Lithium Salt Combining Fluoroethylene Carbonate Initiates Methyl Methacrylate Polymerization Enabling Dendrite-Free Solid-State Lithium Metal Battery

This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.

In Situ High-performance Gel Polymer Electrolyte with Dual-reactive Cross-linking for Lithium Metal Batteries

Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.

In Situ Directional Polymerization of Poly(1,3-dioxolane)Solid Electrolyte Induced by Cellulose Paper-Based Composite Separator for Lithium Metal Batteries

In traditional in situ polymerization preparation for solid-state electrolytes,initiators are directly added to the liquid precursor.In this article,a novel cellulose paper-based composite separator is fabricated,which employs alumina as the inorganic reinforcing material and is loaded with polymerization initiator aluminum trifluoromethanesulfonate.Based upon this,a separator-induced in situ directional polymerization technique is demonstrated,and the extra addition of initiators into liquid precursors is no longer required.The polymerization starts from the surface and interior of the separator and extends outward with the gradually dissolving of initiators into the precursor.Compared with its traditional counterpart,the separator-induced poly(1,3-dioxolane)electrolyte shows improved interfacial contact as well as appropriately mitigated polymerization rate,which are conducive to practical applications.Electrochemical measurement results show that the prepared poly(1,3-dioxolane)solid electrolyte possesses an oxidation potential up to 4.4 V and a high Li+transference number of 0.72.After 1000 cycles at 2 C rate(340 mA g^(−1)),the assembled Li||LiFePO_(4)solid battery possesses a 106.8 mAh g^(−1)discharge capacity retention and 83.5%capacity retention ratio,with high average Coulombic efficiency of 99.5%achieved.Our work may provide new ideas for the design and application of in situ polymerization technique for solid electrolytes and solid batteries.

Mechanistically Novel Frontal-Inspired In Situ Photopolymerization:An Efficient Electrode|Electrolyte Interface Engineering Method for High Energy Lithium Metal Polymer Batteries

The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.

Flame retardant polyamide 6 by in situ polymerization of ε-caprolactam in the presence of melamine derivatives

An improved method for preparing melamine cyanurate （MCA） based flame retardant polyamide 6 （FRPA6） materials has been proposed. This processing method, i.e., improved in situ polymerization, was used to synthesize flame retardant PA6. In situ formed MCA nanoparticles were supposed to be linked to PA6 chains in the ε-caprolactam hydrolytic polymerization system to obtain startype polymers for the first time. Through TEM photographs, it can be found that the in situ formed MCA nanoparticles with diametric size of less than 50 nm, are nanoscaled, highly uniformly dispersed in the PA6 matrix. Synthesized flame retardant PA6 have good fire performance which can achieve UL-94 V-0 rating at 1.6 mm thickness with the presence of 7.34 wt.% MCA in the matrix.

In situ polymerization coating and characteristics of coated NPK compound fertilizer

Controlled release NPK compound fertilizers were prepared by means of in situ polymerization of monomers on the surface of fertilizer granules at room temperature. Methacrylate, α-methyl acrylic acid, and ethylene dimethylacrylate were used as monomers, Dibenzoyl peroxide as initiator, and cobalt naphthenate, and triethyl amine as promoters. The structures of coating materials were characterized by IR spectra. The thermogravimetric analysis result indicated that the coating materials were of good thermal stability. The mean thickness of single coating measured with screw gauge was ca. 140 μm. The morphologies of uncoated and coated fertilizer granules analyzed by using scanning electron microscopy were changed from porosities and gullies to hills and plain. The release rate of coated compound fertilizers in water could be controlled by the hydrophicity and thickness of coating. The increase in coating hydrophicity caused the increase in release rate of fertilizer. The increase in thickness of coating slowed the release rate.

Anion competition for Li^(+)solvated coordination environments in poly(1,3 dioxolane)electrolyte to enable high-voltage lithium metal solid-state batteries

Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during Li^(+)conduction,resulting in the Li^(+)transport kinetics being greatly affected.Here,we designed anion competitive gel polymer electrolyte(ACPE)by introducing lithium difluoro(oxalato)borate(LiDFOB)anion into the 1,3-dioxolane(DOL)in situ polymerisation system.ACPE enhances the ionic dipole interaction between Li^(+)and the solvent molecules and synergizes with Li^(+)across the solvation site of the polymer ethylene oxide(EO)unit,combination that greatly improves the Li^(+)transport efficiency.As a result,ACPE exhibits 1.12 mS cm^(−1)ionic conductivity and 0.75 Li^(+)transfer number at room temperature.Additionally,this intra-polymer solvation sheath allows preferential desolvation of DFOB−,which contributes to the formation of kinetically stable anion-derived interphase and effectively mitigates side reactions.Our results demonstrate that the assembled Li||NCM622 solid-state battery exhibits lifespan of over 300 cycles with average Coulombic efficiency of 98.8%and capacity retention of 80.3%.This study introduces a novel approach for ion migration and interface design,paving the way for high-safety and high-energy-density batteries.

Synthesis of PMA/Eu_2O_3 porous-layered nanocomposite by in situ polymerization and its morphology

The PMA/Eu2O3 porous and layered nanocomposite was prepared by in situ polymerization and characterized by means of X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscope （SEM）, and inflared ray （IR）. Microscopic investigation of the nanocomposite was carded out by atomic force microscopy （AFM）. The results showed that the shape of the composite was layered and porous. Eu2O3 was grafted when methyl acrylate （MA） polymerized; thus Eu2O3 particles appeared on both sides of the chains of polymeric methyl acrylate （PMA）.

STUDY ON NYLON 6/SUPERFINE RUBBER PARTICLES COMPOSITES VIA IN SITU POLYMERIZATION

Two highly cross-linked superfine styrene-butadiene rubber particles, one with 1 wt% of carboxyl groups and theother without such groups having particle sizes of 130-150 nm and 80-100 nm respectively, were used to prepare nylon6/rubber composites via in situ polymerization. It was found that carboxylic styrene-butadiene dispersed uniformly in nylonmatrix and there was strong interfacial interaction because of the graft polymer formed by the reaction of nylon with carboxylgroup of the rubber, resulting in considerably improved impact strength with almost unchanged tensile strength. However,the addition of styrene-butadiene without carboxyl groups showed intensive agglomeration of the rubber particles and weakinterfacial interactions, and the toughness of the materials was improved slightly. The crystallization and rheological behavior of the composites were also discussed.

In situ polymerization preparation and characterization of Li_4Ti_5O_(12)-polyaniline anode material

Li4Ti5O12 powders were prepared by so-gel method using tetrabutyl titanate,lithium acetate and absolute alcohol as starting materials.Li4Ti5O12-polyaniline(Li4Ti5O12-PAn)composite was prepared by in situ polymerization method using aniline, ammonium persulfate and hydrochloricarried as starting materials.Li4Ti5O12-PAn composite was characterized by X-ray diffractometry(XRD),infrared spectrum(IR)combined with electrochemical tests.The results show that the electrical conductivity is enhanced obviously due to the introduction of PAn to Li4Ti5O12.Li4Ti5O12-PAn composite exhibits better high-rate capability and cyclability than Li4Ti5O12.The composite can deliver a specific capacity of 191.3 and 148.9 mA·h/g,only 0.13%and 0.61%of the capacity is lose after being discharged 80 times at 0.1C and 2.0C,respectively.

Thermoelectric properties of Bi_(0.5)Sb_(1.5)Te_3/polyaniline composites prepared by mechanical blending and in-situ polymerization

Bi 0.5 Sb 1.5 Te 3/polyaniline composites were prepared by mechanical blending and in situ polymerization, and their transport properties were measured. It was found that for the composites with 1%, 3%, 5% and 7% polyaniline (mass fraction) respectively, which were prepared by mechanical blending, the power factors decrease by about 30%, 50%, 55% and 65% compared with the Bi 0.5 Sb 1.5 Te 3 samples, which is mainly due to the remarkable decreases of the electrical conductivity. The electrical conductivity and power factor of the composites samples with 7% polyaniline prepared by in situ polymerization are higher by about 65% and 60%, respectively, than that of the corresponding samples prepared by mechanical blending.

Thermal Stability and Crystallinity Study of Polystyrene/SiO2 Nano-Composites Synthesis via Microwave-Assisted In Situ Polymerization

Serials of polystyrene/SiO2 Nano composites (PS/SiO2) with different content of inorganic fillers were successfully prepared by the in situ bulk radical polymerization of styrene under microwave irradiation. The effect of the amount of Nano SiO2 on the properties of the PS/SiO2 Nanocomposites along with the average relative molecular masses (Mn, Mz and Mw) was investigated by thermal analysis and X-Ray Diffraction (XRD). Their structural model was proposed on the basis of the Optical Microscopy, FTIR (Fourier Transform Infrared) analysis, differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and X-Ray Diffraction (XRD). The dispersion of nanoparticles in Polystyrene is observed in the magnified image. The effect of microwave irradiation power on molecular weight of polystyrene was also studied. It was found that, the microwave assisted reaction needs less time as compare to conventional polymerization and found to be in between 10 to 15 min.

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO_(2) separation

Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.

Designing mesostructured iron (Ⅱ) fluorides with a stable in situ polymer electrolyte interface for high-energy-density lithium-ion batteries

As high-energy cathode materials,conversion-type metal fluorides provide a prospective pathway for developing next-generation lithium-ion batteries.However,they suffer from severe performance decay owing to continuous structural destruction and active material dissolution upon cycling,which worsen at elevated temperatures.Here,we design a novel FeF2 cathode with in situ polymerized solid-state electrolyte systems to enhance the cycling ability of metal fluorides at 60 C.Novel FeF2 with a mesoporous structure(meso-FeF2)improves Liþdiffusion and relieves the volume change that typically occurs during the alternating conversion reactions.The structural stability of the meso-FeF2 cathode is strengthened by an in situ polymerized solid-state electrolyte,which prevents the pulverization and ion dissolution that are inevitable for conventional liquid electrolytes.Under the double action of this in situ polymerized solid-state electrolyte and the meso-FeF2's mesoporous structure,the active material maintains an intact SEI layer and part of the mesoporous structure after long charge–discharge cycling,showing excellent cycling stability at high temperatures.

Progress and perspectives of in situ polymerization method for lithium-based batteries

The application of lithium-based batteries is challenged by the safety issues of leakage and flammability of liquid electrolytes.Polymer electrolytes(PEs)can address issues to promote the practical use of lithium metal batteries.However,the traditional preparation of PEs such as the solution-casting method requires a complicated preparation process,especially resulting in side solvents evaporation issues.The large thickness of traditional PEs reduces the energy density of the battery and increases the transport bottlenecks of lithium-ion.Meanwhile,it is difficult to fill the voids of electrodes to achieve good contact between electrolyte and electrode.In situ polymerization appears as a facile method to prepare PEs possessing excellent interfacial compatibility with electrodes.Thus,thin and uniform electrolytes can be obtained.The interfacial impedance can be reduced,and the lithium-ion transport throughput at the interface can be increased.The typical in situ polymerization process is to implant a precursor solution containing monomers into the cell and then in situ solidify the precursor under specific initiating conditions,and has been widely applied for the preparation of PEs and battery assembly.In this review,we focus on the preparation and application of in situ polymerization method in gel polymer electrolytes,solid polymer electrolytes,and composite polymer electrolytes,in which different kinds of monomers and reactions for in situ polymerization are discussed.In addition,the various compositions and structures of inorganic fillers,and their effects on the electrochemical properties are summarized.Finally,challenges and perspectives for the practical application of in situ polymerization methods in solid-state lithium-based batteries are reviewed.

Gel electrolyte via in situ polymerization to promote durable lithium-air batteries

Aprotic lithium-air batteries(LABs)have been known as the holy grail of energy storage systems due to their extremely high energy density.However,their real-world application is still hindered by the great challenges from the Li anode side,like dendrite growth and corrosion reactions,thus a pure oxygen atmosphere is usually adopted to prolong the lifetime of LABs,which is a major obstacle to fully liberate the energy density advantages of LABs.Here,a gel polymer electrolyte has been designed through in-situ polymerization of 1,3-dioxolane(DOL)by utilizing the unique semi-open nature of LABs to protect the Li anode to conquer its shortcomings,enabling the high-performance running of LABs in the ambient air.Unlike common liquid electrolytes,the in-situ formed gel polymer electrolyte could facilitate constructing a gradient SEl film with the gradual decrease of organic components from top to bottom,preventing the Li anode from dendrite growth and air-induced corrosion reactions and thus realizing durable Li repeated plating/stripping(2000h).Benefiting from the anode protection effects of the gradient SEI film,the LABs display a long lifetime of 17o cycles,paving an avenue for practical,long-term,and high-efficiency operation of LABs.

A fiber-reinforced solid polymer electrolyte by in situ polymerization for stable lithium metal batteries

Solid polymer electrolytes(SPEs)by in situ polymerization are attractive due to their good interfacial contact with electrodes.Previously reported in situ polymerized SPEs,however,suffer from the low polymerization degree that causes poor mechanical strength,Li dendrite penetration,and performance decay in Li-metal batteries.Although highly polymerized SPEs are more stable than lowly polymerized ones,they are restricted by their sluggish long-chain mobility and poor ionic conductivity.In this work,a three-dimensional fibrous membrane with ion selectivity was prepared and used as a functional filler for the in situ formed SPE.The obtained SPE has high stability due to its high polymerization degree after the long-term heating process.The fibrous membrane plays a vital role in improving the SPE’s properties.The rich anion-adsorption sites on the fibrous membrane can alleviate the polarization effect and benefit a uniform current distribution at the interface.The fibrous nanostructure can efficiently interact with the polymeric matrix,providing rich hopping sites for fast Li+migration.Consequently,the obtained SPE enables a uniform Li deposition and long-term cycling performance in Li-metal batteries.This work reported an in situ formed SPE with both high polymerization degree and ionic conductivity,paving the way for designing high-performance SPEs with good comprehensive properties.

Poly(imine-amide)Hybrid Covalent Adaptable Networks via in situ Oxidation Polymerization

Polyimine represents a rapidly emerging class of readily accessible and affordable covalent adaptable networks(CANs)that have been extensively studied in the past few years.While being highly malleable and recyclable,the pioneering polyimine materials are relatively soft and not suitable for certain applications that require high mechanical performance.Recent studies have demonstrated the possibility of significantly improving polyimine properties by varying its monomer building blocks,but such component variations are usually not straightforward and can be potentially challenging and costly.Herein,we report an in situ oxidation polymerization strategy for preparation of mechanically strong poly(imine-amide)(PIA)hybrid CANs from simple amine and aldehyde monomers.By converting a portion of reversible imine bonds into high-strength amide linkages in situ,the obtained hybrid materials exhibit gradually improved Young’s modulus and ultimate tensile strength as the oxidation level increased.Meanwhile,the PIAs remain reprocessable and can be depolymerized into small molecules and oligomers similar as polyimine.This work demonstrates the great potential of the in situ transformation strategy as a new approach for development of various mechanically tunable CANs from the same starting building blocks.

Tailoring the interaction of covalent organic framework with the polyether matrix toward high-performance solid-state lithium metal batteries

Solid polymer electrolyte is one of the most promising avenues to construct next-generation energy storage systems with high energy density,high safety,and flexibility,yet the low ionic conductivity at room temperature and poor high-voltage tolerance have limited their practical applications.To address the above issues,we design and synthesize a highly crystalline,vinyl-functionalized covalent organic framework(V-COF)rationally grafted with ether-based segments through solvent-free in situ polymerization.V-COF can afford a fast Li+conduction highway along the one-dimensional nanochannels and improve the high-voltage stability of ether-based electrolytes due to the rigid and electrochemically stable networks.The as-formed solid-state electrolyte membranes demonstrate a superior ionic conductivity of 1.1×10^(−4)S cm^(−1)at 40℃,enhanced wide electrochemical window up to 5.0 V,and high Young's modulus of 92 MPa.The Li symmetric cell demonstrates ultralong stable cycling over 600 h at a current density of 0.1 mA cm^(−2)(40℃).The assembled solid-state Li|LiFePO4 cells show a superior initial specific capacity of 136 mAh g^(−1)at 1 C(1 C=170 mA g^(−1))and a high capacity retention rate of 84%after 300 cycles.This study provides a novel and scalable approach toward high-performance solid ether-based lithium metal batteries.

Chemically Modified Ordered Mesoporous Carbon/Polyaniline Composites for Electrochemical Capacitors

Chemically modified ordered mesoporous carbon CMK-3 materials were prepared by means of an easy wet-oxidative method in 2 mol/L nitric acid aqueous solution. A large amount of oxygen-containing functional groups were introduced onto the CMK-3 surface. Modified CMK-3（m-CMK-3） and aniline monomer were polymerized via an in situ chemical oxidative polymerization method. Morphological characterizations of m-CMK-3/PANI （polyaniline） composites were carried out via field emission scanning electron microscopy（SEM）. Their electrochemical properties were investigated with cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The m-CMK-3/PANI composites have excellent properties in capacitance, and the highest specific capacitance（SC） value was up to 489 F/g, suggesting their potential application in the electrode material for electrochemical capacitors.