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.

An aqueous BiI_(3)-Zn battery with dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox

The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.

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.

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.

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).

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).

Electrodeposition of zinc coatings from the solutions of zinc oxide in imidazolium chloride/urea mixtures

To solve the inherent disadvantages in conventional processes for electrodeposition of zinc, it＇s necessary to develop more high-efficiency and environmentally friendly electrolytes. In this work, it was found that the dissolution of ZnO was remarka- bly enhanced in some imidazolium chloride by the addition of urea, and the solubility of ZnO in 1：1 [Amim]C1/urea mixture was as high as 8.35 wt% at 373.2 K. Electrochemical measurements showed that zinc could be readily electrodeposited from the solutions of ZnO. Bright, dense and well adherent zinc coatings with good purity were obtained from 0.6 M solution of ZnO in 1：1 [Amim]C1/urea at 323.2-343.2 K. It＇s expected that the solutions of ZnO in imidazolium chloride/urea mixtures have the potential to replace the traditional electrolytes, especially toxic zinc chloride-based ones for zinc electroplating, as well as preparation of zinc materials.

Chemical composition of oscillatory zoned garnets from the largescale Mengya'a Pb–Zn skarn deposit: implications for fluid physicochemical conditions and formation

The Mengya’a Lead–zinc deposit is a large skarn deposit in the north of the eastern segment of Gangdese metallogenic belt.The garnet is the main altered mineral in the Mengya’a area.The color of the garnet varies from chartreuse to dark yellow brown and to russet.The brown garnet(Grt1)is related to pyrrhotite and chalcopyrite,and the green garnet(Grt2)is associated with lead–zinc mineralization.LA-ICP-MS is the induced coupled plasma mass spectrometry.This paper has used this technique to investigate Grt1 and Grt2.Grt1 develops core–rim textures with strong oscillation zone occurring in rim,whereas Grt2lacks core–rim textures and featured by oscillation zone.LA–ICP–MS analysis shows that garnets of Mengya’a are rich in CaO(29.90–37.52%)and FeO(21.17–33.35%),but low in Al_(2)O_(3)(0.05–4.85%).The calculated end members belong to grandite(grossular–andradite)garnets andradite.The negative Al(IV)versus Fe^(3+),positive Al(IV)versus total Al stoichiometric number,the positive Al(IV)versus Fe^(3+),and the negative Al(IV)versus total REE,all indicate that the substitution of REEs in garnets is controlled by YAG.All Garnets are depleted in large lithophile elements(e.g.,Rb=0.00–4.01 ppm,Sr=0.03–8.56 ppm).The total REE in Grt1 core is high(ΣREE=233–625 ppm),with HREE enriched pattern(LREE/HREE=0.33–1.69)and weak negative Eu anomalies(δEu=0.21–0.47).In contrast,the total REEs in the Grt1 rim and Grt2 are low(ΣREE=12.4–354 ppm;ΣREE=21.0–65.3 ppm),with LREE enriched pattern(LREE/HREE=0.54–34.4;LREE/HREE=11.4–682)and positive Eu anomalies(δEu=0.35–27.2;δEu=1.02–30.7).After data compilation of garnet chemicals,we found that the early fluid responsible for the core of Grt1 was a relatively closed and chloride-depleted fluid system.It was close-to-neutral,with a low water–rock ratio.The core of garnet was formed by fluid diffusion in metasomatic processes.The fluid was changed into a relatively open system with reduced,chloride-rich,and weakacid fluid.It was fluid infiltration and metasomatism that resulted in the formation of Grt1 rim and Grt2.

Act in contravention:a non-planar coupled electrode design utilizing‘‘tip effect”for ultra-high areal capacity,long cycle life zinc-based batteries

Aqueous zinc-based batteries(ZBBs)have great potential as commercial energy storage devices.However,the poor cycling stability of zinc anode under high areal capacity limits their further application.Herein,a coupled non-planar electrode design achieved by the tailored flat-top pyramid carbon felt(TCF)is proposed for ZBBs,which can effectively increase the zinc deposition sites,adjust the deposition morphology,optimize the current and electrolyte flow velocity distribution and provide necessary space for zinc plating.Interestingly,by utilizing "tip effect",the coupled TCFs enable precise control of the zinc dendrite growth position,effectively reducing the risk of short circuit.Based on such coupled TCFs,zinciodine flow batteries can deliver an ultra-high areal capacity of 240 m Ah cm^(-2) and a superb cycling stability over 300 cycles(areal capacity of 160 m Ah cm^(-2))at a high current density of 40 m A cm^(-2).Therefore,we provide an effective strategy for high areal capacity zinc anode design,which may promote the development of high energy density and long cycle life ZBBs.

Reversible Zn stripping/plating achieved by surface thin Sn layer for high-performance aqueous zinc metal batteries

Aqueous zinc metal batteries (ZMBs) are considered as the most promising candidate for large-scale energy storage system due to their abundant reserves and high safety. To achieve highly stable zinc metalbatteries, it is imperative to inhibit the unavoidable dendrite growth, which leads to the non-uniformzinc deposition and even makes the battery short circuit. Herein, Sn coating is loaded on copper foil(SCF) by a simple electrodeposition to guide the uniform zinc deposition, which not only lowers the zincnucleation overpotential but also promotes the uniform zinc deposition/dissolution. As a result, the Znplated SCF (Zn@SCF) anode presents a low voltage hysteresis of ∼40 mV and a superior stability over270 h in symmetric cells at a current density of 1 mA cm^(−2). Furthermore, the Zn@SCF anode can realizethe improved performance for full cells paired with α-MnO_(2) cathode. This work provides a simple andeffective approach to modify the Zn anode for improved electrochemical performance of ZMBs.