Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Mechanism of high Li-ion conductivity in poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network based electrolyte revealed by solid-state NMR

Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.

Fluorographene with Narrow Lateral Size and Thickness Distributions Prepared for Enhancing Lubrication Performance of Bentonite Grease

Fluorographene(FG)with narrow lateral size and thickness distributions was prepared by a liquid-phase exfoliation method,based on liquid cascade centrifugation.The Rtec MFT-5000 tribo-meter was used to investigate the lubricating performance of bentonite grease enhanced by the as-prepared FG.The results showed that the coefficient of friction and the wear volume of bentonite grease with 0.3 wt%FG were decreased by 20.4%and 44.9%,respectively,as compared to those of the base grease.The main reason is that FG can promote the formation of the tribo-chemical reaction film consisting of complex carbon oxide,Fe_(2)O_(3)and FeF_(3)on the friction surface,which can remarkably improve the performance of friction reduction and prevent the appearance of severe wear.

Effects of synthetic site water on bentonite-concrete system for a potential nuclear waste repository

In high-level nuclear waste(HLW)repositories,concrete and compacted bentonite are designed to be employed as buffer materials,which may raise a problem of interactions between concrete and bentonite.These interactions would lead to mineralogy transformation and buffer performance decay of bentonite under the near field environment conditions in a repository.A small-scale experimental setup was established to simulate the concrete-bentonite-site water interaction system from a potential nuclear waste repository in China.Three types of mortars were prepared to correspond to the concrete at different degradation states.The results permit the determination of the following:(1)The macroproperties of Gaomiaozi(GMZ)bentonite(e.g.swelling pressure,permeability,the final dry density,and water content of reacted samples);(2)The composition evolution of fluids from the synthetic site water-concrete-bentonite interaction systems;(3)The sample characterization including Fourier transform infrared spectroscopy(FTIR)and X-ray powder diffraction(XRD).Under the infiltration of the synthesis Beishan site water(BSW),the swelling pressure of bentonite decreases slowly with time after reaching its second swelling peak.The flux decreases with time during the infiltrations,and it tends to be stable after more than 120 d.Due to the cation exchange reactions in the BSW-concrete-bentonite systems,the divalent cations(Ca and Mg)were consumed,and the monovalent cations(Na and K)were released.The dissolution of minerals in the bentonite such as albite causes Si increasing in the pore water.It was concluded that the hydro-mechanical property degradation of bentonite takes place when it comes into contact with concrete mortar,even under low-pH groundwater conditions.The soil dispersion,the uneven water content,and the uneven dry density in bentonite samples may partly contribute to the swelling decay of bentonite.Therefore,the direct contact with concrete has an obvious effect on the performance of bentonite.

Polyoxometalate Supported on Bentonite as Efficient Adsorbent for the Removal of Methylene Blue Dye and Bacteria from Wastewater

Aiming at developing benign multiple decontamination water adsorbent, using low-cost natural raw local materials, we prepared a modified Bentonite supporting polyoxometalate ionic liquid composite hybrid, where each component targets a specific type of water contaminant. The composite material based on water-insoluble polyoxometalate-ionic liquid (POM-IL) consisting of antimicrobial tetraoctylammonium cations, and saturated Keggin-archetype polyoxometalate [PV3W9O40]6− anions, immobilized on Bentonite having an interesting dye removal capacity. The Q8[PV3W9O40]@Bentonite (Q8 = TetraOctylAmmonium), composite was tested for cationic dye removal from waste water. Batch experiments for the adsorption of Methylene Blue MB were conducted to investigate the effect factors containing the initial concentration, contact time, adsorbent amount, pH and Temperatures. According to the results of the kinetic study, the pseudo-second-order model fitted better the adsorption experimental data compared to the first order model. The experimental isotherm data were found to fit the Langumir model well compared to the Freundlich model. The thermodynamic parameters illustrated that the adsorption process was endothermic and spontaneous. The results of the present study showed that modified Bentonite represents an excellent multicomponent low-cost adsorbent for the removal of cationic dye and Bacteria from waste water.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

Effect of drying cracks on swelling and self-healing of bentonite-sand blocks used as engineered barriers for radioactive waste disposal

Experiments were conducted to evaluate the healing of drying cracks in air-dried bentonite-sand blocks after hydration and swelling in groundwater,providing justifications to simplify the protection of blocks prior to installation in a high-level radioactive waste repository.Synthetic groundwater was prepared to represent the geochemistry of Beishan groundwater,and was used to hydrate the blocks during the swelling pressure and swelling strain measurements,as Beishan is the most promising site for China's repository.Healing of the surface cracks was recorded by photography,and healing of the internal cracks was visualized by CT images and hydraulic conductivity of air-dried blocks.The results indicate that the maximum swelling pressure and swelling strain are primarily affected by the geochemistry of Beishan groundwater,but not affected by the drying cracks.The maximum swelling pressure and swelling strain of air-dried blocks are comparable to or even higher than the pressure and strain of fresh blocks.The maximum swelling pressure measured in strong(i.e.high ion strength)Beishan groundwater was 44%of the pressure measured in deionized(DI)water,and the maximum swelling strain was reduced to 23%of the strain measured in DI water.Nevertheless,the remained swelling of the blocks hydrated in strong Beishan groundwater was sufficient to heal the surface and internal drying cracks,as demonstrated by the pictures of surface cracks and CT images.The hydraulic conductivity of the air-dried block permeated with strong groundwater was comparable(3.7×higher)to the hydraulic conductivity of the fresh block,indicating the self-healing of drying cracks after hydration and swelling in groundwater.A simplified method of protecting the block with plastic wraps before installation is recommended,since the remained swelling of the block hydrated in Beishan groundwater is sufficient to heal the drying cracks.

Anisotropic swelling pressures of compacted GMZ bentonite infiltrated with salt solutions

In the high-level radioactive waste(HLW)deep geological repository,bentonite is compacted uniaxially,and then arranged vertically in engineered barriers.The assembly scheme induces the initial anisotropy,and with hydration,it develops more evidently under chemical conditions.To investigate the anisotropic swelling of compacted Gaomiaozi(GMZ)bentonite and the further response to saline effects,a series of constant-volume swelling pressure tests were performed.Results showed that dry density enhanced the bentonite swelling and raised the final anisotropy,whereas saline inhibited the bentonite swelling but still promoted the final anisotropy.The final anisotropy coefficient(ratio of radial to axial pressure)obeyed the Boltzmann sigmoid attenuation function,decreasing with concentration and dry density,converging to a minimum value of 0.76.The staged evolution of anisotropy coefficient was discovered,that saline inhibited the rise of the anisotropy coefficient(Dd)in the isotropic process greater than the valley(d1)in the anisotropic process,leading to the final anisotropy increasing.The isotropic stage amplified the impact of soil structure rearrangement on the macro-swelling pressure values.Thus,a new method for predicting swelling pressures of compacted bentonite was proposed,by expanding the equations of Gouy-Chapman theory with a dissipative wedge term.An evolutionary function was constructed,revealing the correlation between the occurrence time and the pressure value due to the structure rearrangement and the former crystalline swelling.Accordingly,a design reference for dry density was given,based on the chemical conditions around the pre-site in Beishan,China.The anisotropy promoted by saline would cause a greater drop of radial pressure,making the previous threshold on axial swelling fail.

Molecular Dynamics Study on Hydrothermal Response of PNIPAM:From Single Chain to Cross-Linked Polymer

Thermosensitive hydrogel can integrate vapor molecular capture,in-situ liquefaction,and thermal-induced water release for freshwater capture.This study aimed to examine the dynamic behavior of poly(N-isopropylacrylamide)(PNIPAM)single chain and cross-linking thermosensitive hydrogel through molecular dynamics simulation.Specifically,the impact of lower critical solution temperature(LCST)on the conformation of polymer chain and the interaction between water and polymer chain were also investigated.The polymer chain conformation underwent a transition from coil to globule when the temperature exceeded the LCST,indicating the temperature responsiveness of PNIPAM.Additionally,thermosensitive hydrogel samples with different cross-linking degrees(DOC)were studied,and relevant parameters such as the number of free water,the diffusion coefficient of water,and the pore size distribution were counted to evaluate the temperature responsiveness and water release characteristics of thermosensitive hydrogel.

Effect of shaking time, ionic strength, temperature and pH value on desorption of Cr(III) adsorbed onto GMZ bentonite

The Cr（III） desorption experiments of Gaomiaozi （GMZ） bentonite in aqueous solutions were performed. The variables affecting the desorption behaviors, such as contact time, concentration of the desorbent, pH value of the solution, temperature and desorption isotherms, were investigated by the batch experiments. The results show that the adsorbed Cr（III） on GMZ bentonite can be easily extracted by the desorbent. Kinetics examination shows that desorption is slower than adsorption, and the desorption rate increases with time and reaches the equilibrium after 3 h. The final desorption ratios of Cr（III） are 89.4%, 56.5%and 77.2%in the desorption solution with 0.1 mol/L HCl, 1 mol/L NaCl, and 1 mol/L CaCl2, respectively, and the concentration can promote the desorption progress. Furthermore, the results of successive regeneration cycles indicate that the bentonite has a good regeneration ability and reusability. The pH value is an important factor in the Cr（III） desorption from the GMZ bentonite. The results of adsorption and desorption isotherms show that both adsorption and desorption isotherms are consistent with the Freundlich equation. The comparison of adsorption and desorption isotherms implies that the adsorption/desorption hysteresis is negligible and the transport of Cr（III） in bentonite can be described by a reversible adsorption process.

Synthesis of nano-MoS_2/bentonite composite and its application for removal of organic dye

A nano-MoS2/bentonite composite was synthesized by calcinating MoS3 deposited on bentonite in H2. The obtained composite was characterized using thermogravimetric analysis, X-ray diffractometer, scanning electron microscope and transmission electron microscope. The results show that nano-MoS2 particles are distributed on the surface of bentonite and form layered structures with layer distance of about 0.64 nm. The composite presents an excellent performance for the removal of methyl orange. Some operation conditions affect the removal efficiency of methyl orange, such as dosage of composite, initial concentration of methyl orange, temperature and pH value. However, light source does not influence the removal efficiency. The removal mechanism is attributed to the adsorption of methyl orange on the nano-MoS2/bentonite composite. The adsorption of methyl orange on the composite is in accordance with the pseudo-second-order kinetic model.

Fe离子在Soil-Bentonite Slurry wall中的渗透行为研究

采用实验室研究方法,研究了SB(Soil Bentonite)材料对Fe离子的吸附,以及Fe离子在SB Slurry wall中的穿透行为,实验结果显示,SB对Fe离子的吸附符合langmuir等温线,Fe离子在SB中迁移时,导致SB材料的渗透系数比纯水的渗透系数大一个数量级,Fe离子流出浓度随着时间的增加在不断增加。

纳米级团簇结构Bentonite-DMDAAC-AM乳胶粒的合成与表征

：在 Ｗ／Ｏ乳液的分散相内，使分散于Ｂｅｎｏｎｉｔｅ层间的ＡＭ与预先插层其中的阳离子单体ＤＭＤＡＡ就地共聚合，利用聚合热使 Ｂｅｎｔｏｎｉｔｅ崩解，并进一步层间剥离，从而制备纳米级团簇结构一Ｂｅｎｔｏｎｉｔｅ-ＤＭＤＡＡ-ＡＭ乳胶粒。用动力学方法研究各种因素对聚合热的影响以及聚合热与Ｂｅｎｔｏｎｉｔｅ层片剥离程度的关系；用 ＸＲＤ、ＤＳＣ等手段研究了 Ｂｅｎｔｏｎｉｔｅ的插层与剥离程度，并用乳胶粒的电泳行为及ＩＲ对产物进行了表征。

苯酚在Soil-Bentonite Slurry walls中的传输研究

实验室研究了SB(Soil Bentonite)材料对苯酚的阻截性能,以及无机离子对苯酚在SB Slurry wall中传输的影响。实验结果显示,苯酚在SB Slurry wall材料中的渗透速度与水在材料中的渗透的速度相同。无机离子的加入,改变了墙体材料的渗透系数,使得苯酚在墙体材料中的迁移速度加快。迁移速度变化与无机离子的加入量有关,加入量越大,苯酚在墙体中的迁移速度越快。

Experimental investigation into temperature effect on hydro-mechanical behaviours of bentonite

The bentonite barrier of underground repositories for high-level radioactive waste will be hydrated by the groundwater while it is subjected to high temperatures due to the radioactive decay of the wastes. These changes of temperature affect the hydraulic and mechanical responses of bentonite, which has important effects on design and performance of repositories. The temperature influence on the hydro-mechanical behaviour of bentonite was studied in this paper by experiments, which were carried out with the Spanish FEBEX bentonite compacted at dry densities expected in the＇ repository （from 1.5 to 1.8 Mg/m^3）. The dependence of the swelling strains of bentonite on the temperature has been measured from 30℃ to 90 ℃. At high temperatures the swelling capacity of clay slightly decreases. Also, a clear decrease of swelling pressure as a function of temperature was observed for the same dry densities. Nevertheless, the deformation of bentonite is more dependent on the stress than the temperature. An increase in the permeability of water saturated bentonite with temperature has also been detected. The water retention curves of bentonite compacted at different dry densities were determined under isochoric conditions and in the range of temperatures from 20 ℃ to 120℃. For a given density and water content, the suction decreases as the temperature increases at a rate, which is larger than the one predicted on the basis of water surface tension changing with temperature. Mechanisms related to the physico-chemical interactions that take place at microscopic level, in particular the transfer of interlayer water to the macropores triggered by temperature, seem to explain qualitatively the experimental observations.

Statistical design and kinetic and thermodynamic studies of Ni(Ⅱ) adsorption on bentonite

The adsorption of the bentonite toward Ni(II) from aqueous solution was studied to obtain optimum conditions,equilibrium model,thermodynamic and kinetic parameters.Statistical method was used to evaluate maximum amount of adsorbed Ni(II).In this work,p H of solution during stirring,contact time,initial Ni(II) concentration,particle size of bentonite and amount of bentonite were considered as effective parameters which should be examined.The increase of temperature has negative effect on the Ni(II) adsorption.The equilibrium data were correlated well with Freundlich and Dubinin–Radushkevich isotherm models the correlation coefficients of which are(R^2) 0.994 and 0.971,respectively.This model indicates heterogeneous and chemical absorption or ion exchange process.The values of thermodynamic parameters such as ΔH°,ΔS° and ΔG° of nickel adsorption reveal that it is a spontaneous,exothermic and associative process.The experimental data fit the pseudo-second-order kinetic very well with correlation coefficient(R^2) more than 0.995.

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene （m-DNB） and nitrobenzene to original bentonite in aqueous solution containing different electrolytes （i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide （TMAB）） was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl 〉 NH4Cl 〉〉 TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out effect is insufficient to account for the sorption enhancement by original bentonite with increasing KCI or NH4Cl concentration. X-ray diffraction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K^＋ or NH4^＋ into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K^＋ at high solute-loadings （〉 20（0-400 mg/kg）. The sorption of m-DNB to initially modified TMA^＋-bentonite and K^＋-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA^＋ and K^＋.

Characterization, Acid Activation and Bleaching Performance of Bentonite from Xinjiang

Bentonite produced in Xiazijie, Xinjiang (China) was characterized by X-ray diffraction (XRD), dif- ferential thermal analysis (DTA), thermogravimetric analysis (TG) and cation exchange capacity (CEC). The ben- tonite is composed of dioctahedral montmorillonite with predominant quantity, certain amounts of quartz, feldspar and illite and minor amounts of kaolinite, gypsum, etc. The raw bentonite has a CEC of 0.6497 meq·g-1 and allows to be characterized as typical sodium bentonite. In order to bleach cottonseed oil, optimum conditions for sulfuric acid activation of the raw bentonites were investigated, which were obtained by selecting various acid strength, at 96—98℃ and activating for 4h with 1︰2 solid-liquid ratio. The acid activation bentonites were suitable for decol- orization of cottonseed oil through removing carotene and chlorophyll. The bleaching capabilities of different pig- ments with activated bentonite with treatment of 25% sulfuric acid were 70.3%, 73.1%, 83.2%, 81.8% and 88.9%, respectively. Bleaching with acid activated bentonite gave oils lower peroxide values and acid values.

NBR/ORGANOMODIFIED BENTONITE INTERCALATED HYBRIDS AND THEIR EFFECTS ON THE TOUGHNESS OF PVC

Hybrids of intercalative nitrile-butadiene rubber/organomodified bentonite (NBR/OMB) were prepared by thelatex intercalation technique. Investigation of their mechanical properties and the microstructore of NBR/OMB showed thatthe organomodified bentonite is an effective toughener for NBR. Transmission electronic microscopy (TEM) and X-rnydiffraction (XRD) tests showed that the NBR macromolecule could be intercalated into the galleries of bentonite.Incorporation of NBR/OMB hybrids as tougheners into poly(vinyl chloride) (PVC) results in a substantial increase in theimpact strength of PVC, but little decrease in its tensile strength and flexural strength, compared to the unmodified PVC.

Synthesis and Photocatalytic Activity of Ti-pillared Bentonite

Ti-pillared bentonite has been successfully prepared using a modified method that can induce the transformation of TiO2 pillar from amorphous to anatase phase at a low temperature （150℃）. The value of d0.01 =1.94 nm obtained by Ti-pillared bentonite is larger than that of corresponding raw clay （1.56 nm）. Due to large numbers of Ti-pillars formed, the Ti-pillared bentonite shows an excellent ability in adsorbing Rhodamine B （RB）. The photocatalytic activity and kinetic equation are investigated by decomposing RB solution under the UV irradiation. It is found that the Ti- pillared bentonite shows super photocatalytic activity for the degradation of RB solution compared with the untreated bentonite and pure TiO2, and the kinetic equation of the degradation of RB solution is a 1.5-oder equation.