Layered Cathode with Ultralow Strain Empowers Rapid-Charging and Slow-Discharging Capability in Sodium Ion Battery.

The development of the electric vehicle industry has spurred demand for secondary batteries capable of rapid-charging and slow-discharging. Among them, sodium-ion batteries (SIBs) with layered oxide as the cathode exhibit competitive advantages due to their comprehensive electrochemical performance. However, to meet the requirements of rapid-charging and slow-discharging scenarios, it is necessary to further enhance the rate performance of the cathode material to achieve symmetrical capacity at different rates. Simultaneously, minimizing lattice strain during asymmetric electrochemical processes is also significant in alleviating strain accumulation. In this study, the ordered distribution of transition metal layers and the diffusion pathway of sodium ions are optimized through targeted K-doping of sodium layers, leading to a reduction of the diffusion barrier and endowment of prominent rate performance. At a 20C rate, the capacity of the cathode can reach 94% of that at a 0.1C rate. Additionally, the rivet effect of the sodium layers resulted in a global volume strain of only 0.03% for the modified cathode during charging at a 10C rate and discharging at a 1C rate. In summary, high-performance SIBs, with promising prospects for rapid-charging and slow-discharging capability, are obtained through the regulation of sodium layers, opening up new avenues for commercial applications.

Probing spin waves in Co3O4 nanoparticles for magnonics applications.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated. Our ability to manipulate spin waves using surface and defect engineering in magnetic nanoparticles is the key to designing magnonic devices. We synthesized cubic and spherical nanoparticles of a classical antiferromagnetic material Co3O4 to study the shape and size effects on their static and dynamic magnetic proprieties. Using a combination of experimental methods, we probed the magnetic and crystal structures of our samples and directly measured spin wave dispersions using inelastic neutron scattering. We found a weak, but unquestionable, increase in exchange interactions for the cubic nanoparticles as compared to spherical nanoparticle and bulk powder reference samples. Interestingly, the exchange interactions in spherical nanoparticles have bulk-like properties, despite a ferromagnetic contribution from canted surface spins.

Dual Modification of P3-Type Layered Cathodes to Achieve High Capacity and Long Cyclability for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have garnered extensive attentions in recent years as a low-cost alternative to lithium-ion batteries. However, achieving both high capacity and long cyclability in cathode materials remains a challenge for SIB commercialization. P3-type Na0.67Ni0.33Mn0.67O2 cathodes exhibit high capacity and prominent Na+ diffusion kinetics but suffer from serious capacity decay and structural deterioration due to stress accumulation and phase transformations upon cycling. In this work, a dual modification strategy with both morphology control and element doping is applied to modify the structure and optimize the properties of the P3-type Na0.67Ni0.33Mn0.67O2 cathode. The modified Na0.67Ni0.26Cu0.07Mn0.67O2 layered cathode with hollow porous microrod structure exhibits an excellent reversible capacity of 167.5 mAh g-1 at 150 mA g-1 and maintains a capacity above 95 mAh g-1 after 300 cycles at 750 mA g-1. For one thing, the specific morphology shortens the Na+ diffusion pathway and releases stress during cycling, leading to excellent rate performance and high cyclability. For another, Cu doping at the Ni site reduces the Na+ diffusion energy barrier and mitigates unfavorable phase transitions. This work demonstrates that the electrochemical performance of P3-type cathodes can be significantly improved by applying a dual modification strategy, resulting in reduced stress accumulation and optimized Na+ migration behavior for high-performance SIBs.

Probing Hybrid LiFePO4/FePO4 Phases in a Single Olive LiFePO4 Particle and Their Recovering from Degraded Electric Vehicle Batteries.

The recycling of LiFePO4 from degraded lithium-ion batteries (LIBs) from electric vehicles (EVs) has gained significant attention due to resource, environment, and cost considerations. Through neutron diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy, we revealed continuous lithium loss during battery cycling, resulting in a Li-deficient state (Li1-xFePO4) and phase separation within individual particles, where olive-shaped FePO4 nanodomains (5-10 nm) were embedded in the LiFePO4 matrix. The preservation of the olive-shaped skeleton during Li loss and phase change enabled materials recovery. By chemical compensation for the lithium loss, we successfully restored the hybrid LiFePO4/FePO4 structure to pure LiFePO4, eliminating nanograin boundaries. The regenerated LiFePO4 (R-LiFePO4) exhibited a high crystallinity similar to the fresh counterpart. This study highlights the importance of topotactic chemical reactions in structural repair and offers insights into the potential of targeted Li compensation for energy-efficient recycling of battery electrode materials with polyanion-type skeletons.

Mitigating Jahn-Teller Effect in Layered Cathode Material Via Interstitial Doping for High-Performance Sodium-Ion Batteries.

Layered transition metal oxides are promising cathode materials for sodium-ion batteries due to their high energy density and appropriate operating potential. However, the poor structural stability is a major drawback to their widespread application. To address this issue, B3+ is successfully introduced into the tetrahedral site of Na0.67 Fe0.5 Mn0.5 O2 , demonstrating the effectiveness of small-radius ion doping in improving electrochemical performance. The obtained Na0.67 Fe0.5 Mn0.5 B0.04 O2 exhibits excellent cycling performance with 88.8% capacity retention after 100 cycles at 1 C and prominent rate performance. The structure-property relationship is constructed subsequently by neutron powder diffraction, in situ X-ray diffraction and X-ray absorption spectroscopy, which reveal that the Jahn-Teller distortion and the consequent P2-P2' phase transformation are effectively mitigated because of the occupancy of B3+ at the interstitial site. Furthermore, it is found that the transition metal layers are stabilized and the transition metal dissolution are suppressed, resulting in excellent cycling performance. Besides, the prominent rate performance is attributed to the enhanced diffusion kinetics associated with the rearrangement of Na+ . This work provides novel insight into the action mechanism of interstitial site doping and demonstrates a universal approach to improve the electrochemical properties of P2-type manganese-based sodium cathode materials.

Role of Substitution Elements in Enhancing the Structural Stability of Li-Rich Layered Cathodes.

Element doping/substitution has been recognized as an effective strategy to enhance the structural stability of layered cathodes. However, abundant substitution studies not only lack a clear identification of the substitution sites in the material lattice, but the rigid interpretation of the transition metal (TM)-O covalent theory is also not sufficiently convincing, resulting in the doping/substitution proposals being dragged into design blindness. In this work, taking Li1.2Ni0.2Mn0.6O2 as a prototype, the intense correlation between the "disordered degree" (Li/Ni mixing) and interface-structure stability (e.g., TM-O environment, slab/lattice, and Li+ reversibility) is revealed. Specifically, the degree of disorder induced by the Mg/Ti substitution extends in the opposite direction, conducive to sharp differences in the stability of TM-O, Li+ diffusion, and anion redox reversibility, delivering fairly distinct electrochemical performance. Based on the established paradigm of systematic characterization/analysis, the "degree of disorder" has been shown to be a powerful indicator of material modification by element substitution/doping.

A LaCl3-based lithium superionic conductor compatible with lithium metal.

Inorganic superionic conductors possess high ionic conductivity and excellent thermal stability but their poor interfacial compatibility with lithium metal electrodes precludes application in all-solid-state lithium metal batteries1,2. Here we report a LaCl3-based lithium superionic conductor possessing excellent interfacial compatibility with lithium metal electrodes. In contrast to a Li3MCl6 (M = Y, In, Sc and Ho) electrolyte lattice3-6, the UCl3-type LaCl3 lattice has large, one-dimensional channels for rapid Li+ conduction, interconnected by La vacancies via Ta doping and resulting in a three-dimensional Li+ migration network. The optimized Li0.388Ta0.238La0.475Cl3 electrolyte exhibits Li+ conductivity of 3.02 mS cm-1 at 30 °C and a low activation energy of 0.197 eV. It also generates a gradient interfacial passivation layer to stabilize the Li metal electrode for long-term cycling of a Li-Li symmetric cell (1 mAh cm-2) for more than 5,000 h. When directly coupled with an uncoated LiNi0.5Co0.2Mn0.3O2 cathode and bare Li metal anode, the Li0.388Ta0.238La0.475Cl3 electrolyte enables a solid battery to run for more than 100 cycles with a cutoff voltage of 4.35 V and areal capacity of more than 1 mAh cm-2. We also demonstrate rapid Li+ conduction in lanthanide metal chlorides (LnCl3; Ln = La, Ce, Nd, Sm and Gd), suggesting that the LnCl3 solid electrolyte system could provide further developments in conductivity and utility.

Quantitative analysis of the structural evolution in Si anode via multi-scale image reconstruction.

Despite the high theoretical capacity, silicon (Si) anode suffers from dramatical capacity loss, due to its massive volume swings (up to 300%) during cycling. Hence, thorough understanding of the structural evolution mechanism is necessary and essential for performance optimization of Si anode. Herein, a multi-scale three-dimensional (3D) image reconstruction technique is firstly applied to visualize the structural evolution process of Si anodes. Three key components (Si particles, inactive components, and voids) in the electrode are quantitatively analyzed by the focused ion beam and scanning electron microscope (FIB-SEM) technology. Furthermore, the average sizes of Si particles were run statistics during the cycling. By combining the componential observation within the electrode (macroscopic information) and the 3D models of the particle with solid electrolyte interphase (SEI) layer (microscopic information), the failure mechanism of Si anode is vividly demonstrated. This work establishes a new methodology to quantitatively analyze the structural and compositional evolution of Si anode, which could be further applied for the studies of many other electrode materials with similar issues.

Promoting Surface Electric Conductivity for High-Rate LiCoO2.

The cathode materials work as the host framework for both Li+ diffusion and electron transport in Li-ion batteries. The Li+ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock-salt phase was coherently constructed at the surface of LiCoO2 , promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (Veff ) imposed in the bulk, thus driving more Li+ extraction/insertion and making LiCoO2 exhibit superior rate capability (154 mAh g-1 at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high-rate cathode materials by tuning the surface electron transport property.

Synergistic activation of anionic redox via cosubstitution to construct high-capacity layered oxide cathode materials for sodium-ion batteries.

As a potential substitute for lithium-ion battery, sodium-ion batteries (SIBs) have attracted a tremendous amount of attention due to their advantages in terms of cost, safety and sustainability. Nevertheless, further improvement of the energy density of cathode materials in SIBs remains challenging and requires the activation of anion redox reaction (ARR) activity to provide additional capacity. Herein, we report a high-performance Mn-based sodium oxide cathode material, Na0.67Mg0.1Zn0.1Mn0.8O2 (NMZMO), with synergistic activation of ARR by cosubstitution. This material can deliver an ultra-high capacity of âˆ¼233 mAh/g at 0.1 C, which is significantly higher than their single-cation-substituted counterparts and among the best in as-reported MgMn or ZnMn-based cathodes. Various spectroscopic techniques were comprehensively employed and it was demonstrated that the higher capacity of NMZMO originated from the enhanced ARR activity. Neutron pair distribution function and resonant inelastic X-ray scattering experiments revealed that out-of-plane migration of Mg/Zn occurred upon charging and oxygen anions in the form of molecular O2 were trapped in vacancy clusters in the fully-charged-state. In NMZMO, Mg and Zn mutually interacted with each other to migrate toward tetrahedral sites, which provided a prerequisite for further ARR activity enhancement to form more trapped molecular O2. These findings provide unique insight into the ARR mechanism and can guide the development of high-performance cathode materials through ARR enhancement strategies.

Origin of structural degradation in Li-rich layered oxide cathode.

Li- and Mn-rich (LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density1-3. However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery3-6 Here, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.

Nanoparticle-induced morphological transformation in block copolymer-based nanocomposites.

By controlling the chemical composition and the spatial organization of nanoparticles, hybrid nanocomposites incorporating ordered arrangements of nanoparticles could be endowed with exotic physical and chemical properties to fulfill demands in advanced electronics or energy-harvesting devices. However, a simple method to fabricate hybrid nanocomposites with precise control of nanoparticle distribution is still challenging. We demonstrate that block copolymer-based nanocomposites containing well-ordered nanoparticles with various morphologies can be readily obtained by adjusting the nanoparticle concentration. Moreover, the structural evolution of nanocomposite thin films as a function of nanoparticle loading is unveiled using grazing-incidence transmission small-angle X-ray scattering and atomic force microscopy. The morphological transformation proceeds through a phase transition from perforated lamellae to in-plane cylinder layout, followed by structural changes. The successful achievement of a variety of morphologies represents an effective and straightforward approach to producing functional hybrid nanocomposites for potential applications in various functional devices.

Two-dimensional magneto-photoconductivity in non-van der Waals manganese selenide.

Deficient intrinsic species and suppressed Curie temperatures (Tc) in two-dimensional (2D) magnets are major barriers for future spintronic applications. As an alternative, delaminating non-van der Waals (vdW) magnets can offset these shortcomings and involve robust bandgaps to explore 2D magneto-photoconductivity at ambient temperature. Herein, non-vdW α-MnSe2 is first delaminated as quasi-2D nanosheets for the study of emerging semiconductor, ferromagnetism and magneto-photoconductivity behaviors. Abundant nonstoichiometric surfaces induce the renormalization of the band structure and open a bandgap of 1.2 eV. The structural optimization strengthens ferromagnetic super-exchange interactions between the nearest-neighbor Mn2+, which enables us to achieve a high Tc of 320 K well above room temperature. The critical fitting of magnetization and transport measurements both verify that it is of quasi-2D nature. The above observations are evidenced by multiple microscopic and macroscopic characterization tools, in line with the prediction of first-principles calculations. Profiting from the negative magnetoresistance effect, the self-powered infrared magneto-photoconductivity performance including a responsivity of 330.4 mA W-1 and a millisecond-level response speed are further demonstrated. Such merits stem from the synergistic modulation of magnetic and light fields on photogenerated carriers. This provides a new strategy to manipulate both charge and spin in 2D non-vdW systems and displays their alluring prospects in magneto-photodetection.

Highly Distorted Grain Boundary with an Enhanced Carrier/Phonon Segregation Effect Facilitates High-Performance Thermoelectric Materials.

Grain boundary plays an important role in determining the phonon/carrier transport behaviors of thermoelectric (TE) materials, especially for the polycrystalline materials with the average grain size in nanoscale dimensions. Adjusting the grain size and boundaries of TE materials is considered as an effective approach to decouple TE parameters and thereby synergistically optimize the TE performance. Here, the highly distorted grain boundary with an enhanced carrier/phonon segregation effect is introduced to the commercial n-type Bi2Te2.7Se0.3 matrix. The existence of highly distorted grain boundaries can not only enhance the interfacial Seebeck coefficient without significant detriment to the electrical conductivity but also increase the interfacial thermal resistance of grain boundaries, leading to the synergistic reduction of the thermal conductivity. As a result, a peak figure of merit zTmax ≈ 1.22@425 K and an average zTavg ≈ 1.1(300-500 K) are obtained, which are about 55 and 57% higher than the corresponding values of the commercial Bi2Te2.7Se0.3 matrix, respectively. This work represents a new avenue for improving the commercial Bi2Te2.7Se0.3 TE material, which could further promote the development of the TE technology.

Twin boundary defect engineering improves lithium-ion diffusion for fast-charging spinel cathode materials.

Defect engineering on electrode materials is considered an effective approach to improve the electrochemical performance of batteries since the presence of a variety of defects with different dimensions may promote ion diffusion and provide extra storage sites. However, manipulating defects and obtaining an in-depth understanding of their role in electrode materials remain challenging. Here, we deliberately introduce a considerable number of twin boundaries into spinel cathodes by adjusting the synthesis conditions. Through high-resolution scanning transmission electron microscopy and neutron diffraction, the detailed structures of the twin boundary defects are clarified, and the formation of twin boundary defects is attributed to agminated lithium atoms occupying the Mn sites around the twin boundary. In combination with electrochemical experiments and first-principles calculations, we demonstrate that the presence of twin boundaries in the spinel cathode enables fast lithium-ion diffusion, leading to excellent fast charging performance, namely, 75% and 58% capacity retention at 5 C and 10 C, respectively. These findings demonstrate a simple and effective approach for fabricating fast-charging cathodes through the use of defect engineering.

Enhancing the Electrochemical Performance and Structural Stability of Ni-Rich Layered Cathode Materials via Dual-Site Doping.

Ni-rich layered cathode materials are considered as promising electrode materials for lithium ion batteries due to their high energy density and low cost. However, the low rate performance and poor electrochemical stability hinder the large-scale application of Ni-rich layered cathodes. In this work, both the rate performance and the structural stability of the Ni-rich layered cathode LiNi0.8Co0.1Mn0.1O2 are significantly improved via the dual-site doping of Nb on both lithium and transition-metal sites, as revealed by neutron diffraction results. The dual-site Nb-doped LiNi0.8Co0.1Mn0.1O2 delivers 202.8 mAh·g-1 with a capacity retention of 81% after 200 electrochemical cycles, which is much higher than that of pristine LiNi0.8Co0.1Mn0.1O2. Moreover, a discharge capacity of 176 mAh·g-1 at 10C rate illustrates its remarkable rate capability. Through in situ X-ray diffraction and electronic transport property measurements, it was demonstrated that the achievement of dual-site doping in the Ni-rich layered cathode can not only suppress the Li/Ni disordering and facilitate the lithium ion transport process but also stabilize the layered structure against local collapse and structural distortion. This work adopts a dual-site-doping approach to enhance the electrochemical performance and structural stability of Ni-rich cathode materials, which could be extended as a universal modification strategy to improve the electrochemical performance of other cathode materials.

Super-Necking Crystal Growth and Structural and Magnetic Properties of SrTb2O4 Single Crystals.

We report on single-crystal growths of the SrTb2O4 compound by a super-necking technique with a laser-floating-zone furnace and study the stoichiometry, growth mode, and structural and magnetic properties by scanning electronic microscopy, neutron Laue, X-ray powder diffraction, and the physical property measurement system. We optimized the growth parameters, mainly the growth speed, atmosphere, and the addition of a Tb4O7 raw material. Neutron Laue diffraction displays the characteristic feature of a single crystal. Our study reveals an atomic ratio of Sr:Tb = 0.97(2):2.00(1) and a possible layer by layer crystal growth mode. Our X-ray powder diffraction study determines the crystal structure, lattice constants, and atomic positions. The paramagnetic (PM) Curie-Weiss (CW) temperature θCW = 5.00(4) K, and the effective PM moment M mea eff = 10.97(1) µB per Tb3+ ion. The data of magnetization versus temperature can be divided into three regimes, showing a coexistence of antiferromagnetic and ferromagnetic interactions. This probably leads to the magnetic frustration in the SrTb2O4 compound. The magnetization at 2 K and 14 T originates from both the Tb1 and Tb2 sites and is strongly frustrated with an expected saturation field at ∼41.5 T, displaying an intricate phase diagram with three ranges.

Atomic-scale tuning of oxygen-doped Bi2Te2.7Se0.3 to simultaneously enhance the Seebeck coefficient and electrical conductivity.

Manipulation of oxygen-related impurities is an extreme challenge for most of the thermoelectric materials, especially for those possessing nanostructures, since they normally result in the degradation of the thermoelectric performance. Here, we demonstrate that by atomic-scale controlling of oxygen doping in the form of dislocation clusters in Bi2Te2.7Se0.3 (BTS) thermoelectric materials, the trade-off between the Seebeck coefficient and electrical conductivity is broken, resulting in the simultaneously enhanced Seebeck coefficient and electrical conductivity and the suppressed thermal conductivity. As a consequence, a maximum ZT of 0.91 is achieved, which is approximately 1.4 times higher than that of pristine BTS. Based on HR-STEM investigation, the oxygen-related dislocation clusters can be unambiguously identified and we argue that the optimized carrier/phonon transport behavior can be attributed to the multifunctionality of oxygen-related dislocation clusters in BTS acting as electron donors, electron energy filters and phonon blockers. Our work provides a clear microscopic understanding on the role of oxygen doping in modifying phonon/carrier transport behavior in BTS thermoelectric materials, which provides an efficient avenue for designing high performance thermoelectric materials.

Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery.

Historically long accepted to be the singular root cause of capacity fading, transition metal dissolution has been reported to severely degrade the anode. However, its impact on the cathode behavior remains poorly understood. Here we show the correlation between capacity fading and phase/surface stability of an LiMn2O4 cathode. It is revealed that a combination of structural transformation and transition metal dissolution dominates the cathode capacity fading. LiMn2O4 exhibits irreversible phase transitions driven by manganese(III) disproportionation and Jahn-Teller distortion, which in conjunction with particle cracks results in serious manganese dissolution. Meanwhile, fast manganese dissolution in turn triggers irreversible structural evolution, and as such, forms a detrimental cycle constantly consuming active cathode components. Furthermore, lithium-rich LiMn2O4 with lithium/manganese disorder and surface reconstruction could effectively suppress the irreversible phase transition and manganese dissolution. These findings close the loop of understanding capacity fading mechanisms and allow for development of longer life batteries.

An Ordered Ni6 -Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode.

Sodium-based layered oxides are among the leading cathode candidates for sodium-ion batteries, toward potential grid energy storage, having large specific capacity, good ionic conductivity, and feasible synthesis. Despite their excellent prospects, the performance of layered intercalation materials is affected by both a phase transition induced by the gliding of the transition metal slabs and air-exposure degradation within the Na layers. Here, this problem is significantly mitigated by selecting two ions with very different MO bond energies to construct a highly ordered Ni6 -ring superstructure within the transition metal layers in a model compound (NaNi2/3 Sb1/3 O2 ). By virtue of substitution of 1/3 nickel with antimony in NaNiO2 , the existence of these ordered Ni6 -rings with super-exchange interaction to form a symmetric atomic configuration and degenerate electronic orbital in layered oxides can not only largely enhance their air stability and thermal stability, but also increase the redox potential and simplify the phase-transition process during battery cycling. The findings reveal that the ordered Ni6 -ring superstructure is beneficial for constructing highly stable layered cathodes and calls for new paradigms for better design of layered materials.