Rechargeable Hybrid Research Articles

Ultrathin carbon film as ultrafast rechargeable cathode for hybrid sodium dual-ion capacitor

The development of electrochemical energy storage devices has a decisive impact on clean renewable energy. Herein, novel ultrafast rechargeable hybrid sodium dual-ion capacitors (HSDICs) were designed by using ultrathin carbon film (UCF) as the cathode material. The UCF is synthesized by a simple low temperature catalytic route followed by an acid leaching process. UCF owns a large adsorption interface and number of additional active sites, which is due to the nitrogen doping. In addition, there exists several short-range order carbons on the surface of UCF, which are beneficial for anionic storage. An ultrafast rechargeable remarkable performance, remarkable anion hybrid storage capability and outstanding structure stability is fully tapped employing UCF as cathode for HSDICs. The electrochemical performance of UCF in a half-cell system at the operating voltage between 1.0 and 4.8 V, achieving an admirable specific discharge capacity of 358.52 mAh·g−1 at 500 mA·g−1, and a high capacity retention ratio of 98.42% after cycling 2500 times at 1000 mA·g−1, respectively. Besides, with the support of ex-situ TEM and EDS mapping, the structural stability principle and anionic hybrid storage mechanism of UCF electrode are investigated in depth. In the full-cell system, HSDICs with the UCF as cathode and hard carbon as anode also presents a super-long cycle stability (80.62% capacity retention ratio after cycling 1300 times at 1000 mA·g−1).

An ultrafast rechargeable hybrid potassium dual-ion capacitor based on carbon quantum dot@ultrathin carbon film cathode

An ultrafast rechargeable hybrid potassium dual-ion capacitor based on carbon quantum dot@ultrathin carbon film cathode

High-Power-Density Rechargeable Hybrid Alkali/Acid Zn-Air Battery Performance Through Value-Added Conversion Charging.

Rechargeable Zn-air batteries (ZABs) are considered highly competitive technologies for meeting the energy demands of the next generation, whether for energy storage or portable power. However, their practical application is hindered by critical challenges such as low voltage, CO2 poisoning at the cathode, low power density, and poor charging efficiency Herein, a rechargeable hybrid alkali/acid Zn-air battery (h-RZAB) that effectively separates the discharge process in an acidic environment from the charging process in an alkaline environment, utilizing oxygen reduction reaction (ORR) and glycerol oxidation reaction (GOR) respectively is reported. Compared to previously reported ZABs, this proof-of-concept device demonstrates impressive performance, exhibiting a high power density of 562.7mWcm-2 and a high operating voltage during discharging. Moreover, the battery requires a significantly reduced charging voltage due to the concurrent utilization of biomass-derived glycerol, resulting in practical and cost-effective advantages. The decoupled system offers great flexibility for intermittently generated renewable power sources and presents cost advantages over traditional ZABs. As a result, this technology holds significant promise in opening avenues for the future development of renewable energy-compatible electrochemical devices.

Hierarchical mesoporous NiO nanosheet arrays as integrated electrode for hybrid sodium-air batteries

Attributed to its environmental friendliness, high theoretical energy density, and abundant sodium resource, rechargeable hybrid sodium-air batteries (HSABs) are expected to become a promising pioneer of the new-generation green energy storage device. However, HSABs suffer from the high voltage gap, low energy conversion efficiency, and poor cycle stability due to the low catalytic activity of catalysts caused by the degradation of polymer binders. Herein, hierarchical mesoporous NiO nanosheet arrays grown on carbon papers (CP) (NiO NA@CP) were synthesized by a facile and efficient hydrothermal route and calcination process, which acts as an integrated electrode for HSABs. Compared with traditional air electrodes that contain a polymer binder and conductive carbon, the integrated NiO NA@CP electrode prevents the aggregation of catalysts, improves the electronic conductivity by good electric contact and ensures its robust mechanical stability. In addition, NiO NA@CP electrode with the abundant porosity and large specific area offers plenty of active sites and shortens ion transfer length and rapid mass transport in ORR/OER process, leading to excellent oxygen catalytic activities. HSABs with NiO NA@CP electrode show a low overpotential of 0.65 V, a state-of-the-art power density (7.53 mW cm−2), as well as an excellent cyclability of 170 cycles (over 170 h) at a current density of 0.1 mA cm−2.

A VO2/graphene oxide composite as a cathode material with high rate performance for hybrid Mg-Li batteries

Rechargeable magnesium batteries (RMBs) can meet the urgent demand for large-scale energy storage systems due to their high volumetric energy density, safety, and low cost. RMB development requires the exploitation of cathode materials with high specific capacities and potentials. Layered VO2 is a promising cathode material for RMBs due to its high capacity (>200 mAh g−1) and high voltage (>1.5 V). However, the diffusion kinetics of Mg2+ in the VO2 host are sluggish, which results in poor electrochemical performance. In this study, a VO2/graphene oxide (VO2/GO) composite was constructed via a facile ultrasonication method combined with freeze drying as a cathode material for rechargeable hybrid Mg2+/Li+ batteries (HMLBs). The VO2/GO cathode material has a high discharge capacity (261.7 mAh g−1 at 20 mA g−1), significant discharge platform (above 1.75 V), and satisfactory cycling capacity. The capacity retention of the cathode was maintained at 83% after 200 cycles at 100 mA g−1. Ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements were used to study the Mg2+ storage mechanism of the VO2/GO electrode during the charging and discharging processes.

A True Non-Newtonian Electrolyte for Rechargeable Hybrid Aqueous Battery

The rechargeable aqueous hybrid battery is a unique system in which the Li-ion mechanism dominates the cathode while the first-order metal reaction of stripping/depositing regulates the anode. This battery inherits the advantages of the low-cost anode while possessing the capability of the Li-ion cathode. One of the major challenges is to design a proper electrolyte to nourish such strengths and alleviate the downsides, because two different mechanisms are functioning separately at the node–electrolyte and the cathode–electrolyte interfaces. In this work, we design a non-Newtonian electrolyte which offers many advantages for a Zn/LiMn2O4 battery. The corrosion is kept low while almost non-dendritic zinc deposition is confirmed by chronoamperometry and ex situ microscopy. The gel strength and gelling duration of such non-Newtonian electrolytes can be controlled. The ionic conductivity of such gels can reach 60 mS⋅cm−1. The battery exhibits reduced self-discharge, 6–10% higher specific discharge capacity than the aqueous reference battery, high rate capability, nearly 80% capacity retention after 1000 cycles, and about 100 mAh⋅g−1 of specific discharge capacity at cycle No. 1000th. Negligible amorphization on the cathode surface and no passivation on the anode surface are observed after 1000 cycles, evidenced by X-ray diffraction and scanning electron microscopy on the post-run battery electrodes.

Zeolitic Imidazolate Framework-Derived Co-Fe@NC for Rechargeable Hybrid Sodium–Air Battery with a Low Voltage Gap and Long Cycle Life

Zeolitic Imidazolate Framework-Derived Co-Fe@NC for Rechargeable Hybrid Sodium–Air Battery with a Low Voltage Gap and Long Cycle Life

A High-Voltage Aqueous Rechargeable Zinc-Polyaniline Hybrid Battery Achieved by Decoupling Alkali–Acid Electrolyte

A High-Voltage Aqueous Rechargeable Zinc-Polyaniline Hybrid Battery Achieved by Decoupling Alkali–Acid Electrolyte

Rechargeable hybrid organic Zn battery (ReHOZnB) with non-flammable electrolyte

ReHOB has been constructed by adopting intrinsically safe organic electrolyte through the replacement of the traditional aqueous electrolyte that displayed good cycling stability with TTFP additive. • Aqueous electrolytes for Zn anode have been replaced by TMP based electrolyte. • The strategy addressed safety concerns along with high Zn reversibility. • Zn/Na 2 Mn[Fe(CN) 6 ] battery exhibited excellent stability with TTFP- additive. Zn-based rechargeable batteries suffer from thermodynamic instability of Zn anode in aqueous electrolytes that results in low Coulombic efficiencies (CEs) and decreased anode reversibility. Therefore, as an alternative, non-aqueous Zn-battery chemistry has gained significant attention in the recent times that can effectively resolve the issues of thermodynamic instability along with improvement in CE of Zn plating/stripping. However, the adoption of organic electrolytes over aqueous ones throws a serious safety challenge. In this work, traditional aqueous electrolytes have been replaced by an intrinsically safe organic electrolyte in dual-ion Zn batteries to construct a rechargeable hybrid organic Zn battery (ReHOZnB) that effectively addresses the safety concerns along with providing highly reversible Zn anode. The Zn/ Na 2 Mn[Fe(CN) 6 ] (Na 2 MnHCf) battery delivered a reversible capacity of 89.3 mAh g −1 at a C-rate of 1 (1C = 160 mA g −1 ) exhibiting long term cycling stability with a capacity retention of 77% (66%) after 1000 (2000) charge–discharge cycles. The cycling performance has been stabilized through in-situ generation of cathode electrolyte interphase (CEI). This works provides an alternate electrolyte for the development of safe Zn batteries.

Cobalt tetraphosphate as an efficient bifunctional electrocatalyst for hybrid sodium-air batteries

Economic and efficient bifunctional electrocatalysts are pivotal in realization of rechargeable (hybrid) metal-air batteries. It is ideal to employ noble-metal free bifunctional electrocatalysts that are not selective towards oxygen evolution and reduction (OER and ORR) activities. This work unveils cobalt-based tetraphosphate K2Co(PO3)4 as an economic bifunctional electrocatalyst acting as cathode for rechargeable hybrid sodium-air batteries. Autocombustion route led to the development of homogeneous, carbon-coated, spherical K2Co(PO3)4 nanoparticles enabling active site exposure to incoming guest molecules (O2, OH-). This monoclinic compound exhibited superior oxygen evolution activity with low overpotential (ca. 0.32 V) surpassing the commercial RuO2 catalyst. Tetraphosphate K2Co(PO3)4 was successfully implemented in hybrid Na-air batteries delivering reversible cycling with roundtrip efficiency over 70%. DFT study revealed this catalytic activity stem from the most active and stable surface (001) and half-metallic nature of Co in K2Co(PO3)4. Cobalt tetraphosphates can be harnessed to design low cost electrocatalysts for hybrid sodium-air batteries.

Cobalt Metaphosphates as Economic Bifunctional Electrocatalysts for Hybrid Sodium-Air Batteries.

Bifunctional electrocatalysts are pre-eminent to achieve high capacity, cycling stability, and high Coulombic efficiency for rechargeable hybrid sodium-air batteries. The current work introduces metaphosphate (Na)KCo(PO3)3 nanostructures as noble metal-free bifunctional electrocatalysts suitable for the rechargeable aqueous sodium-air battery. Prepared by the scalable solution combustion method, the metaphosphate class of (Na)KCo(PO3)3 with spherical morphology exhibited robust oxygen reduction as well as evolution activity similar to the state-of-the-art catalysts. NaCo(PO3)3 metaphosphate, when employed as an air cathode in hybrid sodium-air batteries, delivered reasonably low overpotential along with excellent cycling stability with a round-trip energy efficiency of 78%. Cobalt metaphosphates thus form a new class of economical bifunctional catalysts to develop hybrid sodium-air batteries.

Sub-Nanometer Pt Clusters on Defective NiFe LDH Nanosheets as Trifunctional Electrocatalysts for Water Splitting and Rechargeable Hybrid Sodium-Air Batteries.

It is challenging to develop highly efficient and stable multifunctional electrocatalysts for improving the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) for sustainable energy conversion and storage systems such as water-alkali electrolyzers (WAEs) and hybrid sodium-air batteries (HSABs). In this work, sub-nm Pt nanoclusters (NCs) on defective NiFe layered double hydroxide nanosheets (NixFe LDHs) are synthesized by a facile electrodeposition method. Due to the synergistic effect between Pt NCs and abundant atomic M(II) defects, along with hierarchical porous nanostructures, the Pt/NixFe LDHs catalysts exhibit superior trifunctional electrocatalytic activity and durability toward the HER/OER/ORR. A WAE fabricated with Pt/NixFe LDHs electrodes needs 1.47 V to reach a current density of 10 mA cm-2, much lower than that of the mixed 20% Pt/C and 20% Ir/C catalysts. An HSAB assembled by Pt/NixFe LDHs as a binder-free air cathode displays a high open-circuit voltage, a narrow overpotential gap, and remarkable rechargeability. This work provides a feasible strategy for constructing freestanding efficient trifunctional electrocatalysts for sustainable energy conversion and storage systems.

Cost-effective, long-term aqueous rechargeable hybrid sodium/zinc batteries based on Zn anode and Na3MnTi(PO4)3 cathode

Aqueous rechargeable batteries have promising application in large-scale energy storage owing to their cost-effective, eco-friendly, high safety and good electrochemical performance. An aqueous rechargeable hybrid sodium/zinc battery with Zn anode, Na3MnTi(PO4)3 cathode and 0.5 mol L-1 CH3COONa and Zn(CH3COO)2 mixed electrolyte has been designed for the first time. The battery delivered a reversible and stable capacity of 95.0 mAh g−1 at 1.5 C for 50 cycles with a high and flat working voltage of 1.75 V vs. Zn2+/Zn. Impressively, the battery showed the excellent cycling performance and superior rate capability, which can be cycled at 10.0 C for 2000 cycles with a capacity retention of 93.6% and a reversible capacity of 55.6 mAh g−1 at 30.0 C. Meanwhile, the co-intercalation mechanism of hybrid Na+ and Zn2+ in the cathode is elucidated by cyclic voltammogram, ex-situ XRD, ex-situ XPS and Rietveld refinement analysis. This work gets insight into the charge/discharge processes of hybrid ions for NASICON-structured Na3MnTi(PO4)3, providing a feasible way to design cost-effective, high safety and long-term aqueous rechargeable batteries.

Rechargeable quasi-solid-state aqueous hybrid Al3+/H+ battery with 10,000 ultralong cycle stability and smart switching capability

Safe and long lifespan batteries facilitate the development of portable electronics and electric vehicles. Owing to the low-cost, naturally abundance, and trivalent charge carrier of aluminum with the highest theoretical volumetric capacity, rechargeable aqueous aluminum-ion-based batteries are considered as promising next-generation secondary batteries. However, traditional electrolytes and frequent collapse of the host structure of electrode materials greatly jeopardize the cycle stability of the batteries. Here, we develop a novel hydrogel-based electrolyte coupled with stable layered intercalation electrodes for the first time to fabricate a highly safe and flexible rechargeable hybrid Al3+/H+ battery. The as-fabricated hybrid-ion battery (HIB) delivers a high specific capacity of 125 mAh·g−1 at 0.1 A·g−1 and exhibits an unprecedented super long-term cycling stability with no capacity fading over 10,000 cycles at 2 A·g−1. In addition, the hydrogel-based electrolyte possesses smart function of thermoresponsive switching, which can effectively prevent thermal runaway for the batteries. The unprecedented long cycle stability, highly intrinsic safety as well as low-cost indicate that the flexible aqueous HIBs are promising for applications.

Biomass-derived highly dispersed Co/Co9S8 nanoparticles encapsulated in S, N-co-doped hierarchically porous carbon as an efficient catalyst for hybrid Na–CO2 batteries

Na–CO2 batteries are prospective in energy storage and CO2 recycling applications; development of a high-efficiency, low-cost electrocatalyst to promote CO2 reduction and carbonate decomposition is extremely vital for practical Na–CO2 batteries. Herein, a highly efficient cathode catalyst for rechargeable hybrid Na–CO2 batteries is successfully synthesized by encapsulating highly dispersed Co/Co9S8 nanoparticles into carbon skeletons, consisting of biomass-derived S, N-co-doped hierarchically porous carbon (Co/Co9S8@SNHC). The conductive and hierarchically porous framework structure of the Co/Co9S8@SNHC can not only accelerate electron transport, electrolyte infiltration, and CO2 diffusion but also can inhibit overgrowth and agglomeration of Co/Co9S8 nanoparticles and expose numerous high density of active sites, as well as offer sufficient space to store discharge products. Benefiting from the synergistic effect among S and N dopants, carbon defects, and Co/Co9S8 nanoparticles in robust porous carbon structure, the hybrid Na–CO2 batteries displayed a low charge overpotential (only ~0.32 V) at 0.2 mA/cm2 and repeatedly charged and discharged over 200 cycles at 0.1 mA/cm2. Besides, an ultrahigh areal capacity of ~18.9 mAh/cm2 was obtained at 0.5 mA/cm2, the highest value to date for Na–CO2 batteries. Meanwhile, the hybrid Na–CO2 battery charging from Na2CO3@C catalytic cathode demonstrated the high catalytic activity of biomass-derived S,N-co-doped hierarchically porous carbon (Co/Co9S8@SNHC) for CO2 reduction and carbonate decomposition. Given this finding, this work might open up a potential avenue for the reasonable design of low-cost and highly efficient catalysts for advanced metal-CO2 batteries systems.

A Function‐Separated Design of Electrode for Realizing High‐Performance Hybrid Zinc Battery

AbstractA rechargeable hybrid zinc battery is developed for reaching high power density and high energy density simultaneously by introducing an alkaline Zn–transition metal compound (Zn–MX) battery function into a Zn–air battery. However, the conventional single‐layer electrode design cannot satisfy the requirements of both a hydrophilic interface for facilitating ionic transfer to maximize the Zn–MX battery function and a hydrophobic interface for promoting gas diffusion to maximize the Zn–air battery function. Here, a function‐separated design is proposed, which allocates the two battery functions to the two faces of the cathode. The electrode is composed of a hydrophobic MnS layer decorated with Ni–Co–S nanoclusters that allows for smooth gas diffusion and efficient oxygen electrocatalysis and a hydrophilic NixCo1−xS2 layer that favors fast ionic transfer and superior performance for energy storage. The battery with the function‐separated electrode shows a high short‐term discharge voltage of ≈1.7 V, an excellent high‐rate galvanostatic discharge–charge with a power density up to 153 mW cm−2 at 100 mA cm−2, a good round‐trip efficiency of 75% at 5 mA cm−2, and a robust cycling stability for 330 h with an excellent voltage gap of ≈0.7 V at 5 mA cm−2.

Na-containing manganese-based cathode materials synthesized by sol-gel method for zinc-based rechargeable aqueous battery

Zinc-based rechargeable aqueous batteries are regarded as one of the most safe and inexpensive energy storage systems compared to the conventional rechargeable batteries with organic electrolytes. However, the limited cathode materials and the problem of associated metal ion dissolution restrict its practical application. Herein, the inexpensive novel cathode materials of Na-containing manganese-based composite of Na0.44MnO2/Mn2O3 and Na2/3Fe1/2Mn1/2O2 are designed and synthesized correspondingly by sol-gel methods combined with freeze-drying technique, and are applied in the zinc-based aqueous batteries for the first time. The secondary particles of Na0.44MnO2/Mn2O3 composite with a cubic box and the molecular sieve configurations are composed of nano primary particles with about 150–300 nm, and the obtained O3–Na2/3Fe1/2Mn1/2O2 at 850 °C (O3-NFM-850) appears to homogenous distribution with 3D solid block structure and platelet-shaped particles, while the spherical core-shell structure of P2–Na2/3Fe1/2Mn1/2O2 at 850 °C (P3-NFM-850-PVA) after dispersed by poly (vinyl alcohol) are linked to each other by amorphous carbon. Finally, the cathode of Na0.44MnO2/Mn2O3 and P3-NFM-850-PVA deliver the reversible capacities of 68.3 mAh g−1 and 42 mAh g−1 even after 200 cycles at 0.4 A/g respectively without capacity fading. Compared to the reported Na0.44MnO2, the increased capacity of Na0.44MnO2/Mn2O3 composite is attributed to the possible co-insertion of sodium ion and zinc ion for Na0.44MnO2 and the zinc ion insertion for Mn2O3 as well, indicating the synergetic energy storage for rechargeable hybrid aqueous battery and aqueous zinc ion battery. While the improved cyclic performance of Na2/3Fe1/2Mn1/2O2 is ascribed to the structural stability by Fe-doping and carbon-coating.

Tribute to John B. Goodenough: From Magnetism to Rechargeable Batteries

AbstractIn macroeconomics, the rate of economic growth in the world is a historical phenomenon, which will mark the 20th century. It was made possible by an increasing consumption of fossil fuel. However, not only are these resources limited and unrenewable, but combustion has dramatic side effects such as emission of greenhouse gases responsible for global warming and change of climate. As a consequence, major efforts have been taken to move away from fossil fuels and switch to renewable energy including solar and wind energy. These energy sources, however, are intermittent and can be integrated into the electrical network only after regulation. Electrochemical storage is a key solution to regulate these intermittent sources of energy into smart grids. Although governments have only recently become aware of this problem, some scientists have been focusing their attention on rechargeable batteries since the 1970s, and it took until 2019 for the Nobel committee to award the Nobel prize to those who paved the path to their development. John B. Goodenough is one of the three winners of this Nobel prize, for his pioneering research on lithium‐ion batteries (LIBs). The impact of LIBs includes the development of rechargeable hybrid and electric vehicles at the expense of gasoline cars. Before the 1970s, however, John B. Goodenough had already made major contributions to materials science as a solid state physicist, including the investigation of the interplay between the magnetic and transport properties of perovskites. It is the purpose of the present work to report a brief review of the scientific works of John B. Goodenough, through selected works that demonstrate his mastery of chemistry and physics.

Perchlorate Based “Oversaturated Gel Electrolyte” for an Aqueous Rechargeable Hybrid Zn–Li Battery

In this work, for the first time, an “oversaturated gel electrolyte” (OSGE) with extended electrochemical windows for use as electrolytes in aqueous batteries was investigated. The stability window...

Hybrids of LiMn2O4 nanoparticles anchored on carbon nanotubes/graphene sheets as long-cycle-life cathode material for rechargeable hybrid aqueous batteries

A hybrid LiMn2O4-graphene-carbon nanotubes (LMO-GN-CNT) material is synthesized successfully by a facile hydrothermal method. The 15-nm-nanosized LiMn2O4 (LMO) particles anchor uniformly in the cross-linked conductive graphene (GN) and carbon nanotubes (CNT) matrix in the LMO-GN-CNT composite. Rechargeable hybrid aqueous batteries (ReHABs) are assembled by using LMO-based materials as cathodes and zinc metal as anodes. Galvanostatic charging/discharging cycles of the LMO-GN-CNT composite are performed in rechargeable hybrid aqueous batteries (ReHABs) in comparison of LMO-GN composite and pristine LMO material. Electrochemical measurements indicate that the LMO-GN-CNT composite exhibits superior rate capability and cycle ability. The initial discharge capacity of 129 and 100 mAh g−1 can be delivered at 0.2 and 5.0 C. The discharge capacity is still above 93 mAh g−1, and capacity retention of over 82.1% is obtained after 600 cycles at 2.0 C. The satisfactory electrochemical properties can be ascribed to the little aggregation and good dispersion of the nanosized LMO particles and the introduction of GN and CNT, which can enhance the conductivity, shorten the diffusion length of electrolyte, and provide a large specific surface area for lithium storage.