3D flame-retardant skeleton reinforced polymer electrolyte for solid-state dendrite-free lithium metal batteries

For solid polymer electrolytes(SPEs),improving their mechanical and electrochemical properties is the key to obtaining batteries with higher safety and higher energy density.Herein,a novel synergistic strategy proposed is preparing a 3D flame-retardant skeleton(3DPA)and adding nano-multifunctional fillers(Li-ILs@ZIF-8).In addition to providing mechanical support for the polyethylene oxide(PEO)matrix,3DPA also has further contributed to the system’s flame retardancy and further improved the safety.Simultaneously,the electrochemical performance is fully guaranteed by rigid Li-ILs@ZIF-8,which provides fast migration channels forLi^(+),reduces the crystallinity of PEO and effectively inhibits lithium dendrites.The limiting oxygen index of the optimal sample(PL3Z/PA)is as high as 20.5%,and the ionic conductivity reaches 2.89×10^(-4) and 0.91×10^(-3) S cm^(-1) at 25 and 55°C,respectively.The assembled Li|PL3Z/PA|Li battery can be cycled stably for more than 1000 h at a current density of 0.1 m A cm^(-2) without short circuit being pierced by lithium dendrites.The specific capacity of the LFP|PL3Z/PA|Li battery was 160.5 m Ah g^(-1) under a current density of 0.5 C,and the capacity retention rate was 90.0%after 300 cycles.

A new flame-retardant polymer electrolyte with enhanced Li-ion conductivity for safe lithium-sulfur batteries

Flame-retardant polymer electrolytes(FRSPEs)are attractive due to their potential for fundamentally settling the safety issues of liquid electrolytes.However,the current FRSPEs have introduced large quantity of flame-retardant composition which cannot conduct lithium ions,thus decreasing the Li-ion conductivity.Here,we synthesize a novel liquid monomer 2-((bis((2-oxo-1,3-dioxolan-4-yl)methoxy)phosphoryl)oxy)ethyl acrylate(BDPA)for preparing FRSPE by in-situ polymerization,in which PBDPA polymer can not only conduct lithium ions,but also prevent burning.The prepared FRSPE demonstrated outstanding flame-retardant property,favorable lithium-ion conductivity of 5.65×10^(-4) S cm^(-1) at ambient temperature,and a wide electrochemical window up to 4.5 V.Moreover,the Li/in-situ FRSPE/S@pPAN cell exhibited favorable electrochemical performances.We believe that this work provides an effective strategy for establishing high-performance fireproof quasi-solid-state battery system.

High-efficiency single and tandem fullerene solar cells with asymmetric monofluorinated diketopyrrolopyrrole-based polymer

Design and synthesis of low bandgap(LBG) polymer donors is inevitably challenging and their processability from a non-halogenated solvent system remains a hurdle to overcome in the area of highperformance polymer solar cells(PSCs).Due to a high aggregation tendency of LBG polymers,especially diketopyrrolopyrrole(DPP)-based polymers coupled with bithiophenes in the polymer backbones,their widespread adoption in non-ha logena ted solvent-processed PSCs has been limited.Herein,a novel LBG DPP-based polymer,called PDPP4 T-1 F with asymmetric arrangement of fluorine atom,has been successfully synthesized and showed an outstanding power conversion efficiency(PCE) of 10.10% in a singlejunction fullerene-based PSCs.Furthermore,an impressive PCE of 13.21% has been achieved in a tandem device from a fully non-halogenated solvent system,which integrates a wide bandgap PDTBTBz-2 F polymer in the bottom cell and LBG PDPP4 T-1 F polymer in the top cell.The achieved efficiency is the highest value reported in the literature to date in fullerene-based tandem PSCs.We found that a uniformly distributed interpenetrating fibril network with nano-scale phase separation and anisotropy of the polymer backbone orientation for efficient charge transfer/transport and suppressed charge recombination in PDPP4 T-1 F-based PSCs led to outstanding PCEs in single and tandem-junction PSCs.

Strategies for flame-retardant polymer electrolytes for safe lithiumbased batteries

The advancement of lithium-based batteries has spurred anticipation for enhanced energy density,extended cycle life and reduced capacity degradation.However,these benefits are accompanied by potential risks,such as thermal runaway and explosions due to higher energy density.Currently,liquid organic electrolytes are the predominant choice for lithium batteries,despite their limitations in terms of mechanical strength and vulnerability to leakage.The development of polymer electrolytes,with their high Young’s modulus and enhanced safety features,offers a potential solution to the drawbacks of traditional liquid electrolytes.Despite these advantages,polymer electrolytes are still susceptible to burning and decomposition.To address this issue,researchers have conducted extensive studies to improve their flame-retardant properties from various perspectives.This review provides a concise overview of the thermal runaway mechanisms,flame-retardant mechanisms and electrochemical performance of polymer electrolytes.It also outlines the advancements in flame-retardant polymer electrolytes through the incorporation of various additives and the selection of inherently flame-retardant matrix.This review aims to offer a comprehensive understanding of flame-retardant polymer electrolytes and serve as a guide for future research in this field.

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Polymer solar cells(PSCs)with high power conversion efficiency(PCE)and environment-friendly fabrication are the main requirements enabling their production in industrial scale.While the use of non-halogenated solvent processing is inevitable for the PSC fabrication,it significantly reduces the processability of polymer donors(PDS)and small-molecule acceptors(SMAs).This often results in unoptimized blend morphology and limits the device performance.To address this issue,hydrophilic oligoethylene glycol(OEG)side-chains are introduced into a PD(2EG)to enhance the molecular compatibility between the PD and L8-BO SMA.The 2EG PD induces higher crystallinity and alleviates phase separation with the SMA compared to the reference PD(PM7)with hydrocarbon side-chains.Consequently,the 2EG-based PSCs exhibit a higher PCE(15.8%)than the PM7-based PSCs(PCE=14.4%)in the ortho-xylene based processing.Importantly,benefitted from the reduced phase separation and increased crystallinity of 2EG PDS,the 2EG-based PSCs show enhanced thermal stability(84%of initial PCE after 120 h heating)compared to that of the PM7-based PSCs(60%of initial PCE after 120 h heating).This study demonstrates the potential of OEG side-chain-incorporated materials in developing efficient,stable,and eco-friendly PSCs.

A Non-Halogenated Polymer Donor Based on Imide Unit for Organic Solar Cells with Efficiency Nearly 16%

Comprehensive Summary,Non-halogenated polymers have great potential in the commercialization of organic solar cells(OSCs)due to their advantages in the manufacturing process.However,high-performance donor polymers are limited to a small amount of building blocks.Herein,we utilize as building block 4H-dithieno[3,2-e:2',3'-g]isoindole-4,6(5H)-dione(DTID)to design and synthesize a relevant non-halogenated polymer PBTID for active layers in OSCs.PBTID exhibits a strong absorption in the wavelength range of 400—600 nm with a distinctly wide optical bandgap of 2.06 eV,a low-lying highest occupied molecular orbital(HOMO)energy level of−5.53 eV.In addition,this polymer has a very strong aggregation effect in solution and could form nanoscale fibrils in the neat film.Consequently,when blended with the non-fullerene acceptor Y6,the devices achieve a prominent PCE of 15.8%with a high Voc of 0.87 V.The Voc and PCE values are one of the highest values in the non-halogenated polymer donor-based OSCs reported to date.

Asymmetric fireproof gel polymer electrolyte constructed by boron-contained covalent organic framework for dendrite-free sodium metal battery

Gel polymer electrolytes (GPEs) with flexibility, easy processability, and low cost have been regarded as promising alternatives for conventional liquid electrolytes in next-generation sodium metal batteries (SMBs). However, GPEs often suffer from combustion risk and inferior interfacial compatibility toward Na metal anode, which severely limit their wide commercial applications. Here, a rational design of asymmetric fireproof GPE (AFGPE) modified with a boron-contained covalent organic framework (BCOF) on one side is developed through in-situ crosslinking polymerization process. Benefiting from the unique structure and composition, the resulting AFGPE exhibits high Na+ transference number, wide electrochemical window, excellent mechanical properties and high safety. Especially, the nanoscale BCOF layer with uniform nanochannels works as ion sieve that homogenizes Na+ flux during Na plating process, while the abundant Lewis-acid B sites can strongly capture counter anions and decrease space charge layer at anode side, thus promoting the uniform Na deposition to effectively suppress dendrite growth. Consequently, the Na/AFGPE/Na symmetric cells demonstrate remarkable cycling stability for over 1200 h at 0.1 mA·cm^(-2), and the solid-state SMBs exhibit outstanding cycling properties and rate capability, delivering a high capacity retention of 96.4% under current density of 1 C for over 1000 cycles.

Three-in-one fire-retardant poly(phosphate)-based fast ion-conductor for all-solid-state lithium batteries

The development of flame retardant or nonflammable electrolytes is the key to improve the safety of lithium batteries,owing to inflammable organic solvents and polymer matrix in common liquid and polymer electrolytes regarded as the main cause of battery fire.Herein,a series of solid-state polyphosphate oligomers(SPPO)as a three-in-one electrolyte that integrated the roles of lithium salt,dissociation matrix,and flame retardant were synthesized.The well-designed SPPO electrolytes showed an optimal ionic conductivity of 5.5×10^(-4)S cm-1at 30℃,an acceptable electrochemical window up to 4.0 V vs.Li/Li+,and lithium ion transference number of 0.547.Stable Li-ion stripping/plating behavior for 500 h of charge-discharge cycles without internal short-circuit in a Li|SPPO|Li cell was confirmed,together with outstanding interface compatibility between the SPPO electrolyte and lithium foil.The optimal Li|SPPO|LiFePO4cell presented good reversible discharge capacity of 149.4 mA h g-1at 0.1 C and Coulombic efficiency of 96.4%after 120 cycles.More importantly,the prepared SPPO cannot be ignited by the lighter fire and show a limited-oxygen-index value as high as 35.5%,indicating splendid nonflammable nature.The SPPO could be a promising candidate as a three-in-one solid-state electrolyte for the improved safety of rechargeable lithium batteries.

OPTICALLY ACTIVE AND FLAME-RETARDANT POLY(AMIDE-IMIDE)S BASED ON PHOSPHINE OXIDE MOIETY AND N,N′-(PYROMELLITOYL)BIS-L-AMINO ACID IN THE MAIN CHAIN:SYNTHESIS AND CHARACTERIZATION

Six new optically active and flame-retardant poly（amide-imide）s PAls 5a-5f containing phosphine oxide moiety as a flame-retardant unit in the main chain were synthesized from direct polycondensation reaction of six chiral N,N＇-（pyromellitoyl）-bis-L-amino acid 3a-3f with bis（3-aminophenyl）phenyl phosphine oxide 4 in a medium consisting of N-methyl-2-pyrrolidone （NMP）, triphenyl phosphite （TPP）, calcium chloride （CaCl2） and pyridine. The polymerization reactions produced a series of optically active poly（amide-imide）s with good yield and good inherent viscosity of 0.34-0.70 dLg^-1. The resulted polymers were fully characterized by means of FTIR and ^1H-NMR spectroscopy, gel permeation chromatography （GPC）, elemental analyses, inherent viscosity and solubility tests. Thermal properties and flameretardant behavior of the PAIs 5a-5f were investigated using thermal gravimetric analysis （TGA and DTG） and limiting oxygen index （LOI）. Data obtained by thermal analysis （TGA and DTG） revealed that these polymers showed good thermal stability. Furthermore, high char yield in TGA and good LOI values indicated that the resulting polymers were capable of exhibiting good flame retardant properties. N,N＇-（pyromellitoyl）-bis-L-amino acids 3a-3f were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride （1,2,4,5-benzenetetracarboxylicacid-1,2,4,5-dianhydride） 1 with L-alanine 2a, L-valine 2b, L-leucine 2c, L-isoleucine 2d, L-phenyl alanine 2e and L-2-aminobutyric acid 2f in acetic acid solution.

Low temperature,non-halogen solvent processed single-component organic solar cells with 10%efficiency

A double-cable conjugated polymer DCPIC-BO is designed via introducing a long-branched alkyl chains 2-buthyloctyl into the acceptor side unit.Compared with the double-cable polymer(DCPIC-EH)with the 2-ethylhexyl alkyl chains,the solubility of the DCPIC-BO in non-halogen solvents is substantially improved.Therefore,a power conversion efficiency(PCE)of 9.77%can be obtained by the devices processed from o-xylene at 40℃,while the DCPIC-EH cannot be processed due to its poor solubility under this condition.Moreover,PCEs of 10.10%for small-area(0.04 cm^(2))devices and nearly 9%for devices with an area of 1 cm^(2) are achieved using a non-halogenated solid additive in o-xylene,realizing the"absolutely halogen-free"OSC fabrication.

Polybenzimidazole functionalized electrolyte with Li-wetting and self-fluorination functionalities for practical Li metal batteries

Rough Li plating,low ionic conductivity,and low thermal stability of conventional electrolytes post-primary challenges for achieving reliable high-capacity rechargeable lithium batteries,for which lithiummetal is frequently proposed as themost promising anode material.Conventional low-polarity commercial polypropylene/polyethylene separators fail to support the application of high-energy-density Li anodes due to their rigid physicochemical properties and the high reactivity of Li metal,leading to fatal dendrite formation and vigorous exothermic reaction with electrolytes.Herein,we develop a Li-wetting,flame-retardant binary polymer electrolyte by functionalizing poly(vinylidene fluoride)(PVDF)separators with nonflammable polybenzimidazole(PBI)to build safe room-temperature solid-state electrolyte membranes.A dendrite-free LiFePO4 cell with the solid polymer electrolyte(SPE)delivers a discharge capacity of 127 mAh g^(-1) at 25℃ with a capacity retention of 87.5%after 500 cycles at 0.5℃(0.15 mA cm^(-2)).Phase-field simulations and density functional theory calculations demonstrate that the negatively charged benzimidazole chains of PBI own superior affinity to lithium bis(trifluoromethanesulfonyl)imide(LiTFSI),and shares overlapping electron density with Li anode,giving rise to accelerated Li^(+)conduction at room temperature and uniform Li electrodeposition at the electrolyte/Li metal interface.The SPE is also flame-retardant since heat-resistant polytetrafluoroethylene and a dense,heat-blocking graphitized carbon layer are formed in intense heat throughdehydrogenation/fluorination of PVDF under the catalysis of Lewis base imidazole rings and the decomposition of benzimidazole rings in PBI.No such fire-resistant mechanism is ever reported in conventional electrolytes.