An Operando Mechanistic Evaluation of a Solar‐Rechargeable Sodium‐Ion Intercalation Battery

Solar‐intercalation batteries, which are able to both harvest and store solar energy within the electrodes, are a promising technology for the more efficient utilization of intermittent solar radiation. However, there is a lack of understanding on how the light‐induced intercalation reaction occurs within the electrode host lattice. Here, an in operando synchrotron X‐ray diffraction methodology is introduced, which allows for real‐time visualization of the structural evolution process within a solar‐intercalation battery host electrode lattice. Coupled with ex situ material characterization, direct correlations between the structural evolution of MoO₃ and the photo‐electrochemical responses of the solar‐intercalation batteries are established for the first time. MoO₃ is found to transform, via a two‐phase reaction mechanism, initially into a sodium bronze phase, Na_0.33MoO₃, followed by the formation of solid solutions, Na_xMoO₃ (0.33 < x < 1.1), on further photointercalation. Time‐resolved correlations with the measured voltages indicate that the two‐phase evolution reaction follows zeroth‐order kinetics. The insights achieved from this study can aid the development of more advanced photointercalation electrodes and solar batteries with greater performances.     

Photo‐Rechargeable Electric Energy Storage Systems

The global energy demand is increasing at the same time as fossil fuel resources are dwindling. Consequently, the search for alternative energy sources is a major topic worldwide. Solar energy is one of the most promising, effective and emission‐free energy sources. However, the energy has to be stored to compensate the fluctuating availability of the sun and the actual energy demand. Photo‐rechargeable electric energy storage systems may solve this problem by immediately storing the generated electricity. Different combinations of solar cells and storage devices are possible. High efficiencies can be achieved by the combination of dye‐sensitized solar cells (DSSC) and capacitors. However, other hybrid devices including DSSCs or organic photovoltaic systems and redox flow batteries, lithium ion batteries and metal air batteries are playing an increasing role in this research field. This Progress Report reviews the state of the art research of photo‐rechargeable batteries based on organic solar cells, as well as storage modules.     

Integrated Configuration Design for Ultrafast Rechargeable Dual‐Ion Battery

In this work, an integrated dual‐ion battery design is reported with active materials, current collectors, and separator, assembled in one flexible component. An aluminum film is deposited directly onto one side of the 3D porous glass fiber separator to form a porous anode. Cathode active materials are loaded on the other side of the separator with aluminum film deposited on the top as current collector. This design demonstrates ultrafast charge/discharge rate up to 120 C while maintaining high capacity of 116.1 mA h g^?1. Moreover, long‐term stability of over 1500 cycles at a high rate of 60 C is achieved. The estimated energy density remains as high as 232.6 W h kg^?1 at an ultrahigh power density of 22634.5 W kg^?1.     

Highly Efficient Perovskite Solar Cell Photocharging of Lithium Ion Battery Using DC–DC Booster

Solar cells become a viable energy source to charge lithium ion batteries. Here a simple and efficient photocharging design approach is demonstrated, where a promising low cost single junction solar cell such as perovskite solar cell or dye sensitized solar cell efficiently charges a Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell using a DC–DC voltage boost converter. The converter boosts the low input voltage of a single junction solar cell to charge a lithium ion cell and offers advantages including maximum power point tracking of solar photovoltaics and overvoltage protection for the lithium ion cell. This is the first demonstration of this technology. This approach leads to the highest reported overall efficiency of 9.36% and average storage efficiency of 77.2% at 0.5 C discharge for a perovskite solar cell‐converter charging. The high efficiency for the perovskite solar cell‐converter charging is attributed to maximum power harvesting along with high power conversion efficiency of the perovskite solar cell and low potential polarization between the charge and discharge voltage plateaus for the Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell.     

A Novel Aluminum‐Ion Battery: Al/AlCl3‐[EMIm]Cl/Ni3S2@Graphene

Due to an ever‐increasing demand for electronic devices, rechargeable batteries are attractive for energy storage systems. A novel rechargeable aluminum‐ion battery based on Al³⁺ intercalation and deintercalation is fabricated with Ni₃S₂/graphene microflakes composite as cathode material and high‐purity Al foil as anode. This kind of aluminum‐ion battery comprises of an electrolyte containing AlCl₃ in an ionic liquid of 1‐ethyl‐3‐methylimidazolium chloride ([EMIm]Cl). Galvanostatic charge/discharge measurements have been performed in a voltage range of 0.1–2.0 V versus Al/AlCl₄ ^?. An initial discharge specific capacity of 350 mA h g^?1 at a current density of 100 mA g^?1 is achieved, and the discharge capacity remains over 60 mA h g^?1 and coulombic efficiency of 99% after 100 cycles. Typically, for the current density at 200 mA g^?1, the initial charge and discharge capacities are 300 and 235 mA h g^?1, respectively. More importantly, it should be emphasized that the battery has a high discharge voltage plateau (≈1.0 V vs Al/AlCl₄ ^?). These meaningful results represent a significant step forward in the development of aluminum‐ion batteries.     

Large‐Sized Few‐Layer Graphene Enables an Ultrafast and Long‐Life Aluminum‐Ion Battery

To develop high‐power and high‐energy batteries with a long life remains a great challenge, even combining the benefits of metal (fast kinetics and high capacity) and carbon materials (robust structure). Among them, Al‐ion batteries based on aluminum anode and graphite carbon cathode have gained lots of interests as one of the most promising technologies. Here, it is demonstrated that the size of graphitic material in ab plane and c direction plays an important role in anion intercalation chemistry. Sharply decreasing the size of vertical dimension (c direction) strongly facilitates the kinetics and charge transfer of anions (de)intercalation. On the other hand, increasing the size of horizontal dimension (ab plane) contributes to improving the flexibility of graphitic materials, which results in raising the cycling stability. Meanwhile, chloroaluminate anions are reversibly intercalated into the interlayer of graphite materials, leading to the staging behaviors. In the end, an ultrafast Al‐ion battery with exceptional long life is achieved based on large‐sized few‐layer graphene as a cathode and aluminum metal as an anode.     

Room‐Temperature Rechargeable Ca‐Ion Based Hybrid Batteries with High Rate Capability and Long‐Term Cycling Life

Calcium‐ion batteries (CIBs) are promising energy storage devices due to the merits of natural abundance, similar standard reduction potential to lithium, and bivalent‐ion characteristic of calcium. However, the development of CIBs is hindered by the low rate capability and poor cycling performance at room temperature. Here, a highly reversible room‐temperature calcium‐ion based hybrid battery is realized by a tri‐ion strategy, which significantly improves the diffusion kinetics of calcium ions. The optimized CIB shows high rate capability of 15 C as well as excellent cycling stability over 1500 cycles with 86% capacity retention at 5 C, at room temperature, which is the best result of reported calcium‐ion based full batteries.     

Novel Route to Fe‐Based Cathode as an Efficient Bifunctional Catalysts for Rechargeable Zn–Air Battery

Efficient bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts are of great importance for rechargeable metal–air batteries. Herein, FeN_x/C catalysts are synthesized by pyrolysis of thiourea and agarose containing α‐Fe₂O₃ nanoplate as Fe precursor, where α‐Fe₂O₃ nanoplate can prevent the aggregation of carbon sheets to effectively improve the specific surface area during the carbonization process. The FeN_x/C‐700‐20 catalyst displays excellent catalytic performance for both ORR and OER activity in alkaline conditions with more positive onset potential (1.1 V vs the reversible hydrogen electrode) and half‐wave potential, higher stability, and stronger methanol tolerance in alkaline solution, which are all superior to that of the commercial Pt/C catalyst. In this study, the detailed analyses demonstrate that the coexistence of Fe‐based species and high content of Fe‐N_x both play an important role for the catalytic activity. Furthermore, FeN_x/C‐700‐20 as cathode catalyst in Zn–air battery possesses higher charge–discharge stability and power density compared with that of commercial Pt/C catalyst, displaying great potential in practical implementation of for the rechargeable energy devices.     

A Sodium‐Ion Battery with a Low‐Cost Cross‐Linked Gel‐Polymer Electrolyte

The design of a sodium‐ion rechargeable battery with an antimony anode, a Na₃V₂(PO₄)₃ cathode, and a low‐cost composite gel‐polymer electrolyte based on cross‐linked poly(methyl methacrylate) is reported. The application of an antimony anode, on replacement of the sodium metal that is commonly used in sodium‐ion half‐cells, reduces significantly the interfacial resistance and charge transfer resistance of a sodium‐ion battery, which enables a smaller polarization for a sodium‐ion full‐cell Sb/Na₃V₂(PO₄)₃ running at relatively high charge and discharge rates. The incorporation of the gel‐polymer electrolyte is beneficial to maintain stable interfaces between the electrolyte and the electrodes of the sodium‐ion battery at elevated temperature. When running at 60 °C, the sodium‐ion full‐cell Sb/Na₃V₂(PO₄)₃ with the gel‐polymer electrolyte exhibits superior cycling stability compared to a battery with the conventional liquid electrolyte.     

A Phosphonate‐Functionalized Quinone Redox Flow Battery at Near‐Neutral pH with Record Capacity Retention Rate

A highly stable phosphonate‐functionalized anthraquinone is introduced as the redox‐active material in a negative potential electrolyte (negolyte) for aqueous redox flow batteries operating at nearly neutral pH. The design and synthesis of 2,6‐DPPEAQ, (((9,10‐dioxo‐9,10‐dihydroanthracene‐2,6‐diyl)bis(oxy))bis(propane‐3,1‐diyl))bis(phosphonic acid), which has a high solubility at pH 9 and above, is described. Chemical stability studies demonstrate high stability at both pH 9 and 12. By pairing 2,6‐DPPEAQ with a potassium ferri/ferrocyanide positive electrolyte across an inexpensive, nonfluorinated permselective polymer membrane, this near‐neutral quinone flow battery exhibits an open‐circuit voltage of 1.0 V and a capacity fade rate of 0.00036% per cycle and 0.014% per day, which is the lowest ever reported for any flow battery in the absence of rebalancing processes. It is further demonstrated that the negolyte pH drifts upward upon atmospheric oxygen penetration but, when oxygen is excluded, oscillates reversibly between 9 and 12 during cycling. These results enhance the suitability of aqueous‐soluble redox‐active organics for use in large‐scale energy storage, potentially enabling massive penetration of intermittent renewable electricity.     

Rechargeable Dual‐Ion Batteries with Graphite as a Cathode: Key Challenges and Opportunities

Rechargeable graphite dual‐ion batteries (GDIBs) have attracted the attention of electrochemists and material scientists in recent years due to their low cost and high‐performance metrics, such as high power density (≈3–175 kW kg^?1), energy efficiency (≈80–90%), long cycling life, and high energy density (up to 200 Wh kg^?1), suited for grid‐level stationary storage of electricity. The key feature of GDIBs is the exploitation of the reversible oxidation of the graphite network with concomitant and highly efficient intercalation/deintercalation of bulky anionic species between graphene layers. In this review, historical and current research aspects of GDIBs are discussed, along with key challenges in their development and practical deployment. Specific emphasis is given to the operational mechanism of GDIBs and to unbiased and correct reporting of theoretical cell‐level energy densities.     

Metal‐Organic Framework Cathodes Based on a Vanadium Hexacyanoferrate Prussian Blue Analogue for High‐Performance Aqueous Rechargeable Batteries

Despite the unique advantages of the metal‐organic framework of Prussian blue analogues (PBAs), including a favorable crystallographic structure and facile diffusion kinetics, the capacity of PBAs delivered in aqueous systems has been limited to ≈60 mA h g^?1 because only single species of transition metal ions incorporated into the PBAs are electrochemically activated. Herein, vanadium hexacyanoferrate (V/Fe PBA) is proposed as a breakthrough to this limitation, and its electrochemical performance as a cathode for aqueous rechargeable batteries (ARBs) is investigated for the first time. V/Fe PBAs are synthesized by a simple co‐precipitation method with optimization of the acidity and molar ratios of precursor solutions. The V/Fe PBAs provide an improved capacity of 91 mA h^?1 under a current density of 110 mA g^?1 (C‐rate of ≈1.2 C), taking advantage of the multiple‐electron redox reactions of V and Fe ions. Under an extremely fast charge/discharge rate of 3520 mA g^?1, the V/Fe PBA exhibits a sufficiently high discharge capacity of 54 mA h g^?1 due to its opened structure and 3D hydrogen bonding networks. V/Fe PBA‐based ARBs are the most promising candidates for large‐scale stationary energy storage systems due to their high electrochemical performance, reasonable cost, and high efficiency.     

Solar Rechargeable Batteries Based on Lead–Organohalide Electrolyte

A dye‐sensitized solar cell (DSC) with in situ energy storage capacity is demonstrated using a lead–organohalide electrolyte CH₃NH₃I·PbCl₂ (LOC) to replace the conventional I^?/I₃^? electrolyte. The coupling of lead and iodine in one electrolyte creates a dual‐function rechargeable solar battery that combines the working processes of photoelectrochemical cells with electrochemical batteries. Optimization of the H⁺ concentration in the electrolyte leads to increased photocharging efficiency and storage. The power conversion efficiency of the LOC–DSC is 8.6% under one sun illumination (AM 1.5, 100 mW cm^?2) as a DSC. When operating as a battery, Faraday efficiency can be achieved as high as 81.5% using a bromide‐based CH₃NH₃Br·PbBr₂ (LOB) electrolyte in a DSC configuration. This new cell design suggests a means of combining photovoltaic energy conversion and electrical energy storage.     

Charge and Discharge Processes and Sodium Storage in Disodium Pyridine‐2,5‐Dicarboxylate Anode—Insights from Experiments and Theory

A combined experimental and computational study of disodium pyridine‐2,5‐dicarboxylate (Na₂PDC) is presented exploring the possibility of using it as a potential anode for organic sodium‐ion batteries. This electrode material can reversibly insert/release two Na cations per formula unit, resulting in high reversible capacity of 270 mA h g^?1 (236 mA h g^?1 after accounting for the contribution from Super P carbon) with excellent cyclability 225 mA h g^?1, with retention of 83% capacity after 100 cycles, and good rate performance with reversible capacity of 138 mA h g^?1 at a 5 C rate. The performance of disodium pyridine dicarboxylate is therefore found to be superior to that of the related and well investigated disodium terephthalate. The material shows two voltage plateaus at about 0.6 V up to Na₂₊₁PDC and then 0.4 V up to full sodiation, Na₂₊₂PDC. The first plateau is attributed to the coordination of inserted Na to nitrogen atoms with bond formation, i.e., a different mechanism from the terephthalate analog. The subsequent plateau is due to coordination to the carboxylic groups.     

Na‐Ion Batteries for Large Scale Applications: A Review on Anode Materials and Solid Electrolyte Interphase Formation

The urgent need for optimizing the available energy through smart grids and efficient large‐scale energy storage systems is pushing the construction and deployment of Li‐ion batteries in the MW range which, in the long term, are expected to hit the GW dimension while demanding over 1000 ton of positive active material per system. This amount of Li‐based material is equivalent to almost 1% of current Li consumption and can strongly influence the evolution of the lithium supply and cost. Given this uncertainty, it becomes mandatory to develop an energy storage technology that depends on almost infinite and widespread resources: Na‐ion batteries are the best technology for large‐scale applications. With small working cells in the market that cannot compete in cost ($/W h) with commercial Li‐ion batteries, the consolidation of Na‐ion batteries mainly depends on increasing their energy density and stability, the negative electrodes being at the heart of these two requirements. Promising Na‐based negative electrodes for large‐scale battery applications are reviewed, along with the study of the solid electrolyte interphase formed in the anode surface, which is at the origin of most of the stability problems.