Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface

Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herein,we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs.The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes.Consequently,the alloy network-modulated zinc deposition interface realizes high coulombic efficiency of 99.2%and high stability.As proof,Zn//Zn symmetric cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 m A/cm^(2)and 1200 h at 5 m A/cm^(2),significantly superior to Zn//Zn symmetric cells with unmodified zinc deposition interface(whose operation lifetime is shorter than 50 h),and meanwhile,Zn3V3O8cathodebased ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes.As expected,the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8cathodes to deliver superior cycling stability,better than most currently-reported anode-free ZIBs.This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.

Estimation of lead and zinc emissions from mineral exploitation based on characteristics of lead/zinc deposits in China

Nonferrous mining activities are some of the largest sources of heavy metals emissions into the environment and China is one of the largest producers and consumers of lead and zinc in the world.The cumulative productions and emissions of lead and zinc from mining-related activities in China were estimated.Up to 2007,the cumulative productions of lead and zinc in China were estimated to be about 6.69 and 12.59 Mt,respectively;and about 1.62 Mt lead and 3.32 Mt zinc emitted into the ambient environment during the mining,processing and smelting activities,representing 24.39% and 26.36% cumulative production,respectively.Among these three types of mining-related activities,mineral processing contributes the most to the total emission of 50.67% lead and 45.51% zinc.

Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead-zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan-Yunnan-Guizhou （SYG） Pb-Zn-Ag multi- metal mineralization area in China. Sulfides minerals including sphalerite, galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite, quartz, and barite, making this deposit distinct from most lead-zinc deposits in the SYG. This deposit is controlled by tectonic structures, and most mineralization is located along or near faults zones. Emeishan basalts near the ore district might have contributed to the formation of orebodies. The j34S values of sphalerite, galena, pyrite and barite were estimated to be 3.6‰-13.4‰, 3.7‰-9.0‰, -6.4‰ to 29.2‰ and 32.1‰34.7‰, respectively. In view of the similar δ34S values of barite and sulfates being from the Cambrian strata, the sulfur of barite was likely derived from the Cambrian strata. The homogenization temperatures （T ≈ 134--383℃） of fluid inclusions were not suitable for reducing bacteria, therefore, the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district. Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur, it was not the main mechanism. Considering other aspects, it can be suggested that sulfur of sulfides should have been derived from magmatic activities. The δ34S values of sphalerite were found to be higher than those of coexisting galena. The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions, suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.

Order of sphalerite and galena precipitation: A case study from lead-zinc deposits in southwest China

Most of the lead and zinc deposits in Southwest China, are characterized by mineral zoning, which is especially true for the Huize and Zhaotong deposits. The mineral assemblage zoning is consistent for both horizontal and vertical zoning, from the base(center) of the ore body to the top(outermost), the mineral zones are as follows. I-1: coarse-grained pyrite and a little puce sphalerite;I-2: brown sphalerite, galena, and ferro-dolomite;I-3: galena, sandy beige and pale yellow sphalerite, and calcite;and I-4: fine-grained pyrite, dolomite, and calcite. Among them, sphalerite is the landmark mineral of different zoning. From I-1 to I-3, the color of sphalerite changes from dark to light, its crystalline size changes from coarse to fine, and its structure changes from disseminated to veinlet. This mineral zoning is seen not only on a microscopic scale, but is also clear on a mesoscopic and macroscopic scale. It is caused by the order of the sphalerite and galena precipitation. We studied the metallic minerals and fluid inclusions using a thermodynamic phase diagram method, such as lgfO2–lgfS2, pH–lgfO2, pH–lg[Pb^2+] and pH–lg[HS^-], discussed the constraints on the order of the sphalerite and galena precipitation in the migration and precipitation process of lead and zinc under different pH values, oxygen fugacity, sulfur fugacity, and ionic activity. We also explain the formation mechanism and propose that the main controlling factor of the order of the sphalerite and galena precipitation is sulfur fugacity.

A Preliminary Study on Fluid Inclusions and Mineralization of Xitieshan Sedimentary-Exhalative (SEDEX) Lead-Zinc Deposit

The Xitieshan lead-zinc deposit is located at the northern margin of the Qaidam Basin, Qinghai Province, China, and had developed a complete marine sedimentary-exhalative system. Our preliminary study of ore-forming fluids shows that fluid inclusions in quartz from altered stockwork rocks that represent the pipe facies have a wide range of temperature and salinity. The intense fluid activities are characteristics of the pipe facies of the exhalative system. Fluid inclusions in carbonates near the unstratified ore bodies hosted in the thick-bedded marble which represents vent-proximal facies are large in size and have moderate to high temperatures. They represent unerupted sub-seafloor fluid activity. Fluids in altered stockwork rocks and carbonates have similar H20-NaCI-CO2 system, both belonging to the sedimentary-exhalative system. The fluids migrate from the pipe facies to the unstratified ore bodies. Boiling of the fluids causes the separation of CO2 vapor and liquid H2O. When the fluids migrate into the unconsolidated thick-bedded marble, the escape of CO2, decreasing temperature and pressure as well as some involvement of seawater into the fluids result in the unmixing of fluids with high and low salinity and deposition of ore-forming materials. The two unmixed fluids were trapped in unconsolidated carbonates and the ore-forming materials were deposited in the unconsolidated carbonates to form the sedimentary-exhalative type unstratified ore bodies. The oreforming temperature of unstratified ore bodies is up to high temperature indicating that there is a huge ore-forming potential in its deep.

Qinling-Type Lead-Zinc Deposits

Qinling-type Pb-Zn deposits are located in the Qinling fold belt, occurring in the fine-clastic and carbonate rocks of the Devonian marine facies. They are reformed sedimentary deposits originating from hydrothermal waters, and may be subdivided into 2 subtypes: hydrothermal sedimentary deposits (Changba subtype) and reformed hydrothermal sedimentary deposits (Bijiashan-Qiandongshan subtype). In comparison with some of the famous Palaeozoic Pb-Zn deposits in the world, the Qinling-type Pb-Zn deposits constitute an independent type, which possesses some characteristics of both hydrothermal sedimentary deposits (Meggen type) and reformed hydrothermal deposits (Mississippi Valley type).

Sphalerite Chemistry, Niujiaotang Cd-Rich Zinc Deposit, Guizhou, Southwest China

Sphalerite in the Niujiaotang Cd rich zinc deposit, Duyun, Guizhou is characteristically light yellow in color with significant enrichment of cadmium which ranges from 0.83% to 1.97% (averaging 1.38%) in concentration in the mineral, corresponding to an enrichment coefficient as high as 30.47 to 72.96. In comparison with other major Pb Zn deposits in the world (the Mississippi Valley deposits, and the Fankou and Jinding deposits in China) the Niujiaotang deposit is n-n×10 times richer in cadmium. Sphalerite in the deposit is also rich in Ga and Ge, but poor in In, Mn and Fe, suggesting some special mechanisms that govern the geochemical behavior of these trace elements. Except for a minor amount of independent minerals like greenockite, cadmium occurs mainly as isomorphous impurity in the crystal lattice of sphalerite. During weathering and leaching under supergene condition, cadmium was separated from Zn, resulting in some secondary minerals of Cd, including oxides and otavite.

REE Geochemistry of the Lead-Zinc Ores from the Jinding Lead-Zinc Deposit, Lanping, Yunnan

Nineteen volcanic and magmatic rock samples were collected from the Jinding lead-zinc deposit and its surrounding areas in Yunnan. The ICP and AES analyses, referred to the previous results, show that the metal minerals and altered rocks in the Jinding lead-zinc deposit display a decreasing trend of ΣREE from the early to late stages of mineralization, and similarities in REE distribution patterns, indicating that the ore fluids are characterized by high LREE enrichment, markedly negative δCe anomaly and slight δEu anomaly. These REE distribution patterns exhibit striking similarities to those of the Pliocene trachyte in the study area, both of which are similar in ΣREE, LREE/HREE ratio, δEu and δCe. The ore fluids besides the basin fluids in the deposit are also closely related to those associated with Pliocene trachyte magmas.

A review of major non-sulfide zinc deposits in Iran

The numerous non-sulfide zinc ore deposits were the historical basis for the development of zinc mining in Iran.They include the Mehdiabad,Irankouh and Angouran world-class deposits,as well as the Zarigan and Haft-har deposits.These deposits were formed by supergene oxidation of primary sulfide minerals during the complex interplay of tectonic uplift,karst development,changes in the level of the water table,and weathering.Zn(Pb)carbonates,Zn-hydrosilicates and associated hydrated phases directly replace the primary ore bodies or fill cavities along fractures related to uplift tectonics.Direct replacement of primary sulfides is accompanied by distal precipitation of zinc non-sulfide minerals in cavities or internal sediments filling.The mineralogy of the non-sulfide mineralization in all six deposits is generally complex and consists of smithsonite,hydrozincite,and hemimorphite as the main economic minerals,accompanied by iron and manganese oxy-hydroxides and residual clays.Commonly,non-sulfide minerals in these deposits consist of two types of ore:red zinc ore(RZO),rich in Zn,Fe,Pb-(As)and white zinc ore(WZO),typically with very high zinc grades but low concentrations of iron and lead.Typical minerals of the RZO are Fe-oxyhydroxides,goethite,hematite,hemimorphite,smithsonite and/or hydrozincite and cerussite.Common minerals of the WZO are smithsonite or hydrozincite and only minor amounts of Fe-oxyhydroxides and hemimorphite.

LAWS GOVERNING THE DISTRIBUTION OF LEAD-ZINC DEPOSITS IN CHINA

An attempt is made in this paper to describe the following laws governing the distribution of lead-zinc deposits in China: spatial distribution laws, temporal distribution laws, deep level control laws, and deposits association and zoning laws.

Chemical Conversion Film of Mischmetal on Zinc Deposit

A conversion film was obtained on zinc deposit by immersing zinc coated specimens in a mischmetal salt solution. Several factors affecting the anticorrosive efficiency of the conversion film were studied. The suitable technological conditions were established. The composition and the thickness of the conversion film were determined by Auger electron spectroscopy(AES).

An experimental study on metal precipitation driven by fluid mixing: implications for genesis of carbonate-hosted lead–zinc ore deposits

A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping withor without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H_2S, rather than HS^-or S^(2-),dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.

Study on the multi-sources of ore-forming materials and ore-forming fluids in the Huize lead-zinc ore deposit

The Huize large-sized Pb-Zn deposit in Yunnan Province, China, is characterized by favorable metallogenic background and particular geological settings. This suggested that the ore-forming mechanism is relatively unique. On the basis of geological features such as the contents of mineralization elements, the REE concentrations of gangue calcites, the REE concentrations of calcite veins in the NE-trending tectonic zone and the Pb, Sr, C, H and O isotopic compositions of different minerals, this paper presents that the ore-forming materials and ore-forming fluids of the deposit were derived from various types of strata or rocks. This is a very significant conclusion for us to further discuss the mineralization mechanism of the deposit at depth and establish an available genetic model.

EXPERT OPTIMIZED CONTROL TECHNIQUE FOR ELECTROLYTIC DEPOSITION PROCESS OF HYDROMETALLURGY OF ZINC

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Existing state of Cd in the Niujiaotang Cd-rich zinc deposit, Guizhou, China

As a dispersed element, cadmium is difficult to enrich and mineralize. As the Cd tetrahedron is similar tothat of Zn in covalent radius and crystal structure, both the elements possess similar geochemical habits.Cd is present mainly as isomorphous impurity in sphalerite. So Cd, as an associated element, occurslargely in Pb-Zn deposits. Current research both at home and abroad is focused on the environmental effect of Cd, but little work has been done on the mechanism of enrichment and mineralization of Cd. Theresearch papers available are mostly restricted to the ordinary geochemical characteristics of CdFrom the end of 1980s to the early 1990s, independent ore deposits of Te, Tl and other dispersed elements were discovered in the region of Southwest China. Prof. Tu Guangzhr proposed that dispersed elements can form their independent ore deposits. It has been realized that the dispersed

Discovery of seismites in Upper Sinian stratiform lead-zinc deposits in Dadu River valley, Sichuan, China: Implication for ore genesis

A number of lead-zinc sulphide deposits have been discovered in recent years in dolo- mitic rocks of the Upper Sinian Dengying Formation in the Dadu River valley region, Sichuan Province, China. The lead-zinc mineralization is closely associated with a black siliceous exhalite that has been traced over 50 km of strike. This makes Dadu River valley the most extensive stratiform non-ferrous sulphide horizon having been discovered to date in China. In a previous study by the first author (LIN), these deposits were recognised as belonging to the broad spectrum of lead-zinc sedimentary exhala- tive (SEDEX) deposits. In this paper, seismites and seismogenetic structures occurring in close association with the Dadu River valley mineralized zone are described. The close spatial and temporal relationship between the seismites and mineralization provides strong evidence for the hypothesis that the lead-zinc SEDEX deposits formed in direct response to earthquake activities around the Sinian-Cambrian boundary. The earthquakes are postulated to be an effective dynamic mechanism for triggering the upward migration of deep circulating ore fluids along synsedimentary growth faults and their exhalation onto the sea-floor to form the extensive deposits of stratiform lead-zinc sulphide ore.

Synthesis of Zinc Oxide Nanostructures on Graphene/Glass Substrate via Electrochemical Deposition: Effects of Potassium Chloride and Hexamethylenetetramine as Supporting Reagents

The effects of the supporting reagents hexamethylenetetramine(HMTA)and potassium chloride(KCl)mixed in zinc nitrate hexahydrate(Zn(NO3)2 6H2O)on the morphological,structural,and optical properties of the resulting Zn O nanostructures electrodeposited on graphene/glass substrates were investigated.The supporting reagent HMTA does not increase the density of nanorods,but it does remarkably improve the smoothness of the top edge surfaces and the hexagonal shape of the nanorods even at a low temperature of 75°C.Hydroxyl(OH-)ions from the HMTA suppress the sidewall growth of non-polar planes and promote the growth of Zn O on the polar plane to produce vertically aligned nanorods along the c axis.By contrast,the highly electronegative chlorine(Cl-)ions from the supporting reagent KCl suppress the growth of Zn O on the polar plane and promote the growth on non-polar planes to produce vertical stacking nanowall structures.HMTA was found to be able to significantly improve the crystallinity of the grown Zn O structures,as indicated by the observation of much lower FWHM values and a higher intensity ratio of the emission in the UV region to the emission in the visible region.Equimolar mixtures of Zn(NO3)2 6H2O and the supporting reagents HMTA and KCl seem to provide the optimum ratio of concentrations for the growth of high-density,uniform Zn O nanostructures.The corresponding transmittances for such molar ranges are approximately 55–58%(HMTA)and 63–70%(KCl),which are acceptable for solar cell and optoelectronic devices.

Genesis and district mineralization model of lead-zinc deposits from the eastern margin of Kangdian axis

SITUATED on the eastern margin of Kangdian axis the lead-zinc mineral belt is an important mineral occur- rence of lead-zinc in southwestern China. It is 1 200 km in length from Kangding in Sichuan Province tonortheastern Yunnan Province, and 500 km in width from west to east. There are four large deposits,fourteen middle deposits and many small deposits or mineralized spots. Famous large deposits such as Doliangzi, Tianbaoshan, Chipu and Kuangshanchang are distributed in this belt. 1 Geological setting There are many mineral-bearing strata in carbonate-hosted lead-zinc deposits of this mineral belt,such as Dengying formation （Zbdn）, Longwangmiao formation （2 l） Erdaoshui formation （ 3 e ）,Daqing formation（O2 d ）, Daguan formation （S2d ）, the lower Devonian and Baizuo formation （ C1 b）.

Hydrothermal sedimentation and lead-zinc deposit in Dengying formation of the Sinian system in Panxi region

IN addition to vanadium titano-magnetite, lead-zinc ore is also one of the mineral resources with great exploring potentiality in the Panxi region of Sichuan Province, China. In the carbonate rock strata of theSinian Dengying Formation which account for about 3.5%-11.4% of the total thickness of the strataexposed in the Panxi region there are quite a number of the Pb-Zn deposits that account for 53.4% of thetotal Pb-Zn ore reserve in the whole region. Furthermore, some large Pb-Zn deposits such as the Tianbaoshan Pb-Zn deposit in Huili, the Daliangzi Pb-Zn deposit in Huidong and the Yinchanggou Pb-Zn deposit in Ningnan are also hosted in the Sinian Dengying Formation. Why? Previous studies indicated that the high background values of Pb and Zn, favorable lithofacies andpaleogeographic conditions and good ore-hosting structures made the Sinian Dengying Formation a pre-

THE METALLOGENIC STRUCTURE OF VEIN-SHAPED LEAD-ZINCDEPOSIT IN HENGSHANLING-SHEXINGPING,CHENZHOU,HUNAN

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