Design Strategies for Aqueous Zinc Metal Batteries with High Zinc Utilization: From Metal Anodes to Anode-Free Structures

Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of zinc(Zn) metal. However,several issues such as dendrite formation, hydrogen evolution, corrosion, and passivation of Zn metal anodes cause irreversible loss of the active materials. To solve these issues, researchers often use large amounts of excess Zn to ensure a continuous supply of active materials for Zn anodes. This leads to the ultralow utilization of Zn anodes and squanders the high energy density of AZMBs. Herein, the design strategies for AZMBs with high Zn utilization are discussed in depth, from utilizing thinner Zn foils to constructing anode-free structures with theoretical Zn utilization of 100%, which provides comprehensive guidelines for further research. Representative methods for calculating the depth of discharge of Zn anodes with different structures are first summarized. The reasonable modification strategies of Zn foil anodes, current collectors with pre-deposited Zn, and anode-free aqueous Zn metal batteries(AF-AZMBs) to improve Zn utilization are then detailed. In particular, the working mechanism of AF-AZMBs is systematically introduced. Finally, the challenges and perspectives for constructing high-utilization Zn anodes are presented.

Effect of Cu addition on microstructure and properties of Mg-10Zn-5Al-0.1Sb high zinc magnesium alloy

To improve the strength, hardness and heat resistance of Mg-Zn based alloys, the effects of Cu addition on the as-cast microstructure and mechanical properties of Mg-10Zn-5Al-0.1Sb high zinc magnesium alloy were investigated by means of Brinell hardness measurement, scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, XRD and tensile tests at room and elevated temperatures. The results show that the microstructure of as-cast Mg-10Zn-5AI-0.1Sb alloy is composed of α-Mg, τ-Mg32（Al, Zn）49, Ф-Al2MgsZn2 and Mg3Sb2 phases. The morphologies of these phases in the Cu-containing alloys change from semi-continuous long strip to black herringbone as well as particle-like shapes with increasing Cu content. When the addition of Cu is over 1.0wt.%, the formation of a new thermally-stable Mg2Cu phase can be observed. The Brinell hardness, room temperature and elevated temperature strengths firstly increase and then decrease as the Cu content increases. Among the Cucontaining alloys, the alloy with the addition of 2.0wt.% Cu exhibits the optimum mechanical properties. Its hardness and strengths at room and elevated temperatures are 79.35 HB, 190 MPa and 160 MPa, which are increased by 9.65%, 21.1% and 14.3%, respectively compared with those of the Cu-free one. After T6 heat treatment, the strengths at room and elevated temperatures are improved by 20% and 10%, respectively compared with those of the ascast alloy. This research results provide a new way for strengthening of magnesium alloys at room and elevated temperatures, and a method of producing thermally-stable Mg-10Zn-5Al based high zinc magnesium alloys.

Strength properties examination of high zinc aluminium alloys inoculated with Ti addition

This paper includes studies on the influence of grain refinement treatment with respect to the composition and structure of high zinc aluminium casting alloys on the changes of their tensile properties. The Al-20 wt.%Zn alloy was inoculated with master alloys Al Ti5B1 and Al Ti3C0.15 to determine the impact of a variable titanium addition on the tensile properties of Al Zn20 alloy, and determine on this basis an optimal addition of Ti that would ensure the improvement of elongation of alloys cast in the sand mould, at the same time maintaining high tensile strength. Within the studies, light microscopy(LM) and strength tests were applied. Experimental results showed that the inoculation of high zinc aluminium alloy Al Zn20 with the master alloys Al Ti5B1 and Al Ti3C0.15 causes intensive structure refinement, while the intensity of reaction of both master alloys is comparable. The Al Ti3C0.15 master alloy addition, selected for further studies, introducing about 100 ppm Ti, enhances the tensile properties of the alloy; the elongation increases about 20% and tensile strength increases about 10% against the initial values(uninoculated alloy). Further increase of the Ti addition up to 500–600 ppm leads to the "overinoculation" effect that is accompanied by the decrease of elongation. Therefore,the Ti addition should be reduced to the level of about 100 ppm which ensures obtaining a set of optimal properties.

Phase selection of ternary intermetallic compounds during solidification of high zinc magnesium alloy

The phase selection of ternary intermetallic compound τphase (Mg32(Al, Zn)49 ) and φ phase (Al2Mg5Zn2) in high zinc magnesium alloys was studied by using scanning electron microscope, X-ray diffractometer and differential scanning calorimeter, etc. The results indicate that, when adding element Si in Mg-8Zn-4Al-0.3Mn (ZA84) alloy, φ phase is promoted, whereas τ phase is inhibited. The Chinese script-type Mg2Si and matrix microstructure are greatly refined, the formation of τ phase is facilitated and φ phase is restrained when modifier Al-AlP master alloy is added in ZA84 alloy containing Si. The kinetics study of phase selection indicates that there is a critical degree of undercooling of the melt. If the undercooling exceeds the critical value, τ phase preferentially forms while φ phase is restrained; otherwise, φ phase preferentially forms while τ phase is restrained.

Corrosion Test of the Steel Plate in a WJ-8 Fastener for High Speed Rail

It was found that the steel plate in the composite plate in the WJ-8 fastener used in high speed rail is rusty. The objective of this study is to test the zinc coating of the steel plate. A literature review was conducted to identify the zinc coating techniques, and the companies that can provide different coating service was identified. A salt fog chamber was built that was in compliance with the ANSI B117 code, and the steel plates that were coated by the identified companies were tested using the salt fog chamber. The results indicated that the coating technique that had the best performance in preventing corrosion was the Greenkote plates with passivation. The galvanized option had the roughest coating layer, and it was the most reactive in the salt water solution. This makes it non-ideal for the dynamic rail environment because the increased friction of the plate could damage the supports, especially during extreme temperatures that would cause the rail to expand or contract. Greenkote with Phosphate and ArmorGalv also provided increased corrosion prevention with a smooth, strong finish, but it had more rust on the surface area than the Greenkote with ELU passivation. The ArmorGalv sample had more rust on the surface area than the Greenkote samples. This may not be a weakness in the ArmorGalv process;rather, it likely was the result of this particular sample not having the added protection of a colored coating.

Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry （ HR-ICP-MS ） was investigated. To overcome some poteutially problematic spectral iuterference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02μg/ g to 6 μg/ g depending on the elements. The experimental resalts for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

Ultra-High Mass-Loading Cathode for Aqueous Zinc-Ion Battery Based on Graphene-Wrapped Aluminum Vanadate Nanobelts

Rechargeable aqueous zinc-ion batteries(AZIBs)have their unique advantages of cost efficiency,high safety,and environmental friendliness.However,challenges facing the cathode materials include whether they can remain chemically stable in aqueous electrolyte and provide a robust structure for the storage of Zn2+.Here,we report on H11Al2V6O23.2@graphene(HAVO@G)with exceptionally large layer spacing of(001)plane(13.36?).The graphene-wrapped structure can keep the structure stable during discharge/charge process,thereby promoting the inhibition of the dissolution of elements in the aqueous electrolyte.While used as cathode for AZIBs,HAVO@G electrode delivers ideal rate performance(reversible capacity of 305.4,276.6,230.0,201.7,180.6 mAh g?1 at current densities between 1 and 10 A g?1).Remarkably,the electrode exhibits excellent and stable cycling stability even at a high loading mass of^15.7 mg cm?2,with an ideal reversible capacity of 131.7 mAh g?1 after 400 cycles at 2 A g?1.

Sulfuric acid leaching of high iron-bearing zinc calcine

Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.

Comprehensive recovery of Fe,Zn,Ag and In from high iron-bearing zinc calcine

A beneficiation-metallurgy combination process is developed to recover Zn, Fe and to enrich In, Ag from high iron-bearing zinc calcine based on our former researches. In gaseous reductive roasting process, the roasting conditions were tested by magnetic separation of roasted product. It is found that the V_(CO)(P_(CO)/(P_(CO+CO_2)) in roasting atmosphere should be maintained below 30% to avoid the generation of zinc iron solid solution(Fe_(0.85-x)Zn_xO), which can bring a decrease of iron recovery in magnetic separation. After roasting, acid leaching and multistage magnetic separation are carried out for the recovery of Zn, Fe and enrichment of Ag and In. About 90% of zinc is extracted and 83% of iron is recovered in the whole process. The Ag mainly enters the tailings with a recovery of 76%, the Ag grade increases from 0.12 g/t in raw materials to 1.18 g/t in the tailings. However, the In mainly enters the iron concentrations and the recovery reaches 86%. This process was proved to be technically feasible and may be a favorable option in the treatment of high iron-bearing zinc material with high Ag or In content.

Manufacturing Microporous Foam Zinc Materials with High Porosity By Electrodeposition

In order to get foam zinc materials of porous metal electrode,a novel method for preparing foam zinc was proposed,in which the polyurethane foam with diameter of 0.3 mm as substrate was processed by degreasing,roughening,activating,electroless plating and electrodeposition.The main factors affecting the process,such as ZnSO4 content,temperature,pH value,current density,and electrodes distance,were investigated comprehensively.The optimal process conditions are 250 g/L ZnSO4,20 g/L Al2（SO4）3,40 g/L KAl（SO4）2,30 g/L Na2SO4,pH=3.5,4.0 cm of electrodes distance and 0.04 A/cm2 current density at 30 ℃.The result shows that adding ultrasonic on the process can elevate the deepening plating ability and current efficiency.Foam zinc material with a high porosity of 92.2% and a three-dimensional network structure can be fabricated by electrodeposition.

Laboratory Study on the Removal of Fluorine from High Fluorine Bearing Zinc Oxide Ore

An ever increasing demand for zinc has resulted in worldwide efforts to exploit complex and lean grade reserves of zinc oxide ore. In this study experiments were done on zinc recovery from high-fluorine bearing zinc oxide ore. First the effect of different variables on fluorine removal was investigated. Optimum experimental conditions occurred when the temperature was 1173 K, roasting time was 90 min and air flow was at a velocity of 5 m/min, the fluorine removal from the samples reached over 93%. The results obtained indicate that fluorine removal is not enhanced by adding diluted sulfuric acid or water as a binder. Second the roasted materials were leached with a diluted sulfuric acid, neutralized, flocculated and filtrated. The which satisfies the requirement of fluorine residual fluorine content in the leached content in the leached solutions for the solutions was less than 38 mg/L production of electrolytic zinc.

The Zinc Story under High Pressure

A historical review is presented on the experimental and theoretical studies on Zn under high pressure. Based on our high-pressure powder x-ray diffraction experiments that have been done for nearly a decade, we describe the structural change of Zn up to 126 GPa at room temperature. Although several experimental and theoretical studies indicated an anomalous change of the c/a axial ratio with pressure, we found no such an anomaly within our experimental uncertainty. Our high-pressure low-temperature experiments up to 18 GPa at 40 K also gave no evidence of the c/a anomaly. We suspect that the pressure-transmitting media played an important role in producing the anomaly. The structural anisotropy of Zn is drastically reduced at high pressures, which would be a general trend for hexagonal close-packed (hcp) metals.

核电厂海水泵用镀锌高强度螺栓的开裂原因

某核电厂海水泵用双头镀锌高强度螺栓发生开裂失效。通过材料性能(化学成分、显微组织和力学性能等)检测及断口和裂纹形貌观察,分析了螺栓的失效原因。结果表明:镀锌螺栓开裂的原因为氢致开裂。锌镀层破损的高强度螺栓与海水接触时,表面锌镀层和螺栓基体形成电偶对,基体作为阴极析出氢,部分原子氢扩散进入螺栓基体导致氢致损伤,螺栓在预紧力的持续作用下发生氢致开裂。

内蒙古某含碳高硫锌锡矿石选矿试验研究

内蒙古某含碳高硫锌锡矿石锌品位1.02%、锡品位0.86%,硫和碳含量分别为14.02%、1.68%。矿石矿物组成较复杂,主要有用矿物为闪锌矿、锡石和黄铁矿,脉石矿物主要为石英、绿泥石和绢云母等。为确定矿石合理的开发利用工艺,采用预先脱碳—浮重联合工艺流程开展选矿试验研究。结果表明,矿石经预先脱碳、1粗1扫1精锌硫混选、1粗1扫3精锌硫分离浮选流程处理,闭路试验可得到Zn品位为45.16%、Zn回收率为71.19%的锌精矿,S品位为46.92%、S回收率81.91%的硫精矿;浮选尾矿采用摇床重选,经粗选、精选、复选和中矿再选,可获得Sn品位45.52%、Sn回收率81.99%的锡精矿,以及Sn品位3.13%、Sn回收率11.09%的锡中矿。所设计试验流程较好地解决了矿石中有机碳对浮选的不利影响,综合回收了有价矿物,可为同类矿石的开发利用提供理论借鉴。

ZNF772甲基化及HR-HPV检测在意义不明的非典型鳞状细胞病人分流中的意义

目的:探讨锌指蛋白(ZNF)772甲基化及高危型人乳头瘤病毒(HR-HPV)检测在意义不明的非典型鳞状细胞(ASCUS)病人分流中的意义。方法:选取初筛ASCUS病人195例,均接受HC2-HPV-DNA检测及ZNF772基因DNA甲基化检测;比较宫颈上皮内瘤样变(CIN)Ⅱ及以上与CINⅡ以下、CINⅢ及以上及CINⅢ以下病人ZNF772基因位点甲基化水平的差异,并评估ZNF772甲基化水平及HR-HPV对ASCUS病人CINⅡ及以上、CINⅢ及以上的分流价值。结果:病理学检查显示,195例ASCUS病人中炎症80例(41.03%)、CINⅠ64例(32.82%)、CINⅡ29例(14.87%)、CINⅢ/CIS/AIS 18例(9.23%)、SCC/AC 4例(2.05%)。HR-HPV(HC2)阳性141例(72.31%)、HR-HPV(HC2)阴性54例(27.69%);CINⅡ及以上病人HR-HPV(HC2)阳性检出率高于CINⅡ以下(P<0.05);CINⅢ及以上病人HR-HPV(HC2)阳性检出率高于CINⅢ以下(P<0.05)。CINⅡ及以上、CINⅢ及以上病人ZNF772基因-420、-422位点甲基化水平分别高于CINⅡ以下、CINⅢ以下病人(P<0.05)。ZNF772基因-420、-422位点甲基化水平及HR-HPV诊断CINⅡ及以上的AUC(95%CI)分别为0.867(0.811~0.911)、0.806(0.743~0.859)、0.777(0.712~0.834),诊断CINⅢ及以上的AUC(95%CI)分别为0.891(0.838~0.931)、0.868(0.813~0.912)、0.780(0.716~0.836)。ZNF772基因-420位点甲基化水平诊断CINⅡ及以上、CINⅢ及以上的AUC面积最大。结论:相较于HC2-HPV-DNA检测,ZNF772甲基化检测更能准确地识别ASCUS中CINⅡ及以上、CINⅢ及以上病变病人,有望成为分流ASCUS的有效替代手段。

高频燃烧红外吸收法测定铜铅锌多金属矿中的碳、硫

铜铅锌多金属矿中的碳、硫元素对矿产开采、钢铁冶炼及环境保护等方面有着重要的影响,对碳、硫的准确、快速定量检测至关重要,但未见有对铜铅锌多金属矿中的碳、硫同时测定的研究。将铜铅锌多金属矿中碳、硫含量科学分为C1、C2、S1、S2四段,并分别对样品称样量、助熔剂加入比例及种类等因素进行探究,建立了高频燃烧红外吸收法测定铜铅锌多金属矿中的碳、硫的方法,并通过标准物质验证了方法的准确度、精密度与再现性。结果表明,C1、C2、S1、S2称样量分别为0.200 0、0.100 0、0.100 0、0.100 0 g,助熔剂组合方式为Fe+W=(0.6000+0.6000)、(0.6000+0.6000)、(0.9000+0.6000)、(0.6000+0.600 0) g为最佳实验条件。C1、C2、S1、S2曲线的相关系数分别为0.999 4、0.995 9、0.999 9、0.998 9,测定结果的相对标准偏差(RSD,n=11)分别为1.3%、1.5%、1.3%、1.3%,使用3种不同型号的红外碳硫仪进行对比实验,相对标准偏差(RSD,n=11)为0.56%~6.5%。结果均显示,方法准确、可靠,满足铜铅锌多金属矿中碳、硫的同时、准确快速定量检测的要求。

新质生产力与我国有色金属产业高质量发展的关系:以铅锌产业为例

高质量发展是发展新质生产力的首要任务,发展新质生产力的过程中要处理好新兴产业和传统产业的关系,决不能忽视和放弃传统产业。有色金属作为我国国民经济、国防工业、科学技术发展必不可少的基础原材料和重要战略物资,是建设现代化强国的重要支撑和保障,也是最具代表性的传统产业之一。生产过程的特性导致有色金属行业在发展过程中面临更严峻的能耗、排放和污染的问题和困难。创新是引领发展的第一动力,在近十年的发展过程中,有色金属行业产业遵循国家政策指引、积极响应国家号召,依托技术创新和改造在工艺升级、节能减排、绿色低碳等方面取得长足的进步,为行业实现现代化高质量发展奠定了坚实的基础。进入新发展阶段后,有色金属行业上下游、左右岸交叉关联融合程度更深,绿色化、数字化、智能化、高端化转型升级需求更加迫切,此时,新质生产力的提出为行业未来面向高质量发展、重塑竞争新优势提供了全新动力和根本指引。有色金属品种多、应用广、生产流程和规模差异化较为明显,但是全行业产业借力新质生产力实现转型升级和高质量发展的需求和目标是一致的。我国是世界上最大的铅锌生产国和消费国,铅锌产业是有色金属产业最具代表性的传统产业之一。本文以铅锌产业为例,结合铅锌产业近年来在国家支持和指导下取得的发展成果,肯定和明确创新赋能传统产业发展和转型的重大意义以及传统产业未来借力和发展新质生产力的需求和潜力;从政策研究角度梳理近三年与有色金属行业高质量发展紧密相关的针对性政策文件,分析国家在未来对有色金属行业特别是铅锌产业发展新质生产力的支持和指引;针对铅锌产业在新发展阶段发展新质生产力方面已经或未来可能面临的问题和挑战,提出政策需要与时俱进、持续的技术创新能力培育、高素质人才培养和造就,以及坚持不懈地推进国际合作等相关建议。

Influence of minor Sc additions on grain refinement and microstructure characteristics of a high Zn-containing Al-Zn-Mg-Cu-Zr alloy

In the present work, scandium elements with a series of contents(0.06 wt.%, 0.10 wt.%, 0.14 wt.%,0.17 wt.%, 0.20 wt.% and 0.25 wt.%) were added in a high Zn-containing Al-Zn-Mg-Cu-Zr alloy and the corresponding as-cast microstructure characteristics including grains and phases were thoroughly investigated. The results indicated that fine grain boundaries existed in these alloys and fine MgZn2phases discontinuously distributed on them. Besides,AlZnMgCu eutectic phases and Sc, Zr-containing phases with flocculent morphology were observed. As scandium contents vary from 0.06 wt.% to 0.17 wt.%, the average grain size continuously decreased and its equiaxial characteristics were strengthened. Meanwhile, the content of AlZnMgCu eutectic phase showed a decrease trend. When scandium contents were 0.20 wt.% and 0.25 wt.%, no further enhancement on grain refinement was observed, so as to the reduction of AlZnMgCu eutectic phase content. Besides, Sc, Zr-containing phases with blocky morphology were observed and the alloy with a scandium content of 0.25 wt.% possessed a larger amount of blocky Sc, Zr-containing phase than the alloy with a scandium content of 0.20 wt.%. Grain refinement and reduction of AlZnMgCu eutectic phase content associated with scandium addition were discussed.

利用含锌工业固废制备高纯氧化锌的工艺研究

针对氧化锌尾矿和废弃水渣等工业固废中有价锌难以回收的问题,以当地工业含锌固废为原料,利用碳热还原氧化法,制备了高纯氧化锌微粉。通过HSC Chemistry进行热力学计算和试验研究结合的方式,分析了含锌废渣中硅酸锌与碳还原反应的热力学过程。讨论了配碳量、焙烧温度、焙烧时间以及CaF_(2)对硅酸锌还原过程锌产率的影响。结果表明,在以CaF_(2)为催化剂时,1000~1100℃催化效果最显著。得出最佳工艺条件:在温度为1100℃、保温时间40 min、碳含量20 wt%、CaF_(2)添加5 wt%的条件下锌产率(氧化锌回收率)为97.44%。对挥发产物进行结构和成分分析,其物相为六方纤锌矿结构的氧化锌晶体,粒度大小2~4μm,纯度达到了99.47%。

锌转运蛋白-9抑制高脂食物诱导小鼠前列腺炎的机制研究

目的研究锌是否能够抑制高脂食物诱导的前列腺炎症,并阐明其具体机制。方法将3周龄雄性C57BL/6小鼠随机分为普通食物组、高脂食物组和高脂食物+锌组(硫酸锌灌胃),各10只,饲喂10周后处死小鼠。称量小鼠体质量及前列腺质量,计算小鼠的前列腺指数;HE染色法观察各组小鼠前列腺组织中炎症细胞的浸润情况;免疫组织化学法检测前列腺组织中促炎因子IL-6和TNF-α以及锌转运蛋白-9(ZnT-9)的表达情况。结果与普通食物组相比,高脂食物组小鼠的体质量(P<0.001)、前列腺质量(P<0.001)及前列腺指数(P<0.01)均显著升高,高脂食物+锌组小鼠的前列腺质量(P<0.01)、前列腺指数(P<0.05)显著低于高脂食物组。高脂食物组小鼠前列腺组织内炎性细胞浸润较普通食物组显著增多,与高脂食物组相比,高脂食物+锌组小鼠前列腺组织中浸润的炎性细胞显著减少。与普通食物组相比,高脂食物+锌组中IL-6和TNF-α表达显著增加(P<0.05),ZnT-9的表达显著减少(P<0.01)。与高脂食物组相比,高脂食物+锌组中IL-6和TNF-α表达显著减少(P<0.05),ZnT-9的表达显著增加(P<0.05)。结论锌抑制高脂食物诱导的小鼠前列腺炎症,机制可能与ZnT-9的上调有关。