Hexagonal MoO3 Anode with Extremely High Capacity and Cyclability for Lithium-Ion Battery: A Combined Theoretical and Experimental Study.

It is essential and still remains a big challenge to obtain fast-charge anodes with large capacities and long lifespans for Li-ion batteries (LIBs). Among all of the alternative materials, molybdenum trioxide shows the advantages of large theoretical specific capacity, distinct tunnel framework, and low cost. However, there are also some key shortcomings, such as fast capacity decaying due to structural instability during Li insertion and poor rate performance due to low intrinsic electron conductivity and ion diffusion capability, dying to be overcome. A unique strategy is proposed to prepare Ti-h-MoO3-x@TiO2 nanosheets by a one-step hydrothermal approach with NiTi alloy as a control reagent. The density functional theory (DFT) calculations indicate that the doping of Ti element can make the hexagonal h-MoO3-x material show the best electronic structure and it is favor to be synthesized. Furthermore, the hexagonal Ti-h-MoO3-x material has better lithium storage capacity and lithium diffusion capacity than the orthogonal α-MoO3 material, and its theoretical capacity is more than 50% higher than that of the orthogonal α-MoO3 material. Additionally, it is found that Ti-h-MoO3-x@TiO2 as an anode displays extremely high reversible discharge/charge capacities of 1326.8/1321.3 mAh g-1 at 1 A g-1 for 800 cycles and 611.2/606.6 mAh g-1 at 5 A g-1 for 2000 cycles. Thus, Ti-h-MoO3-x@TiO2 can be considered a high-power-density and high-energy-density anode material with excellent stability for LIBs.

In Situ Construction of Biphasic Boride Electrocatalysts on Dealloyed Bulk Ni-Mo Alloy as Self-Supporting Electrode for Water Splitting at High Current Density.

Nickel-molybdenum-boron (Ni-Mo-B)-based catalysts with biphasic interfaces are highly advantageous in bifunctional electrocatalytic activity in alkaline water-splitting. However, it remains an ongoing challenge to obtain porous Ni-Mo alloy substrates that provide stable adhesion to catalysts, ensuring the long-term performance of bifunctional self-supporting electrodes at a high current density. Herein, a porous Ni-Mo alloy substrate was effectively obtained by a cost-effective dealloying process on a commercial Ni-Mo alloy with high-energy crystal planes. Subsequently, the Mo2NiB2/Ni3B bifunctional catalyst was in situ synthesized on this substrate via boriding heat treatment, resulting in outstanding catalytic activity and stability. Density functional theory (DFT) calculations reveal that the abundant biphasic interfaces and surface-reconstructed sites of the Mo2NiB2/Ni3B catalyst can decrease the energy barriers for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Thus, the designed self-supporting electrodes show bifunctional catalytic activity with overpotentials of 151 mV for HER and 260 mV for OER at a current density of 10 mA cm-2. Markedly, the assembled water electrolyzer can be driven up to 10 mA cm-2 at 1.64 V and maintain catalytic activity at a high current density of 1000 mA cm-2 for 100 h. The new strategy is expected to provide a low-cost scheme for designing self-supporting bifunctional electrodes with high activity and excellent stability and contribute to the development of hydrogen energy technology.

Engineering Nano-Sized Silicon Anodes with Conductive Networks toward a High Average Coulombic Efficiency of 90.2% via Plasma-Assisted Milling.

Si-based anode is considered one of the ideal anodes for high energy density lithium-ion batteries due to its high theoretical capacity of 4200 mAh g-1. To accelerate the commercial progress of Si material, the multi-issue of extreme volume expansion and low intrinsic electronic conductivity needs to be settled. Herein, a series of nano-sized Si particles with conductive networks are synthesized via the dielectric barrier discharge plasma (DBDP) assisted milling. The p-milling method can effectively refine the particle sizes of pristine Si without destroying its crystal structure, resulting in large Brunauer-Emmett-Teller (BET) values with more active sites for Li+ ions. Due to their unique structure and flexibility, CNTs can be uniformly distributed among the Si particles and the prepared Si electrodes exhibit better structural stability during the continuous lithiation/de-lithiation process. Moreover, the CNT network accelerates the transport of ions and electrons in the Si particles. As a result, the nano-sized Si anodes with CNTs conductive network can deliver an extremely high average initial Coulombic efficiency (ICE) reach of 90.2% with enhanced cyclic property and rate capability. The C-PMSi-50:1 anode presents 615 mAh g-1 after 100 cycles and 979 mAh g-1 under the current density of 5 A g-1. Moreover, the manufactured Si||LiNi0.8Co0.1Mn0.1O2 pouch cell maintains a high ICE of >85%. This work may supply a new insight for designing the nano-sized Si and further promoting its commercial applications.

Highly Stable Mo-NiO@NiFe-Layered Double Hydroxide Heterojunction Anode Catalyst for Alkaline Electrolyzers with Porous Membrane.

Heterostructure catalysts are considered as promising candidates for promoting the oxygen evolution reaction (OER) process due to their strong electron coupling. However, the inevitable dissolution and detachment of the heterostructure catalysts are caused by the severe reconstruction, dramatically limiting their industrial application. Herein, the NiFe-layered double hydroxide (LDH) nanosheets attached on Mo-NiO microrods (Mo-NiO@NiFe LDH) by the preoxidation strategy of the core NiMoN layer are synthesized for ensuring the high catalytic performance and stability. Owing to the enhanced electron coupling and preoxidation process, the obtained Mo-NiO@NiFe LDH exhibits a superlow overpotential of 253 mV to achieve a practically relevant current density of 1000 mA cm-2 for OER with exceptional stability over 1200 h. Notably, the overall water splitting system based on Mo-NiO@NiFe LDH reveals remarkable stability, maintaining the catalytic activity at a current density of 1000 mA cm-2 for 140 h under industrial harsh conditions. Furthermore, the Mo-NiO@NiFe LDH demonstrates outstanding activity and long-term durability in a practical alkaline electrolyzer assembly with a porous membrane, even surpassing the performance of IrO2. This work provides a new sight for designing and synthesizing highly stable heterojunction electrocatalysts, further promoting and realizing the industrial electrocatalytic OER.

Progress of Polymer Electrolytes Worked in Solid-State Lithium Batteries for Wide-Temperature Application.

Solid-state Li-ion batteries have emerged as the most promising next-generation energy storage systems, offering theoretical advantages such as superior safety and higher energy density. However, polymer-based solid-state Li-ion batteries face challenges across wide temperature ranges. The primary issue lies in the fact that most polymer electrolytes exhibit relatively low ionic conductivity at or below room temperature. This sensitivity to temperature variations poses challenges in operating solid-state lithium batteries at sub-zero temperatures. Moreover, elevated working temperatures lead to polymer shrinkage and deformation, ultimately resulting in battery failure. To address this challenge of polymer-based solid-state batteries, this review presents an overview of various promising polymer electrolyte systems. The review provides insights into the temperature-dependent physical and electrochemical properties of polymers, aiming to expand the temperature range of operation. The review also further summarizes modification strategies for polymer electrolytes suited to diverse temperatures. The final section summarizes the performance of various polymer-based solid-state batteries at different temperatures. Valuable insights and potential future research directions for designing wide-temperature polymer electrolytes are presented based on the differences in battery performance. This information is intended to inspire practical applications of wide-temperature polymer-based solid-state batteries.

Boric acid templating synthesis of highly-dense yet ultramicroporous carbons for compact capacitive energy storage.

Carbon-based supercapacitors have shown great promise for miniaturized electronics and electric vehicles, but are usually limited by their low volumetric performance, which is largely due to the inefficient utilization of carbon pores in charge storage. Herein, we develop a reliable and scalable boric acid templating technique to prepare boron and oxygen co-modified highly-dense yet ultramicroporous carbons (BUMCs). The carbons are featured with high density (up to 1.62 g cm-3), large specific surface area (up to 1050 m2 g-1), narrow pore distribution (0.4-0.6 nm) and exquisite pore surface functionalities (mainly -BC2O, -BCO2, and -COH groups). Consequently, the carbons show exceptionally compact capacitive energy storage. The optimal BUMC-0.5 delivers an outstanding volumetric capacitance of 431 F cm-3 and a high-rate capability in 1 M H2SO4. In particular, an ever-reported high volumetric energy density of 32.6 Wh L-1 can be harvested in an aqueous symmetric supercapacitor. Our results demonstrate that the -BC2O and -BCO2 groups on the ultramicropore walls can facilitate the internal SO42- ion transport, thus leading to an unprecedented high utilization efficiency of ultramicropores for charge storage. This work provides a new paradigm for construction and utilization of dense and ultramicroporous carbons for compact energy storage.

Revealing the Subzero-Temperature Electrochemical Kinetics Behaviors in Ni-Rich Cathode.

The sluggish kinetics in Ni-rich cathodes at subzero temperatures causes decreased specific capacity and poor rate capability, resulting in slow and unstable charge storage. So far, the driving force of this phenomenon remains a mystery. Herein, with the help of in-situ X-ray diffraction and time of flight secondary ion mass spectrometry techniques, the continuous accumulation of both the cathode electrolyte interphase (CEI) film formation and the incomplete structure evolution during cycling under subzero temperature are proposed. It is presented that excessively uniform and thick CEI film generated at subzero temperatures would block the diffusion of Li+ -ions, resulting in incomplete phase evolution and clear charge potential delay. The incomplete phase evolution throughout the Li+ -ion intercalation/de-intercalation processes would further cause low depth of discharge and poor electrochemical reversibility with low initial Coulombic efficiency, as well. In addition, the formation of the thick and uniform CEI film would also consume Li+ -ions during the charging process. This discovery highlights the effects of the CEI film formation behavior and incomplete phase evolution in restricting electrochemical kinetics under subzero temperatures, which the authors believe would promote the further application of the Ni-rich cathodes.

Layered Polymer Stacking for Stable Interfaces and Dendrite Growth Inhibition in All-Solid-State Lithium Batteries.

To improve the ionic conductivity and cycling stability of solid-state lithium batteries based on poly(ethylene oxide) (PEO) electrolytes, we developed a sandwich-structured composite polymer electrolyte (sandwich-CPE) PEO-TiN/PEO-LiYF4/PEO-TiN. The sandwich-CPE delivers a high ionic conductivity of 1.7 × 10-4 S cm-1 at 30 °C and a wide potential window of 0 to 5.0 V (vs Li/Li+). Adding PEO-TiN leads to the formation of Li3N between Li and sandwich-CPE during cycling, which effectively reduces the level of Li dendrite formation. Additionally, PEO-TiN acts as a sacrificial layer to stop the entry of Li dendrites into the interlayer PEO-LiYF4. Using the sandwich-CPE, LiFePO4 retains a reversible capacity of 113.8 mA h g-1 at 30 °C after 300 cycles under 0.5 C. For high-voltage cells, LiNi0.5Co0.2Mn0.3O2 retains a capacity retention of 71.4% at 45 °C after 300 cycles under 0.2 C among 3.0-4.3 V, while Li3V2(PO4)3 delivers an initial discharge capacity of 108.1 mA h g-1 at 60 °C and retains 81.6% after 500 cycles under 1 C among 2.8-4.4 V. These results demonstrate the strong electrochemical compatibility of the sandwich-CPE, enabling high reversible capacity and good cycling stability for solid-state Li batteries with different cathodes at different temperatures and current rates.

Combining Structural Modification and Electrolyte Regulation to Enable Long-Term Cyclic Stability of MoO3-x @TiO2 as Cathode for Aqueous Zn-Ion Batteries.

Orthorhombic MoO3 (α-MoO3 ) with multivalent redox couple of Mo6+ /Mo4+ and layered structure is a promising cathode for rechargeable aqueous Zn-ion batteries (AZIBs). However, pure α-MoO3 suffers rapid capacity decay due to the serious dissolution and structural collapse. Meanwhile, the growth of byproduct and dendrite on the anode also lead to the deterioration of cyclic stability. This article establishes the mechanism of proton intercalation into MoO3 and proposes a joint strategy combining structural modification with electrolyte regulation to enhance the cyclic stability of MoO3 without sacrificing the capacity. In ZnSO4 electrolyte with Al2 (SO4 )3 additive, TiO2 coated oxygen-deficient α-MoO3 (MoO3-x @TiO2 ) delivers a reversible capacity of 93.2 mA h g-1 at 30 A g-1 after 5000 cycles. The TiO2 coating together with the oxygen deficiency avoids structural damage while facilitating proton diffusion. Besides, the additive of Al2 (SO4 )3 , acting as a pump, continuously supplements protons through dynamic hydrolysis, avoiding the formation of Zn4 SO4 (OH)6 ·xH2 O byproducts at both MoO3-x @TiO2 and Zn anode. In addition, Al2 (SO4 )3 additive facilitates uniform deposition of Zn owing to the tip-blocking effect of Al3+ ion. The study demonstrates that the joint strategy is beneficial for both cathode and anode, which may shed some light on the development of AZIBs.

Homogeneous regulation of arranged polymorphic manganese dioxide nanocrystals as cathode materials for high-performance zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries have emerged as attractive energy storage devices by virtue of their low cost, high safety and eco-friendliness. However, zinc-ion cathodes are bottlenecked by their vulnerable crystal structures in the process of zinc embedding and significant capacity fading during long-term cycling. Herein, we report the rational and homogeneous regulation of polycrystalline manganese dioxide (MnO2) nanocrystals as zinc cathodes via a surfactant template-assisted strategy. Benefiting from the homogeneous regulation, MnO2 nanocrystals with an ordered crystal arrangement, including nanorod-like polyvinylpyrrolidone-manganese dioxide (PVP-MnO2), nanowire-like sodium dodecyl benzene sulfonate-manganese dioxide and nanodot-like cetyltrimethylammonium bromide-manganese dioxide, are obtained. Among these, the nanorod-like PVP-MnO2 nanocrystals exhibit stable long-life cycling of 210 mAh g-1 over 180 cycles at a high rate of 0.3 A g-1 and with a high capacity retention of 84% over 850 cycles at a high rate of 1 A g-1. The good performance of this cathode significantly results from the facile charge and mass transfer at the interface between the electrode and electrolyte, featuring the crystal stability and uniform morphology of the arranged MnO2 nanocrystals. This work provides crucial insights into the development of advanced MnO2 cathodes for low-cost and high-performance rechargeable aqueous zinc-ion batteries.

Building K-C Anode with Ultrahigh Self-Diffusion Coefficient for Solid State Potassium Metal Batteries Operating at -20 to 120 °C.

Solid state potassium (K) metal batteries are intriguing in grid-scale energy storage, benefiting from the low cost, safety, and high energy density. However, their practical applications are impeded by poor K/solid electrolyte (SE) interfacial contact and limited capacity caused by the low K self-diffusion coefficient, dendrite growth, and intrinsically low melting point/soft features of metallic K. Herein, a fused-modeling strategy using potassiophilic carbon allotropes molted with K is demonstrated that can enhance the electrochemical performance/stability of the system via promoting K diffusion kinetics (2.37 × 10-8 cm2 s-1 ), creating a low interfacial resistance (≈1.3 Ω cm2 ), suppressing dendrite growth, and maintaining mechanical/thermal stability at 200 °C. A homogeneous/stable K stripping/plating is consequently implemented with a high current density of 2.8 mA cm-2 (at 25 °C) and a record-high areal capacity of 11.86 mAh cm-2 (at 0.2 mA cm-2 ). The enhanced K diffusion kinetics contribute to sustaining intimate interfacial contact, stabilizing the stripping/plating at high current densities. Full cells coupling ultrathin K-C composite anodes (≈50 µm) with Prussian blue cathodes and ß/ß″-Al2 O3 SEs deliver a high energy density of 389 Wh kg-1 with a retention of 94.4% after 150 cycles and fantastic performances at -20 to 120 °C.

Roles of Trimethyl Borate in Constructing an Interphase on Li Anode: Angel or Demon?

Although coupling a lithium metal anode with a Ni-rich layer cathode is a promising approach for high-energy lithium metal batteries, both electrodes are plagued by their intrinsic unstable interfaces which trigger electrolyte decomposition, lithium dendritic growth, and transition metal dissolution during cycling. Making use of electrolyte additives is one of the most effective solutions to address this issue. In this paper, we explore the roles of trimethyl borate (TMB)─a common film-forming additive to protect high-nickel-ratio ternary cathodes─in suppressing lithium dendrite growth. It is found that, on the one hand, the borate-containing solid electrolyte interphase (SEI) derived from the decomposition of TMB facilitates Li+ transport, homogenizing the deposition of Li ions. On the other hand, TMB as an anion receptor provokes LiPF6 decomposition, prompting the formation of SEI with superfluous LiF. As a result, it is imperative to raise awareness of this double-edge additive when using it to be immune to lithium dendrite and cathodic degradation.

Phenylphosphonic acid as a grain-refinement additive for a stable lithium metal anode.

Phenylphosphonic acid (PPOA) has been proposed as a new additive for carbonate electrolytes, in which the complexation reaction between PPOA and Li+ reduces the nucleus size and boosts the nucleation quantity during the plating process. Thus, enhanced cycling stability is obtained in both symmetric cells and full cells.

Phase Separation Induced Binary Core-Shell Alloy Nanoparticles Embedded in Carbon Sheets for Magnesium Storage.

Magnesium-ion batteries (MIBs) have aroused widespread interest in large-scale applications due to their low cost, high volumetric capacity, and safety. However, magnesium (Mg) metals are incompatible with conventional electrolytes, making it difficult to plate and strip reversibly. Therefore, developing novel Mg2+ host anodes remains a huge challenge. Herein, we present a rational design and fabrication of binary Bi@Sn alloy nanoparticles embedded in carbon sheets (Bi@Sn-C) as a superior anode for MIBs employing phase separation during the annealing of bimetallic MOFs. The Bi@Sn-C simultaneously integrates the nanostructure design and multi-element coordination strategies which is favorable to improve the overall structural stability and Mg2+ diffusion kinetics. Benefiting from the aforementioned features, the Bi@Sn-C electrodes deliver good cycling stability of 214 mA h g-1 at 100 mA g-1 after 100 cycles and rate capability with 200 mA h g-1 at 500 mA g-1. And when using all-phenyl complex with lithium chloride (LiCl-APC) dual-salt electrolyte, the electrochemical performance of Bi@Sn-C is further optimized and shows enhanced rate performance (238 mA h g-1 at 500 mA g-1) and reversible capacity (308 mA h g-1 at 100 mA g-1 after 100 cycles). This novel strategy holds great promise for designing efficient alloy electrode materials for MIBs.

Insight into Reversible Conversion Reactions in SnO2 -Based Anodes for Lithium Storage: A Review.

Various anode materials have been widely studied to pursue higher performance for next generation lithium ion batteries (LIBs). Metal oxides hold the promise for high energy density of LIBs through conversion reactions. Among these, tin dioxide (SnO2 ) has been typically investigated after the reversible lithium storage of tin-based oxides is reported by Idota and co-workers in 1997. Numerous in/ex situ studies suggest that SnO2 stores Li+ through a conversion reaction and an alloying reaction. The difficulty of reversible conversion between Li2 O and SnO2 is a great obstacle limiting the utilization of SnO2 with high theoretical capacity of 1494 mA h g-1 . Thus, enhancing the reversibility of the conversion reaction has become the research emphasis in recent years. Here, taking SnO2 as a typical representative, the recent progress is summarized and insight into the reverse conversion reaction is elaborated. Promoting Li2 O decomposition and maintaining high Sn/Li2 O interface density are two effective approaches, which also provide implications for designing other metal oxide anodes. In addition, some in/ex situ characterizations focusing on the conversion reaction are emphatically introduced. This review, from the viewpoint of material design and advanced characterizations, aims to provide a comprehensive understanding and shed light on the development of reversible metal oxide electrodes.

Interface Modification and Halide Substitution To Achieve High Ionic Conductivity in LiBH4-Based Electrolytes for all-Solid-State Batteries.

A fast solid-state Li-ion conductor Li16(BH4)13I3@g-C3N4 was synthesized using a simple ball-milling process. Because of the combined effect of halide substitution and the formation of an interface between Li16(BH4)13I3 and g-C3N4, Li16(BH4)13I3@g-C3N4 delivers a high ionic conductivity of 3.15 × 10-4 S/cm at 30 °C, which is about 1-2 orders of magnitude higher than that of Li16(BH4)13I3. Additionally, Li16(BH4)13I3@g-C3N4 exhibits good electrochemical stability at a wide potential window of 0-5.0 V (vs Li/Li+) and excellent thermal stability. The Li/Li symmetrical cell based on the Li16(BH4)13I3@g-C3N4 electrolyte achieves long-term cycling with a small increase in overpotential, confirming superior electrochemical stability against Li foil. More importantly, Li16(BH4)13I3@g-C3N4-based Li batteries are compatible with S-C and FeF3 cathodes and MgH2 anodes and can achieve long-term cycling with Li4Ti5O12 anodes at a temperature range from 30 to 60 °C. The developed strategy of coupling halide substitution together with interface modifications may open a new avenue toward the development of LiBH4-based high ionic conductivity electrolytes for room-temperature all-solid-state Li batteries.

Tin-Based Anode Materials for Stable Sodium Storage: Progress and Perspective.

Because of concerns regarding shortages of lithium resources and the urgent need to develop low-cost and high-efficiency energy-storage systems, research and applications of sodium-ion batteries (SIBs) have re-emerged in recent years. Herein, recent advances in high-capacity Sn-based anode materials for stable SIBs are highlighted, including tin (Sn) alloys, Sn oxides, Sn sulfides, Sn selenides, Sn phosphides, and their composites. The reaction mechanisms between Sn-based materials and sodium are clarified. Multiphase and multiscale structural optimizations of Sn-based materials to achieve good sodium-storage performance are emphasized. Full-cell designs using Sn-based materials as anodes and further development of Sn-based materials are discussed from a commercialization perspective. Insights into the preparation of future high-performance Sn-based anode materials and the construction of sodium-ion full batteries with a high energy density and long service life are provided.

Boosting Reversibility and Stability of Li Storage in SnO2 -Mo Multilayers: Introduction of Interfacial Oxygen Redistribution.

Among the promising high-capacity anode materials, SnO2 represents a classic and important candidate that involves both conversion and alloying reactions toward Li storage. However, the inferior reversibility of conversion reactions usually results in low initial Coulombic efficiency (ICE, ≈60%), small reversible capacity, and poor cycling stability. Here, it is demonstrated that by carefully designing the interface structure of SnO2 -Mo, a breakthrough comprehensive performance with ultrahigh average ICE of 92.6%, large capacity of 1067 mA h g-1 , and 100% capacity retention after 700 cycles can be realized in a multilayer Mo/SnO2 /Mo electrode. Furthermore, high capacity retentions are also achieved in pouch-type Mo/SnO2 /Mo||Li half cells and Mo/SnO2 /Mo||LiFePO4 full cells. The amorphous SnO2 /Mo interfaces, which are induced by redistribution of oxygen between SnO2 and Mo, can precisely adjust the reversible capacity and cycling stability of the multilayers, while the stable capacities are parabolic with the interfacial density. Theoretical calculations and in/ex situ investigation reveal that oxygen redistribution in SnO2 /Mo heterointerfaces boosts Li-ion transport kinetics by inducing a built-in electric field and improves the reaction reversibility of SnO2 . This work provides a new understanding of interface-performance relationship of metal-oxide hybrid electrodes and pivotal guidance for creating high-performance Li-ion batteries.

Multiscale Observations of Inhomogeneous Bilayer SEI Film on a Conversion-Alloying SnO2 Anode.

SnO2 , storing Li through conversion and alloying reactions, has been regarded as one of the most typical anode materials and has been widely studied for both mechanism exploring and performance tuning. However, the structure of the solid electrolyte interphase (SEI) formed on the SnO2 electrode and its evolution process are rarely focused and still poorly understood. Herein, time of flight secondary ion mass spectrometry is used to observe the bilayer hybrid structure of SEI formed on a SnO2 film. Multiscale observations reveal the SEI accumulation after alloying reactions and distinct dissolving of the organic layer at potentials above de-conversion reactions, which results in the inorganic layer being directly exposed to the electrolyte and thus becoming thick and inhomogeneous. The broken and thick SEI causes rapid capacity decay and low Coulombic efficiencies (CEs) of 97.5%. Accordingly, it is demonstrated that, as the SnO2 is precoated with LiF or Li2 CO3 , a robust and thin SEI layer is induced to form and is stabilized in the continuous cycles, resulting in enhanced cycling stability and promoted CEs to 99.5%. This work adds new insights to the SEI evolution mechanisms on SnO2 -based anodes and suggests an effective strategy to create high performance metal oxide anode for Li-ion batteries.

Tuning Inactive Phases in Si-Ti-B Ternary Alloy Anodes to Achieve Stable Cycling for High-Energy-Density Lithium-Ion Batteries.

Cycle stability improvement of a high-capacity Si anode is a challenge for its wide application in high-energy-density lithium-ion batteries. Active amorphous/nanosized Si embedded in an inactive matrix is a strategy to improve the cycle stability of Si anodes. Ternary Si100-x-yTixBy (5 ≤ y ≤ x ≤ 20) alloys are designed and prepared by ball milling using elemental Si, Ti, and B as starting materials. The formation sequence of inactive phases during mechanical alloying is predicted by an effective heat-of-formation model and verified by microstructural characterization. The local-fine distribution of free amorphous and nanocrystalline Si in the Si100-x-yTixBy is analyzed by confocal µ-Raman spectroscopy. When used as lithium-ion anodes, the capacity and voltage affected by Si and inactive compounds in the Si100-x-yTixBy are concerned to assess their high energy density. Furthermore, the impact of free active Si, the inactive phase, and amorphous Si on the cyclability of Si100-x-yTixBy is studied. The results show that the Si100-x-yTixBy material is a potential anode for high-energy-density Li-ion batteries and could be used to guide the design of multi-component Si-alloy anodes.