Oxygen Reduction Kinetics of Fe-N-C Single Atom Catalysts Boosted by Pyridinic N Vacancy for Temperature-Adaptive Zn-Air Batteries.

The design of temperature-adaptive Zn-air batteries (ZABs) with long life spans and high energy efficiencies is challenging owing to sluggish oxygen reduction reaction (ORR) kinetics and an unstable Zn/electrolyte interface. Herein, a quasi-solid-state ZAB is designed by combining atomically dispersed Fe-N-C catalysts containing pyridinic N vacancies (FeNC-VN) with a polarized organo-hydrogel electrolyte. First-principles calculation predicts that adjacent VN sites effectively enhance the covalency of Fe-Nx moieties and moderately weaken *OH binding energies, significantly boosting the ORR kinetics and stability. In situ Raman spectra reveal the dynamic evolution of *O2- and *OOH on the FeNC-VN cathode in the aqueous ZAB, proving that the 4e- associative mechanism is dominant. Moreover, the ethylene glycol-modulated organo-hydrogel electrolyte forms a zincophilic protective layer on the Zn anode surface and tailors the [Zn(H2O)6]2+ solvation sheath, effectively guiding epitaxial deposition of Zn2+ on the Zn (002) plane and suppressing side reactions. The assembled quasi-solid-state ZAB demonstrates a long life span of over 1076 h at 2 mA cm-2 at -20 °C, outperforming most reported ZABs.

Heterogeneous Catalyst as a Functional Substrate Governing the Shape of Electrochemical Precipitates in Oxygen-Fueled Rechargeable Batteries.

Lithium-oxygen batteries have the potential to become the most eminent solution for future energy storage with their theoretical energy density exceeding all existing batteries. However, the insulating and insoluble discharge product (lithium peroxide; Li2O2) impairs practical application. Conventional catalyst designs based on the electronic structure and interfacial charge transfer descriptors have not been able to overcome these limitations due to Li2O2. Herein, we revisit the role of heterogeneous catalysts as substrates to regulate Li2O2 growth and the formation of solid/solid reaction interfaces. We demonstrate that controlled solid/solid interfacial structure design is a critical performance parameter beyond the inherent electronic structure. In particular, the Cu2O substrate in this study induces a homogeneous deposition of Pd atoms, which leads to well-controlled growth of Li2O2 resolving mass and charge transport limits (i.e., the bottleneck of oxygen reduction/evolution reactions), thus improving reversibility, capacity, and durability of the cells by dissipating electrochemical and mechanical stress. We thus verified the essential role of solid/solid interfaces to regulate the nucleation and growth process of Li2O2 in lithium-oxygen batteries.

A Mechanistic Insight into the Oxygen Redox of Li-Rich Layered Cathodes and their Related Electronic/Atomic Behaviors Upon Cycling.

Li-rich cathodes are extensively investigated as their energy density is superior to Li stoichiometric cathode materials. In addition to the transition metal redox, this intriguing electrochemical performance originates from the redox reaction of the anionic sublattice. This new redox process, the so-called anionic redox or, more directly, oxygen redox in the case of oxides, almost doubles the energy density of Li-rich cathodes compared to conventional cathodes. Numerous theoretical and experimental investigations have thoroughly established the current understanding of the oxygen redox of Li-rich cathodes. However, different reports are occasionally contradictory, indicating that current knowledge remains incomplete. Moreover, several practical issues still hinder the real-world application of Li-rich cathodes. As these issues are related to phenomena resulting from the electronic to atomic evolution induced by unstable oxygen redox, a fundamental multiscale understanding is essential for solving the problem. In this review, the current mechanistic understanding of oxygen redox, the origin of the practical problems, and how current studies tackle the issues are summarized.

Cationic-potential tuned biphasic layered cathodes for stable desodiation/sodiation.

Sodium layered oxides generally suffer from deep-desodiation instability in P2 structure and sluggish kinetics in O3 structure. It will be great to design P2/O3 biphasic materials that bring the complementary merits of both structures. However, such exploration is hindered by the ambiguous mechanism of material formation. Herein, supported by theoretical simulations and various spectroscopies, we prove that P2/O3 biphasic structures essentially originate from the internal heterogeneity of cationic potential, which can be realized by constraining the temperature-driven ion diffusion during solid-state reactions. Consequently, P2/O3 biphasic Na0.7Ni0.2Cu0.1Fe0.2Mn0.5O2-δ with well-designed quaternary composition is successfully obtained, exhibiting much-improved rate capabilities (62 mAh g-1 at 2.4 A g-1) and cycling stabilities (84% capacity retention after 500 cycles) than its single-phase analogues. Furthermore, synchrotron-based diffraction and X-ray absorption spectroscopy are employed to unravel the underlying sodium-storage mechanism of the P2/O3 biphasic structure. This work presents new insights toward the rational design of advanced layered cathodes for sodium-ion batteries.

Hysteresis Induced by Incomplete Cationic Redox in Li-Rich 3d-Transition-Metal Layered Oxides Cathodes.

Activation of oxygen redox during the first cycle has been reported as the main trigger of voltage hysteresis during further cycles in high-energy-density Li-rich 3d-transition-metal layered oxides. However, it remains unclear whether hysteresis only occurs due to oxygen redox. Here, it is identified that the voltage hysteresis can highly correlate to cationic reduction during discharge in the Li-rich layered oxide, Li1.2 Ni0.4 Mn0.4 O2 . In this material, the potential region of discharge accompanied by hysteresis is apparently separated from that of discharge unrelated to hysteresis. The quantitative analysis of soft/hard X-ray absorption spectroscopies discloses that hysteresis is associated with an incomplete cationic reduction of Ni during discharge. The galvanostatic intermittent titration technique shows that the inevitable energy consumption caused by hysteresis corresponds to an overpotential of 0.3 V. The results unveil that hysteresis can also be affected by cationic redox in Li-rich layered cathodes, implying that oxygen redox cannot be the only reason for the evolution of voltage hysteresis. Therefore, appropriate control of both cationic and anionic redox of Li-rich layered oxides will allow them to reach their maximum energy density and efficiency.

Regulating Pseudo-Jahn-Teller Effect and Superstructure in Layered Cathode Materials for Reversible Alkali-Ion Intercalation.

The Jahn-Teller effect (JTE) is one of the most important determinators of how much stress layered cathode materials undergo during charge and discharge; however, many reports have shown that traces of superstructure exist in pristine layered materials and irreversible phase transitions occur even after eliminating the JTE. A careful consideration of the energy of cationic distortion using a Taylor expansion indicated that second-order JTE (pseudo-JTE) is more widespread than the aforementioned JTE because of the various bonding states that occur between bonding and antibonding molecular orbitals in transition-metal octahedra. As a model case, a P2-type Mn-rich cathode (Na3/4MnO2) was investigated in detail. MnO6 octahedra are well known to undergo either elongation or contraction in a specific direction due to JTE. Here, the substitution of Li for Mn (Na3/4(Li1/4Mn3/4)O2) helped to oxidize Mn3+ to Mn4+ suppressing JTE; however, the MnO6 octahedra remained asymmetric with a clear trace of the superstructure. With various advanced analyses, we disclose the pseudo-JTE as a general reason for the asymmetric distortions of the MnO6 octahedra. These distortions lead to the significant electrochemical degradation of Na3/4Li1/4Mn3/4O2. The suppression of the pseudo-JTE modulates phase transition behaviors during Na intercalation/deintercalation and thereby improves all of the electrochemical properties. The insight obtained by coupling a theoretical background for the pseudo-JTE with verified layered cathode material lattice changes implies that many previous approaches can be rationalized by regulating pseudo-JTE. This suggests that the pseudo-JTE should be thought more important than the well-known JTE for layered cathode materials.

In Situ Defect Engineering Route to Optimize the Cationic Redox Activity of Layered Double Hydroxide Nanosheet via Strong Electronic Coupling with Holey Substrate.

A defect engineering of inorganic solids garners great deal of research activities because of its high efficacy to optimize diverse energy-related functionalities of nanostructured materials. In this study, a novel in situ defect engineering route to maximize electrocatalytic redox activity of inorganic nanosheet is developed by using holey nanostructured substrate with strong interfacial electronic coupling. Density functional theory calculations and in situ spectroscopic analyses confirm that efficient interfacial charge transfer takes place between holey TiN and Ni-Fe-layered double hydroxide (LDH), leading to the feedback formation of nitrogen vacancies and a maximization of cation redox activity. The holey TiN-LDH nanohybrid is found to exhibit a superior functionality as an oxygen electrocatalyst and electrode for Li-O2 batteries compared to its non-holey homologues. The great impact of hybridization-driven vacancy introduction on the electrochemical performance originates from an efficient electrochemical activation of both Fe and Ni ions during electrocatalytic process, a reinforcement of interfacial electronic coupling, an increase in electrochemical active sites, and an improvement in electrocatalysis/charge-transfer kinetics.

Elucidating the charge storage mechanism of carbonaceous and organic electrode materials for sodium ion batteries.

Sodium ion batteries (SIB) have received much research attention in the past decades as they are considered to be one alternative to the currently prevalent lithium ion batteries, and carbonaceous and organic compounds present two promising classes of SIB electrode materials advantaged by abundance of their constituent elements and reduced environmental footprints. To accelerate the development of these materials for SIB applications, future research directions must be guided by a thorough understanding of the charge storage mechanism. This review presents recent efforts in mechanism elucidation for these two classes of SIB electrode materials since, compared to their inorganic counterparts, they have unique challenges in material analysis. Topics covered will include characterization techniques and analytical frameworks for mechanism elucidation, emphasizing the advantages and limitations of individual experimental methodologies and providing a commentary on scientific rigor in result interpretation.

Activating a Multielectron Reaction of NASICON-Structured Cathodes toward High Energy Density for Sodium-Ion Batteries.

The increasing demand to efficiently store and utilize the electricity from renewable energy resources in a sustainable way has boosted the request for sodium-ion battery technology due to the high abundance of sodium sources worldwide. Na superionic conductor (NASICON) structured cathodes with a robust polyanionic framework have been intriguing because of their open 3D structure and superior thermal stability. The ever-increasing demand for higher energy densities with NASICON-structured cathodes motivates us to activate multielectron reactions, thus utilizing the third sodium ion toward higher voltage and larger capacity, both of which have been the bottlenecks for commercializing sodium-ion batteries. A doping strategy with Cr inspired by first-principles calculations enables the activation of multielectron redox reactions of the redox couples V2+/V3+, V3+/V4+, and V4+/V5+, resulting in remarkably improved energy density even in comparison to the layer structured oxides and Prussian blue analogues. This work also comprehensively clarifies the role of the Cr dopant during sodium storage and the valence electron transition process of both V and Cr. Our findings highlight the importance of a broadly applicable doping strategy for achieving multielectron reactions of NASICON-type cathodes with higher energy densities in sodium-ion batteries.

Two-Phase Transition Induced Amorphous Metal Phosphides Enabling Rapid, Reversible Alkali-Metal Ion Storage.

Metal phosphides as anode materials for alkali-metal ion batteries have captured considerable interest due to their high theoretical capacities and electronic conductivity. However, they suffer from huge volume expansion and element segregation during repetitive insertion/extraction of guest ions, leading to structure deterioration and rapid capacity decay. Herein, an amorphous Sn0.5Ge0.5P3 was constructed through a two-phase intermediate strategy based on the elemental composition modulation from two crystalline counterparts and applied in alkali-metal ion batteries. Differing from crystalline P-based compounds, the amorphous structure of Sn0.5Ge0.5P3 effectively reduces the volume variation from above 300% to 225% during cycling. The ordered distribution of cations and anions in the short-range ensures the uniform distribution of each element during cycles and thus contributes to durable cycling stability. Moreover, the long-range disordered structure of amorphous material shortens the ion transport distance, which facilitates diffusion kinetics. Benefiting from the aforementioned effects, the amorphous Sn0.5Ge0.5P3 delivers a high Na storage capacity of 1132 mAh g-1 at 0.1 A g-1 over 100 cycles. Even at high current densities of 2 and 10 A g-1, its capacities still reach 666 and 321 mAh g-1, respectively. As an anode for Li storage, the Sn0.5Ge0.5P3 similarly also exhibits better cycling stability and rate performance compared to its crystalline counterparts. Significantly, the two-phase transition strategy is generally applicable to achieving other amorphous metal phosphides such as GeP2. This work would be helpful for constructing high-performance amorphous anode materials for alkali-metal ion batteries.

Tuning local chemistry of P2 layered-oxide cathode for high energy and long cycles of sodium-ion battery.

Layered transition-metal oxides have attracted intensive interest for cathode materials of sodium-ion batteries. However, they are hindered by the limited capacity and inferior phase transition due to the gliding of transition-metal layers upon Na+ extraction and insertion in the cathode materials. Here, we report that the large-sized K+ is riveted in the prismatic Na+ sites of P2-Na0.612K0.056MnO2 to enable more thermodynamically favorable Na+ vacancies. The Mn-O bonds are reinforced to reduce phase transition during charge and discharge. 0.901 Na+ per formula are reversibly extracted and inserted, in which only the two-phase transition of P2 ↔ P'2 occurs at low voltages. It exhibits the highest specific capacity of 240.5 mAh g-1 and energy density of 654 Wh kg-1 based on the redox of Mn3+/Mn4+, and a capacity retention of 98.2% after 100 cycles. This investigation will shed lights on the tuneable chemical environments of transition-metal oxides for advanced cathode materials and promote the development of sodium-ion batteries.

Development of a highly active FeNC catalyst with the preferential formation of atomic iron sites for oxygen reduction in alkaline and acidic electrolytes.

Nitrogen-doped porous carbons containing atomically dispersed iron are prime candidates for substituting platinum-based catalysts for oxygen reduction reaction (ORR) in fuel cells. These carbon catalysts are classically synthesizedviacomplicated routes involving multiple heat-treatment steps to form the desired Fe-Nx sites. We herein developed a highly active FeNC catalyst comprising of exclusive Fe-Nx sites by a simplified solid-state synthesis protocol involving only a single heat-treatment. Imidazole is pyrolyzed in the presence of an inorganic salt-melt resulting in highly porous carbon sheets decorated with abundant Fe-Nx centers, which yielded a high density of electrochemically accessible active sites (1.36 × 1019 sites g-1) as determined by the in situ nitrite stripping technique. The optimized catalyst delivered a remarkable ORR activity with a half-wave potential (E1/2) of 0.905 VRHE in alkaline electrolyte surpassing the benchmark Pt catalyst by 55 mV. In acidic electrolyte, an E1/2 of 0.760 VRHE is achieved at a low loading level (0.29 mg cm-2). In PEMFC tests, a current density of 2.3 mA cm-2 is achieved at 0.90 ViR-free under H2-O2 conditions, reflecting high kinetic activity of the optimized catalyst.

Multifunctionalities of Graphene for Exploiting a Facile Conversion Reaction Route of Perovskite CoSnO3 for Highly Reversible Na Ion Storage.

Transition-metal oxides are promising anode materials for sodium ion batteries (SIBs) and have attracted a great deal of attention because of their natural abundance and high theoretical capacities. However, they suffer from low conductivity and large volumetric/structural variation during sodiation/desodiation processes, leading to unsatisfactory cycling stability and poor rate capability. This study proposes a novel conversion reaction using CoSnO3 (CSO) nanocubes uniformly wrapped in graphene nanosheets, which are fabricated using a wet-chemical strategy followed by low-temperature heat treatment. This optimized composite exhibits durable cyclability and high rate capability, which can be attributed to the strong interaction between reduced graphene oxide and CSO through its surface oxygen moieties. It develops a facile conversion reaction route, thereby leading to SnO2 formation during charging. This interactive phenomenon further contributes to improving the reaction kinetics and restraining the volume expansion during cycling. This study may provide a facile approach for addressing irreversible conversion of high-capacity oxide materials toward advanced SIBs.

Universal Access to Two-Dimensional Mesoporous Heterostructures by Micelle-Directed Interfacial Assembly.

Two-dimensional (2D) mesoporous heterostructures combining ultrathin nanosheet morphology, periodic porous surface structures, and diverse hybrid compositions have become increasingly important for renewable energy storage and electronics. However, it remains a great challenge to develop a universal method to prepare 2D mesoporous heterostructures. Herein, we report a composite-micelle-directed interfacial assembly method to synthesize heterostructures of an ultrathin 2D material covered with mesoporous monolayers assembled on both sides. To demonstrate the concept, we first fabricated a new sandwichlike carbon@MXene@carbon mesoporous heterostructure through the self-assembly of exfoliated MXene nanosheets and block copolymer F127/melamine-formaldehyde resin composite micelles and subsequent thermal treatment. Finally, we demonstrate that the carbon@MXene@carbon mesoporous heterostructured nanosheets manifest remarkably enhanced electrochemical performance as a cathode material for lithium-sulfur batteries.

Interface-Controlled Rhombohedral Li3V2(PO4)3 Embedded in Carbon Nanofibers with Ultrafast Kinetics for Li-Ion Batteries.

We present a unique composite assembly of rhombohedral Li3V2(PO4)3 and carbon nanofiber, which simultaneously facilitates Li-ion transport as well as electron transfer. For the synthesis of this composite, the inorganic precursors were confined in electron-spun nanofibers, and then, through controlled annealing, Na3V2(PO4)3 particulates were grown with controllable crystallite size and partially embedded into carbon nanofibers with precisely controlled diameter. The rhombohedral Li3V2(PO4)3 could be successfully obtained by ion exchange from Na to Li in the prepared Na3V2(PO4)3. The final rhombohedral Li3V2(PO4)3 particles anchored onto the carbon nanofibers exhibited excellent electrochemical performance with fast kinetics for Li-ion batteries. Suprisingly it maintains 69 and 41 mAh/g even at 100C as cathode and anode. Several advanced characterizations revealed that its ultrafast kinetics could be attributed to synergistic effect resulting from the distinctive microstructure of the composite and the structural superiority of highly symmetric rhombohedral Li3V2(PO4)3 over its monoclinic homologue for Li-ion transport.

Highly Reversible and Rapid Sodium Storage in GeP3 with Synergistic Effect from Outside-In Optimization.

The composite GeP3/C@rGO as a sodium ion battery anode material was fabricated by introducing a carbon matrix into GeP3 through high-energy ball milling, followed by encapsulating the resultant composite with graphene via a solution-based ultrasonic method. To delineate the individual role of carbon matrix and graphene, material characterization and electrochemical analyses were performed for GeP3/C@rGO and three other samples: bare GeP3, GeP3 with graphene coating (GeP3@rGO), and GeP3 with carbon matrix (GeP3/C). GeP3/C@rGO exhibits the highest electric conductivity (5.89 × 10-1 S cm-1) and the largest surface area (167.85 m2 g-1) among the four samples. The as-prepared GeP3/C@rGO delivered a reversible high capacity of 1084 mA h g-1 at 50 mA g-1, excellent rate capacity (435.4 mA h g-1 at a high rate of 5 A g-1), and long-term cycling stability (400 cycles with a reversible capacity of 823.3 mA h g-1 at 0.2 A g-1), all of which outperform the other three samples. The kinetics investigation reveals a "pseudocapacitive behavior" in GeP3/C and GeP3/C@rGO, where solely faradic reactions took place in bare GeP3 and GeP3@rGO with a typical "battery behavior". Based on ex-situ X-ray photoelectron spectroscopy and ex-situ electrochemical impedance spectroscopy, the carbon matrix serves to activate and stabilize the interior of the composite, while the graphene protects and restrains the exterior surface. Benefiting from the synergistic combination of these two components, GeP3/C@rGO achieved extremely stable cycling stability as well as outstanding rate performance.

Mesoporous Iron-doped MoS2/CoMo2S4 Heterostructures through Organic-Metal Cooperative Interactions on Spherical Micelles for Electrochemical Water Splitting.

Mesoporous metal sulfide hybrid (meso-MoS2/CoMo2S4) materials via a soft-templating approach using diblock copolymer polystyrene-block-poly(acrylic acid) micelles are reported. The formation of the meso-MoS2/CoMo2S4 heterostructures is based on the sophisticated coassembly of dithiooxamide and metal precursors (i.e., Co2+, PMo12), which are subsequently annealed in nitrogen atmosphere to generate the mesoporous material. Decomposing the polymer leaves behind mesopores throughout the spherical MoS2/CoMo2S4 hybrid particles, generating numerous electrochemical active sites in a network of pores that enable faster charge transfer and mass/gas diffusion that enhance the electrocatalytic performance of MoS2/CoMo2S4. Doping the spherical meso-MoS2/CoMo2S4 heterostructures with iron improves the electronic properties of the hybrid meso-Fe-MoS2/CoMo2S4 material and consequently results in its superior electrochemical activities for both hydrogen evolution reaction and oxygen evolution reaction.

Recent Advances in the Rational Design and Synthesis of Two-Dimensional Materials for Multivalent Ion Batteries.

With the increase of device requirements, rechargeable lithium-ion batteries are facing tremendous challenges in large-scale applications due to the high price and gradual shortage of lithium sources. In contrast, multivalent ion batteries, such as aluminum, magnesium, and zinc, are promising candidates for the next-generation energy-storage systems because of their high volumetric energy density, safe operation, and abundant reserves. The strong intercalation between multivalent ions and the host materials, however, will cause lower ion-diffusion kinetics and a poor discharge capacity. One of the main challenges is to search for a suitable cathode material with a high capacity and good structural stability to overcome the abovementioned problems. Two-dimensional layered materials, with characteristic unique structural features, good conductivity, and high electrochemically active surface, have attracted attention from researchers during the past decade. In this review, the design approach and synthetic procedures for the preparation of two-dimensional materials as cathodes for multivalent ion batteries, including interlayer engineering, two-dimensional heterostructures, pore/hole engineering, and heteroatom doping, are summarized. Meanwhile, the relationship between the design configuration and optimized electrochemical performance is rationally and systematically presented. Additionally, perspectives for the sustainable synthesis of cathode materials are proposed for multivalent metal-ion chemistry.