High Areal Capacitance Research Articles

Molecule Engineering of Sugar Derivatives as Electrolyte Additives for Deep-Reversible Zn Metal Anode.

The cycling performance of zinc-ion batteries is greatly affected by dendrite formation and side reactions on zinc anode, particularly in scenarios involving high depth of discharge (DOD) and low negative/positive capacity (N/P) ratios in full cells. Herein, drawing upon principles of host-guest interaction chemistry, we investigate the impact of molecular structure of electrolyte additives, specifically the -COOH and -OH groups, on the zinc negative electrode through molecular design. Our findings reveal that molecules containing these groups exhibit strong adsorption onto zinc anode surfaces and chelate with Zn2+, forming a H2O-poor inner Helmholtz plane. This effectively suppresses side reactions and promotes dendrite-free zinc deposition of exposed (002) facets, enhancing stability and reversibility of an average coulombic efficiency of 99.89 % with the introduction of Lactobionic acid (LA) additive. Under harsh conditions of 92 % DOD, Zn//Zn cells exhibit stable cycling at challenging current densities of 15 mA ⋅ cm-2. Even at a low N/P ratio of 1.3, Zn//NH4V4O10 full cells with LA electrolyte exhibit high-capacity retention of 73 % after 300 cycles, significantly surpassing that of the blank electrolyte. Moreover, in a conversion type Zn//Br static battery with a high areal capacity (~5 mAh ⋅ cm-2), LA electrolyte sustains an improved cycling stability of 700 cycles.

High Areal Capacitance and Rate Capability of 3D-Printed Thick Electrodes with Optimized Conductive Networks from the Core-Sheath Structure.

Material extrusion 3D printing has received enormous attention to potentially overcome its limits by tailoring and designing thick electrodes. In this work, we prepared a thick reduced graphene oxide/carbon nanotube-reduced graphene oxide/carbon nanotubes/manganese oxide@carbon nanotubes (rGC-rGCMC) electrode with controlled lattice architectures, core-sheath structure, and hierarchical porosity by material coaxial extrusion 3D printing, freeze-drying, and thermal treatment. The volume ratios of core to sheath, including 100%-0%, 0%-100%, 20%-80%, 30%-70%, 40%-60%, and 50%-50%, were designed to investigate the influences of the core-sheath structure on thick electrodes. The electrodes with a core-sheath volume ratio of 30%-70% electrodes exhibited an enhanced areal specific capacitance of 588.27 mF cm-2 (39.48 F g-1) at a scan rate of 0.5 mA cm-2. All capacitance decays from core-sheath electrodes (20%-80%, 30%-70%, 40%-60%, and 50%-50%) were smaller than those from rGCMC (0%-100%) electrodes, indicating the improved rate capability from the core-sheath structure. On comparison of 30%-70% core-sheath electrodes with electrodes made of a homogeneous 30% rGC and 70% rGCMC mixture (30%+70%), lower capacitance (382.27 mF cm-2 and 25.66 F g-1 at 0.5 mA cm-2) of the 30%+70% mixture electrode without a core-sheath structure suggested less efficiency to harvest electrons from the redox reactions. Electrochemical impedance spectroscopy (EIS) data further supported and explained the resistances of thick electrodes with different volume ratios.

Thermal vapor sulfurization of Ti3C2TX MXene to TiS2/carbon nanosheet cathode for long-life and high-loading all-solid-state lithium batteries

Stable and fast operation of all-solid-state lithium batteries (ASSBs) depends on durable and sufficient interfacial contacts between electrode components, especially when the loading and content of electrode active materials are high. Here, we propose promoting ionic/electronic transportations and contacts in sulfide electrolyte-based ASSBs by using TiS2/carbon nanosheets (TiS2/C-s) with large area-to-thickness aspect ratios as the cathode, which are prepared by simple thermal vapor sulfurization of exfoliated Ti3C2Tx MXene. The elastic 2D structure of the TiS2/C-s material can substantially improve interfacial contact with the solid electrolyte, minimize the diffusion distance of lithium ions, and buffer volume/stress changes during cycling, thereby ensuring the electro-chemo-mechanical stability and fast reaction kinetics of electrodes. Consequently, a 50 wt% TiS2/C-s cathode without any conductive carbon additives demonstrates a high discharge capacity (295 mAh g−1), long-term cyclic stability (94.7 and 74.7 % capacity retention after 250 cycles at 0.1 mA cm−2 and after 2300 cycles at 1 mA cm−2, respectively), and decent rate capability (126.0 mAh g−1 at 3 mA cm−2). Moreover, stable cycling with a high areal capacity (5.95 mAh cm−2) can also be achieved.

Facile and scalable fabrication of flexible microsupercapacitor based on boron modified 2D/2D 1 T MoS2/MXene hybrids

Micro-supercapacitors (MSCs) with outstanding flexibility and electrochemical performance are critical for portable and miniaturized electronics. This study utilizes the potential utilization of Boron-modified MoS2/MXene heterostructure for fabricating highly efficient and durable microsupercapacitors. The Boron incorporation and hybrid formation significantly enhance the electrochemical performance of 1 T MoS2 and MXene (Ti3C2Tx) by activating their basal plane. The boron modified MoS2/Ti3C2Tx(B-1 T MoS2/Ti3C2Tx_) demonstrates excellent energy storage performance with a capacitance of around 420 Fg−1 in two-electrode system. Laser scribed graphene (LSG), chosen for its superior wettability, serves as the current collector facilitating the development of these MSC based on B-1 T MoS2/Ti3C2Tx. The resulting MSC demonstrates a high areal capacitance of nearly 72.31 mF/cm2 and excellent stability over 10,000 cycles. Density functional theory (DFT) simulations support these findings, indicating that hybridization with Ti3C2Tx and B substitution enhances the conductivity of the 1 T-MoS2 system. The quantum capacitance of B-substituted hybrid system surpasses that of the pristine material, validating the experimental observations of enhanced charge storage performance.

Ion‐sieving MXene flakes with quantum dots enable high plating capacity for dendrite‐free Zn anodes

AbstractThe commercial utilization of Zn metal anodes with high plating capacity is significantly hindered by the uncontrolled growth of dendrites and associated side reactions. Herein, a robust artificial ion‐sieving MXene flake (MXF)‐coating layer, with abundant polar terminated groups, is constructed to regulate the interfacial Zn2+ deposition behavior. In particular, the fragmented MXF coupled with in situ generated quantum dots not only has strong Zn affinity to homogenize electric fields but also generates numerous zincophilic sites to reduce nucleation energy, thus securing a uniform dendrite‐free surface. Additionally, the porous coating layer with polar groups allows the downward diffusion of Zn2+ to achieve bottom‐up deposition and repels the excessive free water and anions to prevent parasitic reactions. The ion‐sieving effect of MXF is firmly verified in symmetric cells with high areal capacity of 10–40 mAh cm−2 (1.0 mA cm−2) and depth of discharge of 15%–60%. Therefore, the functional MXF‐coated anode manifests long‐term cycling with 2700 h of stable plating/stripping in Zn||Zn cell. Such rational design of MXF protective layer breaks new ground in developing high plating capacity zinc anodes for practical applications.

Fabrication of functional laser-induced graphene using gelatin-2,6-diaminoanthraquinone coating for high-performance micro-supercapacitor

In this investigation, we develop a procedure in which gelatin and 2,6-diaminoanthraquinone (ANQ) are combined and then applied as a coating on laser-induced graphene (LIG). The resulting materials are subjected to laser irradiation, which facilitates the introduction of nitrogen doping and the integration of oxygenated functional groups onto the LIG surface. The gelatin polymer played a pivotal role in introducing oxygenated functional groups, while ANQ molecules contributed to both doping with nitrogen and the inclusion of additional oxygenated groups on the LIG surface. The electrode material's performance was enhanced by these functional groups. When evaluated in a three-electrode setup, the ANQ-LIG configuration exhibited a significantly high areal capacitance of 32.4 mF cm−2 at 0.2 mA cm−2, which is five times that of pristine LIG (6.3 mF cm−2) and three times that of gelatin-LIG (9.0 mF cm−2). When integrated into a micro-supercapacitor using a polyvinyl alcohol (PVA)-sulfuric acid (H2SO4) gel electrolyte, ANQ-LIG demonstrated superior areal capacitance (16.0 mF cm−2 at 0.1 mA cm−2) compared to gelatin-LIG (5.3 mF cm−2) at the same current. Additionally, ANQ-LIG displayed favorable capacitance retention (83.8 % after 10,000 cycles) and coulombic efficiency (98.1 % after 10,000 cycles).

Ultrathin titanium carbide-modified separator for high-performance lithium–sulfur batteries

Despite a high theoretical capacity, the practical application of lithium-sulfur batteries has been primarily limited by the migration of long-chained polysulfide species during the charge/discharge processes. One effective approach to address the issues is to design a functional separator or interlayer. Here, we prepared a modified separator with an ultrathin layer of titanium carbide (TiC) using radio-frequency sputtering on a commercial Celgard polypropylene membrane. The 240-nm TiC coating layer can enhance the interfacial properties of Celgard separators in porosity, wettability, roughness, etc. Hence, via experimental and theoretical investigation, we discovered that TiC can efficiently adsorb polysulfides and boost charge transfer via strong covalent C–S bonds. Using a TiC-modified separator can impede the shuttle effect and improve the kinetics of sulfur conversion reactions. Thus, the Li–S batteries with TiC separator deliver excellent electrochemical performances with a good rate capability (717 mAh g−1 at 7.0C) and an ultra-low decay rate of 0.058 % per cycle over 800 cycles at a C-rate of 2.0C. Furthermore, a high areal capacity of 4.3 mAh cm−2 was achieved with a high mass-loading of sulfur cathode up to 7.0 mg cm−2.

NiCo layered double hydroxides/carbon dots composites with S-doing for high-performance asymmetric supercapacitors

The pursuit of high-performance electrode materials for supercapacitors has led to the exploration of transition metal layered double hydroxides (LDH), which boast an impressive theoretical specific capacitance. However, their intrinsic limitations, such as poor electronic conductivity and slow diffusion kinetics, have posed significant challenges for their practical implementation. In this work, a NiCo LDH/carbon dots (CDs) composite with S-doping has been meticulously designed to overcome the aforementioned limitations through a synergistic combination of heteroatom doping and carbon incorporation. Utilizing a one-pot hydrothermal method, the composite electrode for the application of asymmetric supercapacitors have been in-situ growth on Ni foam substrate, which not only serves as a robust support but also contributes to the formation of NiCo LDH by providing a uniform Ni source, thereby ensuring strong adhesion and structural integrity. The morphology and microstructures of composites could be finely modulated by adjusting CDs amount. With moderate CDs contents, the optimum electrode S-LDH/CDs-2 exhibits distinctive 3D needle-like spherical morphology, coupled with the ample space for ion diffusion. Consequently, the electrode demonstrates outstanding electrochemical performance, featuring a high areal capacitance of 5157 mF cm−2 at a current density of 2 mA cm−2. Additionally, it exhibits noteworthy rate performance and maintains excellent cycling stability. Integrating the innovative electrode into asymmetric supercapacitors configuration, superior energy density (0.24–0.45 mWh cm−2) and power density (4–20 mW cm−2) as well as good stability have been achieved for the S-LDH/CDs-2//AC device. These results indicate that S-doped NiCo LDH/CDs composite electrode has the desirable potential to be a candidate for energy storage devices.

Polyvinyl alcohol/sodium alginate-based conductive hydrogels with in situ formed bimetallic zeolitic imidazolate frameworks towards soft electronics

Bimetallic zeolitic imidazolate frameworks (BZIFs) have received enormous attention due to their unique physi-chemical properties, but are rarely reported for electrically conductive hydrogel (ECH) applications arising from low intrinsic conductivity and poor dispersion. Herein, we propose an innovative strategy to prepare highly conductive and mechanically robust ECHs by in situ growing Ni/Co-BZIFs within the polyvinyl alcohol/sodium alginate dual network (PZPS). 2-methylimidazole (MeIM) ligands copolymerize with pyrrole monomers, enhancing the electrical conductivity; meanwhile, MeIM ligands act as anchor points for in-situ formation of BZIFs, effectively avoiding phase-to-phase interfacial resistance and ensuring a uniform distribution in the hydrogel network. Due to the synergism of Ni/Co-BZIFs, the PZPS hydrogel exhibits a high areal capacitance of 630.3 mF·cm−2 at a current density of 0.5 mA·cm−2, promising for flexible energy storage devices. In addition, PZPS shows excellent mechanical strength and toughness (with an ultimate tensile strength of 405.0 kPa and a toughness of 784.2 kJ·m−3 at an elongation at break of 474.0 %), a high gauge factor of up to 4.18 over an extremely wide stress range of 0–42 kPa when used as flexible wearable strain/pressure sensors. This study provides new insights to incorporating highly conductive and uniformly dispersed ZIFs into hydrogels for flexible wearable electronics.

Promoted Stability and Reaction Kinetics in Ni-Rich Cathodes via Mechanical Fusing Multifunctional LiZr2(PO4)3 Nanocrystals for High Mass Loading All-Solid-State Lithium Batteries.

Sulfide all-solid-state lithium battery (ASSLB) with nickel-rich layered oxide as the cathode is promising for next-generation energy storage system. However, the Li+ transport dynamic and stability in ASSLB are hindered by the structural mismatches and the instabilities especially at the oxide cathode/sulfide solid electrolyte (SE) interface. In this work, we have demonstrated a simple and highly effective solid-state mechanofusion method (1500 rpm for 10 min) to combine lithium conductive NASICON-type LiZr2(PO4)3 nanocrystals (∼20 nm) uniformly and compactly onto the surface of the single crystallized LiNi0.8Co0.1Mn0.1O2, which can also attractively achieve Zr4+ doping in NCM811 and oxygen vacancies in the LZPO coating without solvent and annealing. Benefiting from the alleviated interface mismatches, sufficient Li+ ion flux through the LZPO coating, promoted structural stabilities for both NCM811 and sulfide SE, strong electronic coupling effect between the LZPO and NCM811, and enlarged (003) d-spacing with enriched Li+ migration channels in NCM811, the obtained LZPO-NCM811 exhibits superior stability (185 mAh/g at 0.1C for 200 cycles) and rate performance (105 mAh/g at 1C for 1300 cycles) with high mass loading of 27 mgNCM/cm2 in sulfide ASSLB. Even with a pronounced 54 mgNCM/cm2, LZPO-NCM811 manifests a high areal capacity of 9.85 mAh/cm2. The convenient and highly effective interface engineering strategy paves the way to large-scale production of various coated cathode materials with synergistic effects for high performance ASSLBs.

A Nanofibrous Polypyrrole Membrane with an Ultrahigh Areal Specific Capacitance and Improved Energy and Power Densities.

For conductive polymers to be competitive with carbon-based electrode materials, it is critical to increase their surface area and electroactivity. In this work, a thick nanofibrous polypyrrole (PPy) membrane with communicating interfiber spaces was prepared through one-pot interfacial polymerization for the first time. The electrochemical properties and conductivity of the membrane were studied with cyclic voltammetry, electrochemical impedance spectroscopy, and a four-point probe. Its morphology, chemistry, and thermostability were evaluated by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The areal specific capacitances measured between 0.0 and 0.8 V at 1 mA/cm2 were 19179, 13264, 7238, and 4458 mF/cm2 for the membranes doped with docusate sodium (AOT), camphor-10-sulfonic acid (β) (CSA), Cl-, and poly(sodium 4-styrenesulfonate) (PSS), respectively. The capacity retentions after 1000 cycles were 83, 74, 67, and 61% for the AOT-, CSA-, PSS-, and Cl--doped membranes, respectively. The Coulombic efficiency was above 99% for all of the membranes. They showed energy densities of 1.7, 1.2, 0.7, and 0.4 mWh/cm2 and power densities of 0.61, 0.75, 0.66, and 0.62 mW/cm2 for the AOT-, CSA-, Cl--, and PSS-doped membranes, respectively. The ultrahigh areal specific capacitance of PPy-AOT is due to its nanofibrous structure. A mechanism has been proposed to explain how this structure is formed based on the role of AOT as the surfactant. This nanofibrous PPy membrane is easy to prepare and metal-free and offers a very high areal specific capacitance, making it an excellent candidate to construct electrodes in pseudosupercapacitors.

A Porous Li-Al Alloy Anode toward High-Performance Sulfide-Based All-Solid-State Lithium Batteries.

Compared to lithium (Li) anode, the alloy/Li-alloy anodes show more compatible with sulfide solid electrolytes (SSEs), and are promising candidates for practical SSE-based all-solid-state Li batteries (ASSLBs). In this work, a porous Li-Al alloy (LiAl-p) anode is crafted using a straightforward mechanical pressing method. Various characterizations confirm the porous nature of such anode, as well as rich oxygen species on its surface. To the best knowledge, such LiAl-p anode demonstrates the best room temperature cell performance in comparison with reported Li and alloy/Li-alloy anodes in SSE-based ASSLBs. For example, the LiAl-p symmetric cells deliver a record critical current density of 6.0mA cm-2 and an ultralong cycling of 5000h; the LiAl-p|LiNi0.8Co0.1Mn0.1O2 full cells achieve a high areal capacity of 11.9 mAh cm-2 and excellent durability of 1800 cycles. Further in situ and ex situ experiments reveal that the porous structure can accommodate volume changes of LiAl-p and ensure its integrity during cycling; and moreover, a robust Li inorganics-rich solid electrolyte interphase can be formed originated from the reaction between SSE and surface oxygen species of LiAl-p. This study offers inspiration for designing high-performance alloy anodes by focusing on designing special architecture to alleviate volume change and constructing stable interphase.

High-Entropy Strategy to Suppress Volumetric Strain and Enhance Diffusion Rate of Na3V2(PO4)2F3 Cathode for Durable and High-Areal-Capacity Zinc-Ion Battery Pouch Cells

The burgeoning global environmental awareness and the escalating demand for renewable energy storage have intensified the critical need for next-generation battery technologies.1,2 In recent decades, there has been a sustained pursuit of grid-scale energy storage systems that balance practicality and efficiency. In this context, aqueous zinc-ion batteries (AZIBs) have emerged as a promising contender, driven by the distinct advantages of the 2.8-fold higher volumetric capacity (5849 mAh cm-3) of zinc metal over lithium metal (2062 mAh cm-3), and the use of non-toxic, cost-effective aqueous electrolyte. To date, substantial efforts have been dedicated to investigating suitable AZIB cathode materials, including Prussian blue analogs (PBAs), transition-metal (TM) oxides (e.g., MnO2 and V2O5), organic compounds, and polyanion-type compounds.Recently, there has been a notable surge of interest in polyanion-type compounds. Na3V2(PO4)2F3 (NVPF), demonstrates an operating potential of exceeding 1.60 V and an enhanced energy density of 97.5 Wh kg-1. Regrettably, these advantages are often counterbalanced by undesirable side reactions and sluggish ion kinetics, culminating in incompetent rate capabilities and suboptimal cycling stability.3 High-entropy (HE) materials have emerged as promising candidates for facilitating ion transport and fortifying cathode stability across various energy storage systems due to their exceptional design flexibility and compositional tunability.4,5 Inspired by conventional HE stabilization strategies, this work introduces a carbon-coated Na3V1.9(AlZnMnCrNb)0.1(PO4)2F3 cathode, denoted as HE-NVPF@C. Employing this cathode, coupled with a carbon-film-functionalized Zn anode, referred to as Zn@CF, and acetonitrile(AN)-water hybrid electrolyte, we configured an AZIB with substantial enhancements in long-term cycling stability and high areal capacity. AZIBs based on HE-NVPF@C cathodes presented a high reversible capacity of 77.45 mAh g−1 at 2C and remarkable cycling stability with a capacity loss of a mere 0.0031% per cycle over 6,000 cycles at 20C. In particular, the areal capacity of the HE-NVPF@C cathode reached up to 2.17 mAh cm-2, and HE-NVPF@C also attained a high capacity density of 78.2 mAh g-1 and 61.6 mAh g-1 when working under 50 and -20°C, making it more competitive among the reported cathodes in AZIBs. In addition, the pouch cell provides a long cycling lifespan with 90.8% capacity retention at 5C after 200 cycles. More importantly, the Zn2+ storage mechanism of the high-entropy NASICON-type cathode was systematically studied for the first time. In-situ X-ray diffraction (XRD) and density functional theory (DFT) calculations revealed that NVPF@C with high-entropy doping improved cycling stability due to the mitigated Jahn-Teller distortion, enhanced Zn2+ diffusion rate, and reduced lattice volumetric strain upon Zn2+ extraction and insertion. This work not only lays the door for developing stable AZIBs but also enriches the mechanistic discussion about the improved cycling or structural stability of high-entropy NASICON structures.Keywords: Zinc-ion battery; High-entropy material; NASICON; Na3V2(PO4)2F3; Pouch cellReference1 Cao, Y. et al. Bridging the academic and industrial metrics for next-generation practical batteries. Nat. nanotechnol. 14, 200-207, (2019).2 Xue, M. et al. Carbon-assisted anodes and cathodes for zinc ion batteries: From basic science to specific applications, opportunities and challenges. Energy Storage Mater. 62, 102940, (2023).3 Zhu, L. et al. A comprehensive review on the fabrication, modification and applications of Na3V2(PO4)2F3 cathodes. J. Mater. Chem. A 8, 21387-21407, (2020).4 Zeng, Y. et al. High-entropy mechanism to boost ionic conductivity. Science 378, 1320-1324, (2022).5 Yang, C. et al. All-temperature zinc batteries with high-entropy aqueous electrolyte. Nat. Sustain. 6, 325-335, (2023).

Stable Cycling of Ultrahigh Mass Loaded MnO2 for Low-Cost Sodium-Ion Batteries

Achieving cost-effective and sustainable solutions for large-scale energy storage is critical for advancing the global clean energy transition. The intermittent nature of green energy underscores the inadequacy of current large scale energy storage technologies like pumped hydroelectricity which is susceptible to geographic and water resource constraints, making batteries a prime candidate for this role. Although lithium-ion batteries (LIBs) with high energy and power density are a viable solution, the high cost and uneven distribution of lithium reserves limits the widespread application of LIBs for grid energy storage. Considering these developments and the challenges posed by limited lithium reserves, sustainable and low-cost sodium-ion batteries (SIBs) emerge as a promising alternative.Among the various battery electrode materials, manganese dioxide (MnO2) stands out as a promising choice for large-scale energy storage applications due to its earth abundance, cost-effectiveness and non-toxic nature. Although MnO2 is known as a pseudocapacitive material with superior cycling stability in aqueous electrolytes, its dissolution in non-aqueous electrolytes has restricted its widespread use in long lifetime batteries. In this study, we demonstrate that an ether-based electrolyte solution (1M NaClO4 in diglyme) is able to achieve stable cycling of electrodeposited ε-MnO2 as a cathode for SIBs, reaching a over 75% capacity retention over 1000 cycles. This response surpasses conventional ester-based electrolytes (58% of 1M NaClO4 in EC/PC). A comparative cycling stability study, coupled with electrochemical quartz crystal microbalance characterization, validates the efficacy of the ether-based electrolyte in mitigating MnO2 dissolution. Furthermore, the integration of 3D printed graphene aerogel (3D GA) as a scaffold for electrodeposited MnO2 leads to enhanced electrochemical performance of the MnO2 electrode (3D MnO2/GA), resulting in a high areal capacity of 4.4 mAh cm-2 at a current density of 10 mA cm-2. The 3D MnO2/GA electrode possesses scalable electrochemical performance with mass loadings from 20 mg cm-2 to 80 mg cm-2. Using this electrode, a high mass loaded sodium-ion battery (SIB) device was fabricated by using utilizing 58 mg cm-2 3D MnO2/GA as the cathode and 16 mg cm-2 dip-coated TiO2@Cu foam as the anode. This MnO2 | TiO2 device delivered a notable areal capacity of 6.2 mWh cm-2 and a high areal power density of 70.7 mW cm-2. Moreover, the SIB device demonstrates 85% capacity retention after 500 cycles, underscoring the stable cycling of this high-energy and power-density SIB device.

High-Rate and Durable Zinc-Based Flow Batteries for Large-Scale Energy Storage

Large-scale energy storage is a key enabling technology for the widespread adoption of renewable energy such as wind and solar power. Among various technologies, zinc-based flow batteries stand out as one of the most promising candidates due to the high energy density, low cost, and use of earth-abundant active materials. However, the low operating current density and short cycle life resulting from notorious zinc dendrite formation, large internal resistance, and sluggish reaction kinetics pose a great challenge for their practical applications. Although great efforts have been made to address these issues, previous works mainly focused on one specific aspect, making it challenging to boost the overall performance of zinc-based flow batteries. In this presentation, a systematic study on the effects of key components on the electrochemical performance of zinc-bromine flow batteries will be presented. Our results show that all key components (electrodes, electrolytes, membranes, and flow fields) can exert a significant influence on the electrochemical performance. More impressively, a high areal capacity of >200 mAh/cm2 and an operating current density of as high as 400 mA/cm2 can be achieved by optimizing the design and operating parameters. Underlying mechanisms and perspectives for further improvement will be discussed during the presentation.

High Loading Micro-Si anode with Oxidation Controlled Carbon Nanotube Scaffolds: Towards Pouch Cell Fabrication in Industrial Level

Silicon (Si) emerges as a promising anode material for lithium-ion batteries (LiB) due to its ultrahigh theoretical capacity and cost-effectiveness. However, the large-scale fabrication of high-loading Si anodes remains rarely documented. Herein, we developed large-scale oxidation-controlled carbon nanotube (CNT) scaffolds with high electrical conductivity by regulating oxidation conditions. The oxidation-controlled CNTs are self-assembled into an interwoven network, facilitating their incorporation with micro-Si particles and a polymer binder to form a stable aqueous slurry. We investigated the feasibility of scalable electrode coating through rheological analysis, revealing the viscoelastic slurry suitable for industrial-scale shear-coating. Utilizing the bar-coating method, we fabricated a large-scale electrode (30 cm x 40 cm) and confirmed the uniformity of the electrode layer via statistical quality control charts, demonstrating scalability for industrial production. In terms of electrochemical performance, the optimized Si anode surpassed previously reported Si-based anodes, exhibiting a high areal capacity of 3.9 mAh cm−2 and exceptional capacity retention (94 %) after 50 cycles. Finally, we validated the development of the Si anode, nearing industrial-level standards with exceptional pouch cell performance. The oxidation-controlled CNT scaffolds not only enable scalable coating of electrode materials but also effectively mitigate the expansion of micro-Si particles by uniformly covering the Si surface.

Interfacial Modulation with Phosphorylated Covalent Organic Framework Enabling Highly Durable Sodium Metal Batteries in Carbonate‐Based Electrolytes

AbstractThe practical usage of Na metal anode is severely prohibited by the instability of the natively formed solid electrolyte interface (SEI) layer and the uncontrollable Na dendrite growth, inducing short cycle life and serious safety concerns. Herein, phosphorylated covalent organic frameworks (P‐COF) is first synthesized and rationally used to construct the robust artificial interface layer for Na metal stabilization. The modified Na metal anode demonstrates high rate performance (5 mA cm−2) and ultralong cycling lifespan (1800 h) with dendrite‐free Na deposition in carbonate‐based electrolyte. And the assembled Na|Na3V2(PO4)3 (NVP) cell also reveals extraordinarily stable cycling at 5 C for 4000 cycles with a quite low decay rate of 0.002% per cycle. Moreover, the Na|NVP full cell with high areal capacity (2.0 mAh cm−2) and thin Na metal (30 µm) still demonstrates prolonged cycling over 500 cycles even under the harsh condition of a low negative‐to‐positive‐capacity (N/P) ratio of 2:3. Furthermore, the Na|NVP pouch cell with an ultrathick cathode (≈17 mg cm−2) also manifests significantly prolonged cycling performance. This work demonstrates a facile and effective strategy toward reliable Na metal batteries.

Regulation of Zn2+ Solvation Configuration in Aqueous Batteries via Selenium-Substituted Crown Ether Engineering.

The efficient utilization of the metallic Zn in rechargeable aqueous Zn-ion batteries (RAZBs) struggle to suffer from parasitic Zn dendrite formation, hydrogen evolution reactions as well as severe interfacial degradation at high areal capacity loadings. This study thus proposes to employ the modified crown ether as an aqueous electrolyte additive to regulate the Zn2+ desolvation kinetic and facilitates the horizontally oriented (002) deposition of Zn, extending the lifespan of both the symmetric cell and full cell models. Specifically, zincophilic cyano and hydrophobic selenium atoms are incorporated into the crown ether supramolecule to enhance Zn2+ coordination and desolvation capability. The addition of 4-cyanobenzo-21-crown-7-selenium at a low concentration of 0.5 wt.% effectively mitigates hydrogen evolution and Zn corrosion caused by water, promoting the oriented deposition of Zn2+. The Zn||V2O5 full cell prototype, assembled with the areal capacity loadings of 2 mAh cm-2 and N/P ratio of 2.95, exhibits negligible capacity fading at 2.0A g-1 for 300 cycles, highlighting the commercial feasibility of supramolecular macrocycles additive for practical RAZBs applications.

Universal electrolyte cooling strategy realizes high reversibility of zinc metal anodes

Low temperature operation is often perceived as detrimental due to sluggish reaction kinetics for energy storage systems. However, our investigation underscores a noticeable enhancement in the zinc (Zn) metal reversibility under such conditions. By delving into thermodynamics and kinetics, we demonstrated an electrolyte cooling (e.g. −20 °C) strategy that mitigates the inherent corrosiveness during transient period but also curtails the interaction of reactive species during the battery operations. As a proof concept in a strong-acid electrolyte, Zn metal manifest a reversibility approaching 99.66 % in challenging SUS substrate and 99.94 % in Cu substrate at low current density (e.g. 0.1 mA cm-2), typically plagued by harsh HER. Building on this, we demonstrated a stable Zn-MnO2 full cell at low temperatures over 500 cycles and achieved a high areal-capacity reaching 4.96 mAh cm-2. Additionally, the electrolyte cooling strategy demonstrates impressive universality, proving effective across a diverse range of electrolytes. This investigation provides pivotal insights into modulating the HER and augmenting Zn reversibility, shedding light for the development of aqueous Zn-based storage systems.

A robust polyaniline hydrogel electrode enables superior rate capability at ultrahigh mass loadings

Simultaneously achieving high mass loading and superior rate capability in electrodes is challenging due to their often mutually constrained nature, especially for pseudocapacitors for high-power density applications. Here, we report a robust porous polyaniline hydrogel (PPH) prepared using a facile ice-templated in situ polymerization approach. Owing to the conductive, robust, and porous nanostructures suitable for ultrafast electron and ion transport, the self-supporting pure polyaniline hydrogel electrode exhibits superior areal capacitance without sacrificing rate capability and gravimetric capacitance at an ultrahigh mass loading and notable current density. It achieves a high areal capacitance (15.2 F·cm−2 at 500 mA·cm−2) and excellent rate capability (~92.7% retention from 20 to 500 mA·cm−2) with an ultrahigh mass loading of 43.2 mg cm−2. Our polyaniline hydrogel highlights the potential of designing porous nanostructures to boost the performance of electrode materials and inspires the development of other ultrafast pseudocapacitive electrodes with ultrahigh loadings and fast charge/discharge capabilities.