采用焙烧-水浸法从报废锂离子动力电池中回收金属

锂离子动力电池在新能源汽车中已获得广泛应用,其报废后Li、Ni、Co、Mn等金属清洁高效回收对促进有色金属循环利用具有重要意义.从LiNi_0.5Co_0.2Mn_0.3O₂为正极材料的锂离子动力电池中回收Li、Ni、Co、Mn,并采用TG-DSC、XRD、ICP-OES、XPS、热力学分析等研究了回收过程物相演变规律及影响金属回收率的主要因素.结果表明:由LiNi_0.5Co_0.2Mn_0.3O₂与NaHSO₄·H₂O组成的混合物,经过焙烧后Li、Ni、Co、Mn元素的赋存状态发生改变,从不溶于水的复杂金属氧化物形式,转化为可溶于水的金属硫酸盐形式.焙烧产物在一定条件下用水浸出后,Li、Ni、Co、Mn元素以金属离子的形式转移到水溶液中获得回收.混合物的组成、焙烧温度对Li、Ni、Co、Mn元素在焙烧产物中的赋存形式呈现制约关系,也是影响Li、Ni、Co、Mn金属回收率的主要因素.     

废旧NCM523型锂离子电池正极材料中镍和钴的回收

废旧NCM523型锂离子电池正极材料中含有价金属元素Ni和Co等,必须对其进行回收.用H2 SO4和H2 O2浸出正极活性物质中的Ni和Co,再用KMnO4除去浸出液中的Mn,最后用"水热煅烧法"制NiCoO2材料.分析了各因素对金属浸出率的影响,在H2 SO4浓度2.5 mol/L、H2 O2体积分数10％、浸出温度80℃、浸出时间80 min和固液比1:14 g/mL的条件下,Ni、Co、Mn的浸出率分别为94.03％、99.56％、14.97％,通过Ni、Co的选择性浸出实现Ni、Co与Mn的初步分离;以KMnO4作为氧化剂,浸出液中Mn离子的浓度可降至0.45 mmol/L以下;以聚乙二醇2000作表面活性剂,草酸作沉淀剂,在160℃水热合成、400℃煅烧后可从浸出净化液中制备出形貌均匀的链状NiCoO2材料.初步实现了废旧电池正极材料中有价金属Ni和Co的回收利用.     

Ti掺杂对正极材料LiNi1/3Co1/3Mn1/3O2结构和电化学性能的影响

为研究离子掺杂对锂离子正极材料LiNi1/3Co1/3Mn1/3O2的影响,采用氢氧化物共沉淀法制备了Ti4+掺杂改性的锂离子正极材料LiNi1/3-1/40Co1/3Mn1/3Ti1/40O2、LiNi1/3-Co1/3-1/40Mn1/3Ti1/40O2和LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2,并运用X射线衍射仪和扫描电子显微镜对Ti掺杂改性后正极材料的晶型和微观结构进行表征,通过高精度电池性能检测系统对正极材料的电化学性能进行检测.结果表明:Ti分别取代Ni、Co和Mn对三元复合正极材料进行掺杂改性后,改性材料都保持典型的α-NaFeO2层状结构,且晶型良好;LiNi1/3-Co1/3Mn1/3-1/40Ti1/40O2轮廓最分明,且形貌均一;3种改性材料的电化学性能均有一定程度的提高,其中LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2提高最为明显,在0.1 C、1.0 C和2.0 C倍率下其首次放电比容量分别为145.35、140.79和125.60 mA.h/g,1.0 C倍率下循环30次后的容量保持率为88.06%.     

一种新型锂离子电池复合正极材料的研制与性能研究

将Co3O4与三元前驱体材料（Ni1/3Co1/3Mn1/3）（OH）2分别以重量比5∶5、6∶4、8∶23个不同配比与适量的Li2CO3材料均匀混合,以980℃的温度焙烧15h,制备出一种新型复合正极材料。采用扫描电镜（SEM）、X射线衍射（XRD）对其形貌及物相进行对比分析,并将该材料组装成扣式电池和实效电池,对材料的电性能进行评估。结果表明,以8∶2的比例混合后制备的新型复合材料性能最为优异,该材料综合了LiCoO2材料和三元材料的优点于一身,比LiCoO2材料在安全性、容量以及循环性能等方面有了显著提高,同时还具有较高的压实密度,弥补了三元材料的不足。     

镀Ni废水回收Ni（OH）2在Ni电极材料中的应用

将化学沉淀法回收电镀Ni废液得到的Ni(OH)2作为镍氢电池的正极材料,研究电极各组分对电池充放电性能的影响,并将回收的Ni(OH)2与购买的Ni(OH)2进行对比。实验结果表明:较优的Ni电极组分配比为m(Ni(OH)2)∶m(Ni粉)∶m(乙炔黑)∶m(60%的聚四氟乙烯乳液)=80∶12∶7∶1,电解液浓度为5 mol/L的KOH溶液。所制备电极中回收Ni(OH)2的放电比容量为185.04 mA.h/g,高于购买的Ni(OH)2的放电比容量,且在0.1C倍率下循环性能稳定。     

锂离子电池La2O3包覆LiNi1/3 Co1/3 Mn1/3 O2正极材料的制备

采用液相共沉淀法与高温固相法合成了La2O3包覆Li(Ni1/3 Co1/3 Mn1/3 )O2的锂离子电池正极材料,采用XRD和电化学方法表征了材料的结构与电化学性能.结果表明,在1 000 ℃焙烧10 h制备的Li(Ni1/3 Co1/3 Mn1/3 )O2材料经包覆2%的La2O3后,具有较佳的电化学性能.其0.1 C倍率首次放电容量和首次充放电效率分别为151.2 mAh·g-1 和83 8%,首次循环后的交流阻抗为162.2 Ω,以0.2 C倍率循环20次后的放电容量为140.7 mAh·g-1 .     

废旧钴酸锂离子电池材料中钴、锂的回收工艺研究

针对废旧锂离子电池对环境污染严重、资源浪费大等问题,对锂离子电池材料中的钴、锂回收工艺进行了研究,探索了废旧电池在NaCl溶液中预放电的最佳浓度和时间,对比分析了正极材料与集流体分离的三种方法,优化出酸浸工艺的最佳工艺参数,探索出了钴、锂沉淀的条件.结果显示,废旧电池在1.5 mol/L的NaCl溶液中放电5 h后可降电池电压至安全值;酸浸的最优的工艺参数为C(H~+)=3.5 mol/L,C(Na_2S_2O_3)=0.25 mol/L,T=90℃,Time=2.3 h,浸出率可达到了99.5%;采用NaOH溶液将pH调至8.5左右可以将钴离子完全沉淀,得到Co(OH)_2沉淀物;采用NaOH溶液调节pH12,再加入适量的Na_2CO_3沉淀锂,锂回收率为73%.     

长循环单晶镍钴锰三元正极材料的制备和表征

采用固相法制备出镍钴锰三元氧化物Li Ni0.5Co0.2Mn0.3O2的单晶材料,然后,进行镁、钛掺杂处理。采用XRD,SEM和恒流充放电等测试手段对材料的晶体结构、形貌和电化学性能等进行研究。测试结果表明,材料形成形貌良好的单晶颗粒,且经过镁、钛掺杂处理后的材料单晶形貌没有改变。掺杂镁、钛后,材料的电化学性能得到明显的改善,Li Ni0.5Co0.2Mn0.3O2的单晶材料掺杂镁、钛后容量从159.59 m Ah/g提升到162.57 m Ah/g,做成全电池后,2 C的放电效率从79.6%提高到了87.3%,1 C下循环300圈后的容量保持率从84.89%提高到92.9%。     

多元掺杂尖晶石锰酸锂LiCo0.02La0.01Mn1.97O3.98Cl0.02的电化学性质研究

采用高温固相浸渍法合成了多元复合掺杂的尖晶石锰酸锂正极材料LiCo0.02La0.01Mn1.97O3.98Cl0.02.采用X衍射分析仪、扫描电镜、马尔文激光粒径分析仪、电化学工作站以及充放电分析仪等设备表征了材料的电化学性能与特性.XRD表明所合成的材料具有良好的尖晶石型结构特征,所掺杂是元素Co,La分别占据了元素Mn的位置,元素Cl占据了元素O的位置.合成材料LiCo0.02La0.01Mn1.97O3.98Cl0.02比材料LiMn2O4有更好的电化学特性,150次循环后的比容量保持率在91.7%.     

Ni-Co-Mn-H2O系电位-pH图绘制及其应用

通过热力学计算,绘制出Ni-Co-Mn-H_2O系在298K时的电位-pH图。由图分析可知在溶液pH值大于7.641时可以获得镍、钴、锰共沉淀,如果提高体系的电位,可以在更低的pH值条件下获得镍钴锰共沉淀。由此得出结论,在Ni、Co、Mn元素存在的水溶液体系中通过多因素调控可采用不同的共沉淀工艺制备镍钴锰三元前驱体是可行的,为镍钴锰三元锂离子电池正极材料的制备工艺选择提供了理论指导。     

废旧锂电池正极活性材料硫酸浸出液萃取纯化

研究了酸性膦类萃取剂P204,P507与协萃剂Lix54,Lix84配方对废旧锂电池正极材料的硫酸浸出液萃取除Al的反应规律.研究表明:P507+Lix84复合体系萃取分离Al/Mn的效果最佳.以最优配方5% P507+5% Lix84/煤油,在pH 为 4.0,水油体积相比V_○a/V_○o为1∶1时,Al,Cu,Co,Ni,Mn和Li的单级萃取率分别为89.1%,80.8%,3.4%,2.6%,3.2%和0.3%.在V_○a/V_○o为1∶4时,经两级(理论级)萃取,母液中Al 的质量浓度为0.88g·L^-1,萃取率大于97.7%;负载油相用2.0mol/L硫酸溶液反萃,在V_○a/V_○o为10∶1时,经两级(理论级)反萃,有机相中Al的质量浓度为0.79g·L^-1,反萃率大于99.0%.     

正极材料Li(Ni1/3Co1/3Mn1/3)1-xCrxO2的合成与表征

采用草酸盐共沉淀法合成一系列的Li(Ni_1/3Co_1/3Mn_1/3)_1-xCr_xO₂正极材料(0 ≤x ≤0.1),用X射线衍射仪（XRD）和扫描电子显微镜（SEM）分析合成产物的晶体结构及表面形貌;利用充放电仪测定了产物的电化学性能.结果表明,合成的Li(Ni_1/3Co_1/3Mn_1/3)_1-xCr_xO₂( x = 0.01,0.03,0.05,0.07) 均保持α-2NaFeO₂ 层状结构相,属于空间R3m点群.Li(Ni_1/3Co_1/3Mn_1/3)_0.95Cr_0.05O₂的电化学性能最佳,首次放电容量达158.6 mAh/g,在2.5～4.5 V区间30次循环后比容量衰竭率仅为3.92%.Li(Ni_1/3Co_1/3Mn_1/3)_0.95Cr_0.05O₂和Li(Ni_1/3Co_1/3Mn_1/3)CrO₂ 的电极阻抗变化不同,进而影响其电化学性能.     

LiCoO2的化学分解浸取过程

废旧锂离子电池中钴的含量较高．钴具有较强的毒性,且资源稀少．为此,研究了废旧锂离子电池的湿法回收工艺过程,并分析了废旧锂离子电池中钴和锂在硫酸溶液中的漫取过程动力学．采用了解体电池塑料外壳、钢壳、正负极材料、N-甲基吡咯烷酮(NMP)分离铝箔与正极活性材料以及硫酸浸取钴与锂的回收工艺．结果表明,铝片的回收率接近100％,钴和锂的浸取率均超过99．6％,同时分析了漫取过程中的工艺参数对钴和锂的漫取率的影响．     

直接回收锰酸锂制备超级电容器MnS材料的研究

本文通过将锂离子电池正极废料锰酸锂转化为超级电容器材料MnS的方法来进行锰酸锂废料的再生利用。将正极废料溶解浸出后,调整废料浓度并加入硫源,水热得到MnS材料。X射线衍射、扫描电镜、透射电镜以及比表面分析仪测试的结果显示,水热法制备的MnS呈现良好的晶体结构,并具有较好的电容器特性。探究不同Mn2+浓度对最终产物性能影响发现:浸出液中Mn2+的浓度对最终产物的形貌、比表面积均有影响。其中当Mn2+浓度为0.5 M时,可以得到三维花状辐射结构。该辐射结构有利于提升电解液与材料之间的表面接触,从而促进材料电容性能。该种思路为锂离子电池正极材料的回收提供了新的思路,值得进一步的深入探究。     

Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO4 batteries has received extensive attention due to its environmental impact and economic benefit. In the pretreatment process of spent LiFePO4 batteries, the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality. In this work, a facile and efficient pretreatment process is first proposed. After only freezing the electrode pieces and immersing them in boiling water, LiFePO4 materials were peeled from the Al foil. Then, after roasting under an inert atmosphere and sieving, all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils. The active materials were subjected to acid leaching, and the leaching solution was further used to prepare FePO4 and Li2CO3. Finally, the battery-grade FePO4 and Li2CO3 were used to re-synthesize LiFePO4/C via the carbon thermal reduction method. The discharge capacities of re-synthesized LiFePO4/C cathode were 144.2, 139.0, 133.2, 125.5, and 110.5 mA·h·g?1 at rates of 0.1, 0.5, 1, 2, and 5 C, which satisfies the requirement for middle-end LiFePO4 batteries. The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.     

氯化亚锡作为还原剂在废旧锂离子电池有价金属浸出回收中的应用研究

The reductant is a critical factor in the hydrometallurgical recycling of valuable metals from spent lithium-ion batteries (LIBs). There is limited information regarding the use of SnCl₂ as a reductant with organic acid (maleic acid) for recovering valuable metals from spent LiCoO₂ material. In this study, the leaching efficiencies of Li and Co with 1 mol·L?1 of maleic acid and 0.3 mol·L?1 of SnCl₂ were found to be 98.67% and 97.5%, respectively, at 60°C and a reaction time of 40 min. We investigated the kinetics and thermodynamics of the leaching process in this study to better understand the mechanism of the leaching process. Based on a comparison with H₂O₂ with respect to leaching efficiency, the optimal leaching parameters, and the activation energy, we determined that it is feasible to replace H₂O₂ with SnCl₂ as a leaching reductant in the leaching process. In addition, when SnCl₂ is used in the acid-leaching process, Sn residue in the leachate may have a positive effect on the re-synthesis of nickel-rich cathode materials. Therefore, the results of this study provide a potential direction for the selection of reductants in the hydrometallurgical recovery of valuable metals from spent LIBs.     

不同锂源对富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料性能的影响研究

采用共沉淀的方法将含有一定比例的镍、钴、锰的金属醋酸盐溶液均匀混合,然后加入适当的沉淀剂Na2CO3制备前驱体Mn0.466Ni0.2Co0.2CO3,最后分别与不同锂源（Li2CO3、LiOH）混合煅烧得到富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料。采用XRD和SEM分别对不同锂源制备的Li1.133Mn0.466Ni0.2Co0.2O2的结构和表面形貌进行表征,采用恒电流充放电和循环伏安法测试对不同锂源制备的Li1.133Mn0.466Ni0.2Co0.2O2的电化学性能进行测试。结果表明,以LiOH为锂源合成的样品在0.1C倍率下首次充、放电比容量分别为330.1mAh/g和218.6mAh/g,首次库仑效率为66.23%,在1C倍率内表现为优秀的稳定循环比容量特性,但是在2C以及2C以上高倍率循环稳定性不及以Li2CO3为锂源合成的样品性能。     

Investigation on the electrochemical activation process of Li1.20Ni 0.32Co0.004Mn0.476O2

The lithium-rich layered oxides are one of the most attractive cathode materials for lithium-ion batteries.Here,two types of Li1.20Ni0.32Co0.004Mn0.476O2 were synthesized using Li2CO3 and LiOH as lithium sources.An electrochemical activation process occurs in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from Li2CO3(LLO-1),while no obvious activation in Li1.2Ni0.32Co0.004Mn0.476O2 prepared from LiOH(LLO-2) is observed.Via advanced scanning transmission electron microscopy(STEM),we found that Li2MnO3-like structure is rich in the surface region of LLO-2.The study provides a direct explanation for the electrochemical activation of lithium-rich materials.The sample with more LiMO2-like phase at the surface region shows a better cycling performance.It is likely that more LiMO2-like phase at the surface region could stabilize the interface and improve the cycling performance of the Li-rich cathode materials.     

Nanometer properties of oceanic polymetallic nodules and cobalt-rich crusts

An ammonia leaching process was utilized to extract Co, Ni and Cu from oceanic polymetallic nodules, whereas an acid leaching process was utilized to extract Co, Ni, Cu, Zn and Mn from cobalt-rich crusts. Both processes produced nanometer materials—ammonia leaching residue and acid leaching residue. A systematic study was conducted on the phase, composition and physicochemistry properties of these residues. The result shows that both residues contain a large amount of nanometer minerals. Ammonia l eaching residue mainly consists of rhodochrosite, with the average grain diameter of 17.9 nm; whereas the acid leaching residue mainly consists of well-developed bassanite, with the average grain deameter of 9.5 nm. The bassanite also has a microporous structure, the volume of the pore space is 1.23 × 10⁻² mL/g. Both the ammonia and acid leaching residues have a large specific surface area, and they display a strong adsorption capacity to saturate sodium chloride vapour, N₂ and SO₂. Both residues have high contents of rare earth elements, and most of these elements exist in the state of ionic adsorption. The content of σ FeO is high. The P₂O₅ enrichment is observable in acid leaching residues. The unique composition and nanometer solid properties of the leaching residues displayed their potential value and promised a bright future for their application in the field of environmental protection and materials.