Extending the solid solution range of sodium ferric pyrophosphate:Off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)as a novel cathode for sodium‐ion batteries

Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.

Effect of inorganic salt impurities on seeded precipitation of silica hydrate from sodium silicate solution

To clarify the precipitation of silica hydrate from the real desilication solutions of aluminosilicate solid wastes by adding seeds and improve integrated waste utilization,the seeded precipitation was studied using synthesized sodium silicate solution containing different inorganic salt impurities.The results show that sodium chloride,sodium sulfate,sodium carbonate,or calcium chloride can change the siloxy group structure.The number of high-polymeric siloxy groups decreases with increasing sodium chloride or sodium sulfate concentration,which is detrimental to seeded precipitation.Calcium chloride favors the polymerization of silicate ions,and even the chain groups precipitate with the precipitation of high-polymeric sheet and cage-like siloxy groups.The introduced sodium cations in sodium carbonate render a more open network structure of high-polymeric siloxy groups,although the carbonate ions favor the polymerization of siloxy groups.No matter how the four impurities affect the siloxy group structure,the precipitates are always amorphous opal-A silica hydrate.

Adsorption of sodium polyacrylate at interface of dicalcium silicate-sodium aluminate solution

The adsorption isotherm of sodium polyacrylate on dicalcium silicate（2CaO-SiO2） in sodium aluminate solution at 80 ℃ was studied.The type of surface adsorption of sodium polyacrylate is saturated adsorption,and the adsorption behavior belongs to L-type,according with the monolayer adsorption model of Langmuir equation.The surface coverage of sodium polyacrylate is 1.06 mol/μm2.The relation curve between the surface pressure and the molecular area of adsorption film was obtained by Gibbs formula.The variation of interfacial energy caused by adsorption as well as the relationship between the relation curve and the type of adsorption was discussed.

Removal of S^(2-) ion from sodium aluminate solutions with sodium ferrite

The synthesis of sodium ferrite and its desulfurization performance in S2 -bearing sodium aluminate solutions were investigated. The thermodynamic analysis shows that the lowest temperature is about 810 K for synthesizing sodium ferrite by roasting the mixture of ferric oxide and sodium carbonate. The results indicate that the formation process of sodium ferrite can be completed at 1173 K for 60 min, meanwhile raising temperature and reducing NazCO3 particle size are beneficial to accelerating the formation of sodium ferrite. Sodium ferrite is an efficient desulfurizer to remove the S2- in aluminate solution, and the desulfurization rate can reach approximately 70% at 373 K for 60 min with the molar ratio of iron to sulfur of 1：1-1.5：1. Furthermore, the desulfurization is achieved by NaFeS2·2H2O precipitation through the reaction of Fe（OH）4 and S^2- in aluminate solution, and the desulfurization efficiency relies on the Fe（OH）4^- generated by dissolving sodium ferrite.

Continuous changes in electrical conductivity of sodium aluminate solution in seeded precipitation

The mechanism of seeded precipitation of sodium aluminate solution was studied by measuring the seeded-precipitation rate and electrical conductivity online, as well as calculating the activity and fraction of ion pair. The results show that the electrical conductivity of sodium aluminate slurry linearly decreases with increasing aluminum hydroxide addition. Moreover, both the electrical conductivity of slurry and the difference in electrical conductivity between sodium aluminate solution and slurry remarkably decline in the first 60 min before gradually increasing in the preliminary 10 h and finally reaching almost the same level after 10 h. In low Na2 O concentration solution the activities of Na OH and Na Al（OH）4 in seeded precipitation are high, which can enlarge the difference in conductivity between slurry and solution. Additionally, more ion pairs exist in solution in preliminary seeded precipitation, and the adsorption of Na＋Al（OH）4- on seed surface is likely to break the equilibrium of ion pair formation and to decrease the difference in conductivity in preliminary seeded precipitation.

Measurements of zinc oxide solubility in sodium hydroxide solution from 25 to 100 °C

The solubility of zinc oxide in sodium hydroxide solution was measured in a closed polytetrafluoroethylene vessel from 25 to 100 ℃. The ZnO solubility was determined by employing the method of isothermal solution saturation. The results show that only ZnO solid exists in the equilibrium state in the low concentration alkali regions, and the solubility of zinc oxide is almost invariable with temperature. With the increase of alkali concentration, equilibrium solid turns from ZnO to NaZn（OH）3 suddenly, this mutation is called invariant point. The alkali concentration of the invariant points increases with increasing temperature, but the solubility of NaZn（OH）3 decreases with increasing alkali concentration at the same temperature. At the same Na2O concentration, the higher the temperature is, the higher the solubility of NaZn（OH）3 is.

Influence of the Preparative History on Physico-chemical Properties of Sodium Aluminate Solutions

1.IntroductionSodium aluminate solutions are veryimportant intermediate products in alumin-ium metallurgy.The physico-chemicalproperties of sodium aluminate solutions areconcerned by metallurgists and engineersdealing with alumina production[1].Thedata of viscosity,electroconductivity,UV

Absorption of Sulphur Dioxide with Sodium Citrate Buffer Solution in a Rotating Packed Bed

Absorption of SO2 from a SO2/air mixture with sodium citrate buffer solution was investigated using a rotating packed bed(RPB) in laboratory scale.The effects of operating parameters,such as the rotation speed of RPB,liquid-gas ratio,inlet gas flow rate,inlet concentration of SO2 in flue gas,sodium citrate buffer concentration and initial pH of absorption solution,on the SO2 concentration in the absorption solution or removal efficiency of SO2 were examined.Incremental rate of sulfate radical ions in the absorption solution was also examined.Experimental results indicate that the efficiency of this regenerative process will be improved by using RPB under appropriate operating conditions,and the generation of SO2-4 will be restrained in the process in RPB.

Precipitation of spherical boehmite from concentrated sodium aluminate solution by adding gibbsite as seed

The precipitation of spherical boehmite was studied by surface energy calculations, measurements of precipitation ratios, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The surface energy calculation results show that the(001) and(112) planes of gibbsite surfaces are remarkably stable because of their low surface energies. In addition, the(010) plane of boehmite grows preferentially during precipitation because of its low surface energy. Thus, we propose a method to precipitate spherical boehmite from a supersaturated sodium aluminate solution by adding gibbsite as seed in a heterogeneous system. In this method, gibbsite acts as the preliminary seed and saturation modifier. The results show that the fine boehmite first nucleates on the(001) and(112) planes of gibbsite and then grows vertically on the(001) and(112) basal planes of gibbsite via self-assembly, thereby forming spherical boehmite. Simultaneously, gibbsite is dissolved into the aluminate solution to maintain the saturation for the precipitation of boehmite. The precipitation ratio fluctuates(forming an M-shaped curve) because of gibbsite dissolution and boehmite precipitation. The mechanism of boehmite precipitation was further discussed on the basis of the differences in surface energy and solubility between gibbsite and boehmite. This study provides an environmentally friendly and economical method to prepare specific boehmite in a heterogeneous system.

Mineral transition of desilication products precipitated in synthetic sodium aluminate solution under atmospheric pressure

The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products（DSPs） precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different reaction conditions were systematically researched. The DSPs formed under atmospheric pressure comprise amorphous phase, zeolite A, zeolite and sodalite, and the DSPs concentration and crystallinity increase with the increase of initial silica concentration, initial molar ratio of caustic Na2O to Al2O3（αK） and desilication duration. Decreasing the initial silica concentration, initial αK and increasing the desilication duration can reduce the proportion of zeolite A. The zeolite and sodalite are the stable DSPs, while the precipitation of zeolite A occurs at a high silica-supersaturated state in sodium aluminate solution. The DSPs are precipitated in the form of agglomerates, but the morphologies of various DSPs are quite different. Both the molar ratios of Na2O to Al2O3 and SiO-2 to Al2O3 in DSPs increase with the increasing desilication duration, resulting in the increase of the cell volumes of various DSPs. The precipitation sequence of DSPs under atmospheric pressure is： amorphous phase→zeolite A→zeolite→sodalite.

INFLUENCE OF PREPARATIVE HISTORY ON STRUCTURE AND PROPERTIES OF SODIUM ALUMINATE SOLUTIONS

It has been found that samples of sodium aluminate solutions with the same composition but different preparative history may have difTerent structure and physico-chemical properties.The structure of sodium-bearing aluminate solutions change very slowly during the storage after preparation.Sodium aluminate solutions contain several ammunium-bearing anisons such as Al(OH)^(-)_(4),Al(OH)^(3-)_(6)and[(HO)_(3)Al-O-Al(OH)_(3)]^(2-),etc.These anions can convert to each other but the reactions are very slow owing to the formation or breakage of covalent Al-O bond.Hence the ratio between these anions approaches equilibrium very slowly after the preparation,and the structure or properties of these solution samples before equilibrium is reached depend on their preparative histosive.

Effect of oxalate on seed precipitation of gibbsite from sodium aluminate solution

The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitation process were systematically investigated by physicochemical properties test,using SEM and Raman spectra.As the concentration of sodium oxalate increases,both the precipitation rate and particle size of gibbsite decrease.The presence of sodium oxalate not only increases the viscosity of sodium aluminate solution,but also promotes the transformation of Al(OH)4^? to Al2O(OH)6^2?.The overall reaction rate constant decreases and the apparent activation energy of gibbsite increases with the increasing sodium oxalate concentration,the rate controlling step of which is chemical reaction.The needle-like sodium oxalate precipitates on the gibbsite crystals and covers the active Al(OH)3 seed sites,which leads to the lower precipitation rate and the finer particle size of gibbsite during the seed precipitation process.

Reaction kinetics and mechanism of calcium oxide in dilute sodium aluminate solution with oxalate based on lime causticization

The formation kinetics and mechanism of tricalcium aluminate hydrate and calcium oxalate in dilute sodium aluminate solution and sodium oxalate solution were studied respectively based on the lime causticization, and the optimal conditions for removing the oxalate in dilute sodium aluminate solution as well as the mechanism were finally obtained.The formation processes of tricalcium aluminate hydrate and calcium oxalate are mainly controlled by the chemical reaction and the inner diffusion respectively,and the corresponding reaction rate equations as well as the apparent activation energy were calculated. The hydrocalumite with a spatially interleaved structure will form in dilute sodium aluminate solution with sodium oxalate, greatly removing the oxalate impurity by absorption. Calcium oxalate can be converted to tricalcium aluminate hydrate with the increasing reaction time. The oxalate causticization efficiency and the alumina loss rate can be over 90% and below 31% respectively when reacted at 50℃ with a stirring rate of 200 r/min.

Periodical attenuation of Al(OH)_3 particles from seed precipitation in seeded sodium aluminate solution

Periodical attenuation of particles,which interferes seriously the normal alumina production,exists in Bayer process.In order to solve this problem,the rule of periodical attenuation of Al(OH) 3 particles was investigated by laboratory experiments under simulated industrial conditions.The results show that at higher temperature the variation period of particle size is shortened,while prolongs with more solid content.Particle size fluctuation amplitude reduces with the temperature rising but increases with the solid content increasing.Particle size distribution becomes more uniform by replenishing fine seeds,enabling the periodical fluctuation of Al(OH)3 particle size to be attenuated.Combining properly the additives with controlling the seed size is able to reduce the amplitude of periodical fluctuation and shorten the attenuation time.With unbalance of particle size distribution,the particles gradually become bigger,even inducing the decrease of the specific surface area of seeds,which is the major reason causing explosive attenuation of Al(OH)3 particles in seed precipitation process.

Behavior of calcium oxalate in sodium aluminate solutions

The stability of calcium oxalate is critical for the removal of sodium oxalate from sodium aluminate solutions.This studyinvestigated the behavior of calcium oxalate in sodium aluminate solution containing sodium carbonate.Results show that calciumoxalate can be converted to tricalcium aluminate hydrate(TCA)and calcium carbonate in sodium aluminate solution and sodiumcarbonate solution,respectively.Elevating temperature,extending residence time,or increasing caustic soda concentration enhancesthe conversion ratio of calcium oxalate in sodium aluminate solution;as a consequence,anti-causticisation occurs.Stability ofcalcium-containing compounds in sodium aluminate solution containing sodium carbonate differs from that in sodium aluminatesolution or sodium carbonate solution.Na2CO3in aluminate solution accelerates the transformation of calcium oxalate;thus,aluminais lost because of4CaO·Al2O3·CO2·11H2O and TCA formation.Calcium carbonate,4CaO·Al2O3·CO2·11H2O and calcium oxalatecan change into TCA in sodium aluminate solution at elevated temperature.Calcium oxalate remains relatively stable in dilutealuminate solution within a short residence time at low temperature.Thus,a novel process for removal of sodium oxalate by limecausticisation was presented and employed in an alumina refinery in China.

Equilibrium concentration of lithium ion in sodium aluminate solution

Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.

Comparative study of two bowel preparaton regimens for colonoscopy: Senna tablets vs sodium phosphate solution

AIM: To compare the efficacy and acceptance of senna tablet and sodium phosphate solution for bowel preparation before colonoscopy.METHODS: One hundred and thirty four patients, who needed elective colonoscopy, were randomly allocated to take 180 mg senna tablet or 95 mL sodium phosphate solution on the day before colonoscopy. The effi cacies of both laxatives were compared using the mean difference of colon-cleanliness score of the rectum, sigmoid segments, descending colon, transverse colon and cecum. The scores were rated by two observers who were blinded to the laxatives administered. The higher score means that the colon is cleaner. The efficacy of both laxatives were equivalent if the 95% confidence interval of the mean difference of the score of colon lie within -1 to +1. RESULTS: On intention-to-treat analysis, the mean cleanliness scores in the four segments of colon except the cecum were higher in the sodium phosphate group than those in senna group (7.9 ± 1.7 vs 8.3 ± 1.5, 8.0 ± 1.8 vs 8.5 ± 1.4, 7.9 ± 2.0 vs 8.5 ± 1.3, 7.9 ± 2.0 vs 8.2 ± 1.4 and 7.2 ± 1.7 vs 6.9 ± 1.4, respectively). The 95% conf idence intervals (95% CI) of mean difference in each segment of colon were not found to lie within 1 point which indicated that their effi cacies were not equivalent. The taste of senna was better than sodium phosphate solution. Also, senna had fewer side effects. CONCLUSION: The effi cacy of senna is not equivalentto sodium phosphate solution in bowel preparation for colonoscopy, but senna may be considered an alternative laxative.

RAMAN SPECTRA OF SODIUM ALUMINATE SOLUTIONS WITH HIGH-CAUSTIC RATIO AND HIGH CONCENTRATION

The constitution of high-caustic ratio and highly concentrated sodium aluminate solutions has been investigated by Raman spectra method.By comparison with the Raman spectra of crystalline solids of Ca_3[Al(OH)_6]_2 and Ba_2[Al_2(OH)_(10)],it can be concluded that AI(OH)_6^(3-)ion and perhaps its polymers may be formed in these solutions.

Low-temperature phase transitions of sodium aluminate solutions

A series of low-temperature phase transitions of sodium aluminate solutions were studied by differential scanning calorimetry (DSC) and Raman spectroscopy. The results indicate that NaOH concentration is a primary impact factor for the binary eutectic point and ice melting temperature of sodium aluminate solutions with low NaOH concentration. In addition, the phase transition process of sodium aluminate solutions with low NaOH concentration from 123.15 to 283.15 K is divided into four steps: non-crystal to crystal, ternary eutectic reaction, binary eutectic reaction and ice melt. The projection phase diagram of NaOH-Al(OH)3-H2O system at low temperature was plotted, in which the ternary eutectic temperature for sodium aluminate solutions is 183.15 K.

Influence of silicate anions structure on desilication in silicate-bearing sodium aluminate solution

The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.