Elucidating Structure-Composition-Property Relationships of Ni-Based Prussian Blue Analogues for Electrochemical Seawater Desalination.

Nickel hexacyanoferrate (NiHCF), a type of Prussian blue analogue (PBA), has recently emerged as one of the most promising Na-storage electrodes for use in electrochemical desalination. Previous studies have revealed that NiHCF can be prepared with both cubic and rhombohedral symmetries depending on the oxidation state of Fe (FeII vs FeIII) and the related A-site occupancy. However, our understanding of the effects of the lattice-type of the as-prepared samples on their electrochemical performances, structural transitions that occur during sodiation/desodiation, cyclability, and rate capabilities is presently lacking. Additionally, the optimum structural and compositional features required to prepare high-performing NiHCF electrodes have not yet been clearly established. In this work, we report the synthesis of two sets of cubic and rhombohedral NiHCF samples with different particle sizes, crystallinities, and compositions. Using these samples, we systematically elucidated the structure-composition-property relationships of NiHCF to develop rational design principles to prepare high-performing PBAs. Our results show that high crystallinity, a low number of Fe(CN)6 vacancies, and a large unit cell size to allow for consistent structural changes during cycling are critical factors to produce NiHCF with a high capacity, good cycling stability, and good rate capabilities, and these factors are considerably affected by the synthesis conditions. One of the samples prepared in this study with optimum structural features demonstrates the best performance and stability among any PBA electrode tested in neutral saline solutions to date.

Tandem Desalination/Salination Strategies Enabling the Use of Redox Couples for Efficient and Sustainable Electrochemical Desalination.

As access to fresh water becomes an increasingly serious global issue, developing desalination methods that can reduce not only the cost but also the carbon footprint of desalination has become of utmost importance. In this study, we demonstrate the use of the oxidation and reduction of the same redox couple with fast redox kinetics as the anode and cathode reactions of an electrodialysis (ED) cell. This reduces the thermodynamic equilibrium cell potential to 0 V while also significantly reducing the kinetic overpotentials required for cell operation. As a result, the overall operating voltage of our ED cell is remarkably reduced, making it possible to use ED for seawater desalination and to operate the ED cell by using inexpensive portable power generators that provide a limited voltage. The sustainable use of the redox couple in the ED cell was enabled by a new strategy, where a desalination ED cell and a salination ED cell were operated in tandem. In this tandem system, the electrolytes in the anode and cathode compartments of the two cells were circulated such that the compositional changes of the electrolytes made in the desalination cell could be reversed in the salination cell. As a result, the feedwater (0.6 M NaCl) could be converted to 0 and 1.2 M NaCl solutions in the desalination cell and salination cell, respectively, without the accumulation of salt ions in the anode and cathode compartments. The operating principles and performance of a proof-of-concept tandem desalination/salination system are demonstrated.

Bismuth as a New Chloride-Storage Electrode Enabling the Construction of a Practical High Capacity Desalination Battery.

Materials that can selectively store Na and Cl ions in the bulk of their structures and release these ions with good cycle stability can enable the construction of a high capacity, rechargeable desalination cell for use in seawater desalination. In this study, the ability of a nanocrystalline Bi foam electrode to serve as an efficient and high capacity Cl-storage electrode using its conversion to BiOCl was investigated. When Bi as a Cl-storage electrode was coupled with NaTi2(PO4)3 as a Na-storage electrode, a new type of rechargeable desalination cell, which is charged during desalination and discharged during salination, was constructed. The resulting Bi-NaTi2(PO4)3 cell was tested under various salination and desalination conditions to investigate advantages and potential limitations of using Bi as a Cl-storage electrode. Slow Cl- release kinetics of BiOCl in neutral conditions and an imbalance in Cl and Na storage (i.e., Cl storage requires three electrons/Cl, while Na storage requires one electron/Na) were identified as possible drawbacks, but strategies to address these issues were developed. On the basis of these investigations, optimum desalination and salination conditions were identified where the Bi/NaTi2(PO4)3 cell achieved a desalination/salination cycle at ±1 mA cm-2 with a net potential input of only 0.20 V. The kinetics of Cl- release from BiOCl was significantly improved by the use of an acidic solution, and therefore, a divided cell was used for the salination process. We believe that with further optimizations the Bi/BiOCl electrode will enable efficient and practical desalination applications.

Electrochemically Synthesized Sb/Sb2O3 Composites as High-Capacity Anode Materials Utilizing a Reversible Conversion Reaction for Na-Ion Batteries.

Sb/Sb2O3 composites are synthesized by a one-step electrodeposition process from an aqueous electrolytic bath containing a potassium antimony tartrate complex. The synthesis process involves the electrodeposition of Sb simultaneously with the chemical deposition of Sb2O3, which allows for the direct deposition of morula-like Sb/Sb2O3 particles on the current collector without using a binder. Structural characterization confirms that the Sb/Sb2O3 composites are composed of approximately 90 mol % metallic Sb and 10 mol % crystalline Sb2O3. The composite exhibits a high reversible capacity (670 mAh g(-1)) that is higher than the theoretical capacity of Sb (660 mAh g(-1)). The high reversible capacity results from the conversion reaction between Na2O and Sb2O3 that occurs additionally to the alloying/dealloying reaction of Sb with Na. Moreover, the Sb/Sb2O3 composite shows excellent cycle performance with 91.8% capacity retention over 100 cycles, and a superior rate capability of 212 mAh g(-1) at a high current density of 3300 mA g(-1). The outstanding cycle performance is attributed to an amorphous Na2O phase generated by the conversion reaction, which inhibits agglomeration of Sb particles and acts as an effective buffer against volume change of Sb during cycling.

High-Performance Sb/Sb2 O3 Anode Materials Using a Polypyrrole Nanowire Network for Na-Ion Batteries.

Three-dimensional porous Sb/Sb2 O3 anode materials are successfully fabricated using a simple electrodeposition method with a polypyrrole nanowire network. The Sb/Sb2 O3 -PPy electrode exhibits excellent cycle performance and outstanding rate capabilities; the charge capacity is sustained at 512.01 mAh g(-1) over 100 cycles, and 56.7% of the charge capacity at a current density of 66 mA g(-1) is retained at 3300 mA g(-1) . The improved electrochemical performance of the Sb/Sb2 O3 -PPy electrode is attributed not only to the use of a highly porous polypyrrole nanowire network as a substrate but also to the buffer effects of the Sb2 O3 matrix on the volume expansion of Sb. Ex situ scanning electron microscopy observation confirms that the Sb/Sb2 O3 -PPy electrode sustains a strong bond between the nanodeposits and polypyrrole nanowires even after 100 cycles, which maintains good electrical contact of Sb/Sb2 O3 with the current collector without loss of the active materials.

Template-free electrochemical synthesis of Sn nanofibers as high-performance anode materials for Na-ion batteries.

Sn nanofibers with a high aspect ratio are successfully synthesized using a simple electrodeposition process from an aqueous solution without the use of templates. The synthetic approach involves the rapid electrochemical deposition of Sn accompanied by the strong adsorption of Triton X-100, which can function as a growth modifier for the Sn crystallites. Triton X-100 is adsorbed on the {200} crystallographic planes of Sn in an elongated configuration and suppressed the preferential growth of Sn along the [100] direction. Consequently, the Sn electrodeposits are forced to grow anisotropically in a direction normal to the (112) or (1̅12) plane, forming one-dimensional nanofibers. As electrode materials for the Na-ion batteries, the Sn nanofibers exhibit a high reversible capacity and an excellent cycle performance; the charge capacity is maintained at 776.26 mAh g(-1) after 100 cycles, which corresponds to a retention of 95.09% of the initial charge capacity. The superior electrochemical performance of the Sn nanofibers is mainly attributed to the high mechanical stability of the nanofibers, which originate from highly anisotropic expansion during sodiation and the pore volumes existing between the nanofibers.