface synergism, introducing cascade catalytic sites, and so on, are systematically summarized. In addition, the catalytic mechanism as well as the correlations between the catalyst structure and catalytic efficiency are further discussed. Finally, the prevailing limitations and feasible improvement directions for ethanol electrooxidation are proposed.

High Volumetric Energy Density LiFePO4/C Cathode Materials Synthesized by Dodecyl Polyglucoside-Assisted Glucose-Polyethylene Glycol Composite Carbon Source

Abstract High volumetric energy density LiFePO4/C cathode materials were synthesized by wet ball milling, spray drying, and carbothermal reduction method using glucose and polyethylene glycol (PEG) as composite carbon sources and dodecyl polyglucoside (C12APG) as a milling aid. With the introduction of C12APG during the ball milling process, the prepared cathode materials have uniform particle size (100-200 nm in diameter) and regular primary particle morphology. In addition, PEG substitutes part of glucose as a carbon source, resulting in low carbon content and high graphitization of residual carbon after high-temperature calcination. The prepared LiFePO4/C cathode materials have a high powder compaction density (2.68 g cm-3) and excellent electrochemical performance (discharged capacities of 161.2 and 141.7 mAh g-1 at 0.2 C and 5 C, and cycle retention of 98.6% for 100 cycles at 1 C/1 C). This LiFePO4/C composite was assembled into 14500-type cylindrical batteries with a compaction density of 2.62 g cm-3 for the positive electrode. The volumetric energy densities of the positive electrode were 1135.18 Wh L-1 and 918.16 Wh L-1 at 0.2 C and 5 C, respectively.

In Situ Fabrication of Graphdiyne Nanoisland Anchored Ti3C2Tx Film to Accelerate Intercalation Pseudocapacitance Kinetics

AbstractA key challenge in flexible supercapacitor is balancing the trade‐off between high capacity and fast charging ability caused by dense structure‐induced sluggish ionic diffusion and storage dynamics. Herein, a hydrogen‐rich graphdiyne (GDY)–Ti3C2Tx electrode is reported with tunable interlayer spacing, abundant active sites, and extensive charge storage nanochannels. In particular, the GDY–Ti3C2Tx (12.6 wt.%) electrode has a remarkable volumetric capacitance (2296 F cm−3 at 1 A cm−3) and fast charging behavior (1262 F cm−3 at 50 A cm−3) resulting from the shortened transport pathways, enhanced ionic diffusion rate, and facilitated electrolyte mass transport. Moreover, an all‐solid‐state supercapacitor (ASSC) delivers a high volumetric energy density of 65.6 mWh cm−3, as well as long‐term deformable cyclic stability and high capacitance retention properties under harsh conditions. Density functional theory calculations and molecular dynamic simulation demonstrate the fast electronic responsiveness of the GDY–Ti3C2Tx heterostructure owning to the stronger H+ electrostatic attraction, lower migration resistance, and accelerated intercalation pseudocapacitance kinetics. In situ X‐ray diffraction reveals that a stable Ti─O─C bond bridged organic–inorganic heterostructure can tolerate the repeated high‐current charge/discharge cycling process. The state‐of‐the‐art ASSC delivers multiple functional outputs and shows great potential for efficient energy supply in practical applications.