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Additives strategies to improving cycling stability of Li metal batteries by modifying electrode electrolyte interphases

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Progress in Natural Science:Materials International 2024年第2期34卷 338-344页

作者： Yuan Li Pengfei Huang Chunyu Cui Xiaoyuan Ma Li Chen Zekun Li Linhai Li Yuhong Tian School of biological and chemical Engineering Guangxi University of Science and Technology School of College of Chemistry and chemical Engineering Hunan University Isky Future Energy institute

Li metal batteries（LMBs） have attracted much attention due to the ultra-high theoretical capacity of the Li metal anode（LMA）.However,the uncontrollable dendrites growth and low coulombic efficiency hinder their practical ***,we explore 3,5-difluoropyridine（2F-BD） as a novel electrolyte additive to enable highperformance *** 2F-BD additive participates in and modifies the solvation structure of Li ions by reducing the coordinated number of PF6-at the electrode surface,leading to the formation of a LiF and Li3N-rich solid electrolyte interphase（SEI）.The LiF component increases the robustness of SEI and suppresses the formation of Li dendrites,while the Li3N component facilitates the transportation and reaction kinetics of Li *** a result,the Li‖Li symmetric cell presents a stable cycling performance of up to 500 h at a current density of 1 mA *** coupling with LiFePO4cathode,the obtained full cell achieves high specific capacities of 106.06 mA h g-1and 84.98 mA h g-1at 2.55 mA cm-2and 5.10 mA cm-2,respectively,and maintains a high capacity retention of84.0% after 1000 cycles at 0.13 mA cm-2,with an average cycling CE of 99.58%.

关键词： Li metal batteries Li dendrites Electrolyte additive

A projected Newton algorithm based on chemically allowed interval for chemical equilibrium computations

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Frontiers of chemical Science and Engineering 2024年第3期18卷 25-37页

作者： Hongbin Lu Shaohui Tao Xiaoyan Sun Li Xia Shuguang Xiang institute of Process systems Engineering College of Chemical EngineeringQingdao University of Science and TechnologyQingdao266042China

The chemical equilibrium equations utilized in reactive transport modeling are complex and nonlinear,and are typically solved using the Newton-Raphson *** this algorithm is known for its quadratic convergence near the solution,it is less effective far from the solution,especially for ill-conditioned *** such cases,the algorithm may fail to converge or require excessive *** address these limitations,a projected Newton method is introduced to incorporate the concept of *** method constrains the Newton step by utilizing a chemically allowed interval that generates feasible descending ***,we utilize the positive continuous fraction method as a preconditioning technique,providing reliable initial values for solving the *** numerical results are compared with those derived using the regular Newton-Raphson method,the Newton-Raphson method based on chemically allowed interval updating rules,and the bounded variable least squares method in six different test *** numerical results highlight the robustness and efficacy of the proposed algorithm.

关键词： chemical equilibrium reactive transport modeling numerical methods projected Newton method

Controllable Ring-opening Polymerization ofδ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD systems

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Chinese Journal of Polymer Science 2024年第8期42卷 1103-1110页

作者： Xin-Yu Liu Liang Zhu Su-Yun Jie Bo-Geng Li State Key Laboratory of chemical Engineering College of Chemical and Biological EngineeringZhejiang UniversityHangzhou 310058China

Due to their excellent biocompatibility and biodegradability,aliphatic polyesters are widely used in the biomedical,packaging and agricultural fields,which are usually accessed by the ring-opening polymerization(ROP)of lactones and the catalysts particularly play an important *** a series of quinolinyl-urea catalysts have been synthesized via the reaction between isocyanate and aminoquinoline with an amino group at different substitution positions and *** combination with 7-methyl-1,5,7-triazabicyclo[4,4,0]dec-5-ene(MTBD)as a cocatalyst and benzyl alcohol(BnOH)as an initiator,1-(3,5-bis(trifluoromethyl)phenyl)-3-(quinolin-3-yl)urea(3-QU)was observed to be most active for the ROP ofδ-valerolactone(δ-VL).The polymerization conditions were optimized by varying the type of organic base,catalyst concentration and reaction *** changing the ratio of[M]_0/[I],linear polyvalerolactones(PVLs)with different molecular weights and narrow molecular weight distribution were *** kinetic and chain extension experiments were carried out to prove the"living"/controllable *** the NMR experiments were used to support the proposal of possible mechanism.

关键词： Quinolinyl-urea Ring-opening polymerization PVL

Temperature-dependent solubility of Rebaudioside A in methanol/ethanol and ethyl acetate mixtures:Experimental measurements and thermodynamic modeling

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Chinese Journal of chemical Engineering 2024年第8期72卷 164-176页

作者： Zhenguang Liu Zexiang Ding Yifeng Cao Baojian Liu Qiwei Yang Zhiguo Zhang Qilong Ren Zongbi Bao Key Laboratory of Biomass chemical Engineering of Ministry of Education College of Chemical and Biological EngineeringZhejiang UniversityHangzhou 310058China institute of Zhejiang University-Quzhou Quzhou 324000China

The equilibrium solubility of Rebaudioside A(Reb A)FormⅡin binary mixtures of methanol/ethanol and ethyl acetate was quantitatively determined within the temperature range of 283.15—328.15 K at ambient *** experimental findings indicate a positive correlation between the solubility of Reb A(FormⅡ)and both the temperature and the methanol/ethanol content in the solvent *** describe the solubility data,six distinct models were employed:the modified Apelblat equation,theλh model,the combined nearly ideal binary solvent/Redlich—Kister(CNIBS/R—K)model,the van't HoffJouyban-Acree(VJA)model,the Apelblat-Jouyban-Acree(AJA)model,and the non-random two-liquid(NRTL)*** combined nearly ideal binary solvent/Redlich—Kister model exhibited the most precise fit for solubility in methanol+ethyl acetate mixtures,reflected by an average relative deviation(ARD)of 0.0011 and a root mean square deviation(RMSD)of 12×10^(-7).Conversely,for ethanol+ethyl acetate mixtures,the modified Apelblat equation provided a superior correlation(ARD=0.0014,RMSD=4×10^(-7)).Furthermore,thermodynamic parameters associated with the dissolution of Reb A(FormⅡ),including enthalpy,entropy,and the Gibbs energy change,were inferred from the *** findings underscore that the dissolution process is predominantly endothermic across the solvent systems ***,the entropy changes appear to have a significant influence on the Gibbs free energy associated with the dissolution of Reb A(FormⅡ),suggesting that entropic factors may play a pivotal role in the studied systems.

关键词： Rebaudioside A Solubility Thermodynamic modeling Dissolution Binary solvent

Bifunctional noble-metal-free cocatalyst coating enabling better coupling of photocatalytic CO_(2)reduction and H_(2)O oxidation on direct Z-scheme heterojunction

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Nano Research 2024年第6期17卷 5022-5030页

作者： Wei Zhao Weihao Mo Yan Zhang Lingxuan Hu Yiyi Zheng Zhulei Chen Xiangyue Niu Yuling Zhao Lichun Liu Shuxian Zhong Song Bai Key Laboratory of the Ministry of Education for Advanced Catalysis Materials College of Chemistry and Materials ScienceZhejiang Normal UniversityJinhua 321004China College of biological Chemical Sciences and Engineering and Nanotechnology Research InstituteJiaxing UniversityJiaxing 314001China College of Geography and Environmental Sciences Zhejiang Normal UniversityJinhua 321004China College of chemical and biological Engineering Zhejiang UniversityHangzhou 310058China School of biological and chemical Engineering Panzhihua UniversityPanzhihua 617000China

Selective loading of spatially separated redox cocatalysts on direct Z-scheme heterojunctions holds great promise for advancing the efficiency of artificial photosynthesis,which however is limited to the photodeposition of noble metal cocatalysts and the fabrication of hollow double-shelled semiconductor ***,the co-exposure of discrete cocatalyst and semiconductor increases the product diversity when both the exposed sites of which participate in CO_(2)***,we present a facile and versatile protocol to overcome these limitations via surface coating of Z-scheme heterojunctions with bifunctional noble-metal-free *** Cu_(2)O/Fe_(2)O_(3)(CF)as a model heterojunction and layered Ni(OH)_(2)as a model cocatalyst,it is found that Ni(OH)_(2)lying on the surfaces of Cu_(2)O and Fe_(2)O_(3)separately co-catalyzes the CO_(2)reduction and H_(2)O *** experimental and theoretical investigation reveals that the Ni(OH)_(2)outer layer:(i)mitigates the charge recombination in CF and balances their transfer and consumption;(ii)reduces the rate-determining barriers for CO_(2)-to-CO and H_(2)O-to-O_(2)conversion,(iii)suppresses the side proton reduction occurring on CF,and(iv)protects the CF from component *** expected,the redox reactions stoichiometrically proceed,and significantly enhanced photocatalytic activity,selectivity,and stability in CO generation are achieved by the stacked Cu_(2)O/Fe_(2)O_(3)@Ni(OH)_(2)in contrast to *** study demonstrates the significance of the synergy between bifunctional cocatalysts and Z-scheme heterojunctions for improving the efficacy of overall redox reactions,opening a fresh avenue for the rational design of artificial photosynthetic systems.

关键词： Z-scheme heterojunction bifunctional cocatalyst CO_(2)reduction H_(2)O oxidation stoichiometric redox reaction

Exploring multiple phases and first-order phase transitions in Kármán Vortex Street

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Science China(Physics,Mechanics & Astronomy) 2024年第11期67卷 47-54页

作者： Xu Li Xing Xiang Tingting Xue Limin Wang Xiaosong Chen School of systems Science and institute of Nonequilibrium systems Beijing Normal UniversityBeijing 100875China State Key Laboratory of Multiphase Complex systems Institute of Process EngineeringChinese Academy ofSciencesBeijing 100190China School of chemical Engineering University of Chinese Academy of SciencesBeijing 100049China

Kármán Vortex Street, a fascinating phenomenon of fluid dynamics, has intrigued the scientific community for a long time. Many researchers have dedicated their efforts to unraveling the essence of this intriguing flow pattern. Here, we apply the lattice Boltzmann method with curved boundary conditions to simulate flows around a circular cylinder and study the emergence of Kármán Vortex Street using the eigen microstate approach, which can identify phase transition and its order-parameter. At low Reynolds number, there is only one dominant eigen microstate W_(1) of laminar flow. At Re_(c)^(1)= 53.6, there is a phase transition with the emergence of an eigen microstate pair W^(2,3) of pressure and velocity fields. Further at Re_(c)^(2)= 56, there is another phase transition with the emergence of two eigen microstate pairs W^(4,5) and W^(6,7). Using the renormalization group theory of eigen microstate,both phase transitions are determined to be first-order. The two-dimensional energy spectrum of eigen microstate for W^(1), W^(2,3) after Re_(c)^(1), W^(4-7) after Re_(c)^(2) exhibit-5/3 power-law behavior of Kolnogorov's K41 theory. These results reveal the complexity and provide an analysis of the Kármán Vortex Street from the perspective of phase transitions.

关键词： Kármán Vortex Street first-order phase transition eigen microstate approach renormalization group theory of eigen microstate

Relationship between hydrogenation degree and pyrolysis performance of jet fuel

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Chinese Journal of chemical Engineering 2024年第4期68卷 35-42页

作者： Qing Liu Tinghao Jia Lun Pan Jijun Zou Xiangwen Zhang Key Laboratory for Green chemical and Technology School of Chemical Engineering and TechnologyTianjin UniversityTianjin 300072China Haihe Laboratory of Sustainable chemical Transformations Tianjin 300192China Zhejiang institute of Tianjin University Ningbo 315201China Zhejiang Provincial Key Laboratory of Advanced chemical Engineering Manufacture Technology College of Chemical and Biological EngineeringZhejiang UniversityHangzhou 310027China

Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is *** with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.

关键词： RP-3 Fuel Pyrolysis Hydrogenation Deposition

Digital twin of a droplet microarray platform:Evaporation behavior for multiple droplets on patterned chips for cell culture

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Droplet 2024年第1期3卷 113-124页

作者： Yanchen Wu Joaquin E.Urrutia Gomez Hongmin Zhang Fei Wang Pavel A.Levkin Anna A.Popova Britta Nestler institute for Applied Materials–Microstructure Modeling and Simulation Karlsruhe Institute of TechnologyKarlsruheGermany institute of Nanotechnology Karlsruhe Institute of TechnologyEggenstein‐LeopoldshafenGermany institute of biological and chemical systems(IBCS‐FMS) Karlsruhe Institute of TechnologyEggenstein‐LeopoldshafenGermany institute of Organic Chemistry Karlsruhe Institute of TechnologyKarlsruheGermany institute of Digital Materials Science Karlsruhe University of Applied SciencesKarlsruheGermany

Precise control of the evaporation of multiple droplets on patterned surfaces is crucial in many technological applications,such as anti‐icing,coating,and high‐throughput ***,the complex evaporation process of multiple droplets on well‐defined patterned surfaces is still poorly ***,we develop a digital twin system for real‐time monitoring of key processes on a droplet microarray(DMA),which is essential for parallelization and automation of the operations for cell ***,we investigate the evaporation of multiple nanoliter droplets under different conditions via experiments and numerical *** demonstrate that the evaporation rate is not only affected by the environmental humidity and temperature but is also strongly linked to the droplet distribution on the patterned surfaces,being significantly reduced when the droplets are densely ***,we propose a theoretical method to aid in the experimental detection of volumes and pH variation of evaporating droplets on patterned *** versatile and practical strategy allows us to achieve active maneuvering of the collective evaporation of droplets on a DMA,which provides essential implications for a wide range of applications including cell culture,heat management,microreactors,biochips,and so on.

关键词： coating culture collective

One-step construction of strongly coupled Co_(3)V_(2)O_(8)/Co_(3)O_(4)/MXene heterostructure via in-situ Co-F bonds for high performance all-solid-state asymmetric supercapacitors

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Rare Metals 2024年第2期43卷 682-691页

作者： Ji Zhou Bin-Bin Liu Hu Zheng Wen-Qing Ma Qian Li Cai-Xia Xu institute for Advanced Interdisciplinary Research(iAIR) Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of ShandongSchool of Chemistry and Chemical EngineeringUniversity of JinanJinan250022China

Co_(3)V_(2)O_(8)/Co_(3)O_(4)/Ti_(3)C_(2)T_(x) composite was easily synthesized via one-step succinct-operated hydrothermal *** interconnected Co_(3)V_(2)O_(8)/Co_(3)O_(4) nanowires network can in-situ grow and anchor on the surface of Ti_(3)C_(2)T_(x) via the strong Co-F bonds and contribute tremendously to depress Ti_(3)C_(2)T_(x) *** from the synergistically interplayed effect among the multiple interfaces and high conductivity of Ti_(3)C_(2)T_(x) as well as outstanding stability of the as-designed nanostructure,the optimum Co_(3)V_(2)O_(8)/Co_(3)O_(4)/Ti_(3)C_(2)T_(x)electrode reaches a commendable specific capacitance(up to 3800 mF·cm^(−2)),great rate capability(80%capacitance retention after 20-times current increasing),and preeminent cycling stability(95.4%/85.5%retention at 7000th/20,000th cycle).Moreover,the all-solid-state asymmetric supercapacitor based on Co_(3)V_(2)O_(8)/Co_(3)O_(4)/Ti_(3)C_(2)T_(x) and active carbon can deliver a high energy density of 84.0μWh·cm^(−2) at the power energy of 3.2 mW·cm^(−2),and excellent cycling durability with 87.0%of initial capacitance retention upon 20,000 *** work provides a practicable pathway to tailor MXene-based composites for high-performance supercapacitor.

关键词： Ti_(3)C_(2)T_(x) Co_(3)V_(2)O_(8)/Co_(3)O_(4) Heterostructure Cathode Supercapacitor