Raman and infrared spectroscopic quantification of the carbonate concentration in K_(2)CO_(3)aqueous solutions with water as an internal standard

Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.

Synthesis of ZrO_2-HfO_2-Y_2O_3-Sc_2O_3 Nano-Particles by Sol-Gel Technique in Aqueous Solution of Alcohol

Agglomeration-free nanosized ZrO2-HfO2-Y2O3-Sc2O3 composite powders were successfully synthesized by Sol-Gel technique in heated aqueous solution of alcohol, using analytically pure ZrOCl2 · 8H2O, HfOCl2·8H2O, Y（NO3）3·6H2O, and Sc2O3 as raw materials. The effect of synthesis condition on the size and dispersity of the composite powders was investigated by means of XRD, TEM, and TG-DSC techniques. The results showed that well-dispersed predecessor of ZrO2-HfO2-Y2O3-Sc2O3 composite nanopowders could be obtained. The optional condition ： PEG6000 as dispersant was 1%, alcohol/H2O ratio was 5/1, metallic ion concentration in whole solution was 0.5 mol·L^-1 and the pH value of the solution was 12. After calcined at 620 ℃, the powder obtained was in uniform cubic structure, and its average particle size was about 13 nm, which was good for producing nanocrystalline solid electrolyte.

配位化合物Zn(Met)_3(NO_3)_2·H_2O(s)(Met=L-α-蛋氨酸)的低温热容及标准摩尔生成焓(英文)

利用精密绝热热量仪测定了配合化合物Zn(Met)_3(NO_3)_2·H_2O(s)(Met=L-α-蛋氨酸)在78-371 K温区的摩尔热容.通过热容曲线解析,得到了该配合物的起始脱水温度为T_D=325.10 K.将该温区的摩尔热容实验值用最小二乘法拟合得到了摩尔热容(C_p)对约化温度(T)的多项式方程,由此计算得到了配合物的舒平热容值和热力学函数值.基于设计的热化学循环,选择100 mL 2 mol·L^(-1)HCl溶液为量热溶剂,利用等温环境溶解-反应热量计,得到了298.15 K配合物的标准摩尔生成焓Δ_f H_m^0[Zn(Met)_3(NO_3)_2·H_2O,s]=-(1472.65±0.76)J·mol^(-1).

Bi_(2)S_(3) for Aqueous Zn Ion Battery with Enhanced Cycle Stability

Aqueous Zn ion batteries(ZIBs)are promising in energy storage due to the low cost,high safety,and material abundance.The development of metal oxides as the cathode for ZIBs is limited by the strong electrostatic forces between O2−and Zn2+which leads to poor cyclic stability.Herein,Bi2S3 is proposed as a promising cathode material for rechargeable aqueous ZIBs.Improved cyclic stability and fast diffusion of Zn2+is observed.Also,the layered structure of Bi2S3 with the weak van der Waals interaction between layers offers paths for diffusion and occupancy of Zn2+.As a result,the Zn/Bi2S3 battery delivers high capacity of 161 mAh g−1 at 0.2 A g−1 and good cycling stability up to 100 cycles with ca.100%retention.The battery also demonstrates good cyclic performance of ca.80.3%over 2000 cycles at 1 A g−1.The storage mechanism in the Bi2S3 cathode is related to the reversible Zn ion intercalation/extraction reactions and the capacitive contribution.This work indicates that Bi2S3 shows great potential as the cathode of ZIBs with good performance and stability.

An insight into failure mechanism of NASICON-structured Na3V2（PO4）3 in hybrid aqueous rechargeable battery

NASICON (Na-super-ionic-conductors)-structured materials have attracted extensive research interest due to their great application potential in secondary batteries. However, the mechanism of capacity fading for NASICON-structured electrode materials has been rarely studied. In this paper, we synthesized the NASICON-structured Na3V2(PO4)3/C composite by simple sol-gel and high-temperature solid-phase method and investigated its electrochemical performance in Na-Zn hybrid aqueous rechargeable batteries. After characterizing the structure, morphology and composition variations as well as the interfacial resistance changes of Na3V2(PO4)3/C cathode during cycling, we propose a mechanical and interfacial degradation mechanism for capacity fading of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries. This work will shed light on enhancing the mechanical and in terfacial stability of NASICON-structured Na3V2(PO4)3/C in Na-Zn hybrid aqueous rechargeable batteries.

Weaker Interactions in Zn^(2+)and Organic Ion-pre-intercalated Vanadium Oxide toward Highly Reversible Zinc-ion Batteries

Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.

Local hydrated structure of an Fe^(2+)/Fe^(3+) aqueous solution: an investigation using a combination of molecular dynamics and X-ray absorption fine structure methods

The hydrated shell of both Fe2＋ and Fe3＋ aqueous solutions are investigated by using the molecular dynamics （MD） and X-ray absorption structure （XAS） methods. The MD simulations show that the first hydrated shells of both Fe2＋ and Fe3＋ are characterized by a regular octahedron with an Fe-O distance of 2.08 for Fe2＋ and 1.96 for Fe3＋, and rule out the occurrence of a Jahn-Teller distortion in the hydrated shell of an Fe2＋ aqueous solution. The corresponding X-ray absorption near edge fine structure （XANES） calculation successfully reproduces all features in the XANES spectra in Fe2＋ and Fe3＋ aqueous solution. A feature that is located at energy 1 eV higher than the white line （WL） in an Fe3＋ aqueous solution may be assigned to the contribution of the charge transfer.

水溶液法原位构建ZnO亲锂层稳定锂-石榴石电解质界面

固态电池以其高安全性和高能量密度而备受关注。石榴石型固体电解质(LLZO)由于具有较高的离子导电性和对锂金属的稳定性,在固态电池中具有应用前景,但陶瓷与锂金属较差的界面接触会导致高的界面阻抗和可能形成的枝晶穿透。我们利用LLZO表层独特的H^(+)/Li^(+)交换反应,提出了一种简便有效的金属盐类水溶液诱发策略,在电解质表面原位构建ZnO亲锂层,界面处LiZn合金化实现紧密连续的接触。引入改性层后,界面阻抗可显著降低至约10Ω·cm^(2),对称电池能够在0.1mA·cm^(-2)的电流密度下实现长达1000h的长循环稳定性。匹配正极LiFePO_(4)(LFP)或LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM523)的准固态电池在室温下能够稳定循环100次以上。

Interface engineering of Zn meal anodes using electrochemically inert Al_(2)O_(3)protective nanocoatings

Aqueous rechargeable Zn-ion batteries are regarded as a promising alternative to lithium-ion batteries owing to their high energy density,low cost,and high safety.However,their commercialization is severely restricted by the Zn dendrite formation and side reactions.Herein,we propose that these issues can be minimized by modifying the interfacial properties through introducing electrochemically inert Al_(2)O_(3)nanocoatings on Zn meal anodes(Al_(2)O_(3)@Zn).The Al_(2)O_(3)nanocoatings can effectively suppress both the dendrite growth and side reactions.As a result,the Al_(2)O_(3)@Zn symmetric cells show excellent electrochemical performance with a long lifespan of more than 4,000 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2).Meanwhile,the assembled Al_(2)O_(3)@Zn//V_(2)O_(5)full cells can deliver a high capacity(236.2 mAh·g^(−1))and long lifespan with a capacity retention of 76.11%after 1,000 cycles at 4 A·g^(−1).

高氯酸碳酰肼盐与硝酸碳酰肼盐系列化合物的晶格能与感度性能关系(英文)

为了研究晶格能与感度之间的关系,采用微热量计测定了[M(CHZ)3](NO3)2和[M(CHZ)3](ClO4)2(M=Mn,Zn,Ni)在去离子水中的溶解焓并计算出它们的标准摩尔溶解焓,根据卡普廷斯基经验公式计算了它们的晶格能,得出配阳离子半径[M(CHZ)3]2+(M=Mn,Zn,Ni)分别为2.12,1.89和2.70;讨论了晶格能与机械感度之间的关系:相同外阴离子系列中配合物的晶格能越大,感度越小,并且高氯酸碳酰肼盐要比相应的硝酸碳酰肼盐的晶格能低,感度最高的为[Ni(CHZ)3](ClO4)2,最钝感的为[Zn(CHZ)3](NO3)2。