Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry ...Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping,while they fail to match most cathode materials toward highvoltage magnesium batteries. Herein,reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl_(2) additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg^(2+) desolvation barrier for accelerated redox kinetics,while the Mg^(2+)-conducting polymer coating on the Mg surface ensures the facile Mg^(2+) migration and the e ective isolation of electrolytes. As a result,reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover,benefitting from the wide electrochemical window of carbonate electrolytes,high-voltage(> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.展开更多
The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising propert...The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.展开更多
Thermoelectric technology that utilizes thermodynamic effects to convert thermal energy into electrical energy has greatly expanded wearable health monitoring,personalized detecting,and communicating applications.Enco...Thermoelectric technology that utilizes thermodynamic effects to convert thermal energy into electrical energy has greatly expanded wearable health monitoring,personalized detecting,and communicating applications.Encouragingly,thermoelectric technology assisted by artificial intelligence exerts great development potential in wearable electronic devices that rely on the self-sustainable operation of human body heat.Ionic thermoelectric(i-TE)devices that possess high Seebeck coefficients and a constant and stable electrical output are expected to achieve an effective conversation of thermal energy harvesting.Herein,we developed an i-TE paster for thermal chargeable energy storage,temperature-triggered material recognition,contact/non-contact temperature detection,and photo thermoelectric conversion applications.An all-solid-state organic ionic gel electrolyte(PVDF-HFP-PEO gel)with onion epidermal cells-like structure was sandwiched between two electrodes,which take full advantage of a synergy between the Soret effect and the polymer thermal expansion effect,thus achieving the enhanced ZT value up to 900%compared with the PEO-free electrolyte.The i-TE device delivers a Seebeck coefficient of 28 mV K^(−1),a maximum energy conversion efficiency of 1.3%in performance,and ultra-thin and skin-attachable properties in wearability,which demonstrate the great potential and application prospect of the i-TE paster in self-sustainable wearable electronics.展开更多
Controllable construction of organic heterostructures is key to developing supramolecular materials with sophisticated functions.Herein,block heterostructures with controllable shape and dimension have been successful...Controllable construction of organic heterostructures is key to developing supramolecular materials with sophisticated functions.Herein,block heterostructures with controllable shape and dimension have been successfully constructed from one molecular pair of Ir(Ⅲ)complexes 1 and 2 in H_(2)O/CH_(3)CN.Different volume ratios of H_(2)O/CH_(3)CN led to controllable morphologies of assemblies 1 from nanofibers(1NF)to nanosheets(1NS).Through reasonable experimental design,both 1NF and 1NS could be used as seeds to trigger the heterogeneous nucleation-elongation of 2.Finally,unprecedented dual control on the length and width of supramolecular block copolymers from the same monomer pair was realized smoothly.The corresponding heterogeneous nucleation-elongation process was confirmed by time-dependent UV–vis absorption spectra and emission spectra.The components of each segment of the fibrous and sheet-like block copolymers were identified by TEM,SEM,and CLSM.The results reveal that the previously unappreciated solvation effect can serve as a powerful tool to control the morphologies of heterostructures.展开更多
High level density functional theory (DFT) calculations are performed for the first time to answer the question whether the arginine-carboxylate salt bridge stays in a zwitterionic state or a neutral one. The results ...High level density functional theory (DFT) calculations are performed for the first time to answer the question whether the arginine-carboxylate salt bridge stays in a zwitterionic state or a neutral one. The results indicate that in the gas phase, the neutral form is more stable and hence proton transfer occurs from guanidinium to carboxylate. However, in an aqueous solution the zwitterionic form should be favored. The difference might he caused by the electrostatic interaction between the salt bridge and its molecular environment. Therefore, the solvation effect has to be considered in the modeling of proteins, whose stabilization depends heavily on the salt-bridges.展开更多
The interfacial proton transfer(PT)reaction on the metal oxide surface is an important step in many chemical processes including photoelectrocatalytic water splitting,dehydrogenation,and hydrogen storage.The investiga...The interfacial proton transfer(PT)reaction on the metal oxide surface is an important step in many chemical processes including photoelectrocatalytic water splitting,dehydrogenation,and hydrogen storage.The investigation of the PT process,in terms of thermodynamics and kinetics,has received considerable attention,but the individual free energy barriers and solvent effects for different PT pathways on rutile oxide are still lacking.Here,by applying a combination of ab initio and deep potential molecular dynamics methods,we have studied interfacial PT mechanisms by selecting the rutile SnO_(2)(110)/H_(2)O interface as an example of an oxide with the characteristic of frequently interfacial PT processes.Three types of PT pathways among the interfacial groups are found,i.e.,proton transfer from terminal adsorbed water to bridge oxygen directly(surface-PT)or via a solvent water(mediated-PT),and proton hopping between two terminal groups(adlayer PT).Our simulations reveal that the terminal water in mediated-PT prefers to point toward the solution and forms a shorter H-bond with the assisted solvent water,leading to the lowest energy barrier and the fastest relative PT rate.In particular,it is found that the full solvation environment plays a crucial role in water-mediated proton conduction,while having little effect on direct PT reactions.The PT mechanisms on aqueous rutile oxide interfaces are also discussed by comparing an oxide series composed of SnO_(2),TiO_(2),and IrO_(2).Consequently,this work provides valuable insights into the ability of a deep neural network to reproduce the ab initio potential energy surface,as well as the PT mechanisms at such oxide/liquid interfaces,which can help understand the important chemical processes in electrochemistry,photoelectrocatalysis,colloid science,and geochemistry.展开更多
基金supported by National Key Research and Development Program (2019YFE0111200)the National Natural Science Foundation of China (51722105)+1 种基金Zhejiang Provincial Natural Science Foundation of China (LR18B030001)the Fundamental Research Funds for the Central Universities and the Fundamental Research Funds for the Central Universities。
文摘Magnesium metal anode holds great potentials toward future high energy and safe rechargeable magnesium battery technology due to its divalent redox and dendrite-free nature. Electrolytes based on Lewis acid chemistry enable the reversible Mg plating/stripping,while they fail to match most cathode materials toward highvoltage magnesium batteries. Herein,reversible Mg plating/stripping is achieved in conventional carbonate electrolytes enabled by the cooperative solvation/surface engineering. Strongly electronegative Cl from the MgCl_(2) additive of electrolyte impairs the Mg…O = C interaction to reduce the Mg^(2+) desolvation barrier for accelerated redox kinetics,while the Mg^(2+)-conducting polymer coating on the Mg surface ensures the facile Mg^(2+) migration and the e ective isolation of electrolytes. As a result,reversible plating and stripping of Mg is demonstrated with a low overpotential of 0.7 V up to 2000 cycles. Moreover,benefitting from the wide electrochemical window of carbonate electrolytes,high-voltage(> 2.0 V) rechargeable magnesium batteries are achieved through assembling the electrode couple of Mg metal anode and Prussian blue-based cathodes. The present work provides a cooperative engineering strategy to promote the application of magnesium anode in carbonate electrolytes toward high energy rechargeable batteries.
基金financially supported by National Natural Science Foundation of China(52003231,22065037)Yunnan Fundamental Research Projects(202201AW070015)。
文摘The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.
基金supported by National Natural Science Foundation of China(62474019)Beijing Natural Science Foundation(L223006)BIT Research and Innovation Promoting Project(2024YCXY001).
文摘Thermoelectric technology that utilizes thermodynamic effects to convert thermal energy into electrical energy has greatly expanded wearable health monitoring,personalized detecting,and communicating applications.Encouragingly,thermoelectric technology assisted by artificial intelligence exerts great development potential in wearable electronic devices that rely on the self-sustainable operation of human body heat.Ionic thermoelectric(i-TE)devices that possess high Seebeck coefficients and a constant and stable electrical output are expected to achieve an effective conversation of thermal energy harvesting.Herein,we developed an i-TE paster for thermal chargeable energy storage,temperature-triggered material recognition,contact/non-contact temperature detection,and photo thermoelectric conversion applications.An all-solid-state organic ionic gel electrolyte(PVDF-HFP-PEO gel)with onion epidermal cells-like structure was sandwiched between two electrodes,which take full advantage of a synergy between the Soret effect and the polymer thermal expansion effect,thus achieving the enhanced ZT value up to 900%compared with the PEO-free electrolyte.The i-TE device delivers a Seebeck coefficient of 28 mV K^(−1),a maximum energy conversion efficiency of 1.3%in performance,and ultra-thin and skin-attachable properties in wearability,which demonstrate the great potential and application prospect of the i-TE paster in self-sustainable wearable electronics.
基金financial support from the National Natural Science Foundation of China(No.21978042)the Fundamental Research Funds for the Central Universities(No.DUT22LAB610)。
文摘Controllable construction of organic heterostructures is key to developing supramolecular materials with sophisticated functions.Herein,block heterostructures with controllable shape and dimension have been successfully constructed from one molecular pair of Ir(Ⅲ)complexes 1 and 2 in H_(2)O/CH_(3)CN.Different volume ratios of H_(2)O/CH_(3)CN led to controllable morphologies of assemblies 1 from nanofibers(1NF)to nanosheets(1NS).Through reasonable experimental design,both 1NF and 1NS could be used as seeds to trigger the heterogeneous nucleation-elongation of 2.Finally,unprecedented dual control on the length and width of supramolecular block copolymers from the same monomer pair was realized smoothly.The corresponding heterogeneous nucleation-elongation process was confirmed by time-dependent UV–vis absorption spectra and emission spectra.The components of each segment of the fibrous and sheet-like block copolymers were identified by TEM,SEM,and CLSM.The results reveal that the previously unappreciated solvation effect can serve as a powerful tool to control the morphologies of heterostructures.
文摘High level density functional theory (DFT) calculations are performed for the first time to answer the question whether the arginine-carboxylate salt bridge stays in a zwitterionic state or a neutral one. The results indicate that in the gas phase, the neutral form is more stable and hence proton transfer occurs from guanidinium to carboxylate. However, in an aqueous solution the zwitterionic form should be favored. The difference might he caused by the electrostatic interaction between the salt bridge and its molecular environment. Therefore, the solvation effect has to be considered in the modeling of proteins, whose stabilization depends heavily on the salt-bridges.
基金funding from the National Science Fund for Distinguished Young Scholars(Grant No.22225302)the National Natural Science Foundation of China(Grant Nos.92161113,21991151,21991150,and 22021001)+5 种基金the Fundamental Research Funds for the Central Universities(Grant Nos.20720220008,20720220009,20720220010)Laboratory of AI for Electrochemistry(AI4EC)IKKEM(Grant Nos.RD2023100101 and RD2022070501)M.J.greatly appreciates the financial support from the Natural Science Foundation of Henan Province(Grant No.242300420420570)the Key Scientific Research Projects of Colleges and Universities in Henan Province(No.24A150031)the International Scientific and Technological Cooperation Projects in Henan Province(No.232102520020)。
文摘The interfacial proton transfer(PT)reaction on the metal oxide surface is an important step in many chemical processes including photoelectrocatalytic water splitting,dehydrogenation,and hydrogen storage.The investigation of the PT process,in terms of thermodynamics and kinetics,has received considerable attention,but the individual free energy barriers and solvent effects for different PT pathways on rutile oxide are still lacking.Here,by applying a combination of ab initio and deep potential molecular dynamics methods,we have studied interfacial PT mechanisms by selecting the rutile SnO_(2)(110)/H_(2)O interface as an example of an oxide with the characteristic of frequently interfacial PT processes.Three types of PT pathways among the interfacial groups are found,i.e.,proton transfer from terminal adsorbed water to bridge oxygen directly(surface-PT)or via a solvent water(mediated-PT),and proton hopping between two terminal groups(adlayer PT).Our simulations reveal that the terminal water in mediated-PT prefers to point toward the solution and forms a shorter H-bond with the assisted solvent water,leading to the lowest energy barrier and the fastest relative PT rate.In particular,it is found that the full solvation environment plays a crucial role in water-mediated proton conduction,while having little effect on direct PT reactions.The PT mechanisms on aqueous rutile oxide interfaces are also discussed by comparing an oxide series composed of SnO_(2),TiO_(2),and IrO_(2).Consequently,this work provides valuable insights into the ability of a deep neural network to reproduce the ab initio potential energy surface,as well as the PT mechanisms at such oxide/liquid interfaces,which can help understand the important chemical processes in electrochemistry,photoelectrocatalysis,colloid science,and geochemistry.
