The recycling of spent LiFePO_(4)batteries has received extensive attention due to its environmental impact and economic benefit.In the pretreatment process of spent LiFePO_(4)batteries,the separation of active materi...The recycling of spent LiFePO_(4)batteries has received extensive attention due to its environmental impact and economic benefit.In the pretreatment process of spent LiFePO_(4)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,LiFePO_(4)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 FePO_(4)and Li_(2)CO_(3).Finally,the battery-grade FePO_(4)and Li_(2)CO_(3)were used to re-synthesize LiFePO_(4)/C via the carbon thermal reduction method.The discharge capacities of re-synthesized LiFePO_(4)/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 LiFePO_(4)batteries.The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.展开更多
With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a si...With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.展开更多
The recycling of cathode materials from spent lithium-ion battery has attracted extensive attention,but few research have focused on spent blended cathode materials.In reality,the blended materials of lithium iron pho...The recycling of cathode materials from spent lithium-ion battery has attracted extensive attention,but few research have focused on spent blended cathode materials.In reality,the blended materials of lithium iron phosphate and ternary are widely used in electric vehicles,so it is critical to design an effective recycling technique.In this study,an efficient method for recovering Li and Fe from the blended cathode materials of spent LiFePO_(4)and LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)batteries is proposed.First,87%A1 was removed by alkali leaching.Then,91.65%Li,72.08%Ni,64.6%Co and 71.66%Mn were further separated by selective leaching with H_(2)SO_(4)and H_(2)O_(2).Li,Ni,Co and Mn in solution were recovered in the form of Li_(2)CO_(3)and hydroxide respectively.Subsequently,98.38%Fe was leached from the residue by two stage process,and it is recovered as FePO_(4)·2H_(2)O with a purity of 99.5%by precipitation.Fe and P were present in FePO_(4)·2H_(2)O in amounts of 28.34%and 15.98%,respectively.Additionally,the drift and control of various components were discussed,and cost-benefit analysis was used to assess the feasibility of potential application.展开更多
A hydrometallurgical process for the recovery of cobalt oxalate from spent lithium-ion batteries was used to recycle cobalt compound by using alkali leaching, reductive acid leaching and chemical deposition of cobalt ...A hydrometallurgical process for the recovery of cobalt oxalate from spent lithium-ion batteries was used to recycle cobalt compound by using alkali leaching, reductive acid leaching and chemical deposition of cobalt oxalate. The recycled cobalt oxalate was used to synthesize nano-Co3O4 anode material by sol-gel method. The samples were characterized by thermal gravity analysis and differential thermal analysis （TGA/DTA）, X-ray diffraction （XRD）, scanning electron microscopy （SEM） and charge/discharge measurements. The influence of molar ratio of Co2＋ to citric acid and calcination temperature on the structure and electrochemical performance of nano-Co3O4 was evaluated. As the molar ratio of Co2＋ to citric acid is 1：1, the face-centered cubic （fcc） Co3O4 powder shows the discharge capacity of 760.9 mA h g-1, the high coulombic efficiency of 99.7% in the first cycle at the current density of 125 mA g-l, and the excellent cycling performance with the reversible capacity of 442.3 mA h g-1 after 20 cycles at the current density of 250 mA g-1.展开更多
基金This work was financially supported by the Key-Area Research and Development Program of Guangdong Province,China(No.2020B090919003)the National Natural Science Foundation of China(Nos.51834008,51874040,and U1802253)the Fundamental Research Funds for the Central Universities(No.FRF-TP-18-020A3).
文摘The recycling of spent LiFePO_(4)batteries has received extensive attention due to its environmental impact and economic benefit.In the pretreatment process of spent LiFePO_(4)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,LiFePO_(4)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 FePO_(4)and Li_(2)CO_(3).Finally,the battery-grade FePO_(4)and Li_(2)CO_(3)were used to re-synthesize LiFePO_(4)/C via the carbon thermal reduction method.The discharge capacities of re-synthesized LiFePO_(4)/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 LiFePO_(4)batteries.The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(No.51274075)the National Environmental Technology Special Project(No.201009028)Guangdong Province-department University-industry Collaboration Project(Grant No.2012B091100315)
文摘With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.
基金financially supported by the National Key Research and Development Program(Nos.2019YFC1907801,2019YFC1907803 and 2019YFC1907804)the Natural Science Foundation of Hunan(Nos.2021JJ2020066 and 2020JJ4733)+1 种基金the National Natural Science Foundation of China(No.51904340)the Central South University Innovation-Driven Research Program(No.2023CXQD009)。
文摘The recycling of cathode materials from spent lithium-ion battery has attracted extensive attention,but few research have focused on spent blended cathode materials.In reality,the blended materials of lithium iron phosphate and ternary are widely used in electric vehicles,so it is critical to design an effective recycling technique.In this study,an efficient method for recovering Li and Fe from the blended cathode materials of spent LiFePO_(4)and LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)batteries is proposed.First,87%A1 was removed by alkali leaching.Then,91.65%Li,72.08%Ni,64.6%Co and 71.66%Mn were further separated by selective leaching with H_(2)SO_(4)and H_(2)O_(2).Li,Ni,Co and Mn in solution were recovered in the form of Li_(2)CO_(3)and hydroxide respectively.Subsequently,98.38%Fe was leached from the residue by two stage process,and it is recovered as FePO_(4)·2H_(2)O with a purity of 99.5%by precipitation.Fe and P were present in FePO_(4)·2H_(2)O in amounts of 28.34%and 15.98%,respectively.Additionally,the drift and control of various components were discussed,and cost-benefit analysis was used to assess the feasibility of potential application.
基金the financial support on this research from the Talent Training Program of Yunnan Province, China (No. 202005AC160041)the Major R&D Project of Yunnan Province of China (No. 202002AB0800020102)。
文摘采用湿法冶金从废旧LiFePO_(4)正极粉末中回收有价金属锂和铁,回收产物作为原料制备磷酸铁锂。通过优化浸出工艺参数,在丙酮酸浓度为3.0 mol/L、H_(2)O_(2)体积为2 m L、固液比为0.1 g/m L、反应温度为80℃以及反应时间为20min的条件下,Li的浸出效率达到96.56%。采用XRD、XPS、FE-SEM和EDS对浸出残渣进行表征。结果表明,浸出残渣为FePO_(4),Fe/P摩尔比为0.974。将浸出液的pH值调整到12.0,并在80℃搅拌2 h后,浸出液中的Li通过原位沉淀以Li_(3)PO_(4)形式回收,其纯度为96.5%(质量分数)。丙酮酸/H_(2)O_(2)溶液浸出Li的反应动力学数据符合Avrami模型(R^(2)>0.95)。Li浸出过程的活化能较低,表明扩散限制浸出过程中的反应速率。
基金supported by Project Supported by the Planned Science and Technology Project of Hunan Province, China(Nos.2011F J3160,2011GK2002)Project Supported by Scientific Research Fund of Hunan Provincial Education Department(10B054)
文摘A hydrometallurgical process for the recovery of cobalt oxalate from spent lithium-ion batteries was used to recycle cobalt compound by using alkali leaching, reductive acid leaching and chemical deposition of cobalt oxalate. The recycled cobalt oxalate was used to synthesize nano-Co3O4 anode material by sol-gel method. The samples were characterized by thermal gravity analysis and differential thermal analysis （TGA/DTA）, X-ray diffraction （XRD）, scanning electron microscopy （SEM） and charge/discharge measurements. The influence of molar ratio of Co2＋ to citric acid and calcination temperature on the structure and electrochemical performance of nano-Co3O4 was evaluated. As the molar ratio of Co2＋ to citric acid is 1：1, the face-centered cubic （fcc） Co3O4 powder shows the discharge capacity of 760.9 mA h g-1, the high coulombic efficiency of 99.7% in the first cycle at the current density of 125 mA g-l, and the excellent cycling performance with the reversible capacity of 442.3 mA h g-1 after 20 cycles at the current density of 250 mA g-1.
