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Boosting reversible charging of Li-ion batteries at low temperatures by a synergy of propylene carbonate-based electrolyte and defective graphite

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Nano Research 2024年第3期17卷 1491-1499页

作者： Yingqiang Wu Jiao Zhang Jinli Liu Li Sheng Bo Zhang Limin Wang Siqi Shi Li Wang Hong Xu Xiangming He Institute of Nuclear and New Energy Technology Tsinghua UniversityBeijing 100084China State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied ChemistryChinese Academy of Sciences(CAS)Changchun 130022China China National Quality Supervision and Inspection Center for Industrial Explosive Materials Nanjing University of Science and TechnologyNanjing 210094China School of Materials Science and Engineering Materials Genome InstituteShanghai UniversityShanghai 200444China

propylene carbonate(PC)-based electrolytes have exhibited significant advantages in boosting the low-temperature discharging of graphite-based Li-ion batteries.However,it is still unclear whether they can improve the charging property and suppress lithium plating.Studying this topic is challenging due to the problem of electrochemical compatibility.To overcome this issue,we introduced graphite with phase defects.The results show that the pouch-type full batteries using PC-based electrolyte exhibit steady performance over 500 cycles and can be reversibly charged over 30 times at-20℃ with an average Coulombic efficiency of 99.95%,while the corresponding value for the conventional ethylene carbonate(EC)-based electrolyte sample is only 31.20%.This indicates that the use of PC-based electrolyte significantly suppresses lithium plating during low-temperature charging.We further demonstrate that the improved performance is mainly attributed to the unique solvation structure,where PF-6more anions participate in solvation,leading to the formation of a stable F-rich solid state electrolyte interface on the graphite surface and a lower reduction tendency of Li+ions.This work inspires new ideas for the design of PC-based electrolytes for low-temperature charging and fast-charging batteries.

关键词： lithium-ion batteries graphite propylene carbonate low-temperature charging

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Additives to propylene carbonate-based electrolytes for lithium-ion capacitors

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Rare Metals 2022年第4期41卷 1304-1313页

作者： Peng-Lei Wang Xian-Zhong Sun Ya-Bin An Xiong Zhang Chang-Zhou Yuan Shuang-Hao Zheng Kai Wang Yan-Wei Ma Institute of Electrical Engineering Chinese Academy of SciencesBeijing 100190China University of Chinese Academy of Sciences Beijing 100049China Institute of Electrical Engineering and Advanced Electromagnetic Drive Technology Qilu ZhongkeJinan 250013China School of Materials Science&Engineering University of JinanJinan 250022China State Key Laboratory of Catalysis Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China Dalian National Laboratory for Clean Energy Chinese Academy of SciencesDalian 116023China

Nowadays,lithium-ion capacitors(LICs) have become a type of important electrochemical energy storage devices due to their high power and long cycle life characteristics with fast response time.As one of the essential components of LICs,the electrolytes not only provide the anions and cations required during charge and discharge processes,but also supply the liquid environment for ions to migrate between anodes and cathodes in LIC cells.It is well accepted that propylene carbonate(PC) cannot be used as a single solvent for Li-ion electrolyte due to the failure to form stable SEI film on graphite surface.In this work,the compatibility of PC-based electrolyte with commercial soft carbon anode and activated carbon cathode has been validated by using the laminated pouch LIC cells.The effects of additives on the electrochemical properties of PC-based LICs have been systematically investigated.Ethylene sulfite(ES) was proved to be an effective additive to promote capacity retention at high C-rate,which is superior to vinylene carbonate and fluoroethylene carbonate.The addition of 5 wt% ES plays an important role in reducing internal resistance,as well as improving electrochemical stability and low-temperature performances.This study is expected to be beneficial to explore robust electrolyte/additive combinations for LICs to reduce the internal resistance and to improve the lowtemperature performances.

关键词： Lithium-ion capacitors propylene carbonate Li-ion electrolyte Ethylene sulfite Fluoroethylene carbonate Lithium bis(fluorosulfonyl)imide

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Direct synthesis of propylene carbonate from propylene and carbon dioxide catalyzed by quaternary ammonium heteropolyphosphatotungstate–TBAB system

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Journal of Energy Chemistry 2015年第3期24卷 353-358页

作者： Gongda Zhao Yi Zhang Hengyun Zhang Jun Li Shuang Gao Dalian Institute of Chemical Physics Chinese Academy of SciencesDalian National Laboratory for Clean Energy State Key Laboratory of Fine Chemicals Dalian University of Technology University of Chinese Academy of Sciences

In this paper,we have developed a highly efficient method for the direct preparation of propylene carbonate from propylene and carbon dioxide（CO2） using quaternary ammonium heteropolyphosphatotungstate–quaternary ammonium halide catalytic system with anhydrous hydrogen peroxide as an oxidant through one-pot two-step process.The effects of the amount of tetrabutylammonium bromide（TBAB）,the concentration of hydrogen peroxide and other reaction conditions were investigated.The catalyst system gave an optimum propylene oxide yield（91%） at75°C in oxidation step and the highest propylene carbonate yield（99%） at 140°C and 3.0 MPa in cycloaddition step.Based on the results,a reaction mechanism has been proposed.

关键词： quaternary ammonium heteropolyphosphatotungstate propylene carbonate carbon dioxide tetrabutylammonium bromide

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Color and Gloss Changes of a Lignin-Based Polyurethane Coating under Accelerated Weathering

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Journal of Renewable Materials 2024年第2期12卷 305-323页

作者： Fatemeh Hassani Khorshidi Saeed Kazemi Najafi Farhood Najafi Antonio Pizzi Dick Sandberg Rabi Behrooz Department of Wood Science and Technology Faculty of Natural ResourcesTarbiat Modares UniversityTehranIran Department of Resin and Additives Institute for Color Science and TechnologyP.O.Box 16765-654TehranIran LERMAB University of LorraineBlvd des AiguillettesNancy54000France Wood Science and Engineering LuleåUniversity of TechnologySkellefteåSweden

The purpose of this research study was to investigate the properties of polyurethane coatings based on lignin nano-particles.For this purpose,the prepared coatings were applied to pine wood surfaces and weathered artificially.Subsequently,color and gloss of the coatings were measured before and after the weathering test.Field emission scanning electron microscopy(FE-SEM)micrographs prepared from the coatings showed that the average size of nano-particles in the polyurethane substrate was approximately 500 nm.Nuclear magnetic resonance(13C-NMR)spectroscopy showed that strong urethane bonds were formed in the nano-lignin-based polyurethane.Differential calorimetric analysis(DSC)test revealed that the glass-transition temperature(Tg)of lignin nanoparticles modified with diethylenetriamine(DETA)was 112.8℃ and Tg of lignin nano-particles modified with ethylenediamine(EDA)was 102.5℃,which is lower than the Tg of un-modified lignin(114.6℃)and lignin modified with DETA(126.8℃)and lignin modified with EDA(131.3℃).The coatings modified with lignin nano-particles had a greater change in gloss.The lignin nano-particles in the modified coating are trapping hydroxyl radicals which reduces photoactivity and yellowing of the polyurethane by about 3 times compared to unmodified polyurethane coatings.After weathering test,the nano-lignin-based coating had a rougher surface with a lower contact angle(0.78°)compared to the unmodified polyurethane coating(0.85°).

关键词： Amination propylene carbonate lignin biopolymer polyurethane coating polyol UN SDG 13

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Polarity Effects of propylene carbonate on Breakdown Strength in Microsecond Range

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Chinese Journal of Chemical Physics 2015年第5期28卷 -页

作者： Zhen Wang Zi-cheng Zhang Jian-de Zhang College of Opto-electronic Science and Engineering National University of Defense Technology Changsha 410073 China

We investigate the polarity effects of the propylene carbonate on the breakdown voltage using the needle-plate electrodes with gaps of 0.5, 1.0, and 2.0 mm. The devices used in this study involve a compact capacitive-energy-storage pulse power source with charging time varying from 5 ms to 20 ms and a test cell with the needle-plate electrodes. The breakdown voltage is recorded by a digital oscilloscope for each gap. The results of these three groups indicate that the positive breakdown voltage is higher than the negative one and the breakdown voltage of the PC increases with the ascending electrode gap. In addition, a simulation is conducted to support this experiment. Some explanations about the polarity effect of the PC are also given.

关键词： Breakdown strength propylene carbonate Polarity effect

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A review on transesterification of propylene carbonate and methanol for dimethyl carbonate synthesis

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Carbon Resources Conversion 2019年第3期2卷 198-212页

作者： Wenjie Deng Lei Shi Jie Yao Zhigang Zhang Key Laboratory on Resources Chemicals and Materials of Ministry of Education Shenyang University of Chemical TechnologyShenyang 110142China Institute of Industrial Chemistry and Energy Technology Shenyang University of Chemical TechnologyShenyang 110142China College of Applied Chemistry Shenyang University of Chemical TechnologyShenyang 110142China

Dimethyl carbonate(DMC)is widely applied in various fields according to its outstanding physico-chemical properties,especially as a solvent in electrolyte of lithium-ion batteries.More than 90%DMC in China is industrially produced from the propylene carbonate(PC)and methanol(MeOH)route because it is an environmentally friendly and highly efficient process.This review summarizes different DMC production technologies,homogeneous and heterogeneous catalysts,catalytic mechanisms,reaction kinetics and engineering,with particular focus on the relationship between catalyst preparation and catalytic performances.The advantages and disadvantages of various catalysts are categorically compared.Homogeneous catalysts are highly efficient but prone to deactivate and are difficult to separate.Heterogeneous catalysts are easy to separate and have the promising future in industrial application,but their low catalytic efficiency is still the critical bottleneck.From process aspect,the catalytic distillation technology would be promising to overcome the efficiency problem of solid catalysts.

关键词： Dimethyl carbonate propylene carbonate Transesterification Catalysts Catalytic mechanism

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Adsorption of propylene carbonate on the LiMn2O4(100)surface investigated by DFT+U calculations

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Chinese Physics B 2021年第3期30卷 515-518页

作者：胡伟罗文崴王鹤文欧阳楚英 Department of Physics Laboratory of Computational Materials PhysicsJiangxi Normal UniversityNanchang 330022China College of Chemistry and Chemical Engineering Hubei Key Laboratory for Processing and Application of Catalytic MaterialsHuanggang Normal UniversityHuanggang 438000China

Understanding the mechanism of the interfacial reaction between the cathode material and the electrolyte is a significant work because the interfacial reaction is an important factor affecting the stability,capacity,and cycling performance of Li-ion batteries.In this work,spin-polarized density functional theory calculations with on-site Coulomb energy have been employed to study the adsorption of electrolyte components propylene carbonate(PC)on the LiMn2O4(100)surface.The findings show that the PC molecule prefers to interact with the Mn atom on the LiMn2O4(100)surface via the carbonyl oxygen(Oc),with the adsorption energy of−1.16 eV,which is an exothermic reaction.As the adsorption of organic molecule PC increases the Mn atoms coordination with O atoms on the(100)surface,the Mn3+ions on the surface lose charge and the reactivity is substantially decreased,which improves the stability of the surface and benefits the cycling performance.

关键词： Li-ions batteries electrolyte density functional theory surface propylene carbonate

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Activation of Carbon Dioxide and Synthesis of propylene carbonate

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Chinese Chemical Letters 2002年第11期13卷 1047-1050页

作者： Ying Ju ZHANG Yue E FENG Yu Zhen PAN Ren HE State Key Laboratory of Fine Chemicals Dalian University of TechnologyDalian 116012

Cycloaddition of carbon dioxide and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine (TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine. Comparing different catalysts of diverse metals, (t-Bu)4PcMg is more active than (t-Bu)4PcFe. But (t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction. Moreover, the yield will increase as the temperature increases.

关键词： Cycloaddition reaction carbon dioxide propylene oxide propylene carbonate tetra- tert-butyl metal phthalocyanine.

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Catalytic Formation of propylene carbonate from Supercritical Carbon Dioxide/propylene Oxide Mixture

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Chinese Chemical Letters 2000年第7期11卷 589-592页

作者： Xiao Bing LU Yu Zhen PAN Dong Feng JI Ren HE(Laboratory of Comprehensive utilization for carbonaceous resources, Dalian University of Technology, Dalian 116012) Lab. Compreh. Utiliz. C. Dalian University of Technology Dalian 116012 China

propylene carbonate was synthesized from supercritical carbon dioxide (SC-CO2)/ propylene oxide mixture with phthalocyaninatoaluminium chloride (ClAlPc)/ tetrabutylstmmonium bromide (n-Bu4NBr) as catalyst. The high rate of reaction was attributed to rapid diffusion and the high miscibility of propylene oxide in SC-CO2 under employed conditions. Various reaction periods present different formation rate of propylene carbonate, mainly due to the existence of phase change during the reaction. The experimental results demonstrate that SC-CO2 could be used as not only an environmentally benign solvent but also a carbon precursor in synthesis.

关键词： supercritical carbon dioxide propylene oxide propylene carbonate cycloaddition reaction

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Electrocatalytic Synthesis of propylene carbonate from CO_2 and propylene Oxide

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Chemical Research in Chinese Universities 2011年第2期27卷 300-303页

作者： ZHANG Li WANG Huan LI Rui-na CHEN Bao-li LU Jla-xing Shanghai Key Laboratory of Green Chemistry and Chemical Process Department of Chemistry East China Normal University Shanghai 200062 P. R. China Advanced Analysis and Measurement Center Anhui University of Technology Ma＇anshan 230042 P. R. China

The electrocatalytic synthesis of propylene carbonate（PC） from CO2 and propylene oxide（PO） was studied under mild conditions（PCO2=1.01×105 Pa, t=25 ℃）. Influences of solvents, supporting electrolytes, the passed charge, the nature of electrodes and the current density（j） on the yield of PC were investigated to optimize the electrolytic conditions, with the maximal yield to be 46.2%, the selectivity of propylene carbonate is 100%. The reduction of propylene oxide in the absence and presence of CO2 was examined by cyclic voltammetry. The mechanism of the reaction initiated by the synergistic effect of halides ions of supporting electrolytes with nucleophilicity and the metal ions from scarification anode with Lewis acid acidity was proposed on the basis of our results.

关键词： CO2 Electrocatalytic synthesis propylene carbonate propylene oxide Halide ion

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