Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resu...Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resulting in a large amount of radioactive waste PFPE lubricants annually.Moreover,radioactive waste PFPE lubricants are difficult to be effectively treated due to their high stability,the risk of possible leakage of radionuclides,and hypertoxic fluorine-containing by-products.In this study,without any precedent,a strategy of Mn O_(2)-catalyzed decomposition and Na_(2)CO_(3)-immobilized conversion was proposed for PFPE lubricant decomposition and fluorine immobilization simultaneously based on the Lewis acid-base and oxygen vacancies concept.A high fluorine conversion efficiency of 95.4%was achieved.Meanwhile,the mechanism of decomposition suggested that Mn O_(2)mainly provided Lewis acid sites and attacked the(basic)fluorine or oxygen atoms in PFPE molecules.The decomposition of PFPE chains was proceed down and volatile fluorine-containing gas was released by partial electron transfer,intramolecular disproportionation reaction,and unzipping fashion.Subsequently,gas by-products could be further oxidized and then immobilized into fluoride salts by carbonate solid absorbents.Overall,this study provides a simple,safe,and potentially practical strategy for the harmless conversion of refractory fluorinated organic wastes,especially perfluoropolymers.展开更多
Perfluoropolyether(PFPE)is a promising material for protective coatings on Li metal anodes due to its chemical inertness and minimal swelling in electrolytes.However,a conventional PFPE coating with poor ionic conduct...Perfluoropolyether(PFPE)is a promising material for protective coatings on Li metal anodes due to its chemical inertness and minimal swelling in electrolytes.However,a conventional PFPE coating with poor ionic conductivity and mechanical stability is still not satisfactory for long-term cycling of Li anodes.Here,we design and synthesize an adaptive and high-conductivity supramolecular polymer(PFPE-EG-I).This polymer is constructed from PFPE chains,ethylene glycol(EG)segments,and hydrogen-bonding moieties derived from isophoronediisocyanate,serving as a multifaceted artificial solid electrolyte interphase(SEI).The incorporated EG segments enhance the Li+conductivity of the SEI,and the hydrogen-bonding units introduce a dynamic self-adaptive behavior to the polymer matrix.A solution-processed PFPE-EG-I coating is demonstrated to promote uniform Li deposition and mitigate side reactions between Li and the electrolyte.Consequently,this leads to enhanced coulombic efficiency and prolonged cycle longevity in lithium metal batteries(LMBs).The innovative design of this multifunctional artificial SEI offers a promising avenue for the realization of dendrite-free Li anodes,paving the way for the advancement of high-performance LMBs.展开更多
基金Sichuan Science and Technology Program (No.2021YJ0482)the Fundamental Research Funds for the Central Universities (No.2021SCU12087)。
文摘Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resulting in a large amount of radioactive waste PFPE lubricants annually.Moreover,radioactive waste PFPE lubricants are difficult to be effectively treated due to their high stability,the risk of possible leakage of radionuclides,and hypertoxic fluorine-containing by-products.In this study,without any precedent,a strategy of Mn O_(2)-catalyzed decomposition and Na_(2)CO_(3)-immobilized conversion was proposed for PFPE lubricant decomposition and fluorine immobilization simultaneously based on the Lewis acid-base and oxygen vacancies concept.A high fluorine conversion efficiency of 95.4%was achieved.Meanwhile,the mechanism of decomposition suggested that Mn O_(2)mainly provided Lewis acid sites and attacked the(basic)fluorine or oxygen atoms in PFPE molecules.The decomposition of PFPE chains was proceed down and volatile fluorine-containing gas was released by partial electron transfer,intramolecular disproportionation reaction,and unzipping fashion.Subsequently,gas by-products could be further oxidized and then immobilized into fluoride salts by carbonate solid absorbents.Overall,this study provides a simple,safe,and potentially practical strategy for the harmless conversion of refractory fluorinated organic wastes,especially perfluoropolymers.
基金National Natural Science Foundation of China(grant no.22075164)Fundamental Research Funds for the Central Universities,Southwest Jiaotong University(grant no.2682023CX005).
文摘Perfluoropolyether(PFPE)is a promising material for protective coatings on Li metal anodes due to its chemical inertness and minimal swelling in electrolytes.However,a conventional PFPE coating with poor ionic conductivity and mechanical stability is still not satisfactory for long-term cycling of Li anodes.Here,we design and synthesize an adaptive and high-conductivity supramolecular polymer(PFPE-EG-I).This polymer is constructed from PFPE chains,ethylene glycol(EG)segments,and hydrogen-bonding moieties derived from isophoronediisocyanate,serving as a multifaceted artificial solid electrolyte interphase(SEI).The incorporated EG segments enhance the Li+conductivity of the SEI,and the hydrogen-bonding units introduce a dynamic self-adaptive behavior to the polymer matrix.A solution-processed PFPE-EG-I coating is demonstrated to promote uniform Li deposition and mitigate side reactions between Li and the electrolyte.Consequently,this leads to enhanced coulombic efficiency and prolonged cycle longevity in lithium metal batteries(LMBs).The innovative design of this multifunctional artificial SEI offers a promising avenue for the realization of dendrite-free Li anodes,paving the way for the advancement of high-performance LMBs.
