Application of Sodium-Rich Multifunctional Hard Carbon Synthesized via Multi-Alloy Grafting Strategy for Presodiation in High-Performance Sodium-Ion Batteries.

In sodium-ion pouch batteries based on hard carbon, an additional source of active sodium significantly enhances the battery's initial coulombic efficiency and compensates for the loss of active sodium ions during cycling. This study investigates the interaction between metallic sodium with carbon materials and develops a composite powder material of sodium-rich lithium-aluminum using a multi-alloy grafting strategy, to replenish the initial loss of active sodium in the hard carbon materials. To enhance the stability and utilization of this highly active sodium source, a novel slurry system based on polyethylene oxide (PEO) as a binder and dimethyl carbonate (DMC) as a solvent is introduced. Furthermore, this study designs a hard carbon composite electrode structure with a stable layer and sacrificial layer (NPH), which not only accommodates current battery processing environments but also demonstrates excellent potential in practical applications. Ultimately, the soft-packed sodium-ion battery consists of NPH electrodes with composite sodium ferric pyrophosphate (NFPP) and demonstrates excellent initial coulombic efficiency (91%) and ultra-high energy density (205 Wh kg-1). These results indicate significant technological and application implications for future energy storage.

Precursor Induced Assembly of Si Nanoparticles Encapsulated in Graphene/Carbon Matrices and the Influence of Al2 O3 Coating on their Properties as Anode for Lithium-Ion Batteries.

The theoretical capacity of pristine silicon as anodes for lithium-ion batteries (LIBs) can reach up to 4200 mAh g-1 , however, the low electrical conductivity and the huge volume expansion limit their practical application. To address this challenge, a precursor strategy has been explored to induce the curling of graphene oxide (GO) flakes and the enclosing of Si nanoparticles by selecting protonated chitosan as both assembly inducer and carbon precursor. The Si nanoparticles are dispersed first in a slurry of GO by ball milling, then the resulting dispersion is dried by a spray drying process to achieve instantaneous solution evaporation and compact encapsulation of silicon particles with GO. An Al2 O3 layer is constructed on the surface of Si@rGO@C-SD composites by the atomic layer deposition method to modify the solid electrolyte interface. This strategy enhances obviously the electrochemical performance of the Si as anode for LIBs, including excellent long-cycle stability of 930 mAh g-1 after 1000 cycles at 1000 mA g-1 , satisfied initial Coulomb efficiency of 76.7%, and high rate ability of 806 mAh g-1 at 5000 mA g-1 . This work shows a potential solution to the shortcomings of Si-based anodes and provides meaningful insights for constructing high-energy anodes for LIBs.

High Initial Coulombic Efficiency Hard Carbon Anodes Enabled by Facile Surface Annealing Engineering.

Hard carbon (HC) anode shows great potential due to its high capacity and excellent rate performance. However, state-of-the-art HC anode still suffers insufficient initial Coulomb efficiency (ICE) due to the abundant Li-trapping sites. Herein, we demonstrate a facile annealing engineering for HC anodes to improve the ICE and the mechanism is systematically studied. Accordingly, during the annealing process, metastable O- and N-containing functional groups are pyrolyzed, which cause the microstructure reconstruction of HC. Therefore, irreversible lithium ions adsorption is reduced significantly and the conversion of sp3 to sp2 C contributes to the localized graphitization of HC. Consequently, the optimized HC achieves ultra-high ICE of 90% from initial 61%. It is demonstrated that HC will adsorb H2 O and some organic species from environment gradually, causing conversion of some electrochemical stable functional groups to the irreversible Li-trapping sites. This work provides facile strategy and novel insight for high ICE HC anodes.

Effects of Pyrolysis on High-Capacity Si-Based Anode of Lithium Ion Battery with High Coulombic Efficiency and Long Cycling Life.

We report a facile pyrolysis process for the fabrication of a porous silicon-based anode for lithium-ion battery. Silicon flakes of 100 nm × 800 nm × 800 nm were mixed with equal weight of sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) as the binder and the conductivity enhancement additive, Ketjen Black (KB), at the weight ratio of silicon-binder-KB being 70%:20%:10%, respectively. Pyrolysis was carried out at 700 °C in an inert argon environment for one hour. The process converts the binder to graphitic carbon coatings on silicon and a porous carbon structure. The process led to initial coulombic efficiency (ICE) being improved from 67% before pyrolysis to 75% after pyrolysis with the retention of 2.1 mAh/cm2 areal capacity after 100 discharge-charge cycles at 1 A/g rate. The improved ICE and cycling performance are attributed to graphitic coatings, which protect silicon from irreversible reactions with the electrolyte to form compounds such as lithium-silicon-fluoride (Li2SiF6) and the physical integrity and buffer space provided by the porous carbon structure. By eliminating the adverse effects of KB, the anode made with silicon-to-binder weight ratio of 70%:30% exhibited further improvement of the ICE to approximately 90%. This demonstrated that pyrolysis is a facile and promising one-step process for the fabrication of silicon-based anode with high ICE and long cycling life. This is especially true when the amount and choice of conductivity enhancement additive are optimized.

Simultaneous Coating and Doping of a Nickel-Rich Cathode by an Oxygen Ion Conductor for Enhanced Stability and Power of Lithium-Ion Batteries.

With the rapid development of plug-in hybrid electric vehicles and electric vehicles, high-energy layered lithium nickel-rich oxides have received much attention, but there are still many challenges due to the inherent properties of materials. The poor cycling performance and initial capacity loss of the nickel-rich layered oxide are associated with the structural stability of the material and Li+/Ni2+ cation disorder. Moreover, the synergistic effect of the vacancy of Li and Ni in the delithiation process aggravates the instability of oxygen, eventually resulting in the release of oxygen. It can cause damage to the stability of the structure and even cause safety issues. In this work, we report that Ce0.8Dy0.2O1.9 solid electrolyte inhibits the release of oxygen and improves the structural stability and safety of the Ni-rich cathode material, which is rich in oxygen vacancies. Besides, Ni2+ could be oxidized to Ni3+ along with the strong oxidation of Ce4+ doping into the bulk structure, which suppresses the Li+/Ni2+ cation disorder and improves the initial Coulomb efficiency of the material. This study successfully designed a novel cathode material structure to provide a basis for the future development of layered lithium nickel-rich oxides, which can be used to improve the initial Coulomb efficiency and cycle life.