锂离子电池正极材料LiCoO_2的制备试验

通过以LiOH.H2O和Co2O3为反应原料,高温合成法制备LiCoO2粉体。实验分别考察了用高温制备LiCoO2的合成温度、反应时间、原料研磨时间,及Li、Co配比对合成LiCoO2的影响,确定了LiCoO2的合成条件。     

电解浸出废旧锂电池中钴的热力学和动力学

以废旧锂电池正极条为阴极,以铅板作阳极,在稀硫酸溶液中,电解浸出正极材料中的钴,从热力学和动力学两方面对钴的电解浸出过程进行研究。实验及热力学数据分析表明:LiCoO2主要通过Co(OH)3还原浸出得到Co2+,考查浸出温度和时间表明在电解前期5~30 min电解浸出由缩核模型的化学反应过程控制,浸出率α与时间t满足未反应核收缩模型1-(1-α)1/3=Kt,其表观活化能为7.32 kJ/mol;中期是混合控制;后期75~180 min符合内扩散控制模型1-2α/3-(1-α)2/3=Kt,表观活化能17.05 kJ/mol。浸出液中的铝主要是铝箔表面氧化铝层不受阴极保护而溶于硫酸溶液,正极材料从铝箔上剥离与氧化铝层的溶解有关,剥离时间影响钴的浸出率。     

废旧三元锂离子电池正极材料的淀粉还原浸出工艺及其动力学

根据淀粉在稀酸或加热条件下可水解为还原性单糖的性质,以淀粉作为还原剂,采用酸浸出方法对从废旧三元锂离子电池正极材料中回收Li、Ni、Co、Mn的浸出工艺进行研究;分别考察酸度、淀粉浓度、固液比、浸出温度和浸出时间对4种有价金属浸出率的影响。结果表明:在最佳条件即2mol/LH_2SO_4、4g/L淀粉、固液比50g/L、浸出温度80℃、浸出时间120min时,Li、Ni、Co、Mn的浸出率分别达到98.55%、97.6%、96.73%以及91.92%。此外,基于对数定律方程对浸出动力学参数进行了拟合,表现出较好的线性相关度,计算得出Li、Ni、Co、Mn的表观活化能分别为14.8、21.3、24以及26.4kJ/mol。浸出渣的XRD谱和SEM像显示其主要物相为C和MnO2。     

Synthesis and electrochemical behavior of LiCoO2 recycled from incisors bound of Li-ion batteries

LiCoO2 was separated from AI foil with dimethyl acetamide（DMAC）, and then polyvinylidene fluoride（PVDF） and carbon powders in active material were eliminated by high temperature calcining. The content of the elements in the recovered powders were analyzed. Then the Li2CO3 was added in recycled powders to adjust molar ratio of Li to Co to 1.00, 1.03 and 1.05, respectively. The new LiCoO2 was obtained by calcining the mixture at 850 ℃ for 12 h in air. Structure and morphology of the recycled powders and resulted sample were observed by XRD and SEM technique, respectively. The layered structure of the LiCoO2 is improved with the decrease of molar ratio of Li to Co. The charge/discharge performance, and cyclic voltammograms performance were studied. The recycle-synthesized LiCoO2 powders, whose molar ratio of Li to Co is 1.0, is found to have the best characteristics as cathode material in terms of charge--discharge capacity and cycling performance. And the cyclic voltammograms（CV） curve shows the lithium extraction/insertion characteristics of the LiCoO2 well.     

电化学还原技术从废旧锂离子电池中浸出LiCoO_2

基于电化学还原技术,提出在低酸度溶液中电解浸出废旧锂离子电池正极片(LiCoO2)的新方法。线性伏安扫描结果表明:LiCoO2的还原峰电位为0.30 V(vs SCE),验证了此方法的可行性。通过条件实验对影响钴和铝浸出率的各因素进行考察,得到电解浸出的最佳条件:电流密度15.6 mA/cm2、硫酸浓度40 g/L、柠檬酸浓度36 g/L、温度45℃、时间120 min。在此优化条件下,钴和铝的浸出率分别为90.8%和7.9%。电解浸出后,可直接回收铝箔,用扫描电子显微镜(SEM)对铝箔表面进行观察,结果表明:铝箔在浸出过程中的腐蚀深度远小于其表面原有点蚀坑的深度。     

硫酸肼还原酸浸出废旧锂离子电池中的有价金属（英文）

采用硫酸肼作为锂、镍、钴和锰从废锂离子电池中浸出时的还原剂,结合条件实验对浸出机理和浸出动力学进行研究。在最优条件:硫酸2.0 mol/L、硫酸肼30 g/L、固液比50 g/L、温度80℃和浸出时间60 min下,97%的Li、96%的Ni、95%的Co以及86%的Mn被浸出。通过浸出动力学分析得出Li、Ni以及Co的浸出活化能分别为44.32、59.37和55.62 k J/mol,表明浸出过程受化学反应控制。XRD和SEM-EDS分析结果表明,浸出渣的主要组成为MnO_2。上述研究结果表明,硫酸肼可作为废锂离子电池中有价金属浸出的有效还原剂。     

Co~（2＋）掺杂对Li_2FeSiO_4/C电化学性能的影响

采用溶胶-凝胶法,合成纳米复合材料硅酸亚铁锂（Li2FeSiO4/C）。用XRD、TEM和电化学方法,研究了Co2＋掺杂对Li2FeSiO4/C的影响。结果表明,掺杂适量的Co2＋不会改变Li2FeSiO4的正交晶系结构,可稳定材料结构,改善高倍率充放电性能。室温下,Li2Fe0.97Co0.03SiO4/C以0.1C放电的首次放电比容量为151.8（mA.h）/g,20次充放电循环后放电比容量为131.2（mA.h）/g;Li2FeSiO4/C的首次放电比容量为122.0（mA.h）/g,20次循环后,比容量衰减率为20.3%。交流阻抗测试表明：Li2Fe0.97Co0.03SiO4/C在1.5～4.5V下充放电的可逆性优于Li2FeSiO4/C。     

合成条件对氢氧化物共沉淀法制备锂离子电池层状正极材料Li[Ni_（1/3）Co_（1/3）Mn_（1/3）]O_2的影响

以共沉淀法制备的过渡金属氢氧化物前驱体合成锂离子电池层状正极材料Li[Ni1/3Co1/3Mn1/3]O2。考察氨与过渡金属阳离子的配位效应对Li[Ni1/3Co1/3Mn1/3]O2材料的结构和电化学性能的影响。SEM分析结果表明,当NH3·H2O与过渡金属阳离子的总摩尔比为2.7：1时,获得了分布均一的颗粒为过渡金属氢氧化物共沉淀,合成的Li[Ni1/3Co1/3Mn1/3]O2材料的平均粒径约为500nm,振实密度接近2.37g/cm3,接近商品化的LiCoO2正极材料的振实密度。XRD分析结果表明,合成的Li[Ni1/3Co1/3Mn1/3]O2材料具有六角晶格层状结构。Li/Li[Ni1/3Co1/3Mn1/3]O2电池在2.8-4.5V电压范围内的0.1C倍率测试结果表明,首次放电容量达181.5mA·h/g,0.5C倍率循环50次后的放电容量为170.6mA·h/g。     

电场对废旧锂离子电池中有价金属浸出的影响（英文）

提出一种电场强化浸出工艺，用于提高废旧锂离子电池提取Li、Ni、Co以及Mn过程中的浸出效率。通过产品表征和浸出动力学等手段，对浸出工艺参数进行优化并对浸出机制进行研究。在优化浸出条件下，超过98%Li、97%Ni和Co以及93%Mn被浸出进入到溶液中。浸出动力学研究表明，Li、Ni、Co和Mn的浸出过程由基于核缩减模型的化学反应控制，并确定浸出活化能分别为42.4、46.1、46.2和47.3k J/mol。浸出过程中，施加电场为溶液中Fe²⁺和Cl^-的循环利用提供了便利通道，减少了还原剂的添加量，同时保证了高的金属浸出率。     

Li(Ni1/3Co1/3Mn1/3)O2/Ag电极材料的制备及电化学性能

以碳酸盐为沉淀剂,采用共沉淀法合成晶型良好的亚微米级Li(Ni1/3Co1/3Mn1/3)O2粉末,并将其与AgNO3复合,采用无电流分解沉积法制备出了Ag表面修饰的Li(Ni1/3Co1/3Mn1/3)O2/Ag电极材料.利用X-射线衍射、扫描电镜及电化学测试等方法表征材料的结构、形貌和电化学性能.结果表明:Ag单质的存在可明显改善Li(Ni1/3Co1/3Mn1/3)O2的电化学性能,尤其是倍率特性,以0.2C、0.5C、1C倍率放电进行测试,经过40次循环后比容量分别为156.2、144.3、137.7mAh·g-1,其容量保持率分别为96.2％、95.3％、93.9％.Ag的表面修饰能使Li(Ni1/3Co1/3Mn1/3)O2电荷转移阻抗大幅度减小,阻抗从65Ω减小到50Ω.     

Lithium and manganese extraction from manganese-rich slag originated from pyrometallurgy of spent lithium-ion battery

Mn and Li were selectively extracted from the manganese-rich slag by sulfation roasting?water leaching. The extraction mechanisms of Mn and Li were investigated by means of XRD, TG?DSC, and SEM?EDS. 73.71% Mn and 73.28% Li were leached under optimal experimental conditions: acid concentration of 82 wt.%, acid-to-slag mass ratio of 1.5:1, roasting temperature of 800 °C, and roasting time of 2 h. During the roasting process, the manganese-rich slag first reacted with concentrated sulfuric acid, producing MnSO₄, MnSO₄·H₂O, Li₂Mg(SO₄)₂, Al₂(SO₄)₃, and H₄SiO₄. With the roasting temperature increasing, H₄SiO₄ and Al₂(SO₄)₃ decomposed successively, resulting in generation of mullite and spinel. The mullite formation aided in decreasing the leaching efficiencies of Al and Si, while increasing the Li leaching efficiency. The formation of spinel, however, decreased the leaching efficiencies of Mn and Li.     

Reductive acid leaching of valuable metals from spent lithium-ion batteries using hydrazine sulfate as reductant

Hydrazine sulfate was used as a reducing agent for the leaching of Li, Ni, Co and Mn from spent lithium-ion batteries. The effects of the reaction conditions on the leaching mechanism and kinetics were characterized and examined. 97% of the available Li, 96% of the available Ni, 95% of the available Co, and 86% of the available Mn are extracted under the following optimized conditions: sulfuric acid concentration of 2.0 mol/L, hydrazine sulfate dosage of 30 g/L, solid-to-liquid ratio of 50 g/L, temperature of 80 °C, and leaching time of 60 min. The activation energies of the leaching are determined to be 44.32, 59.37 and 55.62 kJ/mol for Li, Ni and Co, respectively. By performing X-ray diffraction and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy, it is confirmed that the main phase in the leaching residue is MnO₂. The results show that hydrazine sulfate is an effective reducing agent in the acid leaching process for spent lithium-ion batteries.     

Priority recovery of lithium and effective leaching of nickel and cobalt from spent lithium-ion battery

The cathode materials of spent lithium-ion batteries (LIBs) were recovered via reductive roasting, Na₂CO₃ leaching, and ammonia leaching. The effects of roasting parameters, Na₂CO₃ leaching parameters, and ammonia leaching parameters on the leaching efficiencies of metals were explored. The results show that the mineral phase of spent LIBs is reconstructed during reductive roasting, and more than 99% of Li can be preferentially leached via Na₂CO₃ leaching. Ni (99.7%) and Co (99.9%) can be leached via one-step ammonia leaching, and Mn cannot be leached. Thus, good leaching selectivity is achieved. The kinetic study shows that the leaching of Ni and Co conforms to chemical reaction control.     

Synthesis and electrochemical performances of LiCoO<Subscript>2</Subscript> recycled from the incisors bound of Li-ion batteries

A new LiCoO₂ recovery technology for Li-ion batteries was studied in this paper. LiCoO₂ was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li₂CO₃, LiOH·H₂O and LiAc·2H₂O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO₂ was obtained by calcining the mixture at 850°C for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO₂ synthesized by adding Li₂CO₃ is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g⁻¹ between 3.0–4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g⁻¹.     

Microstructural and electrochemical properties of Ti-doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coated LiCoO<Subscript>2</Subscript> films

We studied the microstructural and electrochemical properties of Ti-doped Al₂O₃ (Ti-Al₂O₃) coated LiCoO₂ thin films depending on the Ti composition. The 1.27 at.% Ti-Al₂O₃ coated films had an amorphous structure with better conductivity than that of pure Al₂O₃ films. The Ti-Al₂O₃ coating layer effectively suppressed the dissolution of Co and the formation of lower Li conductivity SEI films at the interface between the LiCoO₂ film and electrolyte. The Ti-Al₂O₃ coating improved the cycling performance and capacity retention at high voltage (4.5 V) of the LiCoO₂ films. The Ti-Al₂O₃ coated LiCoO₂ films showed better electrochemical properties than did the pure Al₂O₃ coated LiCoO₂ films. These results were closely related to the enhanced Li-conductivity and interfacial quality of the Ti-Al₂O₃ film.     

Leaching of iron concentrate separated from kiln slag in zinc hydrometallurgy with hydrochloric acid and its mechanism

It is taken as a novel prospective process to treat iron concentrate from hydrometallurgical zinc kiln slag for comprehensive utilization of valuable metals by a hydrochloric acid leaching-spray pyrolysis method. The leaching mechanism of different valuable metals was studied. The results revealed that the leaching rates of Ag, Pb, Cu, Fe, As and Zn were 99.91%, 99.25%, 95.12%, 90.15%, 87.58% and 58.15%, respectively with 6 mol/L HCl and L/S ratio of 10:1 at 60 °C for 120 min. The action of SiO₂ in leaching solution was also studied. The results showed that the precipitation and settlement of SiO₂(amorphous) adsorbed part of metal ions in solution, which greatly inhibited the leaching of Cu, Fe, As and Zn, so it is crucial to control the precipitation of amorphous SiO₂.     

Kinetics of SiO2 leaching from Al2O3 extracted slag of fly ash with sodium hydroxide solution

Kinetics of SiO₂ leaching from Al₂O₃ extracted slag of fly ash with sodium hydroxide solution was studied. The effect of leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed on SiO₂ leaching rate was investigated. The results show that increasing leaching temperature, mass ratio of NaOH to SiO₂ and stirring speed increases SiO₂ leaching rate. The SiO₂ leaching rate is 95.66% under the optimized conditions. There are two stages for the SiO₂ leaching process, and the leaching reaction is very rapid in the first stage but quite slow in the second stage. The whole leaching process follows the shrinking core model, and the outer diffusion of no product layer is the rate-controlling step. The activation energies of the first and second stages are calculated to be 8.492 kJ/mol and 8.668 kJ/mol, respectively. The kinetic equations of the first and the second stages were obtained, respectively.     

超声空化作用下高温合金废料中战略金属的浸出机理（英文）

为提高高温合金废料中战略金属的回收效率，提出一种超声辅助浸出工艺。在超声辅助浸出过程中，浸出时间为60 min时，高温合金废料中Re、Ni、Co、Al、Cr和W的浸出率分别为92.3%、95.2%、98.5%、98.7%、97.5%和27.2%，明显优于常规浸出工艺中浸出时间为120 min时的浸出效率。高温合金废料中战略金属浸出效率的提高可归因于超声空化作用下产生的物理和化学协同作用。超声空化的物理作用可以阻止高温合金废料表面溶解层的形成，促进浸出液与高温合金废料接触，从而提高高温合金废料中战略金属的浸出率；而超声空化的化学作用可以促进HCl-H₂O₂体系中羟基自由基的产生，从而增强浸出体系的电位，促进体系中Re向ReO₄^-的氧化反应过程。     

Selective recovery of lithium from spent lithium iron phosphate batteries using oxidation pressure sulfuric acid leaching system

Oxidation pressure leaching was proposed to selectively dissolve Li from spent LiFePO₄ batteries in a stoichiometric sulfuric acid solution. Using O₂ as an oxidant and stoichiometric sulfuric acid as leaching agent, above 97% of Li was leached into the solution, whereas more than 99% of Fe remained in the leaching residue, enabling a relatively low cost for one-step separation of Li and Fe. And then, by adjusting the pH of leachate, above 95% of Li was recovered in the form of the Li₃PO₄ product through iron removal and chemical precipitation of phosphate.     

The corrosion behavior of Fe-Cr alloys containing Co,Mn, and/or Ni and of a Co-base alloy in the presence of molten (Li,K)-carbonate

The corrosion behavior or commercial Fe ana Co base alloys and Fe-Cr model alloys with different contents of Co and/or Mn was investigated by continuous exposure tests in the presence of a thin carbonate film. All alloys studied form multi-layered corrosion scales consisting of outer Li containing oxides and inner Cr rich oxides, i.e. spinels or LiCrO₂. The LiCrO₂ is formed on alloys with high Cr contents (≤ 20 wt.%), whereas mixed (Fe,M)_3-x Cr_xO₄ spinels (M = Co, Mn, Ni) were found on alloys with lower Cr content (15–20 wt.%). Insoluble Cr containing oxides occur only in the inner layers of the corrosion scale, whereas on the surface of corroded specimens soluble chromates were detected. Alloys with Mn contents greater than 15 wt.% form Mn₂O₃ in the initial stages of the experiments, this oxide reacts with the melt and formation of Li₂MnO₃ takes place. In exposure tests up to 500 h Fe-Cr alloys with low contents of Mn and Co (10 wt.% Co or Mn) form iron rich oxides (LiFeO₂ and LiFe₅O₈) with varying amounts of dissolved Mn or Co. In the later corrosion stages outward diffusion of Mn and/or Co takes place and LiCoO, and Li₂MnO₃ are formed on top of LiFeO₂, whereby the concentration of Mn and/or Co in the inner layers (LiFeO₂ and spinel) decreases. The outer Li containing oxides LiFeO₂, LiCoO₂ and Li₂MnO₃ are nearly insoluble in the melt and when present at the surface protect the metallic material from further corrosive attack. Fe-Cr model alloys containing Co and Mn form multi-layered corrosion layers after 2000 h of exposure. These layers consist of four oxides in the following sequence from the metal-scale to the scale-melt interface: (Fe,Cr,Co,Mn)₃O₄ spinel, LiFeO₂, Li₂MnO₃ and LiCoO₂.