Electrodes For Rechargeable Batteries Research Articles

A Unified Charge Storage Mechanism to Rationalize the Electrochemical Behavior of Quinone-Based Organic Electrodes in Aqueous Rechargeable Batteries.

Due to their eco-sustainability and versatility, organic electrodes are promising candidates for large-scale energy storage in rechargeable aqueous batteries. This is notably the case of aqueous hybrid batteries that pair the low voltage of a zinc anode with the high voltage of a quinone-based (or analogue of quinone-based) organic cathode. However, the mechanisms governing their charge-discharge cycles remain poorly understood and are even a matter of debate and controversy. No consensus exists on the charge carrier in mild aqueous electrolytes, especially when working in an electrolyte containing a multivalent metal cation such as Zn2+. In this study, we comprehensively investigate the electrochemical reactivity of two model quinones, chloranil, and duroquinone, either diluted in solution or incorporated into carbon-based composite electrodes. We demonstrate that a common nine-member square scheme proton-coupled electron transfer mechanism allows us to fully describe and rationalize their electrochemical behavior in relation to the pH and chemical composition of the aqueous electrolyte. Additionally, we highlight the crucial role played by the pKas associated with the reduced states of quinones in determining the nature of the charge carrier that compensates for the negative charges reversibly injected in the active material. Finally, contrary to the widely reported findings for Zn/organic batteries, we unequivocally establish that the predominant solid-state charge carriers in Zn2+-based mild aqueous electrolytes are not multivalent Zn2+ cations but rather protons supplied by the weakly acidic hexaaqua metal ions (i.e., [Zn(H2O)6]2+]).

General and Facile Synthesis of Co/CoO Nanoparticals Supported by Nitrogen-Doped Graphenic Networks as Efficient Oxygen Electrocatalyst for Zn-Air Batteries.

Reasonable design of low-cost, high-efficiency and stable bifunctional oxygen electrocatalysts is of great significance to improve the reaction efficiency of Zn-air batteries, which is still a huge challenge. Here, we report a highly efficient bifunctional oxygen electrocatalyst with three-dimensional (3D) N-doped graphene network-supported cobalt and cobalt oxide nanoparticles (Co/CoO-NG), which can be in situ synthesized by inducing metal ions on metal plates via graphene oxide as an inducer. This 3D network structure and open active center show excellent bifunctional oxygen electrocatalytic activity under alkaline conditions, and can be used as an air electrode in rechargeable Zn-air batteries, with significantly better power density (244.28 mW cm-2) and stability (over 340 h) than commercial Pt/C+RuO2 mixtures. This work is conducive to advancing the practical application of graphene-based materials as air electrodes for rechargeable zinc-air batteries.

Three‐dimensional interconnected graphene network‐based high‐performance air electrode for rechargeable zinc‒air batteries

AbstractAlthough zinc‒air batteries (ZABs) are regarded as one of the most prospective energy storage devices, their practical application has been restricted by poor air electrode performance. Herein, we developed a free‐standing air electrode that is fabricated on the basis of a multifunctional three‐dimensional interconnected graphene network. Specifically, a three‐dimensional interconnected graphene network with fast mass and electron transport ability, prepared by catalyzing growth of graphene foam on nickel foam and then filling reduced graphene oxide into the pores of graphene foam, is used to anchor iron phthalocyanine molecules with atomic Fe‒N4 sites for boosting the oxygen reduction during discharging and nanosized FeNi hydroxides for accelerating the oxygen evolution during charging. As a result, the obtained air electrode exhibited an ultra‐small electrocatalytic overpotential of 0.603 V for oxygen reactions, a high peak power density of 220.2 mW cm‒2, and a small and stable charge‒discharge voltage gap of 0.70 V at 10 mA cm‒2 after 1136 cycles. Furthermore, in situ Raman spectroscopy together with theoretical calculations confirmed that phase transformation of FeNi hydroxides takes place from α‐Ni(OH)x to β‐Ni(OH)x to γ‐Ni(3+δ)+OOH for the oxygen evolution reaction and Ni is the active center while Fe enhances the activity of Ni active sites.

Toward Ultrahigh Rate and Cycling Performance of Cathode Materials of Sodium Ion Battery by Introducing a Bicontinuous Porous Structure.

The emerging sodium-ion batteries (SIBs) are one of the most promising candidates expected to complement lithium-ion batteries and diversify the battery market. However, the exploitation of cathode materials with high-rate performance and long-cycle stability for SIBs has remained one of the major challenges. To this end, an efficient approach to enhance rate and cycling performance by introducing an ordered bicontinuous porous structure into cathode materials of SIBs is demonstrated. Prussian blue analogues (PBAs) are selected because they are recognized as a type of most promising SIB cathode materials. Thanks to the presence of 3D continuous channels enabling fast Na+ ions diffusion as well as the intrinsic mechanical stability of bicontinuous architecture, the resultant PBAs exhibit excellent rate capability (80 mAh g-1 at 2.5 A g-1) and ultralong cycling life (>3000 circulations at 0.5Ag-1), reaching the top performance of the reported PBA-based cathode materials. This study opens a new avenue for boosting sluggish ion diffusion kinetics in electrodes of rechargeable batteries and also provides a new paradigm for solving the dilemma that electrodes' failure due to high-stress concentration upon ion storage.

Cu2ZnSnS4‐Based Electrode as an Improvement Strategy for Lithium Rechargeable Batteries: A Status Review

Cu2ZnSnS4 (CZTS) is seen as a microstructure electrode due to its high energy density when applied in lithium rechargeable batteries such as lithium‐ion batteries (LIB) and lithium sulfur batteries (LSB). This review provides a systematic observation to evaluate the CZTS electrode capabilities from the perspective of electrode composition and its performance in lithium rechargeable batteries. This review starts by focusing on state‐of‐art lithium rechargeable batteries using common sulfur/sulfide‐based materials reported from literature. The relation between the LSB performance with the active materials ‐ sulfur, binder, solvents, electrolytes, and conducting additive used for lithium sulfide (Li2S) formation required for charge transfer properties is discussed critically. The following section discusses the current progress on CZTS‐based electrode in lithium rechargeable batteries and it is found that the highest capacity obtained with improved interfacial compatibility is 1802 mAh g−1 by hydrothermal techniques using 1 m LiPF6 in EC/EMC/DMC electrolyte. These properties have made sulfide component in CZTS structure as a great substitute to conventional sulfur/sulfide‐based active materials. Therefore, CZTS has become a promising and huge potential electrode in lithium rechargeable batteries.

A general separator modification tactic enables long-term stable cycling of small organic molecule electrodes in aqueous alkaline batteries

Rechargeable aqueous alkaline batteries based on small organic molecule anodes are a promising solution for large-scale energy storage due to their environmental friendliness and high energy efficiency. However, its development is limited by the poor cycling stability caused by the shuttling of soluble organic molecules between electrodes. Here, we propose a cell separator modified by metal organic framework (MOF) grown on the surface of graphene oxide (GO) to inhibit the shuttling of small organic molecules. It is demonstrated that the MOF@GO modified separator acts as an ion sieve in aqueous alkaline cells to effectively hold up small organic molecules without affecting the movement of metal ions. With the protection of the MOF@GO separator, soluble small molecules such as indanthrone (IDT) exhibit an amazing stability in alkaline electrolytes (a high reversible capacity of 137.0 mA h g−1 and a good capacity retention of 95.8% after 1000 cycles at 1 A g−1). It is the first report that employs carbonyl-containing small molecules as the electrodes for stable rechargeable aqueous alkaline batteries. Additionally, this strategy is also proved available to enhance the capacity and cycling stability of other active conjugated small molecules, such as PTCDI and 6CN-DQPZ, which will pave the way for the use of small organic molecules in aqueous alkaline batteries.

A sulfur-rich copolymer hybrid cathode for anchoring polysulfides and accelerating redox reaction in lithium sulfur batteries

In lithium-sulfur batteries (LSBs), sulfur-rich copolymers have attracted wide attention due to the reduced dissolution of active material and alleviated self-discharge problem through the efficient chemical interaction between polysulfide and carbon. Herein, we present an effective strategy to encapsulate sulfur-rich copolymer into NiCo2S4 encapsulated hierarchical porous N/O dual-doped graphitic carbon nanocages (GCNs), named S-DIB@NiCo2S4@PDA@rGO-GCNs. The host NiCo2S4@PDA@rGO-GCNs matrix can not only provide the “lithiophilic”-rich polar sites and tight anchored LiPSnon the N/O dual-doped GCNs surface, and “sulfphilic” NiCo2S4 electrocatalyst for accelerated sulfur electrochemistry, but also offer abundant hierarchical pores for accommodating sulfur and cushioning its volume expansion. Both of the experimental and theoretical analyses reveal the S-DIB@NiCo2S4@PDA@rGO-GCNs possesses the strong chemisorptions and catalytic ability with the synergetic mechanism, suppressing the self-discharge problem. As a proof-of-concept study, the assembled LSBs cells show excellent discharge capacities of 486 and 324 mA h g−1 at 5C and 10C after 1000 cycles, respectively. The corresponding capacity loss rate is as low as 0.032 % and 0.030 % per cycle, respectively. Thanks to the exceptional lithiophilic and sulfiphilic characteristic, the LSBs pouch cell also demonstrates high cycling stability. The proposed hierarchical encapsulation strategy with synergetic chemisorptions and catalytic ability shows great potential for developing advanced electrodes for next-generation high-performance rechargeable batteries.

Metal electrodes for next-generation rechargeable batteries

Metal electrodes for next-generation rechargeable batteries

Bifunctional 2D structured catalysts for air electrodes in rechargeable metal-air batteries

The inherent technical challenges of metal-air batteries (MABs), arising from the sluggish redox electrochemical reactions on the air electrode, significantly affect their efficiency and life cycle. Two-dimensional (2D) nanomaterials with near-atomic thickness have potential as bifunctional catalysts in MABs because of their distinct structures, exceptional physical properties, and tunable surface chemistries. In this study, the chemistry of representative 2D materials was elucidated, and the comprehensive analysis of the primary modification techniques, including geometric structure manipulation, defect engineering, crystal facet selection, heteroatom doping, single-atom catalyst construction, and composite material synthesis, was conducted. The correlation between material structure and activity is illustrated by examples, with the aim of leading the development of advanced catalysts in MABs. We also focus on the future of MABs from the perspective of bifunctional catalysts, definite mechanisms, and standard measurement. We expect this work to serve as a guide for the design of air electrode materials that can be used in MABs.

A Li3P nanoparticle dispersion strengthened ultrathin Li metal electrode for high energy density rechargeable batteries

A Li3P nanoparticle dispersion strengthened ultrathin Li metal electrode for high energy density rechargeable batteries

Copper tetrathiovanadate (Cu3VS4): a newly emerging electrode for rechargeable aqueous aluminum-ion batteries.

We report the electrochemistry of Al3+ ion storage in copper tetrathiovanadate (Cu3VS4) in an aqueous electrolyte for the first time. It is found that Cu3VS4 could deliver an initial discharge capacity of 111 mA h g-1 at a current rate of 0.5 A g-1 and 77 mA h g-1 up to the 300th cycle at 2 A g-1 along with an excellent rate capability. The better electrochemical performance may be attributed to the high theoretical capacity of sulfur and the superior conductivity of copper which allows facile Al3+ ion diffusion in Cu3VS4. The electrochemical mechanism of Al3+ ion storage is also illustrated.

Design Principles for Heterointerfacial Alloying Kinetics at Metallic Anodes in Rechargeable Batteries

How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest. Here we consider the relation between the surface chemistry at such interfaces and the reversibility of electrochemical transformations at rechargeable battery electrodes. Using Zn as a model system, we report that a moderate strength of chemical interaction between the deposit and the substrate—neither too weak nor too strong—enables highest reversibility and stability of the plating/stripping redox processes. Focused-ion-beam and electron microscopy were used to directly probe the morphology, chemistry and crystallography of the heterointerfaces of distinct natures. Analogous to the empirical Sabatier principle for chemical heterogeneous catalysis, our finding arises from the confluence of competing interfacial processes. Using full batteries with stringent N:P ratios, we show that such knowledge provides a powerful tool for designing key materials in highly reversible battery systems based on earth-abundant, low-cost metals such as Zn and Na.Reference: Zheng, Jingxu, et al. "Design principles for heterointerfacial alloying kinetics at metallic anodes in rechargeable batteries." Science Advances 8.44 (2022): eabq6321.

Evaluating the Oxygen Electrode Reactions of La Single-Atom Catalysts with the N/C Coordination Effect.

There is a growing demand for bifunctional electrocatalysts for oxygen electrodes in rechargeable metal-air batteries. This article investigates the bifunctional activity of La single-atom catalysts with N/C coordination (LaNxC6-x@Gra) using density functional theory (DFT). The augmentation of N coordination will result in enhanced synthetic stability. The coordination between nitrogen and carbon (N/C) has a significant influence on the working stability of the system under consideration. In the context of active atoms, the coordination between nitrogen and carbon (N/C coordination) has a significant impact on the electronic structure. This, in turn, influences the adsorption performance and catalytic activity of the catalysts. In the case of stable coordination environments, a correlation exists between the f-orbital center (εf) and the overpotential (η) via the adsorption free energy of intermediates (ΔG*ads). This correlation serves as a useful tool for predicting catalytic performance. The LaNxC6-x@Gra exhibits remarkable bifunctional activity due to its complementary performance, with an overpotential for the oxygen reduction reaction (ηORR) of 0.66 V and an overpotential for the oxygen evolution reaction (ηOER) of 0.43 V. This makes it a promising candidate for use as a bifunctional electrocatalyst in oxygen electrodes.

Modulation of Radical Intermediates in Rechargeable Organic Batteries.

Organic materials have been considered as promising electrodes for next-generation rechargeable batteries in view of their sustainability, structural flexibility, and potential recyclability. The radical intermediates generated during the redox process of organic electrodes have profound effect on the reversible capacity, operation voltage, rate performance, and cycling stability. However, the radicals are highly reactive and have very short lifetime during the redox of organic materials. Great efforts have been devoted to capturing and investigating the radical intermediates in organic electrodes. Herein, this review summarizes the importance, history, structures, and working principles of organic radicals in rechargeable batteries. More importantly, challenges and strategies to track and regulate the radicals in organic batteries are highlighted. Finally, further perspectives of organic radicals are proposed for the development of next-generation high-performance rechargeable organic batteries.

Mixed anion chemistry as a way to tune the electrochemical properties of vanadium oxyfluoride phosphates in alkali-ion batteries

Alkali vanadium fluoride phosphates such as Tavorite LiVPO4F, Na3V2(PO4)2F3 and KTP-type KVPO4F are attractive materials for positive electrodes in rechargeable alkali-ion batteries. In such compounds, the presence of fluoride ions further increases the electrode's electrochemical potential compared to their phosphate counterparts such as Na3V2(PO4)3. Furthermore, the fluoride anions in these structures can be fully or partially substituted by oxide anions, leading to the formation of V4+=O vanadyl centres and a great number of mixed valence and mixed anion compositions. The oxygen substitution for fluorine has a considerable impact on the structural, electronic, and electrochemical properties of the resulting compounds. In this review, the similarities and peculiarities in the crystal structures, electronic structures, and electrochemical properties of the three analogous LiVPO4F–LiVPO4O, Na3V2(PO4)2F3–Na3V2(PO4)2FO2, and KVPO4F−KVPO4O material families will be compared in detail. Such a comparison is expected to provide an insightful understanding on the factors governing the structure and properties of vanadium oxyfluoride phosphates.

Effect of Na2SiO3 and TEA Electrolyte Additives on the Corrosion Inhibition of Zinc Electrodes and Electrochemical Performance of Rechargeable Alkaline Manganese Batteries

To inhibit hydrogen evolution corrosion, passivation, and zinc dendrite growth during the charging and discharging of the zinc negative electrode of rechargeable alkaline manganese battery containing ultra-fine zinc powders, the effects of the single addition amounts of inorganic corrosion inhibitor Na2SiO3 and organic corrosion inhibitor TEA and their compounding ratio on the corrosion inhibition effect and the charging and discharging performance of alkaline manganese battery were systematically investigated in this paper. SEM and XPS were used to observe the microscopic morphology of the zinc anode, and the inhibition mechanisms of the relevant inhibitors were explored. The results show that, the addition of Na2SiO3 and TEA can synergistically improve the coverage of the protective film, thereby inhibiting hydrogen evolution corrosion, passivation and dendrites of zinc electrodes. Compared to blank electrolyte, when the composite concentration of Na2SiO3 and TEA is 1 g l−1 Na2SiO3+56.25 mg l−1 TEA, the hydrogen evolution corrosion inhibition efficiency can reach 70.56%, the initial specific capacity and the specific capacity after 50 cycles can increase from 160.7 mAh g−1, 58 mAh g−1 to 198.4 mAh g−1, 74 mAh g−1, respectively. This study has great theoretical and engineering value for guiding the design of electrolytes for rechargeable alkaline manganese batteries.

Multiple conductive network for KTi2(PO4)3 anode based on MXene as a binder for high-performance potassium storage

KTi2(PO4)3 is a promising anode material for potassium storage, but suffers from low conductivity and difficult balance between high capacity and good structural stability. Herein, the Ti3C2Tx MXene is used as a multifunctional binder to fabricate the KTi2(PO4)3 electrode by the traditional homogenizing-coating method. The MXene nanosheets, together with the conductive agent super P nanoparticles, construct a multiple conductive network for fast electron/ion transfer and high electrochemical kinetics. Moreover, the network ensures the structural stability of the KTi2(PO4)3 electrode during the de-intercalation/intercalation of 4 K+ ions, which is beneficial for simultaneously achieving high capacity and good cycle performance. Therefore, the MXene-bonded KTi2(PO4)3 electrode delivers a reversible capacity of 255.2 mAh/g at 50 mA/g, outstanding rate capability with 132.3 mAh/g at 2 A/g, and excellent cycle performance with 151.6 mAh/g at 1 A/g after 2000 cycles. This work not only suggests a high-performance anode material for potassium-ion batteries, but also demonstrates that the MXene is a promising binder material for constructing conductive electrodes in rechargeable batteries.

Surface Properties‐Performance Relationship of Aluminum Foil as Negative Electrode for Rechargeable Aluminum Batteries

AbstractRechargeable aluminum batteries with aluminum metal as a negative electrode have attracted wide attention due to the aluminum abundance, its high theoretical capacity and stability under ambient conditions. Understanding and ultimately screening the impact of the initial surface properties of aluminum negative electrodes on the performance and lifetime of the battery cell are of great significance. The purity, surface finishing and degree of hardness of aluminum metal may strongly impact the device's performance, but these properties have not been systematically studied so far. Here, we present an investigation of the underestimated but crucial role of the aluminum foil surface properties on its electrochemical behavior in aluminum battery half‐cells. The results show that commercial aluminum foils with the same purity and degree of hardness but with different thicknesses (from 0.025 to 0.1 mm) exhibit different microstructure and surface roughness, which in turn have an impact on the cyclability. Atomic force microscopy studies show that the aluminum foil is corroded after repeated electrochemical cycling, thus leading to cell failure. The sample with 0.075 mm thickness exhibits the best cycling stability.

High-performance nanoribbon-like CuV2O5 hybrid composite as a bifunctional electrode for rechargeable batteries

A nanoribbon-like CuV2O5 hybrid composite material, with a width of 100 nm, was prepared by hydrothermal technique with different reaction time followed by drying process. Structural and morphological characterization of the hybrid composite confirmed its phase arrangement, composition, and nanoribbon-like morphology. The formation reaction mechanism was investigated using time-dependent variables of the hydrothermal reaction, and electrochemical analysis demonstrated a good cyclic behavior. As an anode, the CVO-24 h hybrid composite exhibits the first galvanostatic discharge capacity ∼852 mAh g−1 at an operating current density of 100 mA g−1, whereas when used as positive electrode material, the synthesized hybrid composite exhibited the galvanostatic charge capacity ∼251 mAh g−1 at an operating current density of 50 mA g−1. An improvement in electrochemical properties can be attributed to the metallic copper present in the hybrid structure, which enhances electronic conductivity. Additionally, their porous nanoribbon-like structure promotes Li intercalation and de-intercalation efficiently.

Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs)possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodinebatteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this greatpotential research field.