Incombustible solid polymer electrolytes:A critical review and perspective

Since the advent of the solid-state batteries,employing solid polymer electrolytes(SPEs)to replace routine flammable liquid electrolytes is regarded to be one of the most promising solutions in pursing highenergy-density battery systems.SPEs with superior thermal stability,good processability,and high mechanical modulus obtain increasing attentions.However,SPE-based batteries are not impenetrable due to their decomposition and combustibility under extreme conditions.Researchers believe incorporating appropriate flame-retardant additives/solvents/fragments into SPEs can intrinsically reduce their flammability to solve the battery safety issues.In this review,the recent research progress of incombustible SPEs,with special emphasis on flame-retardant structural design,is summarized.Specifically,a brief introduction of flame-retardant mechanism,evaluation index for safety of SPEs,and a detailed overview of the latest advances on diverse-types SPEs in various battery systems are highlighted.The deep insight into thermal ru naway process,the free-standing incombustible GPEs,and the ratio nal design of pouch cell structures may be the main directions to motivate revolutionary next-generation for safety batteries.

Polymer dispersed ionic liquid electrolytes with high ionic conductivity for ultrastable solid-state lithium batteries

Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.

High-Performance Quasi-Solid-State Pouch Cells Enabled by in situ Solidification of a Novel Polymer Electrolyte

Conventional lithium-ion batteries(LIBs)with liquid electrolytes are challenged by their big safety concerns,particularly used in electric vehicles.All-solid-state batteries using solid-state electrolytes have been proposed to significantly improve safety yet are impeded by poor interfacial solid–solid contact and fast interface degradation.As a compromising strategy,in situ solidification has been proposed in recent years to fabricate quasi-solid-state batteries,which have great advantages in constructing intimate interfaces and cost-effective mass manufacturing.In this work,quasi-solid-state pouch cells with high loading electrodes(≥3 m Ah cm^(-2))were fabricated via in situ solidification of poly(ethylene glycol)diacrylate-based polymer electrolytes(PEGDA-PEs).Both single-layer and multilayer quasi-solid-state pouch cells(2.0 Ah)have demonstrated stable electrochemical performance over500 cycles.The superb electrochemical stability is closely related to the formation of robust and compatible interphase,which successfully inhibits interfacial side reactions and prevents interfacial structural degradation.This work demonstrates that in situ solidification is a facile and cost-effective approach to fabricate quasi-solid-state pouch cells with both excellent electrochemical performance and safety.

A UV cross-linked gel polymer electrolyte enabling high-rate and high voltage window for quasi-solid-state supercapacitors

Serving as a promising alternative to liquid electrolyte in the application of portable and wearable devices,gel polymer electrolytes(GPEs)are expected to obtain more preferable properties rather than just be satisfied with the merits of high safety and deformability.Here,an easy-operated method is employed to fabricate cross-linked composite polymer membranes used for GPEs assisted by UV irradiation,in which N-doped carbon quantum dots(N-CQDs)and TiO2are introduced as photocatalysts and additives to improve the performances of GPEs.Specifically,N-CQDs participate as a cross-linker to construct the inner porous structure,and TiO2nanoparticles serve as a stabilizer to improve the electrochemical stability of GPEs under high voltage(3.5 V).The excellent thermal and mechanical stability of the membrane fabricated in this work guarantee the safety of the supercapacitors(SCs).This GPE based SC not only exhibits prominent rate performance(105%capacitance retention at the current density of 40A g^(-1))and cyclic stability(85%at 1 A g^(-1)under 3.5 V after 20,000 cycles),but also displays remarkable energy density(42.88 Wh kg^(-1))with high power density(19.3 k W kg^(-1)).Moreover,the superior rate and cycling performances of the as-prepared GPE based flexible SCs under flat and bending state confirm the feasibility of its application in flexible energy storage devices.

High Water Resistance and Enhanced Mechanical Properties of Bio-Based Waterborne Polyurethane Enabled by in-situ Construction of Interpenetrating Polymer Network

In this study,acrylic acid was used as a neutralizer to prepare bio-based WPU with an interpenetrating polymer network structure by thermally induced free radical emulsion polymerization.The effects of the content of acrylic acid on the properties of the resulting waterborne polyurethane-poly(acrylic acid)(WPU-PAA)dispersion and the films were systematically investigated.The results showed that the cross-linking density of the interpenetrating network polymers was increased and the interlocking structure of the soft and hard phase dislocations in the molecular segments of the double networks was tailored with increasing the content of acrylic acid,leading to enhancement of the mechanical properties and water resistance of WPU-PAA films.Notably,with the increase in content of acrylic acid,the tensile strength,Young’s modulus,and toughness of the WPU-PAA-110 film increased by 3 times,and 8 times,and 2.4 times compared with WPU-PAA-80,respectively.The WPU-PAA-100 film showed the best water resistance,and the water absorption rate at 96 h was only 3.27%.This work provided a new design scheme for constructing bio-based WPU materials with excellent properties.

Preparation of Ultrafine Water-soluble Polymers Nanofiber Mats via Electrospinning

A series of water-soluble polymers such as poly（ethylene oxide）（PEO）, polyacrylamide（PAM） and poly（vinyl pyrrilidone）（PVP） was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant. The effects of solution properties on the electrospinning of PEO, PAM and PVP solutions were investigated. The viscosity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the morphology and diameter size of the fibers. The viscosity of the solution was measured on a modular compact rheometer. The morphology and the diameter size distribution of the fibers were observed under an environmental scanning electron microscope（ESEM）. The results show that the diameters of the nanofibers electro spun from the solutions of these water soluble polymers were uniform and less than 300 nm.

Application of Water-Soluble Polymer in Dewatering of Fine Coal

The addition of water-soluble polymer to a fine coal slurry to enhance dewatering process is considered to be one of the most effective ways of solving the problems of dewatering of fine coal. A series of tests are conducted with a vacuum dewatering apparatus to study the effects of various factors such as the species of polymer, polymer dosage and its ways of addition, and the pH of fine coal slurry on filtrating and dewatering of fine coal.

SCIENTIFIC PRINCIPLES FOR MODIFICATION OF WATER-SOLUBLE POLYMERS. FORMATION OF MACROMOLECULAR COMPLEXES

The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.

XPS Study on Water-Soluble Polymer Surfactant Film

By means of changing the detection angle, the molecular conformation of a new type of polymer surfactant, acrylamide-poly(oxyethykene alkyl ether)acrylate-anionic monomer random copolymer, was studied by x-ray photoelectron spectroscopy(XPS) in detail.

Tailoring Practically Accessible Polymer/Inorganic Composite Electrolytes for All-Solid-State Lithium Metal Batteries:A Review

Solid-state electrolytes(SSEs)are widely considered the essential components for upcoming rechargeable lithium-ion batteries owing to the potential for great safety and energy density.Among them,polymer solid-state electrolytes(PSEs)are competitive candidates for replacing commercial liquid electrolytes due to their flexibility,shape versatility and easy machinability.Despite the rapid development of PSEs,their practical application still faces obstacles including poor ionic conductivity,narrow electrochemical stable window and inferior mechanical strength.Polymer/inorganic composite electrolytes(PIEs)formed by adding ceramic fillers in PSEs merge the benefits of PSEs and inorganic solid-state electrolytes(ISEs),exhibiting appreciable comprehensive properties due to the abundant interfaces with unique characteristics.Some PIEs are highly compatible with high-voltage cathode and lithium metal anode,which offer desirable access to obtaining lithium metal batteries with high energy density.This review elucidates the current issues and recent advances in PIEs.The performance of PIEs was remarkably influenced by the characteristics of the fillers including type,content,morphology,arrangement and surface groups.We focus on the molecular interaction between different components in the composite environment for designing high-performance PIEs.Finally,the obstacles and opportunities for creating high-performance PIEs are outlined.This review aims to provide some theoretical guidance and direction for the development of PIEs.

Functional additives for solid polymer electrolytes in flexible and high-energy-density solid-state lithium-ion batteries

Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compatibility.However,the commercialization of SPEs remains challenging for flexible and high-energy-density LIBs.The incorporation of functional additives into SPEs could significantly improve the electrochemical and mechanical properties of SPEs and has created some historical milestones in boosting the development of SPEs.In this study,we review the roles of additives in SPEs,highlighting the working mechanisms and functionalities of the additives.The additives could afford significant advantages in boosting ionic conductivity,increasing ion transference number,improving high-voltage stability,enhancing mechanical strength,inhibiting lithium dendrite,and reducing flammability.Moreover,the application of functional additives in high-voltage cathodes,lithium-sulfur batteries,and flexible lithiumion batteries is summarized.Finally,future research perspectives are proposed to overcome the unresolved technical hurdles and critical issues in additives of SPEs,such as facile fabrication process,interfacial compatibility,investigation of the working mechanism,and special functionalities.

Modification of High Performances of Polymer Cement Concrete

The workability,mechanical and physical properties are investigated,based on the requirements of the high properties of polymer cement concrete (PCC).The research results reveal that PCC is greatly improved and strengthened by adding appropriate polymer.At polymer/cement=0-0.15,its porosity decreases greatly due to the improved pore structure.The weak area at interface is strengthened.The workability,mechanical and physical properties are obviously enhanced with the proportion of polymer and cement.At the same time the properties are much improved under the adequate curing conditions and admixture (0-10%).

HETEROAROMATIC POLYMERS—HIGH TEMPERATURE POLYPYRROLONES DERIVED FROM 2,6-BIS(3',4'-DIAMINOPHENYL)-4-BIPHENYLPYRIDINE AND VARIOUS AROMATIC DIANHYDRIDES

A new type of aromatic tetraarnine containing biphenyl moiety in the side chain was synthesized via a modified Chichibabin＇s reaction. 3-Nitro-4-acetamidoacetophenone was reacted with 4-phenyl benzaldehyde in the presence of ammonium acetate to obtain 2,6-bis（3＇,4＇-diaminophenyl）-4-biphenyl pyridine （DPPA）. A series of polypyrrolones （PPys） were prepared using tetraamine and various aromatic dianhydrides via a two-step cyclization procedure. All the PPys show excellent high temperature stabilities with the initial decomposition temperatures of 530-549℃ and residual weight ratio of 49%-80% at 750℃ in nitrogen. The polymers exhibit no apparent glass transition temperatures （Tgs） except PPy-1 （Tg= 327℃）, which is derived from tetraamine DPPA and 2,2-bis[4-（3＇,4＇-dicarboxyphenoxy）-phenyl]propane dianhydride （BPADA）. In addition, the polymers have acceptable mechanical properties with the tensile strength of 65-94 MPa. The PPy films show excellent hydrolysis-resistance in alkaline aqueous medium and could maintain most of the properties even after boiling in 10% aqueous sodium hydroxide solution for a week.

Ultrathin organic polymer with p-πconjugated structure for simultaneous photocatalytic disulfide bond generation and CO_(2)reduction

Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.

Highly Thermally Conductive Polymer/Graphene Composites with Rapid Room‑Temperature Self‑Healing Capacity

Composites that can rapidly self-healing their structure and function at room temperature have broad application prospects.However,in view of the complexity of composite structure and composition,its self-heal is facing challenges.In this article,supramolecular effect is proposed to repair the multistage structure,mechanical and thermal properties of composite materials.A stiff and tough supramolecular frameworks of 2-[[(butylamino)carbonyl]oxy]ethyl ester(PBA)–polydimethylsiloxane(PDMS)were established using a chain extender with double amide bonds in a side chain to extend prepolymers through copolymerization.Then,by introducing the copolymer into a folded graphene film(FGf),a highly thermally conductive composite of PBA–PDMS/FGf with self-healing capacity was fabricated.The ratio of crosslinking and hydrogen bonding was optimized to ensure that PBA–PDMS could completely self-heal at room temperature in 10 min.Additionally,PBA–PDMS/FGf exhibits a high tensile strength of 2.23±0.15 MPa at break and high thermal conductivity of 13±0.2 W m^(−1)K^(−1);of which the self-healing efficiencies were 100%and 98.65%at room temperature for tensile strength and thermal conductivity,respectively.The excellent self-healing performance comes from the efficient supramolecular interaction between polymer molecules,as well as polymer molecule and graphene.This kind of thermal conductive self-healing composite has important application prospects in the heat dissipation field of next generation electronic devices in the future.

Functional copolymer binder for nickel-rich cathode with exceptional cycling stability at high temperature through coordination interaction

Nickel-rich layered oxide LiNi_(1-x-y)Co_(x)Al_yO_(2)(NCA) with high theoretical capacity is a promising cathode material for the next-generation high-energy batteries.However,it undergoes a rapid capacity fading when operating at high temperature due to the accelerated cathode/electrolyte interfacial reactions and adhesive efficacy loss of conventional polyvinylideneffuoride(PVdF) binder.Herein,poly(acrylonitrile-co-methyl acrylate) copolymer is designed with electron-rich-C≡N groups as a novel binder for LiNi_(0.8)Co_(0.1)Al_(0.1)O_(2) cathode at high temperature.The electron-rich-C≡N groups are able to coordinate with the active Ni^(3+) on the surface of NCA,alleviating electrolyte decomposition and cathode structure degradation.Moreover,the strong adhesive ability is conducive to maintain integrity of electrodes upon cycling at 55℃.In consequence,the NCA electrodes with this functional binder display improved cycling stability(81.5% capacity retention after 100 cycles) and rate performance at 55℃.

A cerium-doped NASICON chemically coupled poly(vinylidene fluoride-hexafluoropropylene)-based polymer electrolyte for high-rate and high-voltage quasi-solid-state lithium metal batteries

The isolated inorganic particles within composite polymer electrolytes(CPEs) are not correlated to the Li^(+)transfer network,resulting in the polymer dominating the low ionic conductivity of CPEs.Therefore,we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors(NASICON)Na_(1.3+x)Al_(0.3)Ce_(x)Ti_(1.7-x)(PO_(4))_(3)(NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide(LiTFSI) matrix.A strong interaction between Ce^(3+)from NCATP and TFSI-anion from the polymer matrix contributes to the fast Li+transportation at the interface.The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0^(-3) S cm^(-1) and a Li^(+) transference number of 0.88.A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm^(-2) presents outstanding cycling stability over 2000 h at 25℃.The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO_(4) at 2 C after 400 cycles and Li/CPEs/LiCoO_(2) at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g^(-1) at 25℃,respectively.

Advancements in the preparation of high-performance liquid chromatographic organic polymer monoliths for the separation of small-molecule drugs

The various advantages of organic polymer monoliths, including relatively simple preparation processes,abundant monomer availability, and a wide application range of pH, have attracted the attention of chromatographers. Organic polymer monoliths prepared by traditional methods only have macropores and mesopores, and micropores of less than 50 nm are not commonly available. These typical monoliths are suitable for the separation of biological macromolecules such as proteins and nucleic acids, but their ability to separate small molecular compounds is poor. In recent years, researchers have successfully modified polymer monoliths to achieve uniform compact pore structures. In particular, microporous materials with pores of 50 nm or less that can provide a large enough surface area are the key to the separation of small molecules. In this review, preparation methods of polymer monoliths for high-performance liquid chromatography, including ultra-high cross-linking technology, post-surface modification, and the addition of nanomaterials, are discussed. Modified monolithic columns have been used successfully to separate small molecules with obvious improvements in column efficiency.

High pressure and high temperature induced polymerization of C60 quantum dots

We synthesized C60 quantum dots(QDs) with a uniform size by a modified ultrasonic process and studied its polymerization under high pressure and high temperature(HPHT).Raman spectra showed that a phase assemblage of a dimer(D) phase(62 vol%) and a one-dimensional chain orthorhombic(O) phase(38 vol%) was obtained at 1.5 GPa and 300℃.At 2.0 GPa and 430℃,the proportion of the O phase increased to 46 vol%,while the corresponding D phase decreased to 54 vol%.Compared with bulk and nanosized C60,C60 QDs cannot easily form a high-dimensional polymeric structure.This fact is probably caused by the small particle size,orientation of the disordered structure of C60 QDs,and the barrier of oxide function groups between C60 molecules.Our studies enhance the understanding of the polymerization behavior of low-dimension C60 nanomaterials under HPHT conditions.