Engineering a Dynamic Solvent-Phobic Liquid Electrolyte Interphase for Long-Life Lithium Metal Batteries.

The heterogeneity, species diversity, and poor mechanical stability of solid electrolyte interphases (SEIs) in conventional carbonate electrolytes result in the irreversible exhaustion of lithium (Li) and electrolytes during cycling, hindering the practical applications of Li metal batteries (LMBs). Herein, this work proposes a solvent-phobic dynamic liquid electrolyte interphase (DLEI) on a Li metal (Li-PFbTHF (perfluoro-butyltetrahydrofuran)) surface that selectively transports salt and induces salt-derived SEI formation. The solvent-phobic DLEI with C-F-rich groups dramatically reduces the side reactions between Li, carbonate solvents, and humid air, forming a LiF/Li3PO4-rich SEI. In situ electrochemical impedance spectroscopy and Ab-initio molecular dynamics demonstrate that DLEI effectively stabilizes the interface between Li metal and the carbonate electrolyte. Specifically, the LiFePO4||Li-PFbTHF cells deliver 80.4% capacity retention after 1000 cycles at 1.0 C, excellent rate capacity (108.2 mAh g-1 at 5.0 C), and 90.2% capacity retention after 550 cycles at 1.0 C in full-cells (negative/positive (N/P) ratio of 8) with high LiFePO4 loadings (15.6 mg cm-2) in carbonate electrolyte. In addition, the 0.55 Ah pouch cell of 252.0 Wh kg-1 delivers stable cycling. Hence, this study provides an effective strategy for controlling salt-derived SEI to improve the cycling performances of carbonate-based LMBs.

Aromatic-Free Polymers Based All-Organic Dielectrics with Breakdown Self-Healing for High-Temperature Capacitive Energy Storage.

High-temperature dielectric polymers are becoming increasingly desirable for capacitive energy storage in renewable energy utilization, electrified transportation, and pulse power systems. Current dielectric polymers typically require robust aromatic molecular frameworks to ensure structural thermal stability at elevated temperatures. Nevertheless, the introduction of aromatic units compromises electrical insulation owing to pronounced π─π interactions that facilitate electron transport and eliminate the breakdown self-healing property owing to their high carbon content. Herein, an aromatic-free polynorborne copolymer exhibiting electrical conductivity-two orders of magnitude lower than that of state-of-the-art polyetherimide-at elevated temperatures and high electric fields owing to its large bandgap (≈4.64 eV) and short hopping conduction distance (≈0.63 nm) is described. Density functional theory calculations demonstrate that the copolymer can effectively suppress the excitation of high-field valence electrons. Furthermore, the incorporation of trace semiconductors results in high discharge density (3.73 J cm-3 ) and charge-discharge efficiency (95% at 150 °C), outperforming existing high-temperature dielectric polymers. The excellent electrical breakdown self-healing capability of the copolymer film at elevated temperatures further demonstrates its potential for use in dielectric capacitors capable of continuous operation under extreme conditions.

Engineering the Structural Uniformity of Gel Polymer Electrolytes via Pattern-Guided Alignment for Durable, Safe Solid-State Lithium Metal Batteries.

Ultrathin and super-toughness gel polymer electrolytes (GPEs) are the key enabling technology for durable, safe, and high-energy density solid-state lithium metal batteries (SSLMBs) but extremely challenging. However, GPEs with limited uniformity and continuity exhibit an uneven Li+ flux distribution, leading to nonuniform deposition. Herein, a fiber patterning strategy for developing and engineering ultrathin (16 µm) fibrous GPEs with high ionic conductivity (≈0.4 mS cm-1 ) and superior mechanical toughness (≈613%) for durable and safe SSLMBs is proposed. The special patterned structure provides fast Li+ transport channels and tailoring solvation structure of traditional LiPF6 -based carbonate electrolyte, enabling rapid ionic transfer kinetics and uniform Li+ flux, and boosting stability against Li anodes, thus realizing ultralong Li plating/stripping in the symmetrical cell over 3000 h at 1.0 mA cm-2 , 1.0 mAh cm-2 . Moreover, the SSLMBs with high LiFePO4 loading of 10.58 mg cm-2 deliver ultralong stable cycling life over 1570 cycles at 1.0 C with 92.5% capacity retention and excellent rate capacity of 129.8 mAh g-1 at 5.0 C with a cut-off voltage of 4.2 V (100% depth-of-discharge). Patterned GPEs systems are powerful strategies for producing durable and safe SSLMBs.

Ladderphane copolymers for high-temperature capacitive energy storage.

For capacitive energy storage at elevated temperatures1-4, dielectric polymers are required to integrate low electrical conduction with high thermal conductivity. The coexistence of these seemingly contradictory properties remains a persistent challenge for existing polymers. We describe here a class of ladderphane copolymers exhibiting more than one order of magnitude lower electrical conductivity than the existing polymers at high electric fields and elevated temperatures. Consequently, the ladderphane copolymer possesses a discharged energy density of 5.34 J cm-3 with a charge-discharge efficiency of 90% at 200 °C, outperforming the existing dielectric polymers and composites. The ladderphane copolymers self-assemble into highly ordered arrays by π-π stacking interactions5,6, thus giving rise to an intrinsic through-plane thermal conductivity of 1.96 ± 0.06 W m-1 K-1. The high thermal conductivity of the copolymer film permits efficient Joule heat dissipation and, accordingly, excellent cyclic stability at elevated temperatures and high electric fields. The demonstration of the breakdown self-healing ability of the copolymer further suggests the promise of the ladderphane structures for high-energy-density polymer capacitors operating under extreme conditions.

Flexible, Highly Thermally Conductive and Electrically Insulating Phase Change Materials for Advanced Thermal Management of 5G Base Stations and Thermoelectric Generators.

Thermal management has become a crucial problem for high-power-density equipment and devices. Phase change materials (PCMs) have great prospects in thermal management applications because of their large capacity of heat storage and isothermal behavior during phase transition. However, low intrinsic thermal conductivity, ease of leakage, and lack of flexibility severely limit their applications. Solving one of these problems often comes at the expense of other performance of the PCMs. In this work, we report core-sheath structured phase change nanocomposites (PCNs) with an aligned and interconnected boron nitride nanosheet network by combining coaxial electrospinning, electrostatic spraying, and hot-pressing. The advanced PCN films exhibit an ultrahigh thermal conductivity of 28.3 W m-1 K-1 at a low BNNS loading (i.e., 32 wt%), which thereby endows the PCNs with high enthalpy (> 101 J g-1), outstanding ductility (> 40%) and improved fire retardancy. Therefore, our core-sheath strategies successfully balance the trade-off between thermal conductivity, flexibility, and phase change enthalpy of PCMs. Further, the PCNs provide powerful cooling solutions on 5G base station chips and thermoelectric generators, displaying promising thermal management applications on high-power-density equipment and thermoelectric conversion devices.

High Conduction Band Inorganic Layers for Distinct Enhancement of Electrical Energy Storage in Polymer Nanocomposites.

Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications. Inorganic nanofillers with high insulation property are frequently introduced into fluoropolymer to improve its breakdown strength and energy storage capability. Normally, inorganic nanofillers are thought to introducing traps into polymer matrix to suppress leakage current. However, how these nanofillers effect the leakage current is still unclear. Meanwhile, high dopant (> 5 vol%) is prerequisite for distinctly improved energy storage performance, which severely deteriorates the processing and mechanical property of polymer nanocomposites, hence brings high technical complication and cost. Herein, boron nitride nanosheet (BNNS) layers are utilized for substantially improving the electrical energy storage capability of polyvinylidene fluoride (PVDF) nanocomposite. Results reveal that the high conduction band minimum of BNNS produces energy barrier at the interface of adjacent layers, preventing the electron in PVDF from passing through inorganic layers, leading to suppressed leakage current and superior breakdown strength. Accompanied by improved Young's modulus (from 1.2 GPa of PVDF to 1.6 GPa of nanocomposite), significantly boosted discharged energy density (14.3 J cm-3) and charge-discharge efficiency (75%) are realized in multilayered nanocomposites, which are 340 and 300% of PVDF (4.2 J cm-3, 25%). More importantly, thus remarkably boosted energy storage performance is accomplished by marginal BNNS. This work offers a new paradigm for developing dielectric nanocomposites with advanced energy storage performance.

Enhancing electrical energy storage capability of dielectric polymer nanocomposites via the room temperature Coulomb blockade effect of ultra-small platinum nanoparticles.

Introducing a high dielectric constant (high-k) nanofiller into a dielectric polymer is the most common way to achieve flexible nanocomposites for electrostatic energy storage devices. However, the significant decrease of breakdown strength and large increase of dielectric loss has long been known as the bottleneck restricting the enhancement of practical energy storage capability of the nanocomposites. In this study, by introducing ultra-small platinum (<2 nm) nanoparticles, high-k polymer nanocomposites with high breakdown strength and low dielectric loss were prepared successfully. Core-shell structured polydopamine@BaTiO3 (PDA@BT) and core-satellite ultra-small platinum decorated PDA@BT (Pt@PDA@BT) were used as nanofillers. Compared with PDA@BT nanocomposites, the maximum discharged energy density of the Pt@PDA@BT nanocomposites is increased by nearly 70% because of the improved energy storage efficiency. This research provides a simple, promising and unique way to enhance energy storage capability of high-k polymer nanocomposites.

Vertically Aligned and Interconnected Boron Nitride Nanosheets for Advanced Flexible Nanocomposite Thermal Interface Materials.

The continuous evolution toward semiconductor technology in the "more-than-Moore" era and rapidly increasing power density of modern electronic devices call for advanced thermal interface materials (TIMs). Here, we report a novel strategy to construct flexible polymer nanocomposite TIMs for advanced thermal management applications. First, aligned polyvinyl alcohol (PVA) supported and interconnected 2D boron nitride nanosheets (BNNSs) composite fiber membranes were fabricated by electrospinning. Then, the nanocomposite TIMs were constructed by rolling the PVA/BNNS composite fiber membranes to form cylinders and subsequently vacuum-assisted impregnation of polydimethylsiloxane (PDMS) into the porous cylinders. The nanocomposite TIMs not only exhibit a superhigh through-plane thermal conductivity enhancement of about 10 times at a low BNNS loading of 15.6 vol % in comparison with the pristine PDMS but also show excellent electrical insulating property (i.e., high volume electrical resistivity). The outstanding thermal management capability of the nanocomposite TIMs was practically confirmed by capturing the surface temperature variations of a working LED chip integrated with the nanocomposite TIMs.