Ultrathin, Mechanically Durable, and Scalable Polymer-in-Salt Solid Electrolyte for High-Rate Lithium Metal Batteries.

Polymer-in-salt solid-state electrolytes (PIS SSEs) are emerging for high room-temperature ionic conductivity and facile handling, but suffer from poor mechanical durability and large thickness. Here, Al2O3-coated PE (PE/AO) separators are proposed as robust and large-scale substrates to trim the thickness of PIS SSEs without compromising mechanical durability. Various characterizations unravel that introducing Al2O3 coating on PE separators efficiently improves the wettability, thermal stability, and Li-dendrite resistance of PIS SSEs. The resulting PE/AO@PIS demonstrates ultra-small thickness (25 µm), exceptional mechanical durability (55.1 MPa), high decomposition temperature (330 °C), and favorable ionic conductivity (0.12 mS cm-1 at 25 °C). Consequently, the symmetrical Li cells remain stable at 0.1 mA cm-2 for 3000 h, without Li dendrite formation. Besides, the LiFePO4|Li full cells showcase excellent rate capability (131.0 mAh g-1 at 10C) and cyclability (93.6% capacity retention at 2C after 400 cycles), and high-mass-loading performance (7.5 mg cm-2). Moreover, the PE/AO@PIS can also pair with nickel-rich layered oxides (NCM811 and NCM9055), showing a remarkable specific capacity of 165.3 and 175.4 mAh g-1 at 0.2C after 100 cycles, respectively. This work presents an effective large-scale preparation approach for mechanically durable and ultrathin PIS SSEs, driving their practical applications for next-generation solid-state Li-metal batteries.

EQCM Investigation of a Dual-Doped Polymer Electrode for Li-Ion Batteries with Improved Reversible Capacity.

Polymer-based materials with the incorporation of redox-active dopants serve as promising electrodes for Li-ion batteries but their use is restricted by the limited doping level and inevitable dissolution behavior of the dopants. Here, we proposed a conjugated polymer-based electrode with an assistant dopant to realize the reversible capacity contribution of a redox-active dopant. By employing phosphate anion (PO) as the assistant dopant to stable the polymer matrix, the reversible capacity was improved by introducing indigo carmine (IC) into the polymer electrode. Based on the real-time monitoring of the electrochemical quartz crystal microbalance toward the mass change, the charge storage behavior of the redox-active dopant IC was observed and the stabilizing effect of the assistant dopant PO was revealed. The modified electrode delivered an increased capacity of 191 mA h g-1, and the reversible capacity remained 56% higher than that of the PO-undoped electrode after 200 cycles. The dual-doping strategy with the assistant dopant and the redox-active dopant is used to develop advanced polymer-based electrodes for high-capacity and long-cycling batteries.

Insight into the reversible conversion-(de)incorporation of redox-active dopants within a polymer-based electrode.

We combined a microporous polymer backbone with an organic redox-active dopant to construct a reversible electrode system based on the conversion-(de)incorporation behaviour of the dopant. The correspondence between the reversible conversion-(de)incorporation mechanism of the dopant and the electrochemical performance of the designed electrode system was established by electrochemical quartz crystal microbalance and in situ Fourier transform infrared spectroscopy.

Two π-Conjugated Covalent Organic Frameworks with Long-Term Cyclability at High Current Density for Lithium Ion Battery.

Organic lithium ion batteries (LIBs) are considered as one of the next-generation green electrochemical energy storage (EES) devices. However, obtaining both high capacity and long-term cyclability is still the bottleneck of organic electrode materials for LIBs because of weak structural and chemical stability and low conductivity. Covalent organic frameworks (COFs) show potential to overcome these problems owing to its good stability and high capacity. Herein, the synthesis and characterization of two π-conjugated COFs, derived from the Schiff-base reaction of 2,4,6-triaminopyrimidne (TM) respectively with 1,4-phthalaldehyde (PA) and 1,3,5-triformylbenzene (TB) by a mechanochemical process are presented. As anode materials for LIBs, the COFs exhibit favorable electrochemical performance with the highest reversible discharge capacities of up to 401.3 and 379.1 mAh g-1 at a high current density (1 A g-1 ), respectively, and excellent long-term cyclability with 74.8 and 72.7 % capacity retention after 2000 cycles compared to the initial discharge capacities.