Toward High-Energy-Density Initial-Anode-Free Lithium-Metal Batteries via Ultra-Thin Protective Ion-Transport-Promoting Interface Modification and Surface Prelithiation.

Anode-free lithium-metal batteries (AFLMBs) are desirable candidates for achieving high-energy-density batteries, while severe active Li+ loss and uneven Li plating/stripping behavior impede their practical application. Herein, a trilaminar LS-Cu (LiCPON + Si/C-Cu) current collector is fabricated by radio frequency magnetron sputtering, including a Si/C hybrid lithiophilic layer and a supernatant carbon-incorporated lithium phosphorus oxynitride (LiCPON) solid-state electrolyte layer. Joint experimental and computational characterizations and simulations reveal that the LiCPON solid-state electrolyte layer can decompose into an in situ stout ion-transport-promoting protective layer, which can not only regulate homogeneous Li plating/stripping behavior but also inhibit the pulverization and deactivation of Si/C hybrid lithiophilic layer. When combined with surface prelithiated Li1.2Ni0.13Co0.13Mn0.54O2 (Preli-LRM) cathode, the Preli-LRM||LS-Cu full cell delivers 896.1 Wh kg-1 initially and retains 354.1 Wh kg-1 after 50 cycles. This strategy offers an innovative design of compensating for active Li+ loss and inducing uniform Li plating/stripping behavior simultaneously for the development of AFLMBs.

Anomalous Redox Features Induced by Strong Covalency in Layered NaTi1-y Vy S2 Cathodes for Na-Ion Batteries.

The rising demand for energy density of cathodes means the need to raise the voltage or capacity of cathodes. Transition metal (TM) doping has been employed to enhance the electrochemical properties in multiple aspects. The redox voltage of doped cathodes usually falls in between the voltage of undoped layered cathodes. However, we found anomalous redox features in NaTi1-y Vy S2 . The first discharge platform potential (2.4 V) is significantly higher than that of undoped NaTiS2 and NaVS2 (both around 2.2 V), and the energy density is raised by 15 %. We speculate that the anomalous voltage is mainly attributed to the strong hybridization in the Ti-V-S system. Ti3+ and V3+ undergo charge transfer and form a more stable Ti (t2g 0 eg 0 ) and V (t2g 3 eg 0 ) electronic configuration. Our results indicate that higher voltage of cathode materials could be achieved by strong TM-ligand covalency, and this conclusion provides possible opportunities to explore high voltage materials for future layered cathodes.

Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries.

Most P2-type layered oxides suffer from multiple voltage plateaus, due to Na+/vacancy-order superstructures caused by strong interplay between Na-Na electrostatic interactions and charge ordering in the transition metal layers. Here, Mg ions are successfully introduced into Na sites in addition to the conventional transition metal sites in P2-type Na0.7[Mn0.6Ni0.4]O2 as new cathode materials for sodium-ion batteries. Mg ions in the Na layer serve as "pillars" to stabilize the layered structure, especially for high-voltage charging, meanwhile Mg ions in the transition metal layer can destroy charge ordering. More importantly, Mg ion occupation in both sodium and transition metal layers will be able to create "Na-O-Mg" and "Mg-O-Mg" configurations in layered structures, resulting in ionic O 2p character, which allocates these O 2p states on top of those interacting with transition metals in the O-valence band, thus promoting reversible oxygen redox. This innovative design contributes smooth voltage profiles and high structural stability. Na0.7Mg0.05[Mn0.6Ni0.2Mg0.15]O2 exhibits superior electrochemical performance, especially good capacity retention at high current rate under a high cutoff voltage (4.2 V). A new P2 phase is formed after charge, rather than an O2 phase for the unsubstituted material. Besides, multiple intermediate phases are observed during high-rate charging. Na-ion transport kinetics are mainly affected by elemental-related redox couples and structural reorganization. These findings will open new opportunities for designing and optimizing layer-structured cathodes for sodium-ion batteries.

A Novel Small-Molecule Compound of Lithium Iodine and 3-Hydroxypropionitride as a Solid-State Electrolyte for Lithium-Air Batteries.

A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I(-)-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium-air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g(-1) with a cyclic performance over 10 cycles. Our findings provide a new way to design solid-state electrolytes toward high-performance lithium-air batteries.

Galvanic replacement-free deposition of Au on Ag for core-shell nanocubes with enhanced chemical stability and SERS activity.

We report a robust synthesis of Ag@Au core-shell nanocubes by directly depositing Au atoms on the surfaces of Ag nanocubes as conformal, ultrathin shells. Our success relies on the introduction of a strong reducing agent to compete with and thereby block the galvanic replacement between Ag and HAuCl4. An ultrathin Au shell of 0.6 nm thick was able to protect the Ag in the core in an oxidative environment. Significantly, the core-shell nanocubes exhibited surface plasmonic properties essentially identical to those of the original Ag nanocubes, while the SERS activity showed a 5.4-fold further enhancement owing to an improvement in chemical enhancement. The combination of excellent SERS activity and chemical stability may enable a variety of new applications.

The role of etching in the formation of Ag nanoplates with straight, curved and wavy edges and comparison of their SERS properties.

We investigate the role of etching in the formation of Ag nanoplates with different morphologies. By examining the reduction of AgNO3 with poly(vinyl pyrrolidone) in an aqueous solution under a hydrothermal condition, we confirm that etching plays an essential role in promoting the growth of Ag triangular nanoplates with straight edges at the expense of multiple twinned particles via Ostwald ripening. Once all the multiple twinned particles are gone, etching will continue at the corners of nanoplates, leading to the formation of enneahedral nanoplates with curved edges. When the nanoplates with straight edges are transferred into ethanol and subjected to a solvothermal treatment, we obtain nanoplates with wavy edges and sharp corners due to etching on the edges. A comparison study indicates that, at the same particle concentration, Ag nanoplates with wavy edges embraces a SERS enhancement factor at least 6 and 13 times stronger than those with straight and curved edges, respectively. The results from finite difference time domain calculations support our experimental observation that the sharp features on nanoplates with wavy edges are the most active sites for SERS.

A hierarchical three-dimensional NiCo2O4 nanowire array/carbon cloth as an air electrode for nonaqueous Li-air batteries.

A 3D NiCo2O4 nanowire array/carbon cloth (NCONW/CC) was employed as the cathode for Li-air batteries with a non-aqueous electrolyte. After its discharge, novel porous ball-like Li2O2 was found to be deposited on the tip of NiCo2O4 nanowires. The special structure of Li2O2 and active sites of catalysts are also discussed.

Activation of trace LiNO3 additives by BF3 in high-concentration electrolytes towards stable lithium metal batteries.

The activation of trace LiNO3 additives in high-concentration electrolytes is achieved by BF3 due to its Lewis acidity. This advanced electrolyte can promote the decomposition of LiNO3 into Li3N, attaining enhanced cycle reversibility of lithium anodes, which broadens the application of LiNO3 additives.

Anionic Redox Regulated via Metal-Ligand Combinations in Layered Sulfides.

The increasing demand for energy storage is calling for improvements in cathode performance. In traditional layered cathodes, the higher energy of the metal 3d over the O 2p orbital results in one-band cationic redox; capacity solely from cations cannot meet the needs for higher energy density. Emerging anionic redox chemistry is promising to access higher capacity. In recent studies, the low-lying O nonbonding 2p orbital was designed to activate one-band oxygen redox, but they are still accompanied by reversibility problems like oxygen loss, irreversible cation migration, and voltage decay. Herein, by regulating the metal-ligand energy level, both extra capacities provided by anionic redox and highly reversible anionic redox process are realized in NaCr1- y Vy S2 system. The simultaneous cationic and anionic redox of Cr/V and S is observed by in situ X-ray absorption near edge structure (XANES). Under high d-p hybridization, the strong covalent interaction stabilizes the holes on the anions, prevents irreversible dimerization and cation migration, and restrains voltage hysteresis and voltage decay. The work provides a fundamental understanding of highly reversible anionic redox in layered compounds, and demonstrates the feasibility of anionic redox chemistry based on hybridized bands with d-p covalence.

Graphite prelithiation by solid electrochemical corrosion of lithium metal with a superficial mosaic structure.

A transformative concept of solid electrochemical corrosion has been put forward, in which solid-state electrolyte LiPON has been applied to replace the liquid one to prelithiate graphite with Li-metal. Thus, high prelithiation efficiency and low polarization of the treated anode can be obtained, with a unique mosaic structure left at the surface.

Anionic redox reaction triggered by trivalent Al3+ in P3-Na0.65Mn0.5Al0.5O2.

P3-Na0.65Mn0.5Al0.5O2 (NMAO) has been synthesized and studied as a cathode for sodium batteries, and shows anionic redox reaction (ARR) and exhibits a first charging capacity of ∼110 mA h g-1. The electrochemical mechanism of NMAO was comprehensively investigated by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and density functional theory (DFT) calculations. The reversible oxygen redox behaviour is triggered by Al3+ through oxygen quasi non-bonding states generated by the relatively ionic interaction of Al and O. Furthermore, the presence of Al3+ can suppress oxygen loss in ARR. This work provides new insights into the design and mechanism of anionic redox active cathode materials.

Whole-Voltage-Range Oxygen Redox in P2-Layered Cathode Materials for Sodium-Ion Batteries.

Oxygen-redox of layer-structured metal-oxide cathodes has drawn great attention as an effective approach to break through the bottleneck of their capacity limit. However, reversible oxygen-redox can only be obtained in the high-voltage region (usually over 3.5 V) in current metal-oxide cathodes. Here, we realize reversible oxygen-redox in a wide voltage range of 1.5-4.5 V in a P2-layered Na0.7 Mg0.2 [Fe0.2 Mn0.6 □0.2 ]O2 cathode material, where intrinsic vacancies are located in transition-metal (TM) sites and Mg-ions are located in Na sites. Mg-ions in the Na layer serve as "pillars" to stabilize the layered structure during electrochemical cycling, especially in the high-voltage region. Intrinsic vacancies in the TM layer create the local configurations of "□-O-□", "Na-O-□" and "Mg-O-□" to trigger oxygen-redox in the whole voltage range of charge-discharge. Time-resolved techniques demonstrate that the P2 phase is well maintained in a wide potential window range of 1.5-4.5 V even at 10 C. It is revealed that charge compensation from Mn- and O-ions contributes to the whole voltage range of 1.5-4.5 V, while the redox of Fe-ions only contributes to the high-voltage region of 3.0-4.5 V. The orphaned electrons in the nonbonding 2p orbitals of O that point toward TM-vacancy sites are responsible for reversible oxygen-redox, and Mg-ions in Na sites suppress oxygen release effectively.

Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S-S.

The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2- and (S2)2- through dimerization of S-S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g-1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S-S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n- species with shortened S-S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

All-Solid-State Rechargeable Lithium Metal Battery with a Prussian Blue Cathode Prepared by a Nonvacuum Coating Technology.

A Prussian blue LiFeFe(CN)6 thin-film cathode is fabricated by a nonvacuum coating technology without post-annealing process. The thin film of the solid electrolyte lithium phosphorus oxynitride (LiPON) is deposited onto the cathode by using radio-frequency magnetron sputtering. Then, the lithium metal anode is deposited on the LiPON film by the thermal evaporation method to fabricate the all-solid-state LiFeFe(CN)6/LiPON/Li battery with a thickness of 16 µm and a size of ∼10 cm2. Electrochemical properties of LiFeFe(CN)6/LiPON/Li battery are first investigated at various temperatures from -30 to 80 °C. Our results demonstrated that the all-solid-state LiFeFe(CN)6/LiPON/Li battery exhibits a discharge capacity of 82.5 mA h/g for the third cycle at 60 °C and shows stable cyclic performance within 200 cycles. These results provide the feasibility to assemble an all-solid-state lithium-ion battery by combining nonvacuum and vacuum techniques through an environmentally friendly process at low temperature.

A highly efficient bifunctional heterogeneous catalyst for morphological control of discharged products in Na-air batteries.

Heterogeneous catalysts with Co3O4 and liquid redox mediators were utilized for the morphological control of discharged products in SABs. With Co3O4 nanowires/C as air cathodes, the discharge product tended to be like nanoflakes. However, after the addition of ferrocene to the electrolyte, the discharge product tended to be like nanofilms and the cyclic performance can achieve 570 cycles.

Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66Co x Mn0.66-x Ti0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66Co x Mn0.66-x Ti0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide.

The intercalation compounds with various electrochemically active or inactive elements in the layered structure have been the subject of increasing interest due to their high capacities, good reversibility, simple structures, and ease of synthesis. However, their reversible intercalation/deintercalation redox chemistries in previous compounds involve a single cationic redox reaction or a cumulative cationic and anionic redox reaction. Here we report an anionic redox chemistry and structural stabilization of layered sodium chromium sulfide. It was discovered that the sulfur in sodium chromium sulfide is electrochemically active, undergoing oxidation/reduction rather than chromium. Significantly, sodium ions can successfully move out and into without changing its lattice parameter c, which is explained in terms of the occurrence of chromium/sodium vacancy antisite during desodiation and sodiation processes. Our present work not only enriches the electrochemistry of layered intercalation compounds, but also extends the scope of investigation on high-capacity electrodes.The rational design of intercalation electrodes is largely confined to the optimization of redox chemistry of transition metals and oxygen. Here, the authors report the single anionic redox process in NaCrS2 where it is sulfur rather than chromium that works as the electrochemical active species.

A long-life Na-air battery based on a soluble NaI catalyst.

A Na-air battery with NaI dissolved in a typical organic electrolyte could run up to 150 cycles with a capacity limit of 1000 mA h g(-1). The low charge voltage plateau of 3.2 V vs. Na(+)/Na in a Na-air battery should mainly be attributed to the oxidation reaction of active iodine anions.

Improved electrochemical performance of CoS2-MWCNT nanocomposites for sodium-ion batteries.

A CoS2/multi-walled carbon nanotube (MWCNT) nanocomposite was synthesized and its sodium storage performances in ether-based electrolyte and commonly used carbonate-based electrolyte were investigated for the first time. A high capacity of 568 mA h g(-1) after 100 cycles in ether-based electrolyte can be achieved.

A quinary layer transition metal oxide of NaNi1/4Co1/4Fe1/4Mn1/8Ti1/8O2 as a high-rate-capability and long-cycle-life cathode material for rechargeable sodium ion batteries.

A well-crystallized single-phase quinary layer transition metal oxide of NaNi1/4Co1/4Fe1/4Mn1/8Ti1/8O2 was successfully synthesized. It exhibited excellent cycle performance and high rate capability as a cathode material for sodium-ion batteries.