Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteri...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.展开更多
Metal hydroxides (MAH) consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1-2 were surface-modified by γ-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilaned...Metal hydroxides (MAH) consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1-2 were surface-modified by γ-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene (LLDPE) composite, filled with 50% (mass fraction) of MAH modified by 5.0% (mass fraction) of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.展开更多
Nickel-based catalyst [N,N]NiBr2, in which [N,N] stands for N-(2,6-diisopropylphenyl)pyridine-2-carboxaldimine, shows high activity for ethylene polymerization in the presence of organoaluminum compounds under high et...Nickel-based catalyst [N,N]NiBr2, in which [N,N] stands for N-(2,6-diisopropylphenyl)pyridine-2-carboxaldimine, shows high activity for ethylene polymerization in the presence of organoaluminum compounds under high ethylene pressure to yield polyethylene characteristic of low molecular weight and highly branched chains. Toluene as the solvent is more in favor of catalyst activity, higher molecular weight and branched chains in polyethylene structure as compared to hexane solvent.展开更多
The synthesis route was investigated and optimized for the preparation of iminodiacetic acid-polyethylene glycol (IDA-PEG) for immobilized metal ion affinity partitioning in aqueous two-phase systems. IDA-PEG was synt...The synthesis route was investigated and optimized for the preparation of iminodiacetic acid-polyethylene glycol (IDA-PEG) for immobilized metal ion affinity partitioning in aqueous two-phase systems. IDA-PEG was synthesized from PEG in two steps by the reaction of iminodiacetic acid with a monosubstituted derivative of epichlorohydrin-activated PEG. The Cu2+ content combined with IDA-PEG was determined by atomic absorption spectrometry as 0.5 mol·mol^-1 (PEG). Furthermore, the affinity partitioning behavior of lactate dehydrogenase in polyethylene glycol/hydroxypropyl starch aqueous two-phase systems was studied to clarify the affinity effect of the Cu(Ⅱ)-IDA-PEG.展开更多
An in situ polymerization method was investigated to prepare long-branched polyethylene (LBPE) with ethylene alone and a single cocatalyst, methylalumoxane (MAO), by using a dual functional catalytic system containing...An in situ polymerization method was investigated to prepare long-branched polyethylene (LBPE) with ethylene alone and a single cocatalyst, methylalumoxane (MAO), by using a dual functional catalytic system containing late transition metal oligomerization catalyst and metal-locene copolymerization catalyst. The obtained long-branched polyethylene has the characteristics of low melting point, high activity and well-dispersed sequence distribution.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with flexibility,easy processability,low cost and especially strong ability to dissolve lithium salts have been regarded as promising alternatives to tradi...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with flexibility,easy processability,low cost and especially strong ability to dissolve lithium salts have been regarded as promising alternatives to traditional flammable liquid electrolytes in next-generation highsafety and high-energy-density lithium metal batteries.However,the inferior mechanical strength and thermostability of PEO-based SPEs will raise the lithium dendritic penetration issue,further leading to the short circuit in batteries.In this work,aiming at enhancing the interfacial stability against Li dendrites of PEO-based SPEs,poly(mphenylene isophthalamide)(PMIA)is introduced as a reinforcing phase for the rational design of PEO/PMIA composite electrolyte.Impressively,PMIA chain with meta-type benzene-amide linkages significantly improves the mechanical strength(1.60 MPa),thermal stability(260℃)and ability to inhibit the growth of lithium dendrites(>300 h at 0.1 mA·cm^(-2))of SPEs.Meanwhile,allsolid-state LiFePO_(4)‖PEO/PMlA‖Li cell demonstrates superior electrochemical performance in terms of high specific capacity(159.1 mAh·g^(-1)),remarkable capacity retention(82.2%after 200 cycles at 0.5 C)and excellent safety characteristics.No burning or explosion occurs under pressing,bending and cutting conditions.This work opens a new door in developing high-performance PEObased electrolytes for advanced all-solid-state lithium metal batteries.展开更多
Plasto-Foam brand,medium size of 30 mm thickness(black and green)commonly used polyethylene bags for preparing foods were selected from those available in local markets.The polyethylene bag samples were crushed into p...Plasto-Foam brand,medium size of 30 mm thickness(black and green)commonly used polyethylene bags for preparing foods were selected from those available in local markets.The polyethylene bag samples were crushed into pieces,ashed and then acid digested to determine the concentrations of heavy metals selected(Pb,Cr,Co and Cd)using Atomic Absorption spectrophotometer.All the polyethylene samples were tested positive for heavy metals.Concentrations of heavy metals in polyethylene bags ranged from 1080 ppm to 1725 ppm,76 ppm to 112 ppm,35 ppm to 52 ppm,18 ppm to 31 ppm for Pb,Cd,Cr and Co,respectively.Forty-eight posho(Ugali)samples were prepared and wrapped in these polyethylene bags and migration studies were carried out at 65°C and 80°C.The experimental data obtained were then compared to the modeled data using the models developed by Baner et al.,and Limm and Hollifield to determine which model was a better estimator.Model fitting was done based on Non-linear least square analysis using Microsoft EXCEL 2003.Diffusion and partition coefficients both between food and the contact material were also obtained by fitting experimental data to the model equation.The modeling approaching could best describe the experimental data of the measured contaminants.The study revealed that all polyethylene bags showed highest contaminant concentration(above USFDA limit)of Pb,Cd,Cr and Co,respectively confirming the potential health risk to individuals if continuously eat food thermally prepared in polyethylene bags.展开更多
Polyethylene oxide(PEO)-based solid-state electrolytes are considered ideal for electrolyte materials in solid-state lithium metal batteries(SSLMBs).However,practical applications are hindered by the lower conductivit...Polyethylene oxide(PEO)-based solid-state electrolytes are considered ideal for electrolyte materials in solid-state lithium metal batteries(SSLMBs).However,practical applications are hindered by the lower conductivity and poor interfacial stability.Here,we propose a strategy to construct a three-dimensional(3D)fiber network of metal-organic frameworks(MOFs).Composite solid electrolytes(CSEs)with continuous ion transport pathways were fabricated by filling a PEO polymer matrix in fibers containing interconnected MOFs.This 3D fiber network provides a fast Li+transport path and effectively improves the ionic conductivity(1.36×10^(-4) S·cm^(-1),30℃).In addition,the network of interconnected MOFs not only effectively traps the anions,but also provides sufficient mechanical strength to prevent the growth of Li dendrites.Benefiting from the advantages of structural design,the CSEs stabilize the Li/electrolyte interface and extend the cycle life of the Li-symmetric cells to 3000 h.The assembled SSLMBs exhibit excellent cycling performance at both room and high temperatures.In addition,the constructed pouch cells can provide an areal capacity of 0.62 mA·h·cm^(-2),which can still operate under extreme conditions.This work provides a new strategy for the design of CSEs with continuous structure and stable operation of SSLMBs.展开更多
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.
基金Project(20574020) supported by the National Natural Science Foundation of ChinaProject(20061001) supported by the Opening Project of the Key Laboratory of Polymer Processing Engineering, Ministry of Education, ChinaProject (20060106-2) supported by Guangdong Key Projects
文摘Metal hydroxides (MAH) consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1-2 were surface-modified by γ-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene (LLDPE) composite, filled with 50% (mass fraction) of MAH modified by 5.0% (mass fraction) of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.
文摘Nickel-based catalyst [N,N]NiBr2, in which [N,N] stands for N-(2,6-diisopropylphenyl)pyridine-2-carboxaldimine, shows high activity for ethylene polymerization in the presence of organoaluminum compounds under high ethylene pressure to yield polyethylene characteristic of low molecular weight and highly branched chains. Toluene as the solvent is more in favor of catalyst activity, higher molecular weight and branched chains in polyethylene structure as compared to hexane solvent.
基金Supported by the National Natural Science Foundation of China(No.29736180).
文摘The synthesis route was investigated and optimized for the preparation of iminodiacetic acid-polyethylene glycol (IDA-PEG) for immobilized metal ion affinity partitioning in aqueous two-phase systems. IDA-PEG was synthesized from PEG in two steps by the reaction of iminodiacetic acid with a monosubstituted derivative of epichlorohydrin-activated PEG. The Cu2+ content combined with IDA-PEG was determined by atomic absorption spectrometry as 0.5 mol·mol^-1 (PEG). Furthermore, the affinity partitioning behavior of lactate dehydrogenase in polyethylene glycol/hydroxypropyl starch aqueous two-phase systems was studied to clarify the affinity effect of the Cu(Ⅱ)-IDA-PEG.
基金This work was supported hy the National Natural Science Foundation of China and China Petroleum Corporation (Grant No. 29734141).
文摘An in situ polymerization method was investigated to prepare long-branched polyethylene (LBPE) with ethylene alone and a single cocatalyst, methylalumoxane (MAO), by using a dual functional catalytic system containing late transition metal oligomerization catalyst and metal-locene copolymerization catalyst. The obtained long-branched polyethylene has the characteristics of low melting point, high activity and well-dispersed sequence distribution.
基金financially supported by the Natural Science Foundation of Zhejiang Province(Nos.LY21E020005,2022C01173 and LD22E020006)China Postdoctoral Science Foundation(Nos.2020M671785 and 2020T130597)+1 种基金the National Natural Science Foundation of China(Nos.U20A20253,51777194,21972127 and 21905249)Zhejiang Provincial Special Support Program for High-level Talents(No.2020R51004)。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with flexibility,easy processability,low cost and especially strong ability to dissolve lithium salts have been regarded as promising alternatives to traditional flammable liquid electrolytes in next-generation highsafety and high-energy-density lithium metal batteries.However,the inferior mechanical strength and thermostability of PEO-based SPEs will raise the lithium dendritic penetration issue,further leading to the short circuit in batteries.In this work,aiming at enhancing the interfacial stability against Li dendrites of PEO-based SPEs,poly(mphenylene isophthalamide)(PMIA)is introduced as a reinforcing phase for the rational design of PEO/PMIA composite electrolyte.Impressively,PMIA chain with meta-type benzene-amide linkages significantly improves the mechanical strength(1.60 MPa),thermal stability(260℃)and ability to inhibit the growth of lithium dendrites(>300 h at 0.1 mA·cm^(-2))of SPEs.Meanwhile,allsolid-state LiFePO_(4)‖PEO/PMlA‖Li cell demonstrates superior electrochemical performance in terms of high specific capacity(159.1 mAh·g^(-1)),remarkable capacity retention(82.2%after 200 cycles at 0.5 C)and excellent safety characteristics.No burning or explosion occurs under pressing,bending and cutting conditions.This work opens a new door in developing high-performance PEObased electrolytes for advanced all-solid-state lithium metal batteries.
基金Project RU/CGS/GRG/15/10/10,the RUFORUM,Kampala,Uganda.The scientific responsibility is assumed by its authors.
文摘Plasto-Foam brand,medium size of 30 mm thickness(black and green)commonly used polyethylene bags for preparing foods were selected from those available in local markets.The polyethylene bag samples were crushed into pieces,ashed and then acid digested to determine the concentrations of heavy metals selected(Pb,Cr,Co and Cd)using Atomic Absorption spectrophotometer.All the polyethylene samples were tested positive for heavy metals.Concentrations of heavy metals in polyethylene bags ranged from 1080 ppm to 1725 ppm,76 ppm to 112 ppm,35 ppm to 52 ppm,18 ppm to 31 ppm for Pb,Cd,Cr and Co,respectively.Forty-eight posho(Ugali)samples were prepared and wrapped in these polyethylene bags and migration studies were carried out at 65°C and 80°C.The experimental data obtained were then compared to the modeled data using the models developed by Baner et al.,and Limm and Hollifield to determine which model was a better estimator.Model fitting was done based on Non-linear least square analysis using Microsoft EXCEL 2003.Diffusion and partition coefficients both between food and the contact material were also obtained by fitting experimental data to the model equation.The modeling approaching could best describe the experimental data of the measured contaminants.The study revealed that all polyethylene bags showed highest contaminant concentration(above USFDA limit)of Pb,Cd,Cr and Co,respectively confirming the potential health risk to individuals if continuously eat food thermally prepared in polyethylene bags.
基金support from the China Postdoctoral Science Foundation(Nos.2022TQ0173 and 2023M731922).
文摘Polyethylene oxide(PEO)-based solid-state electrolytes are considered ideal for electrolyte materials in solid-state lithium metal batteries(SSLMBs).However,practical applications are hindered by the lower conductivity and poor interfacial stability.Here,we propose a strategy to construct a three-dimensional(3D)fiber network of metal-organic frameworks(MOFs).Composite solid electrolytes(CSEs)with continuous ion transport pathways were fabricated by filling a PEO polymer matrix in fibers containing interconnected MOFs.This 3D fiber network provides a fast Li+transport path and effectively improves the ionic conductivity(1.36×10^(-4) S·cm^(-1),30℃).In addition,the network of interconnected MOFs not only effectively traps the anions,but also provides sufficient mechanical strength to prevent the growth of Li dendrites.Benefiting from the advantages of structural design,the CSEs stabilize the Li/electrolyte interface and extend the cycle life of the Li-symmetric cells to 3000 h.The assembled SSLMBs exhibit excellent cycling performance at both room and high temperatures.In addition,the constructed pouch cells can provide an areal capacity of 0.62 mA·h·cm^(-2),which can still operate under extreme conditions.This work provides a new strategy for the design of CSEs with continuous structure and stable operation of SSLMBs.
