Direct lithium extraction from spent batteries for efficient lithium recycling.

The flourishing expansion of the lithium-ion batteries (LIBs) market has led to a surge in the demand for lithium resources. Developing efficient recycling technologies for imminent large-scale retired LIBs can significantly facilitate the sustainable utilization of lithium resources. Here, we successfully extract active lithium from spent LIBs through a simple, efficient, and low-energy-consumption chemical leaching process at room temperature, using a solution comprised of polycyclic aromatic hydrocarbons and ether solvents. The mechanism of lithium extraction is elucidated by clarifying the relationship between the redox potential and extraction efficiency. More importantly, the reclaimed active lithium is directly employed to fabricate LiFePO4 cathode with performance comparable to commercial materials. When implemented in 56 Ah prismatic cells, the cells deliver stable cycling properties with a capacity retention of ∼90% after 1200 cycles. Compared with the other strategies, this technical approach shows superior economic benefits and practical promise. It is anticipated that this method may redefine the recycling paradigm for retired LIBs and drive the sustainable development of industries.

A "tug-of-war" effect tunes Li-ion transport and enhances the rate capability of lithium metal batteries.

"Solvent-in-salt" electrolytes (high-concentration electrolytes (HCEs)) and diluted high-concentration electrolytes (DHCEs) show great promise for reviving secondary lithium metal batteries (LMBs). However, the inherently sluggish Li+ transport of such electrolytes limits the high-rate capability of LMBs for practical conditions. Here, we discovered a "tug-of-war" effect in a multilayer solvation sheath that promoted the rate capability of LMBs; the pulling force of solvent-nonsolvent interactions competed with the compressive force of Li+-nonsolvent interactions. By elaborately manipulating the pulling and compressive effects, the interaction between Li+ and the solvent was weakened, leading to a loosened solvation sheath. Thereby, the developed electrolytes enabled a high Li+ transference number (0.65) and a Li (50 µm)‖NCM712 (4 mA h cm-2) full cell exhibited long-term cycling stability (160 cycles; 80% capacity retention) at a high rate of 0.33C (1.32 mA cm-2). Notably, Li (50 µm)‖LiFePO4 (LFP; 17.4 mg cm-2) cells with a designed electrolyte reached a capacity retention of 80% after 1450 cycles at a rate of 0.66C. An 6 Ah Li‖LFP pouch cell (over 250 W h kg-1) showed excellent cycling stability (130 cycles, 96% capacity retention) under practical conditions. This design concept for an electrolyte provides a promising path to build high-energy-density and high-rate LMBs.

Passivating Lithiated Graphite via Targeted Repair of SEI to Inhibit Exothermic Reactions in Early-Stage of Thermal Runaway for Safer Lithium-Ion Batteries.

The self-exothermic in early stage of thermal runaway (TR) is blasting-fuse for Li-ion battery safety issues. The exothermic reaction between lithiated graphite (LiCx ) and electrolyte accounts for onset of this behavior. However, preventing the deleterious reaction still encounters hurdles. Here, we manage to inhibit this reaction by passivating LiCx in real time via targeted repair of SEI. It is shown that 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane (D3 F) can be triggered by LiCx to undergo ring-opening polymerization at elevated temperature, so as to targeted repair of fractured SEI. Due to the high thermal stability of polymerized D3 F, exothermic reaction between LiCx and electrolyte is inhibited. As a result, the self-exothermic and TR trigger temperatures of pouch cell are increased from 159.6 and 194.2 °C to 300.5 and 329.7 °C. This work opens up a new avenue for designing functional additives to block initial exothermal reaction and inhibit TR in early stage.

Facile Replacement Reaction Enables Nano-Ag-Decorated Three-Dimensional Cu Foam as High-Rate Lithium Metal Anode.

In developing advanced lithium (Li) metal batteries with high-energy density, excellent cycle stability, and high-rate capability, it is imperative to resolve dendrite growth and volume expansion during repeated Li plating/stripping. 3D hosts featuring lithiophilic sites are expected to realize both spatial control and dendrite inhibition over Li nucleation. Herein, this work prepares silver (Ag) nanoparticle-decorated 3D copper (Cu) foam via a facile replacement reaction. The 3D host provides rigid skeleton to accommodate volume expansion during cycling. Ag nanoparticles show micro-structural affinity to guide efficient nucleation of Li, leading to reduced overpotential and enhanced electrochemical kinetics. As the result, under an ultrahigh current density of 10 mA cm-2, Cu@Ag foam/Li half cells demonstrate outstanding Coulombic efficiency (CE) of 97.2% more than 100 cycles. Also, Cu@Ag foam-Li symmetric cells sustain preeminent cycling over 900 h with a small voltage hysteresis of 32.8 mV at 3 mA cm-2. Moreover, the Cu@Ag foam-Li||LiFePO4 full cell demonstrates a high discharge capacity of 2.33 mAh cm-2 over 200 cycles with an excellent CE up to 99.9% at 0.6C under practical conditions (N/P = 1.3, 17.4 mg cm-2 LiFePO4). Notably, the full cell with LiFePO4 exhibits a higher areal capacity of 1 mAh cm-2 over 700 cycles under a high rate of 5C, corresponding to capacity retention up to 100% (N/P = 3, 17.4 mg cm-2 LiFePO4). This study provides a novel and simple strategy for constructing high-rate and long-life Li metal batteries.

Non-flammable fluorobenzene-diluted highly concentrated electrolytes enable high-performance Li-metal and Li-ion batteries.

Lithium-ion batteries with Ni-rich cathode and flammable carbonate electrolytes are breeding severe safety concerns which hinds their application in electric vehicles. Herein, by introducing the fluorobenzene (FB) with low-density and low-cost as a cosolvent and bridge solvents in triethyl phosphate (TEP)-based diluted high-concentration electrolytes (DHCEs) system, we design a non-flammable electrolyte with a special solvation structure containing internal-external flame retardants. This non-flammable electrolyte not only solves successfully the incompatibility problem of TEP-based electrolyte to the Li-metal anode (LMA) and the graphite (Gr) anode, but also ensures the stable cycling of Li||LiNi0.7Co0.1Mn0.2O2 (86% capacity retention after 120 cycles) and Gr|| LiNi0.7Co0.1Mn0.2O2 (75% capacity retention after 200 cycles) full cells. Such design opens up a new window for developing new electrolyte systems and building safer high-energy-density batteries.

Exchange of Li and AgNO3 Enabling Stable 3D Lithium Metal Anodes with Embedded Lithophilic Nanoparticles and a Solid Electrolyte Interphase Inducer.

Three-dimensional (3D) current collectors can effectively mitigate the volumetric expansion of working lithium metal anodes (LMAs). However, the practical utilization of 3D current collectors for lithium metal batteries remains unsatisfactory because of inhomogeneous deposition of lithium ions and an unstable solid electrolyte interphase (SEI). Herein, a facile method based on the exchange reaction between Li and AgNO3 is exploited to embed Ag nanoparticles (NPs) and LiNO3 in a carbon paper (ALCP@Li). The Ag NPs act as a seed for even lithium deposition inside the carbon matrix by virtue of their excellent lithiophilicity. Simultaneously, LiNO3 plays an effective role in stabilizing LMAs by evolving a robust N-rich SEI. As a result, such 3D LMAs show a high Coulombic efficiency in half-cells (200 cycles, 99% at 1 mA cm-2, 1 mAh cm-2) and a low overpotential (60 mV). When paired with commercial thick NCM622 and LiFePO4 cathodes, the 3D LMA-based full cells exhibit stable cycling in carbonate electrolytes.

Chemically Presodiated Hard Carbon Anodes with Enhanced Initial Coulombic Efficiencies for High-Energy Sodium Ion Batteries.

Hard carbon (HC) is an attractive anode material for low-cost and high-energy density sodium-ion batteries (SIBs); however, its low initial Coulombic efficiency (ICE) limits its practical battery application. To overcome this problem, we reported a facile strategy to compensate the irreversible capacity loss of HC anodes simply by a chemical presodiation reaction of the HC electrode with a sodiation reagent (sodium biphenyl, Na-Bp). Benefiting from the strong sodiation ability of Na-Bp, HC anodes can be presodiated rapidly in a very short time and the presodiated HC (NaxHC) is found to have a desirable ICE of 100%. When coupled with the Na3V2(PO4)3 cathode to build a SIB full cell, the NaxHC||Na3V2(PO4)3 cell exhibits a high ICE of ∼95.0% and an elevated energy density of 218 W h kg-1, which are far superior to those of the control cell using a pristine HC anode (50% ICE and 120 W h kg-1, respectively), suggesting great advantages brought about by the chemical presodiation process. More importantly, this presodiation reaction is very mild and highly efficient and can be widely extended to a variety of Na-storage materials, offering a new route to develop high-performance Na-storage materials for practical battery applications.

Relaxation-Induced Memory Effect of LiFePO4 Electrodes in Li-Ion Batteries.

In Li-ion batteries, memory effect has been found in several commercial two-phase materials as a voltage bump and a step in the (dis)charging plateau, which delays the two-phase transition and influences the estimation of the state of charge. Although memory effect has been first discovered in olivine LiFePO4, the origination and dependence are still not clear and are critical for regulating the memory effect of LiFePO4. Herein, LiFePO4 has been synthesized by a home-built spray drying instrument, of which the memory effect has been investigated in Li-ion batteries. For as-synthesized LiFePO4, the memory effect is significantly dependent on the relaxation time after phase transition. Besides, the voltage bump of memory effect is actually a delayed voltage overshooting that is overlaid at the edge of stepped (dis)charging plateau. Furthermore, we studied the kinetics of LiFePO4 electrode with electrochemical impedance spectroscopy (EIS), which shows that the memory effect is related to the electrochemical kinetics. Thereby, the underlying mechanism has been revealed in memory effect, which would guide us to optimize two-phase electrode materials and improve Li-ion battery management systems.