Electrochemical Energy Conversion Research Articles

Shear Field-Controlled Synthesis of Nitrogen-Doped Carbon Nanochains Forest with High-Density sp3 Defects for Efficient CO2 Electroreduction Reaction.

Defect engineering and nitrogen doping being effective strategies for modulating the surface chemical state of the carbon matrix have been widely explored to promote the catalytic activity in the territory of electrochemical energy storage and conversion devices. However, the controllable synthesis of carbon material with high-density specific defects and high nitrogen doping is still full of challenges. Here, we first synthesize one-dimensional necklace-like nitrogen-doped carbon nanochains (N-CNCs) with abundant defects on carbon fiber paper (CFP) by chemical vapor deposition (CVD) method. The resultant nanostructures are a bunch of interconnected carbon spheres with a hollow structure at the internode and present the complete one-dimensional nanochain configuration. Specifically, the N-CNCs with a corrugated surface possesses high content of sp3 defects (31.2%) and nitrogen (23.6 at %). Combining finite element analysis and experimental results, it reveals that the robust shear field generated by etching gas releasing from thermal decomposition of melamine in situ modulates the CVD process via changing the size and force environment of the metal catalyst droplets for formation of N-CNCs. Benefiting from the high ratio of sp3/sp2 and nitrogen doped on the surface, the N-CNCs@CFP displays a superior electrocatalytic performance for CO2RR, delivering CO Faradaic efficiency of 95.9% and a current density of 23.2 mA cm-2 at -0.86 V vs RHE. This work provides promising synthesis strategy and some inspirations for construction of ultradense and specific defects coupling with nitrogen doping sites into carbon materials to achieve high-efficiency electrocatalysis applications.

The current state of transition metal-based electrocatalysts (oxides, alloys, POMs, and MOFs) for oxygen reduction, oxygen evolution, and hydrogen evolution reactions

Climate change is showing its impacts now more than ever. The intense use of fossil fuels and the resulting CO2 emissions are mainly to blame, accentuating the need to develop further the available energy conversion and storage technologies, which are regarded as effective solutions to maximize the use of intermittent renewable energy sources and reduce global CO2 emissions. This work comprehensively overviews the most recent progress and trends in the use of transition metal-based electrocatalysts for three crucial reactions in electrochemical energy conversion and storage, namely, the oxygen evolution (OER), oxygen reduction (ORR), and hydrogen evolution (HER) reactions. By analyzing the state-of-the-art polyoxometalates (POMs) and metal-organic frameworks (MOFs), the performance of these two promising types of materials for OER, ORR, and HER is compared to that of more traditional transition metal oxides and alloy-based electrocatalysts. Both catalytic activity and stability are highly influenced by the adsorption energies of the intermediate species formed in each reaction, which are very sensitive to changes in the microstructure and chemical microenvironment. POMs and MOFs allow these aspects to be easily modified to fine-tune the catalytic performances. Therefore, their chemical tunability and versatility make it possible to tailor such properties to obtain higher electrocatalytic activities, or even to obtain derived materials with more compelling properties towards these reactions.

Electrochemistry of 2D-materials for the remediation of environmental pollutants and alternative energy storage/conversion materials and devices, a comprehensive review

This review article explores into the complicated relationship between electrochemistry and 2D materials, exploring their mutual influences and the consequential advancements in energy conversion, storage, and environmental applications. Electrochemical reactions, manifested through oxidations and reductions at submerged electrodes, form the linchpin connecting the electrochemistry of 2D materials with their practical utility. Various electrochemical cell topologies are investigated for their role in enhancing material flexibility, operational states, energy conversion efficiency, and device design adaptability. The comprehensive discussion extends to diverse applications, emphasizing the pivotal roles of 2D materials in environmental remediation, alternate energy storage and conversion, and chemical reactivity. Noteworthy applications include pollutant detection, adsorption and absorption of pollutants, elimination of both organic and inorganic pollutants, and photocatalytic degradation. The review also addresses materials synthesis via electrochemical processes, detailing functionalization, handling, and deposition techniques. Particular focus is directed towards local electrochemical techniques enabling the analysis and local alteration of 2D materials. Moreover, this paper concludes the article published in the recent years with this topic and most significant trends observed in 2022 and 2023 with electrochemistry of materials for the remediation of environmental pollutants. While the trends of article publishing increased from 2020 to 2023 with topic alternative energy storage/conversion materials. Finally, offering a comprehensive overview of the synergistic relationship between electrochemistry and 2D materials and their transformative potential in sustainable technologies. Broader contextThe decreasing availability of energy resources and the contamination of the environment are two significant worldwide concerns that need immediate attention. The focus on 2D materials and associated technologies is important for the efficient conversion of solar energy into chemical energy. These materials have diverse applications in fields such as energy (e.g., water splitting), synthesis (e.g., production of valuable chemicals and N2 reduction), and the environment (e.g., CO2 reduction and environmental remediation). Furthermore, Electrochemical energy storage and conversion (EESC) technologies are widely acknowledged as the most viable solutions to address the escalating energy crisis and environmental degradation because to their exceptional energy efficiency and little environmental footprint. Currently, there have been several reports discussing the use of 2D-materials in energy applications and wastewater treatment. However, there is a lack of comprehensive reviews that summarize the electrochemistry of 2D-materials, their preparation strategies, modification techniques, and related properties. Furthermore, there is a need for detailed analysis of the progress in applying 2D-materials for environmental pollution remediation, electrocatalytic performance, energy storage, and conversion technologies and devices. In this paper, we systematically and comprehensively review the electrochemistry of 2D-materials and innovatively analyze the design principles and difficulties of 2D-materials. We discussed comprehensively the remediation of environmental pollutants through 2D-materials in water treatment fields such as photocatylsts, adsorption/absorption and dyes removal as an entry point and provide an in-depth knowledge and outlook on the current status and development potential of specific applications of energy storage and conversion materials and devices.

Anisotropic polyphenylene-based anion exchange membranes with flexible side chains via click reaction for high performance water electrolysis

Anion-exchange membrane water electrolysis (AEMWE) represents a promising and cost-effective electrochemical energy conversion system for green hydrogen production owing to its utilization of earth-abundant metals for various cell components (catalysts, porous transport layers, bipolar plates) and the zero-gap design. However, the lack of high-performance anion-exchange membranes (AEMs) has hampered the advancement of AEMWE technology. Here, by using colon coupling and click reactions, the ether-free polyphenylene-based AEMs (QPPBTF-TMA-w) with flexible side chains that containing triazole linkers. The QPPBTF-TMA-w membranes stand out for their lower activation energy for hydroxide conduction which is attributed to the well-structured ion-conducting channels via distinct phase separation facilitated by the triazole linker, which optimizes hydrophilicity and ensures efficient ion transport within the membrane. In addition, the QPPBTF-TMA-w membranes exhibit unique anisotropic swelling and ion conduction behaviors, such as lower in-plane swelling and higher through-plane conductivity, which are advantageous for practical cell applications. Therefore, despite having a modest ion exchange capacity (IEC) value of 2.0, the QPPBTF-TMA-w membrane delivers high performance in anion exchange membrane water electrolysis (AEMWE), achieving 6.4 A cm-2 at 2.0 V at 70 °C using a 1.0 M KOH solution.

Carbon aerogel supported Ni–Fe catalysts for superior oxygen evolution reaction activity

AbstractElectrochemical water splitting presents an optimal approach for generating hydrogen (H2), a highly promising alternative energy source. Nevertheless, the slow kinetics of the electrochemical oxygen evolution reaction (OER) and the exorbitant cost, limited availability, and susceptibility to oxidation of noble metal-based electrocatalysts have compelled scientists to investigate cost-effective and efficient electrocatalysts. Bimetallic nanostructured materials have been demonstrated to exhibit improved catalytic performances for the oxygen evolution reaction (OER). Herein, we report carbon aerogel (CA) decorated with different molar ratios of Fe and Ni with enhanced OER activity. Microwave irradiation was involved as a novel strategy during the synthesis process. Inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscope (SEM), Energy dispersive X-ray spectroscopy (EDAX spectra and EDAX mapping), Transmission Electron Microscope (TEM), High-Resolution Transmission Electron Microscope (HR-TEM), and Selected Area Electron Diffraction (SAED) were used for physical characterizations of as-prepared material. Electrochemical potential towards OER was examined through cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS). The FeNi/CA with optimized molar ratios exhibits low overpotential 377 mV at 10 mAcm−2, smaller Tafel slope (94.5 mV dec−1), and high turnover frequency (1.09 s−1 at 300 mV). Other electrocatalytic parameters were also calculated and compared with previously reported OER catalysts. Additionally, chronoamperometric studies confirmed excellent electrochemical stability, as the OER activity shows minimal change even after a stability test lasting 3600 s. Moreover, the bimetallic (Fe and Ni) carbon aerogel exhibits faster catalytic kinetics and higher conductivity than the monometallic (Fe), which was observed through EIS investigation. This research opens up possibilities for utilizing bi- or multi-metallic anchored carbon aerogel with high conductivities and exceptional electrocatalytic performances in electrochemical energy conversion.

An organic proton cage that is ultra-resistant to hydroxide-promoted degradation

Alkaline polymer membrane electrochemical energy conversion devices offer the prospect of using non-platinum group catalysts. However, their cationic functionalities are currently not sufficiently stable for vapor-phase applications, such as fuel cells. Herein, we report 1,6-diazabicyclo[4.4.4]tetradecan-1,6-ium (in-DBD), a cationic proton cage, that is orders of magnitude more resistant to hydroxide-promoted degradation than state-of-the-art organic cations under ultra-dry conditions and elevated temperature, and the first organic cation-hydroxide to persist at critically low hydration levels ( < 10% RH at 80 °C). This high stability against hydroxide-promoted degradation is due to the unique combination of endohedral protection and intra-bridgehead hydrogen bonding that prevents the removal of the inter-cavity proton and lowers the susceptibility to Hofmann elimination. We anticipate this discovery will facilitate a step-change in the advancement of materials and electrochemical devices utilizing anion-exchange membranes based on in-DBD that will enable stable operation under extreme alkaline conditions.

Regulation of V2O5 layer spacing by controlling H2O/C2H5OH ratio in hydrothermal process for application in electrochemical conversion of salinity gradient energy

Another abundant source of renewable energy exists in the oceans, where the chemical energy released from the mixing of seawater and river water is known as salinity gradient energy or blue energy. Salinity gradient energy is a sustainable, clean and renewable energy source that produces electricity without emitting greenhouse gasses or other pollutants. In this work, we constructed a new salinity gradient energy extraction device by preparing V2O5 in a very simple way by controlling H2O/C2H5OH ratio in hydrothermal process and using the V2O5 as an anode to obtain salinity gradient energy by utilizing the salinity change of the solution and thus the potential difference power generation. The results show that ethanol forms hydrogen bonds or van der Waals forces with the layered material, which enters the interlayer to enlarge the spacing between the layers of V2O5 and further increase the electrochemical properties of V2O5. The maximum energy density produced by the device was 6.29 J g−1 after one complete cycle. The device is environmentally friendly with low cost, easy to synthesize raw materials and does not use ionic membranes, which provides a new way to harvest the salinity gradient energy.

Selectivity-Enhanced Electroreduction of CO2 to CO at Novel Ru-Linked-GO Nanohybrids: the Role of Nanoarchitecture.

Recently, global-scale efforts have been conducted for the electroreduction of CO2 as a potentially beneficial pathway for the conversion of greenhouse gases to useful chemicals and renewable fuels. This study focuses on the development of selective and sustainable electrocatalysts for the reduction of aqueous CO2 to CO. A RuIIcomplex [Ru(tptz)(ACN)Cl2] (RCMP) (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, ACN = acetonitrile) was prepared as a molecular electrocatalyst for the CO2 reduction reaction in an aqueous solution. Density functional theory-calculated frontier molecular orbitals suggested that the tptz ligand plays a key role in dictating the electrocatalytic reactions. The RCMP electrocatalyst was grafted onto the graphene oxide (GO) surface both noncovalently (GO/RCMP) and covalently (GO-RCMP). The field emission scanning electron microscopy and elemental distribution analyses revealed the homogeneous distribution of the complex onto the GO sheet. The photoluminescence spectra confirmed accelerated charge-transfer in both nanohybrids. Compared to the bare complex, the GO-RCMP and GO/RCMP nanohybrids showed enhanced electrocatalytic activity, achieving >95% and 90% Faradaic efficiencies for CO production at more positive onset potentials, respectively. The GO-RCMP nanohybrid demonstrated outstanding electrocatalytic activity with a current of ∼84 μA. The study offers a perspective on outer- and inner-sphere electron-transfer mechanisms for electrochemical energy conversion systems.

Anion exchange membranes derived from poly(ionic liquid) of poly(bis-piperidinium) and polybenzimidazole blends

Anion exchange membranes (AEMs) play a critical role in various environmentally friendly electrochemical energy conversion and storage devices such fuel cells, water electrolysis and flow batteries. Recently, AEMs based on ether-free ionomers or ionenes have attracted much attention due to their excellent alkaline stabilities, however normally suffering from multiple-step synthetic procedure, post-functionalization and the use of precious metal catalysts. In this study, we develop a facile method to synthesize bis-piperidinium main-chain poly(ionic liquid)s devoid of ether linkages through the nucleophilic reaction between a bis-piperidine monomer of 4,4′-trimethylene bis(1-methyl-piperidine) and various bifunctional alkyl or aryl bromides. Seven poly(ionic liquid)s of poly(bis-alkyl piperidinium) are subsequently blended with polybenzimidazole (PBI) to give mechanically robust and dimensionally stable AEMs. The membrane performances are readily adjusted by changing the chemical structure of poly(bis-alkyl piperidinium)s. The membrane based on the poly(bis-alkyl piperidinium) containing a flexible butylidene spacer chain achieves the highest Br- conductivity of 67 mS cm−1 at 80 °C, tensile strength of around 13 MPa at room temperature, and a superior alkaline stability in 1 mol/L KOH at 60 °C during 1250 h. Density functional theory calculations further support the enhanced alkaline stability of the piperidinium cation with alkyl group compared with the one with benzyl group.

Special issue on electrochemical conversion and utilization of hydrogen energy

Special issue on electrochemical conversion and utilization of hydrogen energy

In Situ Determination of the Potential Distribution within a Copper Foam Electrode in a Zinc‐Air/Silver Hybrid Flow Battery

AbstractThis work describes a novel methodology for measuring the potential distribution within the porous copper foam electrode of a zinc‐air/silver hybrid (ZASH) flow battery by using local potential probes. The suitability of dynamic hydrogen electrodes (DHEs) and a quasi‐reference electrode as probes is evaluated, with the latter chosen in view of stability. Liquid and solid‐phase potentials are recorded at varying applied current densities over multiple charge‐discharge cycles. Various zinc structures are found within specific overpotential ranges, with moss‐like structures appearing between 7.8 mV and 13.2 mV and the desired boulder structures in the range of 22 mV to 100 mV. Regardless of the current density, the highest liquid‐phase potentials are always measured in the outermost region of the porous foam near to the separator. In practice, this means that increasing the thickness of the copper foam over about 5 mm does not provide significant performance benefits. Conversely, solid‐phase potentials across the copper foam remain nearly uniform, resulting in negligible effects on local overpotential. The presented technique provides unique insights into the behavior of porous electrodes in electrochemical energy conversion technologies, facilitating the determination of the optimal properties for maximum efficiency, such as electrode thickness.

Chitosan Composite Membrane with Efficient Hydroxide Ion Transport via Nano-Confined Hydrogen Bonding Network for Alkaline Zinc-Based Flow Batteries.

The development of membranes with rapid and selective ionic transport is imperative for diverse electrochemical energy conversion and storage systems, including fuel cells and flow batteries. However, the practical application of membranes is significantly hindered by their limited conductivity and stability under strong alkaline conditions. Herein, a unique composite membrane decorated with functional Cu2+ cross-linked chitosan (Cts-Cu-M) is reported and their high hydroxide ion conductivity and stability in alkaline flow batteries are demonstrated. The underlying hydroxide ions transport of the membrane through Cu2+ coordinated nano-confined channels with abundant hydrogen bonding network via Grotthuss (proton hopping) mechanism is proposed. Consequently, the Cts-Cu-M membrane achieves high hydroxide ion conductivity with an area resistance of 0.17Ωcm2 and enables an alkaline zinc-based flow battery to operate at 320mAcm-2, along with an energy efficiency of ≈80%. Furthermore, the membrane enables the battery for 200cycles of long-cycle stability at a current density of 200mAcm-2. This study offers an in-depth understanding of ion transport for the design and preparation of high-performance membranes for energy storage devices and beyond.

Large-Scale Synthesis of Highly Porous CuO/Cu2O/Cu/Carbon Derived from Aerogels for Lithium-Ion Battery Anodes.

In this work, an effective strategy for the large-scale fabrication of highly porous CuO/Cu2O/Cu/carbon (P-Cu-C) has been established. Cu-cross-linked aerogels were first continuously prepared using a continuous flow mode to form uniform beads, which were transformed into P-Cu-C with a subsequent pyrolysis process. Various pyrolysis temperatures were used to form a series of P-Cu-C including P-Cu-C-250, P-Cu-C-200, P-Cu-C-350, and P-Cu-C-450 to investigate suitable pyrolysis conversion processes. The obtained P-Cu-C series were utilized as anodes of lithium-ion batteries, in which P-Cu-C-250 exhibited a higher reversible gravimetric capacity, excellent rate capability, and superior cycle stability. The enhanced behavior of P-Cu-C-250 was benefitted from the synergistic interaction between uniformly dispersed CuO, Cu2O, Cu nanoparticles, and highly graphitized carbon with a large surface area and highly porous structure. More importantly, the preparation of P-Cu-C-250 could be scaled up by taking advantage of the continuous flow synthesis mode, which may provide pilot- or industrial-scale applications. The large-scale fabrication proposed here may give a universal method to fabricate highly porous metal oxide-carbon anode materials for electrochemical energy conversion and storage applications. Porous CuO/Cu2O/Cu/carbon derived from Cu-crosslinked aerogels was used as Li-ion battery anode materials, exhibiting a high reversible areal capacity, large gravimetric capacity, superior cycling performance, and excellent rate capacity. A continuous preparation method is established to ensure the product scaled up.

Superior supercapacitor performance with tuneable 2D/3D morphological microporous carbons of zeolitic imidazolate frameworks synthesized by recycling mother liquors

Carbonized metal–organic frameworks (MOFs)-based nanoporous carbon materials (NPCs) offer attractive activities in electrochemical energy conversion and storage (EECS) applications; however, there is the need for scalable MOFs production under reduced energy/environmental impact. This study reports a green synthesis route for model zeolitic imidazolate framework (ZIF-8) materials via recycling methanol-based mother liquors (ZIF-RMLx) under room temperature stirring and their carbonized materials (CZC-RMLx) for high-performance supercapacitors. Series of ZIF-RMLx samples produced in four recycles offer rod-/sheet-/polyhedral-like 2D/3D microstructures with tuneable internal and external framework and morphological features. Accordingly, CZC-RMLx, obtained by direct pyrolysis, with high microporosity and surface area of 1500 m2 g−1 deliver excellent capacitance values of 200–340 F g−1, compared to typical MOFs-derived or chemically activated/templated NPCs, produced via extended chemical processing. Structure-relevant and comparative performance analysis reveal insights for improved charge storage and carbonization-dependent graphitization, nitrogen-doping and microporosity-controlled capacitance characteristics in the CZC-RMLx over typical NPCs in literature. The device-level performance with a long-term durability over 21,000 cycles is demonstrated. The practical potential of CZC-RMLx is further evaluated by fabricating solid-state cells and their parallel and series circuit combinations result in overall capacitance and voltage boost to 450 F g−1 and 2.4 V, respectively.

Special issue on electrochemical energy storage and conversion

Special issue on electrochemical energy storage and conversion

New Understanding and Improvement in Sintering Behavior of Cerium‐Rich Perovskite‐Type Protonic Electrolytes

AbstractProtonic ceramic cells show great promises for electrochemical energy conversion and storage, while one of the key challenges lies in fabricating dense electrolytes. Generally, the poor sinterability of most protonic ceramic electrolytes, such as BaZr0.1Ce0.7Y0.1Yb0.1O3‐δ, is attributed to the Ba evaporation at high temperatures. In a systematic and comparative study of BaCeO3 and BaZrO3, the results demonstrated that Ba tends to segregate to grain boundaries rather than evaporate. Additionally, thermal reduction of Ce4+ to Ce3+ promotes the displacement of Ce to the Ba‐site or the exsolution of CeO2 phase, leading to an abnormal lattice shrinkage of perovskite phase and hindering the electrolyte densification. Contrary to previous beliefs that Ba deficiency inhibits the electrolyte sintering, the findings indicate that it surprisingly promotes the sintering of BaZrO3 perovskites, while excess Ba negatively affects its sintering behavior due to the accumulation of Ba species at grain boundaries. As to BaCeO3, excess Ba improves electrolyte sintering by suppressing the Ce exsolution at high temperatures. Meanwhile, Co‐doping Zr and Ce in the B‐site of protonic perovskite can optimize the sintering characteristic. These findings offer new insights into sintering of protonic perovskites and provide guidance for the development of new protonic devices.

Carbon materials derived by crystalline porous materials for capacitive energy storage

Abstract The controlled synthesis of precise carbon nanostructures with high electron conductivity, high reaction activity, and structural stability plays a significant role in practical applications yet largely unmet. Metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and coordination polymers (CPs) as crystalline porous materials (CPMs) have shown extraordinary porosity, tremendous structural diversity, and highly ordered pores, offering a platform for precise controlled carbon materials (CMs) with regular porous structures and high performances. Some recent studies have shown that CMs derived from CPMs with high specific surface area, superior chemical stability, excellent electrical conductivity offer a great opportunity for electrochemical energy storage and conversion. In this review, we summarize recent milestones of CPMs derived CMs in the field of capacitive energy storage. We hope the more precise design and control at the atomic level of CPMs could provide us a constructive view of the structure-activity relationship between CMs and electrochemical capacitors, as well as future trends and prospects.

ACS Spotlight: Bipolar Membranes for Electrochemical Energy Conversion, Chemical Manufacturing, and Separations

ACS Spotlight: Bipolar Membranes for Electrochemical Energy Conversion, Chemical Manufacturing, and Separations

Structural reconstruction of electrocatalysts

Efficient and durable electrocatalysts are essential for achieving high electrocatalytic efficiency in electrocatalytic reactions, forming the bedrock of effective electrochemical energy technologies. Electrocatalysis is a complex process, marked by intricate reaction system and crucial interfacial interactions, leading to diverse degrees of reconstruction changes in electrocatalysts, affecting both catalytic capabilities and structural integrity. This review delves into the development and prospects of electrocatalyst reconstruction within the electrochemical energy conversion and storage technologies. It elucidates the underlying motivation and mechanism driving reconstruction in various oxidation/reduction reaction systems. Moreover, it elucidates the evolution and comprehension of highly effective electrocatalysts that emerge as a result of this reconstruction phenomenon. The characterizations of catalyst reconstruction are thoroughly examined through the cutting-edge imaging/spectroscopy technologies, enabling dynamic reconstruction tracking and identification. Finally, this work highlights the challenges and opportunities associated with advancing reconstructed electrocatalysts. The primary objectives are to fathom the intricacies of reconstruction and its structural evolution for precise catalyst design. Additionally, it aims to regulate the reconstruction process to enhance the electrocatalyst longevity, stabilize catalytic reactions, and ultimately facilitate the implementation of electrochemical technologies.

Confined grotthuss proton-conduction along polyoxometalate chains inside carbon nanotubes for high-rate charge storage

Redox-active materials with excellent rate capability and cycling performance are in highly demand for electrochemical energy storage and conversion applications. Here, we unveil the confined proton-conduction behavior of one-dimensional polyoxometalate chains inside single-walled carbon nanotubes (SWNTs). The polyoxometalate molecules including phosphomolybdic acid {HPMo} and phosphotungstic acid {HPW} are encapsulated within SWNTs via host–guest recognition, driven by the electron transfer from nanotubes to polyoxometalates. Impressively, the redox hybrids of polyoxometalate@SWNTs deliver abnormal rate performance in acidic solution with capacity retentions over 73 % at high sweep rate of 1000 mV s−1, relative to the capacity at 10 mV s−1. This value is comparable to that of the pure SWNTs, typically known as double-layer capacitive materials. Electrochemical analyses reveal the Grotthuss proton-conduction mechanism of {HPMo} in SWNTs with a low activation energy of 0.11 eV. Therefore, the {HPMo}@SWNT hybrid demonstrates quasi diffusion-free characteristic with dominant capacitive contribution over 60 % at different sweep rates. Molecular dynamic simulations and density functional theory calculations evidence the strong burst-like transport of protons in the {HPMo}@SWNT hybrid. This process is dynamically favored in the continuous and long-range hydrogen-bond network along polyoxometalate chains with bound/free water molecules inside SWNTs. The superiority of nanoconfined Grotthuss mechanism may engender an exciting avenue for developing high-performance energy storage materials.