High-rate Lithium-ion Battery Anodes Research Articles

High-Rate Performance of a Designed Si Nanoparticle–Graphite Nanosheet Composite as the Anode for Lithium-Ion Batteries

A silicon nanoparticle–graphite nanosheet composite was prepared via a facile ball milling process for use as the anode for high-rate lithium-ion batteries. The size effect of Si nanoparticles on the structure and on the lithium-ion battery performance of the composite is evaluated. SEM and TEM analyses show a structural alteration of the composites from Si nanoparticle-surrounded graphite nanosheets to Si nanoparticle-embedded graphite nanosheets by decreasing the size of Si nanoparticles from 250 nm to 40 nm. The composites with finer Si nanoparticles provide an effective nanostructure containing encapsulated Si and free space. This structure facilitates the indirect exposure of Si to electrolyte and Si expansion during cycling, which leads to a stable solid–electrolyte interphase and elevated conductivity. An enhanced rate capability was obtained for the 40 nm Si nanoparticle–graphite nanosheet composite, delivering a specific capacity of 276 mAh g−1 at a current density of 1 C after 1000 cycles and a rate capacity of 205 mAh g−1 at 8 C.

Surface surgery on TiNb2O7 electrode via N2/Air atmospheric pressure plasma jet for high-rate lithium-ion battery anode

TiNb2O7 (TNO) is regarded as a potential anode material for its high capacity compared to Li4Ti5O12 and high safety due to its adequate Fermi level in lithium-ion batteries. This work represents a promising method of modifying the electrode, which includes polyvinylidene fluoride (PVDF), conductive carbon, and TiNb2O7, using an atmospheric pressure plasma jet (APPj) treatment. Our results reveal that atmospheric pressure plasma jet improves the electrochemical performance by N-doped decoration on conductive carbon, electrolyte wettability enhancement on polyvinylidene fluoride binder, and defects manufacturing in TiNb2O7 anode materials. Good wettability of surface free energy to 44.6 mJ/m2 in the APPj-treated (APP-10) sample contributes to improved cycling performance. Both N-doped carbon and modified TiNb2O7 promote the high-rate capability. The C-rate performance of APP-10 improves by over 200 % at 10C compared to the non-treated sample (APP-0). APP-10 sample also shows 81.9 % retention after 300 cycles at 1C. The formation of Li3N or LiNxOy after cycling due to the nitro-group in the electrode with atmospheric pressure plasma jet offers good protection and high ionic-conductivity interface. This work demonstrates a potential solution to achieve a roll-to-roll modification without any complex synthesis processes, which is a promising technology for the affordable manufacturing of lithium-ion battery.

Amorphous Sb/C composite with isotropic expansion property as an ultra-stable and high-rate anode for lithium-ion batteries

Amorphous Sb/C composite with isotropic expansion property as an ultra-stable and high-rate anode for lithium-ion batteries

Expanded graphite incorporated with Li4Ti5O12 nanoparticles as a high-rate lithium-ion battery anode.

Due to their small interlayer spacing and a low lithiation potential close to Li+ deposition, current graphite anodes suffer from weak kinetics, and lithium deposition in a fast-charging process, hindering their practical application in high-power lithium-ion batteries (LIBs). In this work, expanded graphite incorporated with Li4Ti5O12 nanoparticles (EG/LTO) was synthesized via moderate oxidization of artificial graphite following a solution coating process. The EG/LTO has sufficient porosity for fast Li+ diffusion and a dense Li4Ti5O12 layer for decreased interface reaction resistance, resulting in excellent fast-charging properties. EG/LTO presented a high reversible capacity of 272.8 mA h g-1 at 3.74 A g-1 (10C), much higher than that of the original commercial graphite (50.1 mA h g-1 at 10C) and even superior to that of hard carbon. In addition, EG/LTO exhibited capacity retention rate of 98.4% after 500 cycles at 10C, demonstrating high structural stability during a long cycling process. This study provides a protocol for a solution chemistry method to prepare fast-charging graphite anode materials with high stability for high-power LIBs.

A-site deficient perovskite lithium praseodymium titanate as a high-rate anode for lithium-ion batteries

On account of the low operating potential and slow electrochemical kinetics, graphite anode suffers from poor rate performance and severe safety problems in lithium-ion batteries (LIBs). Therefore, it’s urgent to find alternatives. Due to the abundant intrinsic vacancies and ion migration channels, A-site deficient perovskites could be used as not only solid state electrolytes (SSEs), but also anodes for LIBs. Here, Li0.38Pr0.54TiO3 is firstly demonstrated as a high-rate anode material without any additional modification. With an average operating potential of 0.76 V vs. Li+/Li, the Li0.38Pr0.54TiO3 anode possesses a high specific capacity of 217 mAh g−1 at 0.1C (1C = 200 mA g−1), impressive rate capability (124 mAh g−1 at 40C), and excellent cycling performance (96.75 % capacity retention over 2100 cycles at 10C). Through in-situ analysis and theoretical computations, we confirm the outstanding performance originates from small cell volume change (5.98 %), low band gap (2.57 eV), and low diffusion energy barrier (0.11 eV). The LiFePO4//Li0.38Pr0.54TiO3 full cell shows superior cycling stability (79.78 % capacity retention over 1000 cycles at 5C). Moreover, the relationship between A-site structure and electrochemical properties is discussed from the perspective of vacancy concentration. Our finding also provides a novel perspective for the discovery of high-performance oxide perovskite anodes.

Rapid and Reversible Lithium Insertion in the Wadsley-Roth-Derived Phase NaNb13O33.

The development of new high-performing battery materials is critical for meeting the energy storage requirements of portable electronics and electrified transportation applications. Owing to their exceptionally high rate capabilities, high volumetric capacities, and long cycle lives, Wadsley-Roth compounds are promising anode materials for fast-charging and high-power lithium-ion batteries. Here, we present a study of the Wadsley-Roth-derived NaNb13O33 phase and examine its structure and lithium insertion behavior. Structural insights from combined neutron and synchrotron diffraction as well as solid-state nuclear magnetic resonance (NMR) are presented. Solid-state NMR, in conjunction with neutron diffraction, reveals the presence of sodium ions in perovskite A-site-like block interior sites as well as square-planar block corner sites. Through combined experimental and computational studies, the high rate performance of this anode material is demonstrated and rationalized. A gravimetric capacity of 225 mA h g-1, indicating multielectron redox of Nb, is accessible at slow cycling rates. At a high rate, 100 mA h g-1 of capacity is accessible in 3 min for micrometer-scale particles. Bond-valence mapping suggests that this high-rate performance stems from fast multichannel lithium diffusion involving octahedral block interior sites. Differential capacity analysis is used to identify optimal cycling rates for long-term performance, and an 80% capacity retention is achieved over 600 cycles with 30 min charging and discharging intervals. These initial results place NaNb13O33 within the ranks of promising new high-rate lithium-ion battery anode materials that warrant further research.

Synergetic-modified porous Co2SiO4 conductive network with ZIF-8 derived carbon and reduced graphene oxide for high-rate lithium-ion battery anode

Aiming at the key problems such as low conductivity, volume expansion rate and poor rate performance faced by high-capacity silicon-based anode, a three-dimensional porous Co2SiO4/rGO/ZIFC conductive network is designed and prepared by synergistic modifying Co2SiO4 with reduced graphene oxide (rGO) and ZIF-8 derived carbon (ZIFC). The internal rGO as a lamellar template, supporting substrate and conductive bridge accelerates the transfer of electrons, while the external reasonable coating of ZIF-8 derived carbon greatly maintains the overall structure of the material and supplies fields for lithium-ion diffusion. The obtained porous structure can not only lead to excellent ion diffusion rate and promote the electrochemical interface reaction, but also relieve volume expansion of the material during the cycling, thus heightening the electrochemical performance. The obtained Co2SiO4/rGO/ZIFC electrode offers an outstanding specific capacity of 1295 mA h g−1 at 0.2 A g−1 and 650 mA h g−1 even at a high electric current density of 5 A g−1. The pseudocapacitance ratio of the Co2SiO4/rGO/ZIFC anode at a scan rate of 0.8 mV s−1 is as high as 91%, verifying its excellent lithium ion kinetics and promising rate performance.

Confined oriented growth of FeSe2 on a porous graphene film as a binder-free anode for high-rate lithium-ion batteries

The FeSe2 nanorod@porous graphene film prepared by vacuum filtration, annealing, and subsequent selenylation is developed as an anode for lithium ion batteries. These FeSe2 nanorods are formed via confined oriented growth of FeSe2 nanoparticles.

Pre-zeolite framework super-MIEC anodes for high-rate lithium-ion batteries

New physical insights and a robust approach are provided to develop super-MIEC anodes for high-rate batteries, which would bridge two materials families—nanoporous framework materials and conductive oxides.

Deficient TiO2−x coated porous SiO anodes for high-rate lithium-ion batteries

The porous structure of SiO particles provide abundant diffusion channels for lithium ions and the outer TiO2−x favor the generation of stable SEI layer, ensuring the superb electrochemical performance of porous SiO/TiO2−x composites.

Ultrasmall Co3O4 nanoparticles as a long-lived high-rate lithium-ion battery anode.

Herein, ultrasmall nanostructured Co3O4 particles have been prepared by a facile two-step synthetic method and furthermore applied to lithium-ion batteries. Benefitting from an increased specific surface area and improved tolerance for volume expansion, they deliver an extremely high specific capacity of 1432.7 mA h g-1 at 0.1 A g-1 and an outstandingly long cycle life with about 511.2 mA h g-1 at 10 A g-1 after 2000 cycles. This work will pave a new way to engineer advanced electrode materials for long-lived high-rate lithium-ion batteries.

Through-hole graphite made from waste graphite for high-rate lithium-ion battery anodes

The electrolyte stored in the through-hole graphite can be used as a Li transport buffer layer and shorten the migration distance to the graphite layer, showing excellent rate performance.

Core-shell structured Si@Cu3Si-Cu nanoparticles coated by N-doped carbon as an enhanced capacity and high-rate anode for lithium-ion batteries

• Both Cu 3 Si and NC of Si@Cu 3 Si-Cu@NC are formed during the carbonization of dopamine. • Core-double shell structured Si@Cu3Si-Cu@NC nanoparticles can effectively enhance the stability of Si-based anode. • Si@Cu3Si-Cu@NC nanoparticles shows a high performance (1105.5 mAh g -1 ) under 5A g -1 as LIB anode. Silicon based anode material is regarded as a promising candidate for Lithium ionic batteries (LIBs) due to its high theoretical specific capacity. Nevertheless, the capacity degradation triggered by high volume expansion has seriously hindered its application in LIBs. Herein, a novel structure of core-shell structured Si@Cu 3 Si-Cu nanoparticles coated by N-doped carbon (Si@Cu 3 Si-Cu@NC) is designed and synthesized via a two-step thermal reduction process. In this design, the copper shell and N-doped carbon can significantly limit and accommodate the volume change of Si during cycling. The in-situ formation of Cu 3 Si at the interface further improves the structural stability. The doping of N in carbon is conducive to the rapid transmission of electrons and ions as well as optimizes the electrochemical performance of the material. Therefore, the optimized Si@Cu 3 Si-Cu@NC nanocomposite anode shows prominent rate performance and delivers a reversible capacity of 1105.5 mAh g -1 after 100 cycles at a high current density of 5 A g -1 , which exhibits the great potential of the nanocomposite as high-performance LIBs anode material.

Facile molten salt synthesis of carbon-anchored TiN nanoparticles for durable high-rate lithium-ion battery anodes

Transition metal nitrides (TMNs), including titanium nitride (TiN), exhibit remarkable application prospects as anodes for durable high-rate lithium-ion batteries (LIBs). Regrettably, the absence of simple synthesis methods restricts their further development. Herein, a facile and low-cost molten salt synthesis strategy was proposed to prepare carbon-anchored TiN nanoparticles as an advanced anode material for LIBs with high rate capabilities. This nanosized TiN obtained is ∼5 nm in size and well-distributed onto carbon plates, which could release a reversible capacity of ∼381.5 mAh g−1 at 0.1 A g−1 after 250 cycles and ∼141.5 mAh g−1 at 1.0 A g−1 after 1000 cycles. Furthermore, it was confirmed that the conversion reaction between TiN and Li-ions happened during the electrochemical reaction process, resulting in the formation of Li3N and Ti. This unique microstructure attributed from TiN nanoparticles anchored by carbon could support the structural volume during cycling. This work highlights the method superiority of TiN prepared via a molten salt synthesis strategy as an anode for LIBs with impressive rate performances.

Nb and Ni Nanoparticles Anchored on N-Doped Carbon Nanofiber Membrane as Self-Supporting Anode for High-Rate Lithium-Ion Batteries.

A flexible N-doped carbon nanofiber membrane loaded with Nb and Ni nanoparticles (Nb/Ni@NC) was prepared using electrospinning technology and a subsequent thermal annealing method and used as a self-supporting anode material for lithium-ion batteries. The Nb/Ni@NC nanofiber membrane had excellent flexibility and could be folded and bent at will without fragmentation and wrinkling; the nanofibers also had a uniform and controllable morphology with a diameter of 300-400 nm. The electrochemical results showed that the flexible Nb/Ni@NC electrode could deliver a high discharge capacity of 378.7 mAh g-1 after 200 cycles at 0.2 A g-1 and an initial coulombic efficiency of 67.7%, which was higher than that of the pure flexible NC anode in contrast. Moreover, a reversible discharge capacity of 203.6 mAh g-1 after 480 cycles at 1.0 A g-1 was achieved by the flexible Nb/Ni@NC electrode with a capacity decay for each cycle of only 0.075%, which showed an excellent rate capability and cycling stability.

In Situ Conformal Carbon Coating for Constructing Hierarchical Mesoporous Titania/Carbon Spheres as High-Rate Lithium-Ion Battery Anodes

In Situ Conformal Carbon Coating for Constructing Hierarchical Mesoporous Titania/Carbon Spheres as High-Rate Lithium-Ion Battery Anodes

High Pressure Rapid Synthesis of LiCrTiO4 with Oxygen Vacancy for High Rate Lithium-Ion Battery Anodes.

Lithium-ion battery based on LiCrTiO4 (LCTO) is considered to be a promising anode material, as they provide higher safety and durability beyond than that of graphite electrode. However, the applications of this transformative technology demand improved inherent electrical conductivity of LCTO as well as a simple and rapid synthetic route. Here, LCTO with oxygen vacancies (OVs) is fabricated using high-pressure synthesis technology in only 40min. The optimal synthesis pressure is 0.8GPa (LCTO-0.8). The reversible capacity of LCTO-0.8 at 1C is 131mA h g-1 after 1000 cycles and the capacity retention is nearly 97%, and the reversible capacity of LCTO synthesized at atmospheric pressure (LCTO-P) is 85mA h g-1 under the same circumstances. Even at 5C, the reversible capacity is 110mA h g-1 , which is 77% higher than LCTO-P. Furthermore, it is confirmed by theoretical calculations that the introduction of OVs has the occupation of electronic states at the Fermi level, which greatly enhances the intrinsic conductivity of LCTO. Specifically, the electronic conductivity has increased by two orders of magnitude compared with LCTO-P. Therefore, high-pressure synthesis technology endows LCTO with superior characteristics, providing a new avenue for industrialization.

Spindle-like Fe7S8/C anchored on S-doped graphene nanosheets as a superior long-life and high-rate anode for lithium-ion batteries

Transition metal sulfide, as a highly anticipated anode material for high performance lithium-ion batteries (LIBs). Ingenious structural design and reasonable surface modification are used to inhibit the volume expansion of transition metal sulfide during cycling and improve its specific capacity. In this work, a spindle-like Fe7S8/C@rGO composite was synthesized by two-step hydrothermal method. The prepared anode material shows superior electrochemical properties and extraordinary electrical conductivity. Which delivering a considerable specific capacity of 1465.1 mAh g−1 at 0.1A g−1 after 150 cycles and an impressively long cycle life with a capacity of 689.4 mAh g−1 at 1 A g−1 after 100 cycles. These satisfactory performances are attributed to the special nanostructure and the addition of rGO. In addition, the pseudocapacitive behavior effectively increases the extra reversible capacity of Fe7S8/C@rGO. This practical synthesis strategy provides a novel way to pursue extraordinary performance anode materials for lithium-ion batteries.

Si nanoparticles seeded in carbon-coated Sn nanowires as an anode for high-energy and high-rate lithium-ion batteries

Abstract High-capacity and high-rate anode materials are desperately desired for applications in the next generation lithium-ion batteries. Here, we report preparation of an anode showing a structure of Si nanoparticles wrapped inside Sn nanowires. This anode inherits the advantages of both Si and Sn, endowing lithiation/delithiation of Si nanoparticles inside the conducting networks of Sn nanowires. It demonstrates a high and reversible capacity of ∼1500 mAh g−1 over 300 cycles at 0.2 °C and a good rate capability (0.2 °C–5 °C) equivalent to Sn. The excellent cycling performance is attributed to the novel structure of the anode as well as the strong mechanical strength of the nanowires which is directly confirmed by in-situ lithiation and bending experiments.

Ultrafast anchored SnO2 nanoparticles revealed capacity fade and hysteresis abated stable cycling performance for high-rate lithium-ion batteries

Ultrafast nanostructured SnO2/graphene nanoplatelets (SnO2/GNP) composite material is synthesized by direct microwave irradiation technique. The tetragonal SnO2 phase is confirmed using powder X-ray diffraction pattern and revealed the D-band and G-band in Raman analysis for the presence of graphene nanoplatelets, quantified with 20% mass in thermogravimetric analysis. The measured surface area of SnO2/GNP composite is 50 m2 g−1 and the transmission electron microscopic results shows nanocrystalline SnO2 particles (10 nm), well-decorated on graphene nanoplatelets. The electrochemical impedance spectroscopic analyses confirm that there is no charge storage buildup in Li vs SnO2/GNP lithium cell with additive electrolyte and the cyclic voltammetric analyses reveal highly reversible characteristics of alloying-dealloying mechanism of Sn. The Galvanostatic discharge-charge studies of Li vs SnO2/GNP lithium cells with additive electrolyte are exhibited capacity fade/hysteresis abated stable cycling performance and delivered three-fold higher discharge-charge capacities of 745/738 mAh g−1 than the conventional electrolyte (220/219 mAh g−1) for the 100th cycle at 100 mA g−1. The rate studies are yielded the discharge-charge capacities of 387/383 mAh g−1 at 3000 mA g−1 and 412/410 mAh g−1 for the 500th cycle at 1000 mA g−1, as a superior anode for high-rate lithium-ion batteries.