Regulating zinc ion transport behavior and solvated structure towards stable aqueous Zn metal batteries

Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.

THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.

Synthesis and Crystal Structure of 5-(p-Tolyl)-4-[2-(2,4-dichlorophenoxy)acetamido]-1,2,4-triazole-3-thione Ethyl Acetate Solvate

A novel compound 5-（p-tolyl）-4-[2-（2,4-dichlorophenoxy）acetamido]-1,2,4-tria zole- 3-thione 2a has been synthesized by the reaction of 5-（p-tolyl）-4-amino-1,2,4-triazole-3-thione 1 with 2-（2,4-dich/orophenoxy）acetyl ch/oride. Interestingly, the title compound 2 was obtained when 2a crystallizes from a mixed solution of petroleum ether and ethyl acetate, and it has been characterized by elemental analysis, IR, ^1H NMR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.780（5）, b = 10.876（6）, c = 11.615（6） /A, a = 104.822（7）, β= 94.105（6）, ）, = 94.305（6）°, V= 1185.7（11）/A3, Z = 2,μ = 0.397 mm^-1, Mr= 497.39, Dx= 1.393 g/cm^3, F（000） = 516, S = 1.097, the final R = 0.0730 and wR = 0.2133 for 4111 unique reflections （Rint = 0.0525） with 3212 observed ones. The dihedral angles made by the triazole ring with the methyl- and chloro-substituted benzene rings are 43.5（7） and 50.2（9）°, respectively. Some intra- and intermolecular hydrogen bonds together with C-H…π interactions existing in the lattice stabilize the crystal structure.

Intercalation of multiply solvated hexafluorophospate anion into graphite electrode from mixtures of methyl acetate,ethyl methyl and ethylene carbonates

Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.

Preparation of Nano-Sized γ-Al_2O_3 Supported Iron Catalyst for Fischer-Tropsch Synthesis by Solvated Metal Atom Impregnation Methods

Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The iron atom precursor complex, bis（toluene）iron（0） formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, Mǒssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis（toluene）iron（0）, and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced γ-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.

Crystal Structure of Norfloxacin Methanol Solvate: C_(16)H_(18)FN_3O_3·CH_3OH·H_2O

Norfloxacin methanol solvate （ 1 -ethyl-6-fluoro- 1,4-dihydro-4-oxo-7-（ 1 -piperazinyl）-3- quinoline carboxylic acid methanol solvate） has been prepared. The crystal and molecular structures of the title compound, C16H18FN3O3·CH3OH·H2O, were determined by X-ray diffraction method. The compound crystallizes in monoclinic, space group P21/c with a = 7.8660（16）, b = 22.525 （5）, c = 10.253（2）A, β= 108.31°, Mr = 369.39, V = 1724.7（6）A^3, Z = 4, Dc= 1.423 g/cm^3, F（000） = 784, R = 0.0557 and wR = 0.1224. The TGA analysis indicates that it decomposes completely at 723.75℃.

Ternary phase diagrams and solvate transformation thermodynamics of omeprazole sodium in different solvent mixtures

Omeprazole sodium(OMS), a typical non-hydrogen bond donors API, is only available in solvates so far, including monohydrate, ethanol solvate and methanol solvate. The methanol solvate was found for the first time. Solvate transformation thermodynamics of OMS was studied in this paper. First, the ternary phase diagrams forming two solvates for OMS in binary solvent mixtures including methanol + water, ethanol + water, and methanol+ ethanol were measured at temperature ranging of T =(278.15 to 313.15) K under atmospheric pressure. Further, the standard equilibrium constants of the solvate transformation reactions were evaluated according to the chemical reaction isothermal equation. The standard molar Gibbs free energy, the standard molar enthalpy, and the standard molar entropy of solvate transformation reactions were then calculated based on van't Hoff equation. Moreover, the thermodynamic stability of the OMS solvate was analyzed based on phase diagram. The results are of great importance to develop a crystallization process for manufacturing OMS solvate, and could be helpful to other solvate transformation research.

The Role of Solvent in Tautomer Solvate Crystallization: A Case of 6-Amino-1,3-Dimethyl-5-Nitrosouracil

Tautomers are structural isomers that readily interconvert and may exhibit diff erent properties.The eff ect of solvent on tautomeric equilibria in solution has been a subject of some research.Tautomer solvate is less common,and the role of solvent in the crystallization of tautomer solvate remains an interesting topic.In this work,we used 6-amino-1,3-dimethyl-5-nitrosouracil(NAU)as the tautomeric model material,which can present in nitrone–enamine form(Tautomer A)or oxime–imine form(Tautomer B).A solvate with NAU/DMSO ratio of 1:1 was discovered and characterized using single/powder X-ray diff raction and thermogravimetry.The crystal structure of NAU·DMSO was determined for the fi rst time,where only Tautomer A was formed in the tautomeric crystal.Quantum chemical calculation and molecular dynamics simulation were conducted to determine the tautomeric form in DMSO solution.Electrostatic potential analysis,radial distribution function analysis,and binding energy suggested possible DMSO–NAU interaction modes and stable tautomer complexes in solution.Tautomer A-containing complexes were found to dominate in solution,as verifi ed by comparing predicted and experimental 1 H NMR spectra.Findings reveal that the hydrogen bonding between DMSO and NAU is similar in solution and in NAU–DMSO solvate crystal,which helps preserve the form of Tautomer A during solvate crystallization.

PROPERTIES OF POLYMER SUPPORTED Ni-Cu BIMETALLIC CATALYSTS PREPARED BY SOLVATED METAL ATOM IMPREGNATION

D-72 resin supported nickel-copper catalysts prepared by solvated metal atom impregnation (SMAI) were studied by magnetic measurements and X-ray photoelectron spectroscopy (XPS). The Ni particles on the catalysts are very highly dispersed and display superparamagnetic behaviour. Ni-Cu alloy clusters were found to be formed. The surface compositions are different from the bulk concentrations. In contrast with the surface enrichment in copper generally observed on conventional Ni-Cu catalysts, the surfaces of these catalysts are enriched in nickel. The nickel is in both zero and valent states, while copper is mainly in metallic state. Catalytic data show that the formation of Ni-Cu alloy clusters has a profound effect on the catalytic activities of the catalysts in the hydrogenation of furfural. The activity of the Ni:Cu ratio of one bimetallic catalysts is much higher than that of the Ni or Cu monometallic catalyst.

Promotion Effect of Lantanum ions on Co/SiO_2 Catalysts Prepared via Solvated Metal Atom Impregnation Method

order to assess the promotional effects of La3+ on CO hydrogenation of Co/SiO2 catalyst, solvated metal atom impregnation (SMAI) method was used to prepare unpromoted 10% (mass fraction) Co/SiO2 and a series of La3+-promoted 10% (mass fraction) Co/SiO2 catalyst with different La/Co atomic ratios (0.1, 0.3, 0.5). X-ray diffraction (XRD), and CO chemisorption measurements show that the cobalt particle size decreases as the La/Co ratios increase. X-ray photoelectron spectrescopy indicates that cobalt is in zero-valent state for all the samples. Catalytic test shows that the catalytic activity of La3+-promoted Co/SiO2 in CO hydrogenation is higher than that of unpromoted Co/SiO2, and enhances with the La/Co ratios increase. La3+ promotion also causes the enhanced selectivity of Co/SiO2 catalyst for higher hydrocarbon products.

Preparation of Highly Dispersed Supported Metal Catalysts via Solvated Metal Atom Impregnation ( V) --The Effects of Hydroxyl Group on the Surface Concentrations of SiO2 on the Properties of Supported Fe Clusters

Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor complex, bis (toluene) iron(0) formed in the metal atom reactor, was impregnated into SiO2 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by THM, Mosbauer and chemisorption measurements, and the resules show that higher concentration of surface hydroxyl groups of SiO2-200 favours the formation of more positively charged support iron cluster Fen/SiO2-200 and the lower concentration of surface hydroxyl groups of SiO2-600 favours the formation of basically neutral supported iron cluster Fe2/SiO2-600. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the precursor complex,bis(toluene) fron(0), to decompose more rapidly, and favours the formation of relatively large iron cluster. As a consequence, these two kinds of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fe/SiO2-200 in F-T reaction is similar to that of the unreduced a-Fe2O2, while Fe2/SiO2 -600 is similar to that of reduced α-Fe2O2.

A robust solid electrolyte interphase enabled by solvate ionic liquid for high-performance sulfide-based all-solid-state lithium metal batteries

All-solid-state lithium metal batteries(ASSLMBs)that incorporate solid electrolyte(SE)and lithium metal anode suggest considerable potential in addressing the security concerns and energy density limitation of conventional lithium-ion batteries(LIBs).However,the practical application of ASSLMBs is always restricted by the interfacial instability of lithium metal anode/electrolyte and inevitable lithium dendrites propagation in SE.Herein,a solvate ionic liquid is adopted to modify the interface stability of lithium metal anode/electrolyte and inhibit the growth of lithium dendrites via an in-situ formation of a robust solid electrolyte interphase(SEI)on the surface of lithium metal anode.Consequently,the ASSLMBs assembled with Li_(6)PS_(5)Cl(LPSCl)electrolyte,lithium metal anode that protected by robust SEI layer,and LiNbO_(3)@NCM622 cathode exhibit high initial capacity of 126.5 mAh·g^(−1)and improved cycling stability with a capacity retention of 80.3%over 60 cycles at 0.1 C.This work helps to provide a facile route for the design of robust SEI in the application of ASSLMBs.

Solvation Engineering via Fluorosurfactant Additive Toward Boosted Lithium-Ion Thermoelectrochemical Cells

Lithium-ion thermoelectrochemical cell(LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat-to-current behavior limit the application of LTECs using LiPF_6 electrolyte. Introducing additives into bulk electrolyte is a reasonable strategy to solve such problem by modifying the solvation structure of electrolyte ions. In this work, we develop a dual-salt electrolyte with fluorosurfactant(FS) additive to achieve high thermopower and durability of LTECs during the conversion of low-grade heat into electricity. The addition of FS induces a unique Li~+ solvation with the aggregated double anions through a crowded electrolyte environment,resulting in an enhanced mobility kinetics of Li~+ as well as boosted thermoelectrochemical performances. By coupling optimized electrolyte with graphite electrode, a high thermopower of 13.8 mV K^(-1) and a normalized output power density of 3.99 mW m^(–2) K^(–2) as well as an outstanding output energy density of 607.96 J m^(-2) can be obtained.These results demonstrate that the optimization of electrolyte by regulating solvation structure will inject new vitality into the construction of thermoelectrochemical devices with attractive properties.

Critical Solvation Structures Arrested Active Molecules for Reversible Zn Electrochemistry

Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13) full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.

Long‐life lithium batteries enabled by a pseudo‐oversaturated electrolyte

The specific energy of Li metal batteries(LMBs)can be improved by using high‐voltage cathode materials;however,achieving long‐term stable cycling performance in the corresponding system is particularly challenging for the liquid electrolyte.Herein,a novel pseudo‐oversaturated electrolyte(POSE)is prepared by introducing 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether(TTE)to adjust the coordination structure between diglyme(G2)and lithium bis(trifluoromethanesulfonyl)imide(LiTFSI).Surprisingly,although TTE shows little solubility to LiTFSI,the molar ratio between LiTFSI and G2 in the POSE can be increased to 1:1,which is much higher than that of the saturation state,1:2.8.Simulation and experimental results prove that TTE promotes closer contact of the G2 molecular with Li^(+)in the POSE.Moreover,it also participates in the formation of electrolyte/electrode interphases.The electrolyte shows outstanding compatibility with both the Li metal anode and typical high‐voltage cathodes.Li||Li symmetric cells show a long life of more than 2000 h at 1 mA cm^(−2),1 mAh cm^(−2).In the meantime,Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cell with the POSE shows a high reversible capacity of 134.8 mAh g^(−1 )after 900 cycles at 4.5 V,1 C rate.The concept of POSE can provide new insight into the Li^(+)solvation structure and in the design of advanced electrolytes for LMBs.

Tackling application limitations of high-safetyγ-butyrolactone electrolytes:Exploring mechanisms and proposing solutions

Developing wide-temperature and high-safety lithium-ion batteries(LIBs)presents significant challenges attributed to the absence of suitable solvents possessing broad liquid range and non-flammability properties.γ-Butyrolactone(GBL)has emerged as a promising solvent;however,its incompatibility with graphite anode has hindered its application.This limitation necessitates a comprehensive investigation into the underlying mechanisms and potential solutions.In this study,we achieve a molecular-level understanding of the perplexing interphase formation process by employing in-situ spectroelectrochemical techniques and density function calculations.Our findings reveal that,even at high salt concentrations,GBL consistently occupies the primary Li^(+)solvation sheath,leading to extensive GBL decomposition and the formation of a high-impedance and inorganic-poor solid-electrolyte interphase(SEI)layer.Contrary to manipulating solvation structures,our research demonstrates that the utilization of filmforming additives with higher reduction potential facilitates the pre-establishment of a robust SEI film on the graphite anode.This approach effectively inhibits GBL decomposition and significantly enhances the battery's lifespan.This study provides the first reported intrinsic understanding of the unique GBLgraphite incompatibility and offers valuable insights for the development of wide-temperature and high-safety LIBs.

Solvates and polymorphs of clindamycin phosphate： Structural, thermal stability and moisture stability studies

Clindamycin phosphate （CP）, an antibacterial agent, has been reported to form several solid-state forms. The crystal structures of two CP solvates, a dimethyl sulfoxide （DMSO） solvate and a methanol/water solvate （solvate V）, have been determined by single crystal X-ray diffraction. The properties and transformations of these forms were characterized by powder X-ray diffraction, Single-crystal X-ray diffraction, differential scanning calorimetry, thermo gravimetric analysis, hot-stage microscopy, and dynamic vapor sorption. Very different hydrogen bonding networks exist among the host-host and host-solvent molecules in the two crystal structures, resulting in different moisture stabilities. The thermal stabilities of the two solvates upon heating and desolvation were also studied. When the temperature was above the boiling point of methanol, solvate V converted to a polymorphic phase after a one step desolvation process, whereas the desolvation temperature of the DMSO solvate was below the boiling point of DMSO. At the relative humidity above 43%, the DMSO solvate transformed to a hydrate at 25 ℃. In contrast, solvate V did not transform at any of the humidities studied.

Synthesis and Structure of Solvated Protons Incorporating Weakly Coordinating Anions. Precursors of Superacids

Six new solvated proton salts of highly halogenated carborane anions, [H(solvent),] [carborane] (carborane = 1-R-CB11-Y5X6-(R=H, Me; X, Y=CI, Br, I), 1-H-CB9Br9?) were prepared from the salt metathesis reaction of Ag(carborane) and HO in high yields. Single-crystal X-ray analyses show that they are all discrete molecules in the solid-state. The number of the solvated molecules surrounding H+ ion can not be determined with the knowledge of the size and substituents of the carborane anions. These salts provide convenient weighable sources of Br?nsted acid reagents having a wide range of acidities and good thermal stabilities. TGA results indicate that the solvated molecules (water or organic molecules) in the cations [H(solvent)n]+ can be removed under high temperature and high vacuum conditions to give superacidic materials H(carborane) which can protonate olefin.

Cell-nucleus structured electrolyte for low-temperature aqueous zinc batteries

Rechargeable aqueous zinc(Zn) batteries hold great promise for large-scale energy storage,but their implementation is plagued by poor Zn reversibility and unsatisfactory low-temperature performance.Herein,we design a cell-nucleus structured electrolyte by introducing low-polarity 1,2-dimethoxyethane(DME) into dilute 1 M zinc trifluoromethanesulfonate(Zn(OTf)_(2)) aqueous solution,which features an OTf--rich Zn2^(+)-primary solvation sheath(PSS,inner nucleus) and the DMEmodulated Zn^(2+)-outer solvation sheath(outer layer).We find that DME additives with a low dosage do not participate in the Zn2+-PSS but reinforce the Zn-OTf-coordination,which guarantees good reaction kinetics under ultralow temperatures.Moreover,DME breaks the original H-bonding network of H2O,depressing the freezing point of electrolyte to-52.4℃.Such a cell-nucleus-solvation structure suppresses the H_(2)O-induced side reactions and forms an anion-derived solid electrolyte interphase on Zn and can be readily extended to 1,2-diethoxyethane.The as-designed electrolyte enables the Zn electrode deep cycling stability over 3500 h with a high depth-of-discharge of 51.3% and endows the Zn‖V_(2)O_(5)full battery with stable cycling over 1000 cycles at 40℃.This work would inspire the solvation structure design for low-temperature aqueous batteries.

1,3,5-Trifluorobenzene endorsed EC-free electrolyte for high-voltage and wide-temperature lithium-ion batteries

Ethylene carbonate(EC)is susceptible to the aggressive chemistry of nickel-rich cathodes,making it undesirable for high-voltage lithium-ion batteries(LIBs).The arbitrary elimination of EC leads to better oxidative tolerance but always incurs interfacial degradation and electrolyte decomposition.Herein,an EC-free electrolyte is deliberately developed based on gradient solvation by pairing solvation-protection agent(1,3,5-trifluorobenzene,F_(3)B)with propylene carbonate(PC)/methyl ethyl carbonate(EMC)formulation.F_(3)B keeps out of inner coordination shell but decomposes preferentially to construct robust interphase,inhibiting solvent decomposition and electrode corrosion.Thereby,the optimized electrolyte(1.1 M)with wide liquid range(-70–77℃)conveys decent interfacial compatibility and high-voltage stability(4.6 V for LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2),NCM622),qualifying reliable operation of practical NCM/graphite pouch cell(81.1%capacity retention over 600 cycles at 0.5 C).The solvation preservation and interface protection from F_(3)B blaze a new avenue for developing high-voltage electrolytes in next-generation LIBs.