Application In Rechargeable Batteries Research Articles

A novel layered cobalt oxide Ba2Co9O14 as an efficient and durable bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

In this work, a layered cobalt oxide Ba2Co9O14 (BCO), belongs to a Ban+1ConO3n+3(Co8O8) family composed by alternating CdI2 based layers (Co8O8) with n (111) perovskite blocks (Ban+1ConO3n+3), has been developed as a potential bifunctional oxygen electrocatalyst candidate for efficient and durable rechargeable zinc-air battery (ZAB) application. Because of the greatly increased the specific surface area caused by ball-milling, the as-milled BCO material exhibits strongly enhanced bifunctional electrocatalytic activity towards oxygen reduction and oxygen evolution reaction in alkaline medium. Moreover, the assembled BCO-based ZAB yields an effectively improved maximum output power density of 166 mW cm−2, a considerable specific capacity of 789 mAh g−1, and excellent charge-discharge cycle stability of over 250 h at 10 mA cm−2 with over 1500 cycles.

Coal-based carbon nanosheets contained carbon microfibers modified with grown carbon nanotubes as efficient air electrode material for rechargeable zinc-air batteries

Coal-based oxygen electrocatalysts hold immense promise for cost-effective applications in rechargeable Zn-air batteries (ZABs) and the value-added, clean utilization of traditional coal resources. Herein, an electrospun membrane electrode comprising coal-derived carbon nanosheets and directly grown carbon nanotubes (CNS/CMF@CNT) was successfully synthesized. The hierarchical porous structure of the electrode, composed of multiple components, significantly facilitates mass and ion transportation, resulting in exceptional electrochemical performance. Employing Fe as the catalyst for CNT growth, the CNS/CMF@CNT electrode exhibits a remarkable onset potential of 0.96 V and a half-wave potential of 0.87 V in the oxygen reduction reaction (ORR). In-situ surface-enhanced Raman spectroscopy reveals that hydroxyl radical desorption on the surface of CNS/CMF@CNT(Fe) is the rate-determining step of the ORR. Notably, the aqueous ZAB featuring the CNS/CMF@CNT(Fe) electrode achieved a peak power density of 216.0 mW cm−2 at a current density of 414 mA cm−2 and maintained a voltage efficiency of 65.1 % after 2000 charge/discharge cycles at 5 mA cm−2. Furthermore, the all-solid-state ZAB incorporating this electrode displayed an open-circuit voltage of 1.43 V, a peak power density of 70.1 mW cm−2 at a current density of 110 mA cm−2, and a voltage efficiency of 66.5 % after 150 charge/discharge cycles. The utilization of abundant coal as the raw material for electrode fabrication not only brings conceivable economic benefits in ZAB construction, but also commendably advances the effective application of traditional coal resources in a more sustainable manner.

High-Entropy Oxides for Rechargeable Batteries.

High-entropy oxides (HEOs) have garnered significant attention within the realm of rechargeable batteries owing to their distinctive advantages, which encompass diverse structural attributes, customizable compositions, entropy-driven stabilization effects, and remarkable superionic conductivity. Despite the brilliance of HEOs in energy conversion and storage applications, there is still lacking a comprehensive review for both entry-level and experienced researchers, which succinctly encapsulates the present status and the challenges inherent to HEOs, spanning structural features, intrinsic properties, prevalent synthetic methodologies, and diversified applications in rechargeable batteries. Within this review, the endeavor is to distill the structural characteristics, ionic conductivity, and entropy stabilization effects, explore the practical applications of HEOs in the realm of rechargeable batteries (lithium-ion, sodium-ion, and lithium-sulfur batteries), including anode and cathode materials, electrolytes, and electrocatalysts. The review seeks to furnish an overview of the evolving landscape of HEOs-based cell component materials, shedding light on the progress made and the hurdles encountered, as well as serving as the guidance for HEOs compositions design and optimization strategy to enhance the reversible structural stability, electrical properties, and electrochemical performance of rechargeable batteries in the realm of energy storage and conversion.

Electron redistribution and proton transfer induced by atomically fully exposed Cu-O-Fe clusters coupled with single-atom sites for efficient oxygen electrocatalysis

Single-atom catalysts have garnered significant attention by showing sparkling performance in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the air cathode side of energy devices such as metal-air batteries and fuel cells. This work presents a novel catalyst, AC-CuFe-NC, that incorporates Fe-doped CuO atomic clusters (CuOFe) synergistically with single-atom sites. The AC-CuFe-NC demonstrates outstanding ORR performance (half-wave potential of 0.92 V) and an oxygen overpotential gap between ORR and OER as low as 0.61 V, which is among the top reported performances. Combined with in situ ATR-SEIRAS and DFT calculations, it is shown that the synergistic CuOFe atomic clusters are effective in inducing the electronic structure redistribution of the Fe single-atom site, modulating oxygen adsorption energy, and lowering ORR barriers. More importantly, it is revealed that the synergistic adsorption of clusters and single-atom sites establishes hydrogen bonds between the oxygenated intermediates and the electrolyte H2O molecules. The constructed hydrogen bond can provide a pathway for efficient proton transport as supported by kinetic isotope experiments, leading to a substantial enhancement in reaction kinetics. Additionally, the oxygenated intermediates are stabilized, and the Fe-O bond is elongated during the final step of ORR, thereby facilitating the desorption of OH*. The excellent bifunctional electrocatalytic performance of AC-CuFe-NC enable it to show promising application in rechargeable Zn-air batteries. The innovative catalyst structure and synergistic mechanism demonstrated in this study shed light on the development of high-performance catalysts in energy devices.

Emerging Chemistry for Wide-Temperature Sodium-Ion Batteries.

The shortage of resources such as lithium and cobalt has promoted the development of novel battery systems with low cost, abundance, high performance, and efficient environmental adaptability. Due to the abundance and low cost of sodium, sodium-ion battery chemistry has drawn worldwide attention in energy storage systems. It is widely considered that wide-temperature tolerance sodium-ion batteries (WT-SIBs) can be rapidly developed due to their unique electrochemical and chemical properties. However, WT-SIBs, especially for their electrode materials and electrolyte systems, still face various challenges in harsh-temperature conditions. In this review, we focus on the achievements, failure mechanisms, fundamental chemistry, and scientific challenges of WT-SIBs. The insights of their design principles, current research, and safety issues are presented. Moreover, the possible future research directions on the battery materials for WT-SIBs are deeply discussed. Progress toward a comprehensive understanding of the emerging chemistry for WT-SIBs comprehensively discussed in this review will accelerate the practical applications of wide-temperature tolerance rechargeable batteries.

Synthesis and electrochemical studies of 1,1’-binaphthyl-2,2’-diol for aqueous rechargeable lithium-ion battery applications

The constant increase in the utilization of lithium-ion batteries (LIBs) in various field applications, including electrical vehicles and electronic devices, has led researchers to focus on their multiple path developments to obtain new electrode materials. The practical development of these electrode materials, based on organic and inorganic moieties, is challenging for various groups of LIB scientists. The concept of organic electrode materials is highly competitive with inorganic electrode materials because of the accessibility of more active sites with structural diversity, high energy and power density, environmental friendliness potential sustainability, and low cost. Herein, 1,1’-binaphthyl-2,2’-diol (BINOL) is investigated as an organic electrode material that contains two hydroxyl groups that act as active centers. The oxidative coupling process is employed to synthesize BINOL and so obtained product was characterized by using FT-IR, 1H-NMR and MASS techniques. The electrochemical investigations were carried out using sat. Li2SO4 electrolytic medium at three-electrode cell system. The Cyclic voltammetry (CV) has provided information on the anodic behavior of the material and its stability studied at different scan rates. The battery performance of the cell BINOL | Sat. Li2SO4 | LiMn2O4 by galvanostatic charge-discharge potential limit (GCPL) shows 197/171mAhg−1 specific capacity and 90% columbic efficiency. The electrochemical kinetic obtained by potentiostatic electrochemical impedance spectroscopy (PEIS) shows a semi-infinite diffusion process.

Releasing Free Anions by High Donor Number Cosolvent in Noncorrosive Electrolytes of Commercially Available Magnesium Salts.

Passivation of the magnesium (Mg) anode in the chloride-free electrolytes using commercially available Mg salts is a critical issue for rechargeable Mg batteries. Herein, a high donor number cosolvent of 1-methylimidazolium (MeIm) is introduced into Mg(TFSI)2- and Mg(HMDS)2-based electrolytes to address the passivation problem and realize highly reversible Mg plating/stripping. Theoretical calculations and experimental characterization results reveal that the strong coordination ability of MeIm with Mg2+ can weaken the anion-cation interactions and promote the formation of free anions that have higher reduction stability, thus significantly suppressing anion-derived passivation layer formation. By adding MeIm cosolvent into Mg(TFSI)2-based electrolyte, the average Coulombic efficiency of the Mg//Cu cell is increased from less than 20% to over 90%, and the Mg//Mg cell can stably cycle for over 800 h with a low overpotential. In the MeIm-regulated Mg(HMDS)2-based electrolyte, the solvation structure change, featured by an effective separation of Mg2+ and HMDS-, greatly increases the ionic conductivity by more than 30 times. This solvation structure regulation strategy for noncorrosive electrolytes of commercially available Mg salts has a great potential for application in future rechargeable Mg metal batteries.

Achieving Long-Cycle-Life Zinc-Ion Batteries through a Zincophilic Prussian Blue Analogue Interphase.

The practical application of rechargeable aqueous zinc-ion batteries (ZIBs) has been severely hindered by detrimental dendrite growth, uncontrollable hydrogen evolution, and unfavorable side reactions occurring at the Zn metal anode. Here, we applied a Prussian blue analogue (PBA) material K2Zn3(Fe(CN)6)2 as an artificial solid electrolyte interphase (SEI), by which the plentiful -C≡N- ligands at the surface and the large channels in the open framework structure can operate as a highly zincophilic moderator and ion sieve, inducing fast and uniform nucleation and deposition of Zn. Additionally, the dense interface effectively prevents water molecules from approaching the Zn surface, thereby inhibiting the hydrogen-evolution-resultant side reactions and corrosion. The highly reversible Zn plating/stripping is evidenced by an elevated Coulombic efficiency of 99.87% over 600 cycles in a Zn/Cu cell and a prolonged lifetime of 860 h at 5 mA cm-2, 2 mAh cm-2 in a Zn/Zn symmetric cell. Furthermore, the PBA-coated Zn anode ensures the excellent rate and cycling performance of an α-MnO2/Zn full cell. This work provides a simple and effective solution for the improvement of the Zn anode, advancing the commercialization of aqueous ZIBs.

Low-Overpotential Rechargeable Na-CO2 Batteries Enabled by an Oxygen-Vacancy-Rich Cobalt Oxide Catalyst.

Rechargeable sodium-carbon dioxide (Na-CO2) batteries have been proposed as a promising CO2 utilization technique, which could realize CO2 reduction and generate electricity at the same time. They suffer, however, from several daunting problems, including sluggish CO2 reduction and evolution kinetics, large polarization, and poor cycling stability. In this study, a rambutan-like Co3O4 hollow sphere catalyst with abundant oxygen vacancies was synthesized and employed as an air cathode for Na-CO2 batteries. Density functional theory calculations reveal that the abundant oxygen vacancies on Co3O4 possess superior CO2 binding capability, accelerating CO2 electroreduction, and thereby improving the discharge capacity. In addition, the oxygen vacancies also contribute to decrease the CO2 decomposition free energy barrier, which is beneficial for reducing the overpotential further and improving round-trip efficiency. Benefiting from the excellent catalytic ability of rambutan-like Co3O4 hollow spheres with abundant oxygen vacancies, the fabricated Na-CO2 batteries exhibit extraordinary electrochemical performance with a large discharge capacity of 8371.3 mA h g-1, a small overpotential of 1.53 V at a current density of 50 mA g-1, and good cycling stability over 85 cycles. These results provide new insights into the rational design of air cathode catalysts to accelerate practical applications of rechargeable Na-CO2 batteries and potentially Na-air batteries.

Dual-Parasitic Effect Enables Highly Reversible Zn Metal Anode for Ultralong 25,000 Cycles Aqueous Zinc-Ion Batteries.

The use of electrolyte additives is an efficient approach to mitigating undesirable side reactions and dendrites. However, the existing electrolyte additives do not effectively regulate both the chaotic diffusion of Zn2+ and the decomposition of H2O simultaneously. Herein, a dual-parasitic method is introduced to address the aforementioned issues by incorporating 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIm]OTf) as cosolvent into the Zn(OTf)2 electrolyte. Specifically, the OTf- anion is parasitic in the solvent sheath of Zn2+ to decrease the number of active H2O. Additionally, the EMIm+ cation can construct an electrostatic shield layer and a hybrid organic/inorganic solid electrolyte interface layer to optimize the deposition behavior of Zn2+. This results in a Zn anode with a reversible cycle life of 3000 h, the longest cycle life of full cells (25,000 cycles), and an extremely high initial capacity (4.5 mA h cm-2), providing a promising electrolyte solution for practical applications of rechargeable aqueous zinc-ion batteries.

Multiscale nanoengineering fabrication of air electrode catalysts in rechargeable Zn-air batteries

The development of cost-effective, high-activity and stable catalysts to accelerate the sluggish kinetics of cathodic oxygen reduction/evolution reactions (ORR/OER) plays a critical part in commercialization application of rechargeable Zn-air batteries (RZABs). Herein, a multiscale nanoengineering strategy is developed to simultaneously stabilize Co-doped Fe nanoparticles originated from metal-organic framework-derived approach and atomic Fe/Co sites derived from metal nanoparticle-atomized way on N-doped hierarchically tubular porous carbon substrate. Thereinto, metal nanoparticles and single atoms are respectively used to expedite the OER and ORR. Consequently, the final material is acted as an oxygen electrode catalyst, displaying 0.684 V of OER/ORR potential gap, 260 mW cm-2 of peak power density for liquid-state RZAB, 110 mW cm-2 of peak power density for solid-state RZAB, and 1000 charge-discharge cycles without decay, which confirms great potential for energy storage and conversion applications.

Bifunctional ligand Co metal-organic framework derived heterostructured Co-based nanocomposites as oxygen electrocatalysts toward rechargeable zinc-air batteries

Rational construction of efficient and robust bifunctional oxygen electrocatalysts is key but challenging for the widespread application of rechargeable zinc-air batteries (ZABs). Herein, bifunctional ligand Co metal–organic frameworks were first explored to fabricate a hybrid of heterostructured CoOx/Co nanoparticles anchored on a carbon substrate rich in CoNx sites (CoOx/Co@CoNC) via a one-step pyrolysis method. Such a unique heterostructure provides abundant CoNx and CoOx/Co active sites to drive oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. Besides, their positive synergies facilitate electron transfer and optimize charge/mass transportation. Consequently, the obtained CoOx/Co@CoNC exhibits a superior ORR activity with a higher half-wave potential of 0.88 V than Pt/C (0.83 V vs. RHE), and a comparable OER performance with an overpotential of 346 mV at 10 mA cm−2 to the commercial RuO2. The assembled ZAB using CoOx/Co@CoNC as a cathode catalyst displays a maximum power density of 168.4 mW cm−2, and excellent charge–discharge cyclability over 250 h at 5 mA cm−2. This work highlights the great potential of heterostructures in oxygen electrocatalysis and provides a new pathway for designing efficient bifunctional oxygen catalysts toward rechargeable ZABs.

Designing an Air-Stable Interphase on Lithium Metal Anode to Improve Cycling Performance.

The application of rechargeable lithium metal batteries is challenged by intractable issues of uncontrollable Li dendrite growth that result in poor cycle life and safety risks. In this work, an air-stable interphase is developed to protect the lithium metal anode (LMA) via a facile solution-based approach. The Ag-embedded fluoride-rich interphase not only creates abundant lithiophilic sites for homogenizing Li nucleation and growth but also resists severe air erosion to protect the LMA beneath and enable decent cycling stability. As a result, the Ag-F-rich interphase enables flat Li deposition on LMA, which is clearly observed in the operando Li plating experiments. Paired with a LiFePO4 cathode (11.8 mg cm-2), the Ag-F-rich interphase-modified LMA enables 300 stable cycles at 0.5 C, delivering a capacity retention ratio as high as 91.4%. Even after being exposed to air for 1 h, the modified LMA still runs smoothly for over 120 cycles with ignorable capacity decay, exhibiting great air stability. This work proves the concept of functionalizing the interphase on the LMA to enable good cycling performance even under severe air erosion.

Synergistic Fe and Co binary single atoms based air cathodes for high performance and ultra-stable Zn-air batteries

Cost-effective highly efficient and stable air cathodes are critical for practical applications of rechargeable Zn-air batteries (ZABs). In this work, air cathodes constructed by loading carbon nanotube supported N-doped carbon anchored Fe and Co binary single atoms, f-Fe1Co1/CNT, in carbon paper composited nickel foams, NF/CP, were developed for ZABs, exhibiting outstanding bifunctional oxygen electrocatalytic activities (ΔE = 0.671 V) with a half-wave potential (E1/2) of 0.880 V (vs. RHE) for oxygen reduction reaction (ORR) and an overpotential of 321 mV at 10 mA cm−2 (η10) for oxygen evolution reaction (OER) in 0.1 M KOH, which outperformed the benchmark (Pt/C+IrO2)-based air cathode (ΔE = 0.773 V, E1/2 = 0.850 V, η10 = 393 mV). With the unique air cathode design of compositing catalyst-loading layer (nickel foam) with gas diffusion layer (carbon paper), the f-Fe1Co1/CNT@NF/CP//Zn ZAB delivered a remarkable discharge peak power density of 282.1 mW cm−2 at an ultra-high current density of 427.7 mA cm−2 and maintained an ultra-small potential gap of 0.75 V after operations at 10 mA cm−2 for 3300 cycles (1100 h), largely outperforming the (Pt/C+IrO2)@NF/CP//Zn ZAB (162.4 mW cm−2 at 247.3 mA cm−2, 0.86 V, 590 cycles). Density functional theory calculations revealed the positive long-range synergy between Fe-N4 and Co-N4 single atoms, significantly reducing the free energies of the rate-determining steps, oxygen protonation for ORR and formation of oxyhydroxides for OER at the main active site Fe-N4, to realize the much enhanced oxygen electrocatalytic activities.

Vertically Aligned Conductive Metal–Organic Frameworks with Switchable Electrical Conductivity for Li Metal Anode

AbstractLithium (Li) metal, with its unparalleled theoretical capacity and lowest electrochemical potential, is a promising anode material for rechargeable batteries. Yet, challenges such as dendrite formation, severe electrode volume change, and ongoing Li consumption impede its practical adoption. To address these challenges, a novel approach is introduced, harnessing the switchable electrical conductivity of a nanoporous current collector for Li metal anode. A vertically aligned Nickel‐catecholate (VANC) is directly grown on the copper foil as the nanoporous current collector, and the Li intercalation and de‐intercalation of VANC reversibly decrease and increase the electrical conductivity in the direction perpendicular to the electrode, respectively. The switchable conductivity induces uniform deposition and stripping of Li metal without forming dendrite and dead Li during the Li plating/stripping process and thus enables high coulombic efficiency of over 98% even after 200 cycles. This nanoporous structure with switchable conductivity will open up a new path for reliable lithium metal anode for rechargeable battery applications.

Surface Patterning of Metal Zinc Electrode with an In-Region Zincophilic Interface for High-Rate and Long-Cycle-Life Zinc Metal Anode

HighlightsA stable Zn anode was obtained by patterning Zn foil surfaces and endowing a zincphilic interface in microchannels.The accumulation of electrons in the microchannel and the zincphilic interface promoted preferential heteroepitaxial Zn deposition in the microchannel region and subsequent homoepitaxial Zn deposition on the array surface.The Zn symmetrical cells could undergo repeated plating/stripping for more than 25,000 cycles at the current densities of 10 and 20 mA cm−2.

Artificial Li3N SEI-Enforced Stable Cycling of Li Powder Composite Anode in Carbonate Electrolytes

Lithium metal is considered one of the most attractive anode materials for next-generation batteries. However, the practical application of rechargeable Li-metal batteries has been hindered by the uncontrollable growth of Li dendrites and large volume changes during electrochemical cycling, leading to low Coulombic efficiency and safety concerns. This study reports a facile process of printing copper nitride nanowires (Cu3N NWs) onto Li metal powder (LMP) composite anode surface via a roll-pressing technique. Cu3N readily reacts with Li to form lithium nitride (Li3N), which is regarded as an excellent component for the interfacial layer on Li metal. The Li3N layer possesses a high ionic conductivity and ensures a homogeneous Li-ion flux, resulting in the suppression of dendrites. As a result, Li/Li symmetric cells assembled with the Li3N-LMP electrode exhibited lower overpotentials and superior cycling performance. Furthermore, NCM622/Li3N-LMP full cells demonstrated better capacity retention behavior (over 90% after 250 cycles) and higher discharge capacities during rate capability tests compared to the bare LMP cell. This study highlights the importance of a rational design of interfacial layers on LMP anodes for stable and long-term cycling.

Gallium-Based Liquid Metals in Rechargeable Batteries: From Properties to Applications.

Gallium-based (Ga-based) liquid metals have attracted considerable interest due to their low melting points, enabling them to feature both liquid properties and metallic properties at room temperature. In light of this, Ga-based liquid metals also possess excellent deformability, high electrical and thermal conductivity, superior metal affinity, and unique self-limited surface oxide, making them popular functional materials in energy storage. This provides a possibility to construct high-performance rechargeable batteries that are deformable, free of dendrite growth, and so on. This review primarily starts with the property of Ga-based liquid metal, and then focuses on the potential applications in rechargeable batteries by exploiting these advantages, aiming to construct the correlation between properties and structures. The glorious applications contain interface protection, self-healing electrode construction, thermal management, and flexible batteries. Finally, the opportunities and obstacles for the applications of liquid metal in batteries are presented.

On the ionic conductivity and mechanical behavior of cellulose-based electrolytes: Applications for rechargeable batteries

Our paper presents two approaches that are potentially industrially scalable to prepare polymer electrolytes for the development of next-generation rechargeable batteries involving new atoms like Na, Zn or Mg: (1) gel polymer electrolytes, GPE, and (2) solid polymer electrolytes, SPE. Cellulose nanocrystals (CNC) are used with different surface functions, surface charge and concentrations as a functional component in both systems. Systematic testing of their ionic conductivity as well as their dynamic mechanical behavior, which is critical for creating mechanically durable systems, has been performed. Higher ionic conductivity reaching up to 2.60 ± 0.57 mS/cm was obtained for cellulose based GPE, which is more than double the ionic conductivity tested for non-renewable Celgard® 2400 (1.15 ± 0.06 mS/cm). Whereas cellulose based SPE showed an ionic conductivity of up to 2.34 ± 0.28 × 10−6 S/cm, and in both systems, tailoring the surface charge on CNC surfaces significantly influenced the counterion mobility thereby improving the ionic conductivity.

Atomic-scale inorganic carbon additive with rich surface polarity and low lattice mismatch for zinc to boost Zn metal anode reversibility

The renaissance of aqueous zinc-ion batteries (ZIBs) is impeded by the disordered Zn deposition and notorious water attack at the Zn-electrolyte interface. Electrolyte additive engineering plays a vital role in tuning the electrode–electrolyte interface chemistry to stabilize Zn anode but its long-term performance at high plating/stripping rates and capacities remains a challenge. Herein, we demonstrate highly reversible Zn anodes by employing the atomic-scale inorganic carbon nanomaterials (ICN) as a multifunctional electrolyte additive into the common ZnSO4 solution to regulate the Zn deposition behaviors. The ICN with rich surface polar groups modulates the primary Zn2+ solvation structure to avoid the side reactions, and preferentially absorbs on the Zn anode surface to build a passivated-protect interface to suppress Zn corrosion and dendrite growth. More importantly, its low lattice mismatch with zinc navigates the preferred Zn (002) deposition to induce smooth and dense Zn plating morphology, fundamentally eradicating the Zn dendrite issues and further Zn corrosion. Consequently, the electrolyte containing ICN additive endows the symmetric Zn cells with fabulous cumulative capacity (3500 mAh cm−2), decent Coulombic efficiency (99.69 %) at 10 mA cm−2, and excellent stability of 800 cycles with only 0.022 % capacity decay per cycle in the Zn||VOX battery under practical conditions of limited Zn supply, high-loading cathode and lean electrolyte. This work presents an effective strategy to advance the practical applications of rechargeable aqueous zinc batteries.