Boosting Li-ion storage in Li2MnO3 by unequal-valent Ti4+-substitution and interlayer Li vacancies building

Lithium rich layered oxide (LRLO) has been considered as one of the promising cathodes for lithium-ion batteries (LIBs). The high voltage and large capacity of LRLO depend on Li₂MnO₃ phase. To ameliorate the electrochemical performance of Li₂MnO₃, also written as Li(Li_1/3Mn_2/3)O₂, we propose a strategy to substitute Mn⁴⁺ and Li⁺ in Mn/Li transition metal layer with Ti⁴⁺, which can stabilize the structure of Li₂MnO₃ by inhibiting the excessive oxidation of O^2? above 4.5 V. More significantly, the unequal-valent substitution brings about the emergence of interlayer Li vacancies, which can promote the Li-ion diffusion based on the enlarged interlayer and increase the capacity by activating the Mn^3+/4+ redox. We designed Li_0.7[Li_1/3Mn_2/3]_0.7Ti_0.3O₂ with high interlayer Li vacancies, which presents a high capacity (290 mAh/g at 10 mA/g) and stable cycling performance (84% over 60 cycles at 50 mA/g). We predict that this strategy will be helpful to further improve the electrochemical performance of LRLOs.     

Graphene-supported cobalt nanoparticles used to activate SiO2-based anode for lithium-ion batteries

Although SiO₂-based anode is a strong competitor to supersede graphite anode for lithium-ion batteries, it still has problems such as low electrochemical activity, enormous loss of active lithium, and serious volume expansion. In order to solve these problems, we used a graphene network loaded with cobalt metal nanoparticles (rGO–Co) to coat SiO₂ porous hollow spheres (SiO₂@rGO–Co). The construction of porous hollow structure and graphene network can shorten the lithium-ion (Li⁺) diffusion distance and enhance the conductivity of the composite, which improves the electrochemical activity of SiO₂ effectively. They also alleviate the volume expansion of the anode in the cycling process. Moreover, nano-scale cobalt metal particles dispersed on graphene catalyze the conversion reaction of SiO₂ and activate the locked Li⁺ in Li₂O through a reversible reaction, which improves the charge and discharge capacity of the anode. The capacity of SiO₂@rGO–Co reaches 370.4 mAh/g after 100 cycles at 0.1 A/g, which is 6.19 times the capacity of pure SiO₂ (59.8 mAh/g) under the same circumstance. What is more, its structure also exhibits excellent cycle stability, with a volume expansion rate of only 13.0% after 100 cycles at a current density of 0.1 A/g.     

Surface oxygen-deficient Ti2SC for enhanced lithium-ion uptake

Recently, MAX phases show great potential in lithium-ion uptake due to their excellent electrical conductivity and unique lamellar-structure accommodating lithium ions. However, the reports about MAX electrodes for lithium-ion battery up to now are relatively low. Herein we report the preparation of surface oxygen-deficient Ti₂SC with abundant oxygen vacancies by a facile surface engineering method. When using as a lithium storage anode, this oxygen-deficient Ti₂SC delivers a high capacity of 350 mAh/g at a current density of 400 mA/g as well as excellent rate performance, doubling the capacity compared to that of Ti₂SC without oxygen vacancies. Confirmed by electrochemical impedance spectroscopy (EIS) and kinetic mechanism analyses, after reducing surface oxides and generation of oxygen vacancies, the as-received Ti₂SC exhibits higher electrical conductivity and faster lithium ion diffusion. Thus this work offers a facial and effective strategy of optimizing the surface structure of MAX phases, further to achieve an enhanced lithium-ion uptake for lithium-ion batteries or capacitors.     

Preparation of Li4Ti5O12 Microspheres with a Pure Cr2O3 Coating Layer and its Effect for Lithium Storage

The pure Cr₂O₃ coated Li₄Ti₅O₁₂ microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr₂O₃ works as an adhesive interface to strengthen the connections between Li₄Ti₅O₁₂ particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr₂O₃, formed by the lithiation of Cr₂O₃, can further stabilize Li₇Ti₅O₁₂ with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr₂O₃, Li₂CrO₄ and TiO₂ phases were also found in the final product. Li₂CrO₄ is toxic and the presence of TiO₂ is not welcome to improve the electrochemical performance of Li₄Ti₅O₁₂ microspheres. The reversible capacity of 1% Cr₂O₃-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.     

Synthesis of Li4Ti5O12 fibers as a high-rate electrode material for lithium-ion batteries

Porous lithium titanate (Li₄Ti₅O₁₂) fibers, composed of interconnected nanoparticles, are synthesized by thermally treating electrospun precursor fibers and utilized as an energy storage material for rechargeable lithium-ion batteries. The material is characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and thermal analysis. Scanning electron microscopy results show that the Li₄Ti₅O₁₂ fibers calcined at 700?°C have an average diameter of 230?nm. Especially, the individual fiber is composed of nanoparticles with an average diameter of 47.5?nm. Electrochemical properties of the material are evaluated using cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The results show that as-prepared Li₄Ti₅O₁₂ exhibits good cycling capacity and rate capability. At the charge–discharge rate of 0.2, 0.5, 1, 2, 10, 20, 40, and 60?C, its discharge capacities are 172.4, 168.2, 163.3, 155.9, 138.7, 123.4, 108.8, and 90.4?mAh?g^?1, respectively. After 300 cycles at 20?C, it remained at 120.1?mAh?g^?1. The obtained results thus strongly support that the electrospun Li₄Ti₅O₁₂ fibers could be one of the most promising candidate anode materials for lithium-ion batteries in electric vehicles.     

Hydrothermal synthesis of rod-like CoMoO4 and its excellent properties for the anode of lithium-ion batteries

CoMoO₄ has attracted extensive interest as an anode for lithium-ion batteries due to its high theoretical capacity and low cost. Nevertheless, achieving controlled synthesis of CoMoO₄ with definite morphology by simply adjusting a certain synthesis condition is a very meaningful topic. Here, rod-like CoMoO₄ formed by lamellar stacking was successfully synthesized through the control pH value of one-step hydrothermal route, and its excellent electrochemical performance was investigated. The rod-like CoMoO₄ prepared at 190°C and pH = 7 has a high initial discharge capacity of 1,482.8 mAh/g at 200 mA/g. The discharge capacity of 1,041 mAh/g was maintained after 500 cycles, and the capacity retention was 70.2%. The improved electrochemical performance of rod-like CoMoO₄ can be attributed to the rod structures, which could shorten ion diffusion and electronic conduction pathway, provide more efficient charge storage sites, and alleviate the volume changes during Li + intercalation/deintercalation.     

β-MnO2/Metal–Organic Framework Derived Nanoporous ZnMn2O4 Nanorods as Lithium-Ion Battery Anodes with Superior Lithium-Storage Performance

Nanoporous ZnMn₂O₄ nanorods have been successfully synthesized by calcining β-MnO₂/ZIF-8 precursors (ZIF-8 is a type of metal–organic framework). If measured as an anode material for lithium-ion batteries, the ZnMn₂O₄ nanorods exhibit an initial discharge capacity of 1792 mA h g⁻¹ at 200 mA g⁻¹, and an excellent reversible capacity of 1399.8 mA h g⁻¹ after 150 cycles (78.1 % retention of the initial discharge capacity). Even at 1000 mA g⁻¹, the reversible capacity is still as high as 998.7 mA h g⁻¹ after 300 cycles. The remarkable lithium-storage performance is attributed to the one-dimensional nanoporous structure. The nanoporous architecture not only allows more lithium ions to be stored, which provides additional interfacial lithium-storage capacity, but also buffers the volume changes, to a certain degree, during the Li⁺ insertion/extraction process. The results demonstrate that nanoporous ZnMn₂O₄ nanorods with superior lithium-storage performance have the potential to be candidates for commercial anode materials in lithium-ion batteries.     

Effects of carbon coating from sucrose and PVDF on electrochemical performance of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/C composites in different potential ranges

The carbon coated nanoflower-like Li₄Ti₅O₁₂/C composites were prepared via hydrothermal method followed by surface modification using sucrose or polyvinylidene fluoride (PVDF) as carbon sources. X-ray diffraction, SEM, TEM, Raman spectroscopy, TGA, and the electrochemical measurements were used for the materials characterization. Such modification leads to the formation of a high-conductive carbon coating. In the case of polyvinylidene fluoride use, fluorination of Li₄Ti₅O₁₂ surface takes place also. As a result, electrochemical performance of the obtained composites is improved. In the potential range of 1–3 V, Li₄Ti₅O₁₂, Li₄Ti₅O₁₂/C_PVDF, and Li₄Ti₅O₁₂/C_sucrose exhibit, respectively, the discharge capacities of 142.5, 154.3, and 170.4 mAh/g at a current of 20 mA/g and 57.2, 82.1, and 89.3mAh/g at a current of 3200 mA/g. When cycled in a potential range of 0.01–3 V, the discharge capacity of Li₄Ti₅O₁₂/C_PVDF increases up to 252 mAh/g at 20 mA/g.     

Porous nanostructured V2O5 film electrode with excellent Li-ion intercalation properties

Porous nanostructured V₂O₅ films were prepared by electrodeposition from V₂O₅ sol with the addition of block copolymer Pluoronic P123, and they can be readily applied as Li-ion battery cathode without adding any polymer binder or conductive additives. SEM images showed an ideal morphology for Li⁺ intercalation favored charge transfer kinetics, which is a combination of homogeneously distributed nano-pores and V₂O₅ nanoparticles. Electrochemical measurements revealed that, the porous nanostructured V₂O₅ films have a high discharge capacity of 160 mAh/g at 9 A/g, and maintain 240 mAh/g after 40 cycles at 300 mA/g. The excellent Li⁺ intercalation property could be ascribed to the high surface area, sufficient contact between electrode materials and electrolyte, short Li⁺ diffusion path, as well as the good accommodation for volume change which are benefited from homogeneously distributed nano-pores and V₂O₅ nanoparticles.     

Booting the electrochemical properties of Fe-based anode by the formation multiphasic nanocomposite for lithium-ion batteries

Fe-based compounds with good environmental friendliness and high reversible capacity have attracted considerable attention as anode for lithium-ion batteries.But,similar to other transition metal oxides(TMOs),it is also affected by large volume changes and inferior kinetics during redox reactions,resulting in the destruction of the crystal structure and poor electrochemical performance.Here,Fe_3O_4/C nanospheres anchored on the two-dimensional graphene oxide as precursors are phosphated and sintered to build the multiphasic nanocomposite.XRD results confirmed the multiphasic nanocomposite composed of Fe_2O_3,Fe_3O_4 and Fe_3PO_7,which will facilitate the Li~+ diffusion.And the carbonaceous matrix will buffer the volume changes and enhance electron conduction.Consequently,the multiphasic Febased anode delivers a large specific capacity of 1086 mAh/g with a high initial Coulombic efficiency of 87% at 0.1 C.It also has excellent cycling stability and rate property,maintaining a capacity retention of～87% after 300 cycles and a high reversible capacity of 632 mAh/g at 10 C.The proposed multiphasic structure offers a new insight into improving the electrochemical properties of TMO-based anodes for advanced alkali-ion batteries.     

Effect of the Synthesis Method on the Functional Properties of Lithium-Rich Complex Oxides Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript>

Layered Li-rich transition metal oxides are considered among the most promising cathode materials for high energy density lithium-ion batteries. It was studied how the method and conditions of synthesis of Li-rich oxides Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ affect their electrochemical properties. Coprecipitation methods and modified Pechini process were used. It was shown that it is necessary to carefully choose the synthesis conditions when using the modified Pechini method because of their significant effect on the morphology of Li-rich oxides. Samples were obtained with high electrochemical characteristics: capacity discharge of 260–270 mAh/g (16 mA/g) and 60–70 mAh/g (988 mA/g) within the voltage range of 2.5–4.8 V.     

高倍率尖晶石型Li_4Ti_5O_(l2)/TiN锂离子电池负极材料的合成及其电化学性能

以乙酰丙酮(ACAC)为螯合剂、聚乙二醇(PEG)为分散剂,采用溶胶-凝胶法合成了尖晶石型Li4Ti5Ol2/TiN材料.考察了TiN膜对尖晶石型Li4Ti5Ol2锂离子电池负极材料电化学性能的影响.利用X射线光电子能谱(XPS)对Li4Ti5O12表面的TiN膜进行了分析.X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明,Li4Ti5Ol2/TiN材料为结晶良好的亚微米纯相尖晶石型钛酸锂.电化学性能测试表明,该材料的首次放电比容量为173.0mAh·g-1,并且具有良好的循环性能,以0.2C、1C、2C、5C倍率放电进行测试,10次循环后比容量分别为170.6、147.6、135.6、111.0mAh·g-1,较之表面无TiN膜的钛酸锂材料表现出更好的倍率特性.循环伏安曲线(CV),交流阻抗图谱(EIS)进一步论证了TiN膜改善了尖晶石型Li4Ti5Ol2锂离子电池负极材料的电化学性能.     

High-performance thin-film Li4Ti5O12 electrodes fabricated by using ink-jet printing technique and their electrochemical properties

Li₄Ti₅O₁₂ thin-film anode with high discharge capacity and excellent cycle stability for rechargeable lithium ion batteries was prepared successfully by using ink-jet printing technique. The prepared Li₄Ti₅O₁₂ thin film were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammograms, and galvanostatic charge–discharge measurements. It was found that the average thickness of 10-layer Li₄Ti₅O₁₂ film was about 1.7~1.8 μm and the active material Li₄Ti₅O₁₂ in the thin film was nano-sized about 50–300 nm. It was also found that the prepared Li₄Ti₅O₁₂ thin film exhibited a high discharge capacity of about 174 mAh/g and the discharge capacity in the 300th cycle retained 88% of the largest discharge capacity at a current density of 10.4 μA/cm² in the potential range of 1.0–2.0 V.     

High performance Si/MgO/graphite composite as the anode for lithium-ion batteries

The Si/MgO/graphite composite was synthesized by high energy ball-milling and evaluated as a durable anode for lithium-ion batteries. EDX mapping indicated that Si was dispersed homogeneously in the MgO matrix. The composite delivered an initial capacity of ~ 700 mAh/g and maintained a capacity of 630 mAh/g after 74 cycles at 0.5 mA/cm²; even at 8 mA/cm² it delivered more than 85% of its capacity. Its volumetric capacity is double that of carbon. The coulombic efficiency climbed from 77% in the first cycle to above 99.5% after 20 cycles, and retained that value.     

Natural Soft/Rigid Superlattices as Anodes for High-Performance Lithium-Ion Batteries

Volume expansion and poor conductivity are two major obstacles that hinder the pursuit of the lithium-ion batteries with long cycling life and high power density. Herein, we highlight a misfit compound PbNbS₃ with a soft/rigid superlattice structure, confirmed by scanning tunneling microscopy and electrochemical characterization, as a promising anode material for high performance lithium-ion batteries with optimized capacity, stability, and conductivity. The soft PbS sublayers primarily react with lithium, endowing capacity and preventing decomposition of the superlattice structure, while the rigid NbS₂ sublayers support the skeleton and enhance the migration of electrons and lithium ions, as a result leading to a specific capacity of 710 mAh g⁻¹ at 100 mA g⁻¹, which is 1.6 times of NbS₂ and 3.9 times of PbS. Our finding reveals the competitive strategy of soft/rigid structure in lithium-ion batteries and broadens the horizons of single-phase anode material design.     

Electrolytic molybdenum oxides in lithium batteries

Nonstoichiometric molybdenum oxides (e-Mo_xO_y) were synthesized by cathodic reduction of aqueous ammonium and sodium molybdate solutions. Surface morphology of electrolytic (e) deposits, the chemical composition, crystal lattice structure, and the characteristics of electrochemical Li⁺ intercalation for such synthesized oxides were determined by the cation composition of molybdate solution and the conditions of deposit annealing. The electrochemical intercalation of Li⁺ ions in these Mo-oxides was investigated in thin-layer ballast-free electrodes, as a pasted mposite cathode in lithium batteries, and as an anode in lithium-ion batteries, with liquid organic and polymer electrolytes. The reversible discharge capacity of e-Mo₄O₁₁ synthesized from ammonium molybdate electrolyte in thin-layer ballast-free electrodes can exceed 225 mAh g^–1 for more than 170 cycles.     

In-situ growth of hybrid NaTi8O13/NaTiO2 nanoribbons on layered MXene Ti3C2 as a competitive anode for high-performance sodium-ion batteries

In the work, we successfully explore a two-step hydrothermal method for scalable synthesis of the hybrid sodium titanate (NaTi₈O₁₃/NaTiO₂) nanoribbons well in-situ formed on the multi-layered MXene Ti₃C₂ (designed as NTO/Ti₃C₂). Benefiting from the inherent structural and componential superiorities, the resulted NTO/Ti₃C₂ composite exhibits long-duration cycling stability and superior rate behaviors when evaluated as a hybrid anode for advanced SIBs, which delivers a reversible and stable capacity of ∼82 mAh/g even after 1900 cycles at 2000 mA/g for SIBs.     

Matryoshka-type carbon-stabilized hollow Si spheres as an advanced anode material for lithium-ion batteries

Silicon(Si) is regarded as the potential anode for lithium-ion batteries(LIBs), due to the remarkable theoretical specific capacity and low voltage plateau. However, the rapid capacity decay resulting from volume variation and slow electron/ion transportation of Si limit its practical application. Here, matryoshka-type carbon-stabilized hollow silicon spheres(Si/C/Si/C) are synthesized by an aluminothermic reduction and calcination process. The Si/C/Si/C anode materials prepared at 500 ℃(Si/C/Si...     

Phosphorus-Doping-Induced Surface Vacancies of 3D Na2Ti3O7 Nanowire Arrays Enabling High-Rate and Long-Life Sodium Storage

Sodium-ion batteries have attracted interest as an alternative to lithium-ion batteries because of the abundance and cost effectiveness of sodium. However, suitable anode materials with high-rate and stable cycling performance are still needed to promote their practical application. Herein, three-dimensional Na₂Ti₃O₇ nanowire arrays with enriched surface vacancies endowed by phosphorus doping are reported. As anodes for sodium-ion batteries, they deliver a high specific capacity of 290 mA h g⁻¹at 0.2 C, good rate capability (50 mA h g⁻¹at 20 C), and stable cycling capability (98 % capacity retention over 3100 cycles at 20 C). The superior electrochemical performance is attributed to the synergistic effects of the nanowire arrays and phosphorus doping. The rational structure can provide convenient channels to facilitate ion/electron transport and improve the capacitive contributions. Moreover, the phosphorus-doping-induced surface vacancies not only provide more active sites but also improve the intrinsic electrical conductivity of Na₂Ti₃O₇, which will enable electrode materials with excellent sodium storage performance. This work may provide an effective strategy for the synthesis of other anode materials with fast electrochemical reaction kinetics and good sodium storage performance.     

Synergistic Modulation of In-Situ Hybrid Interface Construction and pH Buffering Enabled Ultra-Stable Zinc Anode at High Current Density and Areal Capacity

In aqueous electrolytes, the uncontrollable interfacial evolution caused by a series of factors such as pH variation and unregulated Zn²⁺ diffusion would usually result in the rapid failure of metallic Zn anode. Considering the high correlation among various triggers that induce the anode deterioration, a synergistic modulation strategy based on electrolyte modification is developed. Benefitting from the unique pH buffer mechanism of the electrolyte additive and its capability to in situ construct a zincophilic solid interface, this synergistic effect can comprehensively manage the thermodynamic and kinetic properties of Zn anode by inhibiting the pH variation and parasitic side reactions, accelerating de-solvation of hydrated Zn²⁺, and regulating the diffusion behavior of Zn²⁺ to realize uniform Zn deposition. Thus, the modified Zn anode can achieve an impressive lifespan at ultra-high current density and areal capacity, operating stably for 609 and 209 hours at 20 mA cm⁻², 20 mAh cm⁻² and 40 mA cm⁻², 20 mAh cm⁻², respectively. Based on this exceptional performance, high loading Zn||NH₄V₄O₁₀ batteries can achieve excellent cycle stability and rate performance. Compared with those previously reported single pH buffer strategies, the synergistic modulation concept is expected to provide a new approach for highly stable Zn anode in aqueous zinc-ion batteries.