核桃壳低温还原辅助废NCM正极金属浸出的研究

针对废旧三元锂离子电池中有价金属进行高效回收的瓶颈问题,本研究提出以生物质为还原剂的低温碳热还原强化正极材料中有价金属浸出的方法,探讨了核桃壳作为还原剂的低温碳热还原预处理对废旧NCM523正极金属浸出回收效率的影响。结果表明,在450~500℃的较低温区,混合物较核桃壳或废旧NCM523存在明显的相变峰,还原产物中的Li₂CO₃经水洗后即可高效回收;再经柠檬酸酸洗后,Ni、Co和Mn分别有45.53%、47.49%和90.08%进入到酸洗液中而实现浸提回收。     

退役锂离子电池电化学还原浸出及热力学研究

近年来锂离子电池的需求量快速增长,产生了大量退役锂离子电池（LIBs）。回收退役LIBs对保障中国的清洁能源安全具有重要意义。电化学浸出退役LIBs正极材料是一种绿色经济的回收方法。目前,电化学法回收退役LIBs存在浸出时间长、电流效率低、槽压高的问题。基于此,提出了一种牺牲阳极的电化学还原回收退役LIBs的方法。该方法以退役LIBs正极材料为阴极,以铜板为阳极,在盐酸体系下进行电化学浸出。在最佳条件下锂离子和钴离子的浸出率均达到99.9%、电流效率高达99.8%、槽压小于0.427 V。使用基于Eh-pH和Matlab的热力学计算方法,对电化学还原浸出体系进行了热力学研究。研究结果表明,温度升高,配合物种类增多、配位物种占比增大,有助于浸出反应平衡正向移动。     

废旧锂电池中有价金属回收及三元正极材料的再制备

探讨了磷酸体系下不同因素对废旧锂电池正极材料中有价金属浸出效率的影响，结果表明：在浸出时间60min，反应温度60℃，磷酸浓度2mol/L，液固比20mL/g，还原剂(H₂O₂)体积分数为4%时，可得最佳浸出效果，Co、Li、Mn、Ni浸出效率分别可达96.3%、100%、98.8%和99.5%；浸出液添加相应比例金属离子，采用草酸共沉淀法制备前体材料(Ni_1/3Co_1/3Mn_1/3)C₂O₄，并得到相应再生磷酸溶液。再生磷酸进行循环浸出实验，实验研究结果表明：循环浸出5次之后Li的浸出率仍可保持在90.1%，而Co、Mn和Ni的浸出率在75.0%以上。前体添加锂源Li₂CO₃煅烧合成Li(Ni_1/3Co_1/3Mn_1/3)O₂材料，考察了不同温度对Li(Ni_1/3Co_1/3Mn_1/3)O₂材料合成的影响，结果显示，当合成温度为800℃时，得到的材料性能最优良，初次放电容量可达136.4mA·h/g。在0.2C下经过50圈循环后容量保持率为97.2%。     

废旧混合锂电池正极材料还原酸浸行为研究

针对废旧混合锂电池正极材料中有价金属元素镍钴锰的高效分离浸出,设计开发了2种不同混合废料体系：LiCoO₂与Li （Ni_1/3Co_1/3Mn_1/3） O₂、LiMn₂O₄与Li （Ni_1/3Co_1/3Mn_1/3） O₂,研究了还原剂用量、硫酸初始浓度、浸出温度、液固比对浸出过程的影响。LiCoO₂与Li （Ni_1/3Co_1/3Mn_1/3） O₂混合废料较适宜浸出参数为：浸出温度80℃、反应时间90 min、H₂SO₄浓度2.3 mol·L^-1,液固比R=8 mL·g^-1、还原剂Na₂SO₃用量=1.2倍理论量;LiMn₂O₄与Li （Ni_1/3Co_1/3Mn_1/3） O₂组成的混合废料的较适宜浸出实验参数为：浸出温度60℃、反应时间90 min、H₂SO₄浓度2.3 mol·L^-1,R=8 mL·g^-1、还原剂Na₂SO₃用量=1.2倍理论量。得到的浸出规律为混合锂离子电池正极废料回收工艺的广泛适应性提供了参考思路。     

柱淋滤模式下生活垃圾焚烧炉渣中Cu2+和Zn2+浸出规律

垃圾焚烧炉渣是一种活性材料,在其储存、预处理及应用等过程与雨水频繁接触时,炉渣中重金属随着水域环境发生迁移和浸出现象。本研究采用连续柱淋滤试验装置模拟自然降雨,开展了0～5mm和5～10mm焚烧炉渣的动态淋滤毒性浸出分析,重点研究了pH和降雨强度对Cu²⁺和Zn²⁺的浸出影响。结果表明,动态淋滤过程中,淋滤液pH变化对Cu²⁺和Zn²⁺的浸出水平影响显著,且在酸性较强淋滤液作用下Cu²⁺浸出水平比Zn²⁺更强,与Ⅴ类地表水环境浓度限值对比,在整个淋滤时间内Cu²⁺浸出浓度严重超标,在炉渣工程应用时需预防相关的环境风险;原生炉渣粒径大小与重金属浸出水平无直接相关性,但是0～5mm细炉渣中可浸出Zn²⁺含量更高,这与细颗粒物中Zn赋存形态和可溶出态含量较高有关;淋滤强度对重金属浸出水平影响主要反应了动态淋滤过程液固比和水分运移速率情况,当较低淋滤强度时具有低液固比,溶出液中重金属含量较高。     

Direct regeneration of LiNi0.5Co0.2Mn0.3O2 cathode material from spent lithium-ion batteries

At present, metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure, which unavoidably introduces potential pollutants to the environment. Therefore, it is necessary to develop more direct and effective green recycling methods. In this research, a method for the direct regeneration of anode materials is reported, which includes the particles size reduction of recovered raw materials by jet milling and ball milling, followed by calcination at high temperature after lithium supplementation. The regenerated LiNi_0.5Co_0.2Mn_0.3O₂ single-crystal cathode material possessed a relatively ideal layered structure and a complete surface morphology when the lithium content was n(Ni + Co + Mn):n(Li) = 1:1.10 at a sintering temperature of 920 ℃, and a sintering time of 12 h. The first discharge specific capacity was 154.87 mA·h·g^-1 between 2.75 V and 4.2 V, with a capacity retention rate of 90% after 100 cycles.     

电化学阴阳极协同降解有机磷及同步回收磷酸钙

为解决工业循环水系统中有机磷阻垢剂添加引发的磷污染和磷资源短缺等问题,本文构建了电化学阴-阳极协同反应体系,利用硼掺杂金刚石（BDD）阳极氧化反应实现有机磷的降解,同时阴极电解反应营造的局域强碱性氛围有利于磷酸钙在阴极的富集。以乙二胺四亚甲基膦酸（EDTMP）为目标阻垢剂,研究了不同参数对EDTMP降解和无机磷回收性能的影响,结果表明：BDD阳极电化学反应产生的强氧化性?OH是氧化EDTMP的主要活性物种,增加电流密度有利于EDTMP的降解,电流密度从3mA/cm²增加到30mA/cm²时,总有机碳（TOC）去除率从14%增加到72%,无机磷产量从6.5mg/L增加到9.9mg/L,磷回收效率从21%同步增加到83%。初始pH（3.0～12.0）对磷回收效率影响较小。Ca²⁺浓度增加有利于水体中磷的回收,Ca²⁺浓度从25mg/L增加到100mg/L时,磷回收效率相应地从46%提升到83%。电化学反应体系内,磷主要以非晶态的磷酸钙形式在阴极表面富集,沉积物种Ca/P物质的量之比约为0.6。     

废CeO x -MnO x 基SCR脱硝催化剂还原酸浸综合回收铈锰

废选择性催化还原（SCR）脱硝催化剂中含有大量的有价金属,直接废弃易造成资源浪费及环境污染。以废CeO _x -MnO _x 基SCR脱硝催化剂为原料,采用热力学分析结合湿法冶金实验方法,研究了浸出条件对Ce、Mn元素浸出率的影响。结果表明,废催化剂直接酸浸Ce、Mn元素浸出率低,还原-酸浸Ce、Mn元素热力学条件上可行,抗坏血酸对Ce、Mn高价氧化物有明显的还原作用。当抗坏血酸质量分数为30%、硫酸浓度2mol/L、液固比6∶1、搅拌速度350r/min、80℃恒温反应5h时,Ce、Mn的浸出率分别达到92.09%、95.51%。加入抗坏血酸后,部分Ce⁴⁺和Mn⁴⁺还原为Ce³⁺和Mn²⁺,Ce⁴⁺/Ce的比值由75.82%降低到71.62%,Mn⁴⁺/Mn的比值由29.39%降低到27.17%,同时削弱了高价Ce辅助低价Mn向高价Mn转化的作用,使得Ce、Mn高效浸出,为CeO _x -MnO _x 基废催化剂中Ce、Mn资源化利用奠定了基础。     

Investigation of solution chemistry to enable efficient lithium recovery from low-concentration lithium-containing wastewater

In the production of lithium-ion batteries (LIBs) and recycling of spent LIBs, a large amount of low-concentration lithium-containing wastewater (LCW) is generated. The recovery of Li from this medium has attracted significant global attention from both the environmental and economic perspectives. To achieve effective Li recycling, the features of impurity removal and the interactions among different ions must be understood. However, it is generally difficult to ensure highly efficient removal of impurity ions while retaining Li in the solution for further recovery. In this study, the removal of typical impurity ions from LCW and the interactions between these species were systematically investigated from the thermodynamic and kinetics aspects. It was found that the main impurities (e.g., Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺) could be efficiently removed with high Li recovery by controlling the ionic strength of the solution. The mechanisms of Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺ removal were investigated to identify the controlling steps and reaction kinetics. It was found that the precipitates are formed by a zero-order reaction, and the activation energies tend to be low with a sequence of fast chemical reactions that reach equilibrium very quickly. Moreover, this study focused on Li loss during removal of the impurities, and the corresponding removal rates of Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺ were found to be 99.8%, 99.5%, 99%, and 99.7%, respectively. Consequently, high-purity Li₃PO₄ was obtained via one-step precipitation. Thus, this research demonstrates a potential route for the effective recovery of Li from low-concentration LCW and for the appropriate treatment of acidic LCW.     

Barium-doped Pr2Ni0.6Cu0.4O4+δ with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell

Proton conducting solid oxide fuel cell (H-SOFC) is an emerging energy conversion device, with lower activation energy and higher energy utilization efficiency. However, the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC. Therefore, in this work, K₂NiF₄-type cathode materials Pr_2-xBaNi_0.6Cu_0.4O_4+δ (x=0, 0.1, 0.2, 0.3), single-phase triple-conducting (e^-/O^2-/H⁺) oxides, are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity. The investigation demonstrates that doping Ba into Pr_2-xBaNi_0.6Cu_0.4O_4+δ can increase its electrochemical performance through enhancing electrical conductivity, oxygen vacancy concentration and proton conductivity. EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2, which are 0.068 Ω·cm² in air and 1.336 Ω·cm² in wet argon, respectively. The peak power density of the cell with Pr_1.8Ba_0.2Ni_0.6Cu_0.4O_4+δ cathode is 298 mW·cm^-2 at 750℃ in air with humidified hydrogen as fuel. Based on the above results, Ba-doped Pr_2-xBaNi_0.6Cu_0.4O_4+δ can be a good candidate material for SOFC cathode applications.     

一步法回收和再生废旧钴酸锂电池中的钴酸锂

采用酸浸法和溶胶-凝胶法耦合的一步法技术路线回收和再生LiCoO₂，简化了流程。先使用柠檬酸浸出正极材料中的Co和Li元素，然后采用溶胶-凝胶法从浸出液中直接再生LiCoO₂，柠檬酸在过程中起到了浸出剂和螯合剂的双重作用，简化了回收和再生流程。摸索了柠檬酸浓度、固液比、浸出温度、H₂O₂体积浓度和浸出时间对Co和Li浸出效率的影响规律，探究了煅烧温度对再生钴酸锂结构组成、颗粒形貌以及电化学性能的影响规律。结果表明，最佳浸出条件为：柠檬酸浓度为1.5mol/L，固液比为20g/L，浸出温度为80℃，H₂O₂体积分数为2%，浸出时间为60min。在此条件下，Co和Li的浸出率分别达到93.7%、98.2%。通过电化学分析表明，在700℃下煅烧得到的再生LiCoO₂电化学性能最佳，在1C下经50次循环后可逆放电比容量为118.7mA·h/g，容量保持率为93%。     

铜阳极泥分铜液综合回收稀贵金属

以铜阳极泥硫酸化焙烧-酸浸脱铜所得分铜液为原料,采用Fe²⁺原位还原分铜液中的Te、Au、Pt和Pd,协同生成新生态胶体状碲选择性高效捕集Au、Pt和Pd等贵金属。根据铜阳极泥的预处理工艺,分析了贵金属在分铜液中的溶解机理;通过热力学计算绘制了As-Fe-H₂O系电位-pH图,指导调控分铜液电极电位;根据分铜液中主要金属离子的电极电位,探讨了分铜液原位还原稀贵金属机理。在Fe²⁺浓度为2g/L、搅拌速度为300r/min和85℃的优化条件下反应1.5h,贵金属Au、Ag、Pt和Pd的沉淀率分别为100%、100%、99.2%和99.6%,Se、Te和As的沉淀率分别为33.3%、36.1%和16.8%,沉淀渣中Te、Au、Ag、Pt、Pd品位分别为18.24%、124g/t、10.54%、1010g/t、320g/t,XRD分析表明,沉淀渣物相组成主要为AgCl,其他成分呈非晶态或含量较低未出现明显衍射峰,微观形态主要为细微颗粒和较规则晶体状,SEM面扫描图谱显示银和氯具有明显一致的富集区域,砷与铁具有较一致的富集区域,主要形成AgCl、FeAsO₄物相赋存渣中。该工艺简单、成本低、对环境友好,实现了分铜液中稀贵金属的高效综合回收。     

汽车粉碎残渣中提取金属:不同浸出体系的初步实验结果(英文)

The study is focused on the extraction of valuable metals from automotive shredder residue (ASR) by different leaching solutions. First, ASR samples were roasted at 600 °C to simulate a thermal treatment processing. Distil ed water, citric and sulphuric acid were preliminarily investigated, thus two further full factorial systems entailing H2SO4–H2O2 and H2SO4–H2O2–Fe3+ were tested. The preliminary experimental results showed that 0.1 mol·L?1 H2SO4 solution extracted 100%of Cu, Fe and Zn, whereas citric acid leached 100%of Zn and Pb, 59%of Fe and 62%of Cu;whereas, H2SO4–H2O2 and H2SO4–H2O2–Fe3+(Fenton's) leaching media showed that Cu, Fe and Zn can be extracted simultaneously and completely from the ASR ashes before final disposal.     

锂电解过程中杂质元素的电化学行为

采用循环伏安法研究了锂电解过程中杂质元素的电化学行为。电解过程中杂质元素镁将优先于锂在阴极析出, 然后是金属锂的欠电位沉积形成镁锂合金, 最后才是金属锂的析出, Mg ²⁺的还原电极过程受扩散控制, 扩散系数为1.44×10 ^-5 cm ²/s;微量的Ca ²⁺即发生钙锂共沉积;在含少量氯化钠的熔盐体系中, 杂质元素钠被锂还原并形成合金, 随着电解质体系中氯化钠含量的增加, 金属锂中的钠含量有较大的增加;杂质元素铁优先于锂在阴极析出, 在阴极被还原成海绵铁使阴极钝化, 引起熔盐体系锂的析出电流急剧降低, Fe ³⁺的还原电极过程受扩散控制, 扩散系数为3.14×10 ^-5 cm ²/s。     

高炉矿渣-粉煤灰基地质聚合物固化铅离子及防辐射性能研究

研究利用高炉矿渣（BFS）、粉煤灰（FA）作为原材料制备地质聚合物。以氢氧化钠与水玻璃作为碱激发剂,在碱激发条件下制备地质聚合物固化二价铅离子（Pb²⁺）。研究Pb²⁺的掺量对固化体强度的影响,并通过浸出毒性实验、X射线衍射分析（XRD）、红外光谱分析（FT-IR）、扫描电镜（SEM）等表征分析、防辐射实验测试,探究其固化效果与固化机理。结果表明,高炉矿渣-粉煤灰基地质聚合物与Pb²⁺具有良好的相容性,且固化体在28 d最高抗压强度可以达到43 MPa,Pb²⁺的添加质量分数为1%时能提高其固化体的强度。浸出实验表明,固化体对质量分数为1% Pb²⁺的固化效率在97%以上。微观分析认为大部分重金属是以羟基配合离子的形式被物理封装在地质聚合物内部。防辐射实验测试表明,Pb²⁺的掺量与高炉矿渣-粉煤灰基地质聚合物的γ射线屏蔽效果成正相关,实验中Pb²⁺最优掺入质量分数为3%,线性吸收系数和半衰减层厚度最优值分别为0.222 0 cm^-1和2.309 5 cm。     

Cesium Release From Tungstate and Titanate Waste Form Materials in Simulated Canister Corrosion Product-Containing Solutions

The leaching of two potential ¹³⁷Cs waste form ceramics (Cs-containing hexagonal tungsten bronze (HTB) and hollandite) has been investigated in Fe(NO₃)₃ solutions of increasing concentration at 150°C over a period of 4 days. These ceramics contain within their structures reduced Mo⁵⁺/W⁵⁺ and Ti³⁺ species for the HTB and hollandite, respectively, which therefore might render them susceptible to oxidation-induced leaching. Elucidation of the extent and the mechanism of leaching of the Cs from these ceramics in the REDOX active iron nitrate medium has been investigated. Cesium (Cs) leached severely from both the Cs-loaded HTB and hollandite materials in iron nitrate solutions with virtually all of the immobilized Cs being extracted from both waste form materials in a period of 4 days at 150°C. In the case of hollandite, conversion to ilmenite and hematite was observed at low concentrations and was virtually complete in 0.5 mol/L Fe(NO₃)₃ over 4 days. In the case of the HTB, all of the Cs was extracted presumably by an ion-exchange mechanism because the structure of this oxide remained intact and iron was found in the composition. Iron oxide with a hematite structure was also easily observed in the reacted sample at high solution iron concentrations. It is shown that the leach resistance of the Cs-containing HTB can be improved by substitution of up to 20% Ti for W.     

尖晶石型三元高电压正极材料的合成及其性能

LiNi_0.5Mn_1.5O₄（LNMO）是一种有前景的下一代高能密度锂离子电池正极材料,但其中的锰离子溶解严重、容量衰减严重,阻碍了其应用。本工作通过水热-煅烧合成了LiNi_0.4Co_0.1Mn_1.5O₄（LNCMO）三元尖晶石型高电压复合材料,探究了煅烧温度和升温速率等制备条件对样品形貌和结构的影响。本文合成的LNCMO样品微观形貌呈类菱形结构,物相纯净,比表面积为3.72m²/g,平均孔径为11.60nm,放电电压接近4.75V,在20mA/g下初始放电比容量达143.90mAh/g,和LNCMO的理论比容量（146.71mAh/g）的比值达98%。根据XRD和XPS等表征分析可知,复合材料中的Mn⁴⁺比例较大,Mn³⁺较少,且合适的煅烧温度和升温速率避免了Li _x Ni_1-x O杂质相的生成,因此本文制备的材料相比LNMO材料结构稳定性增强,电荷转移阻力低,电性能尤其是比容量大幅提升。本文还对比了循环前后的样品,发现其物相基本一致,但高电流密度下形貌结构坍塌严重,影响了循环稳定性。本研究提供了一种有效制备三元高电压材料的策略。     

Highly selective and green recovery of lithium ions from lithium iron phosphate powders with ozone

Since lithium iron phosphate cathode material does not contain high-value metals other than lithium, it is therefore necessary to strike a balance between recovery efficiency and economic benefits in the recycling of waste lithium iron phosphate cathode materials. Here, we describe a selective recovery process that can achieve economically efficient recovery and an acceptable lithium leaching yield. Adjusting the acid concentration and amount of oxidant enables selective recovery of lithium ions. Iron is retained in the leaching residue as iron phosphate, which is easy to recycle. The effects of factors such as acid concentration, acid dosage, amount of oxidant, and reaction temperature on the leaching of lithium and iron are comprehensively explored, and the mechanism of selective leaching is clarified. This process greatly reduces the cost of processing equipment and chemicals. This increases the potential industrial use of this process and enables the green and efficient recycling of waste lithium iron phosphate cathode materials in the future.     

Cr2O3 promoted skeletal Cu catalysts for the reactions of methanol steam reforming and water gas shift

Promotional effects of chromia on the structure and activity of skeletal copper catalysts for methanol steam reforming and water gas shift have been studied. Catalysts were prepared by leaching CuAl₂ alloy particles in aqueous NaOH solutions containing sodium chromate at various concentrations. XPS spectra showed that the surface of the resulting catalysts mainly consisted of Cr³⁺ compounds and Cu⁰. Cu⁺ and/or Cu²⁺ were not observed by XPS.

Increasing the concentration of chromate in the leach liquor resulted in decreases in pore diameter and copper crystallite size but significant enhancement of BET surface area was observed while the total pore volume was maintained. The addition of small amounts of chromate to the leach liquor significantly enhanced the Cu surface area. However, higher concentrations of chromate in the leach liquor decreased the Cu surface areas although the total surface areas increased.

The activities of Cr₂O₃ promoted skeletal copper catalysts for both methanol steam reforming and water gas shift reactions were determined separately. The results indicated that deposition of Cr₂O₃ on skeletal copper catalysts significantly improved the specific activities for these reactions. Chromia is found to act as a structural and catalytic promoter for these reactions.     

Li3VO4修饰富镍LiNi0.8Co0.1Mn0.1O2正极材料的电化学性能

采用湿法融合技术及高温固相法合成Li₃VO₄包覆的LiNi_0.8Co_0.1Mn_0.1O₂正极材料。通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等方法研究材料的结晶相、形貌、微观结构。研究表明,Li₃VO₄均匀地包覆在LiNi_0.8Co_0.1Mn_0.1O₂表面,未改变原材料的材料结构和形貌,包覆层厚度为1～2 nm。不同含量的Li₃VO₄对LiNi_0.8Co_0.1Mn_0.1O₂正极材料进行修饰研究表明,3%（质量）Li₃VO₄包覆的LiNi_0.8Co_0.1Mn_0.1O₂在1 C下100次循环后容量保持率为94.13%,具有最佳的倍率性能和循环性能。此外,循环伏安（CV）和交流阻抗（EIS）分析表明,Li₃VO₄能提高Li⁺电导率,抑制活性材料与电解液之间的副反应,提高材料的电化学性能。