The rapid growth of lithium ion batteries （LIBs） for portable electronic devices and electric vehicles has resulted in an increased number of spent LIBs. Spent LIBs contain not only dangerous heavy metals but also t...The rapid growth of lithium ion batteries （LIBs） for portable electronic devices and electric vehicles has resulted in an increased number of spent LIBs. Spent LIBs contain not only dangerous heavy metals but also toxic chemicals that pose a serious threat to ecosystems and human health. Therefore, a great deal of attention has been paid to the development of an efficient process to recycle spent LIBs for both economic aspects and environmental protection. In this paper, we review the state-of-the-art processes for metal recycling from spent LIBs, introduce the structure of a LIB, and summarize all available technologies that are used in different recovery processes. It is notable that metal extraction and pretreatment play impor- tant roles in the whole recovery process, based on one or more of the principles of pyrometallurgy, hydrometallurgy, biometallurgy, and so forth. By further comparing different recycling methods, existing challenges are identified and suggestions for improving the recycling effectiveness can be proposed.展开更多
A two-step alkaline-acidic leaching process was conducted to separate the cryolite from spent pot lining and to purify the carbon. The influencing factors of temperature, time, and the ratio of liquid to solid in alka...A two-step alkaline-acidic leaching process was conducted to separate the cryolite from spent pot lining and to purify the carbon. The influencing factors of temperature, time, and the ratio of liquid to solid in alkaline and acidic leaching were investigated. The results show that the recovery of soluble compounds of Na3AlF6 and Al2O3 dissolving into the solution during the NaOH leaching is 65.0%,and the purity of carbon reaches 72.7%. During the next step of HCl leaching, the recovery of soluble compounds of CaF2 and NaAl11O17 dissolving into the HCl solution is 96.2%, and the carbon purity increases to 96.4%. By mixing the acidic leaching solution and the alkaline leaching solution, the cryolite precipitates under a suitable conditions of pH value 9 at 70 °C for 2 h. The cryolite precipitating rate is 95.6%, and the purity of Na3AlF6 obtained is 96.4%.展开更多
Cathode material of spent lithium-ion batteries was refined to obtain high value-added cobalt and lithium products based on the chemical behaviors of metal in different oxidation states. The active substances separate...Cathode material of spent lithium-ion batteries was refined to obtain high value-added cobalt and lithium products based on the chemical behaviors of metal in different oxidation states. The active substances separated from the cathode of spent lithium-ion batteries were dissolved in H2SO4 and H2O2 solution, and precipitated as CoC2O4·2H2O microparticles by addition of （NH4）2C2O4. After collection of the CoC2O4·2H2O product by filtration, the Li2CO3 precipitates were obtained by addition of Na2CO3 in the left filtrate. The experimental study shows that 96.3% of Co （mass fraction） and 87.5% of Li can be dissolved in the solution of 2 mol/L H2SO4 and 2.0% H2O2 （volume fraction）, and 94.7% of Co and 71.0% of Li can be recovered respectively in the form of CoC2O4·2H2O and Li2CO3.展开更多
The spent mushroom compost of Lentinus edodes was used as a biosorbent for adsorbing cadmium, lead and chromium from solutions under batch conditions for the first time. Titration of the biomass revealed that it conta...The spent mushroom compost of Lentinus edodes was used as a biosorbent for adsorbing cadmium, lead and chromium from solutions under batch conditions for the first time. Titration of the biomass revealed that it contained at least three types of functional groups. The Fourier transform infrared spectrometry showed that the carboxyl, phosphoryl, phenolic groups were the main groups. The simulated values of pK, and molar quantity were 5.00 and 0.44 mmol/g, 7.32 and 1.38 mmol/g, 10.45 and 1.44 mmol/g, respectively. The biosorption ability increased with pH in acid condition. When 10 mg/L biomass dosage was added in, there was no significant increment of metal uptake. The maximum uptake estimated with the Langmiur isotherm model were 833.33 mg/g for Cd（ Ⅱ ）, 1000.00 mg/g for Pb（ Ⅱ ） and 44.44 mg/g for Cr（ Ⅲ ）, respectively. All the results showed that vast potential sorption capacity was existed in the biomass for adsorbing these three kinds of metals studied.展开更多
The number of lithium-ion batteries(LIBs)is steadily increasing in order to meet the ever-growing demand for sustainable energy and a high quality of life for humankind.At the same time,the resulting large number of L...The number of lithium-ion batteries(LIBs)is steadily increasing in order to meet the ever-growing demand for sustainable energy and a high quality of life for humankind.At the same time,the resulting large number of LIB waste certainly poses safety hazards if it is not properly disposed of and will seriously harm the environment due to its inherent toxicity due to the use of toxic substances.Moreover,the consumption of many scarce precious metal resources is behind the mass production of batteries.In the light of severe environmental,resources,safety and recycling problems,recycling spent LIBs have become an essential urgently needed action to achieve sustainable social development.This review therefore critically analyses the value and the need for recycling of spent LIBs from a variety of resources and the environment.A range of existing technologies for recycling and reusing spent LIBs,such as pretreatment,pyrometallurgy,hydrometallurgy,and direct recycled methods,is subsequently summarized exclusively.In addition,the benefits and problems of the methods described above are analyzed in detail.It also introduces recycling progress of other LIB components,such as anodes,separators,and electrolytes,as well as the high-value cathode.Finally,the prospects for recycling LIBs are addressed in four ways(government,users,battery manufacturers,and recyclers).This review should contribute to the development of the recycling of used LIBs,particularly in support of industrialization and recycling processes.展开更多
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 ...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℃,and leaching time of 60 min.The activation energies of the leaching are determined to be 44.32,59.37 and 55.62 k J/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.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
Lithium-ion batteries(LIBs)are booming in multiple fields due to a rapid devel-opment in the last decade.However,limited by operational lifespans,a grow-ing number of spent LIBs reaching the end of their lives are con...Lithium-ion batteries(LIBs)are booming in multiple fields due to a rapid devel-opment in the last decade.However,limited by operational lifespans,a grow-ing number of spent LIBs reaching the end of their lives are consequently faced with serious accumulation and descended to hazardous waste.Without proper disposal,the spent LIBs will inevitably cause negative influence on the ecol-ogy and undermine the sustainable manufacture of LIBs.The initial research of recycling strategies mainly focused on the optimization of metallurgical pro-cesses.Recently,the sustainability of the recycling process has attracted much more attention and become an important factor.Here,we summarize the recent progress of the spent LIBs recycling from a sustainable perspective,especially discussing the green innovations in recycling strategies for spent LIBs.Through this article,we expect to reveal the challenges and developing tendency of the recycling strategies and provide a guideline for future researches on process-ing spent LIBs and beyond,like the recycling of the solid-state lithium metal batteries.展开更多
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
Lithium and cobalt recovery from spent lithium-ion batteries(LIBs) is a major focus because of their increased production and usage. The conventional method for recycling spent LIBs using inorganic acids produces harm...Lithium and cobalt recovery from spent lithium-ion batteries(LIBs) is a major focus because of their increased production and usage. The conventional method for recycling spent LIBs using inorganic acids produces harmful byproducts. In this work, the leaching agent was substituted with a less expensive and more environmentally friendly alternative—acetic acid—and a mathematical model was developed to describe the kinetics of the recovery process. The variables used were the pH value, temperature, H_2O_2 concentration, and the solid-to-liquid(S/L) ratio. The mathematical model used was the shrinking core model, which was modified to accommodate an equilibrium reaction. The experimental results show that the rate of recovery of Li and Co over time was only affected by temperature. The leaching behaviors of Li and Co were found to oppose each other. An increase in temperature resulted in increased recovery of Li but decreased recovery of Co because of the product-favoring endothermic reaction of Li and the reactant-favoring exothermic reaction of Co. The product of Li has a lower entropy value than the reactant as a free-moving ion, whereas the product of Co leaching has a higher entropy value as a stiff crystal complex. Thus, temperature conditioning is a pivotal factor in the leaching of spent LIBs.展开更多
A simplistic and novel leaching process is developed to dispose spent lithium iron phosphate(LiFePO_(4))batteries.In this paper,oxalic acid is selected as a leaching reagent to recover lithium as a resource and remove...A simplistic and novel leaching process is developed to dispose spent lithium iron phosphate(LiFePO_(4))batteries.In this paper,oxalic acid is selected as a leaching reagent to recover lithium as a resource and remove phosphorus from LiFePO_(4) batteries,benefiting from its low natural effects.The physical properties of spent cathode materials(before leaching)and residues(after leaching)are identified by X-ray diffraction(XRD)and scanning electronic microscopy(SEM)with energy dispersive X-ray spectroscopy(EDS).The total amounts of Li and Fe are analyzed by inductively coupled plasma-atomic emission spectroscopy(ICP-AES).The process occurs under conditions of a 0.3 mol·L^(-1) oxalic acid concentration,a temperature of 80℃,a reaction time of 60 min and a solid/liquid ratio of 60 g·L^(-1).It can effectively precipitate92%ferrum in terms of FeC_(2)O_(4)·2H_(2)O from LiFePO4,with the leaching efficiency of Li achieving up to 98%.This method demonstrates a new strategy for dealing with spent lithium iron phosphate batteries with a low cost and low environmental impact.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
The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted...The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.展开更多
With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （...With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （12%-21%） of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°Cfor 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.展开更多
Nanocrystalline Mn-Zn ferrites （Mno.GZno.4Fe204） with particle size of 12 nm were synthesized hydrotherreally using spent alkaline Zn-Mn batteries, and accompanied by a study of the influencing factors. The nanocrys...Nanocrystalline Mn-Zn ferrites （Mno.GZno.4Fe204） with particle size of 12 nm were synthesized hydrotherreally using spent alkaline Zn-Mn batteries, and accompanied by a study of the influencing factors. The nanocrystals were examined by powder X-ray diffraction （XRD） for crystalline phase identification, and scanning electron microscopy （SEM） for grain morphology. The relationship between concentration of Fe（II）, Mn（II）, and Zn（II） and pH value was obtained through thermodynamic analysis of the Fe（II）-Mn（II）-Zn（II）-NaOH-H2O system. The results showed that all ions were precipitated completely at a pH value of 10-11. The optimal preparation conditions are： co-precipitation pH of 10.5, temperature of 200 ℃ and time of 9 h.展开更多
The extraction of rare earths from acid leach solutions of spent nickel-metal hydride batteries using a primary amine ex- tractant of N 1923 was studied. The effects of feed pH, temperature, agitation rate and time on...The extraction of rare earths from acid leach solutions of spent nickel-metal hydride batteries using a primary amine ex- tractant of N 1923 was studied. The effects of feed pH, temperature, agitation rate and time on the extraction of rare earths, as well as stripping agent composition and concentration, phase ratio on the stripping were investigated. In addition, the extraction isotherm was determined. The pilot plant test results showed that the extraction of rare earths reached 99.98% after a five-stage counter current extraction. The mixed rare earths oxalates with the 99.77% purity of rare earth elements and impurity content less than 0.05% were obtained by the addition of oxalic acids in loaded strip liquors. The extractant exhibited good selectivity of rare earths over base metals of iron, nickel, copper and manganese.展开更多
Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of sp...Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of spent LiFePO_(4)power batteries have been scrapped and entered the recycling stage.Herein,a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO_(4)powder without any treatment.Various electrochemical test results show that spent LiFePO_(4)electrode has appropriate lithium capacity(14.62 mg_(Li)/g_(LiFePO_(4))),excellent separation performance(α_(Li-Na)=210.5)and low energy consumption(0.768 Wh/g_(Li))in electrochemical lithium extraction from simulated brine.This work not only provides a novel idea for lithium extraction from brine,but also develops an effective strategy for recycling spent LIBs.The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.展开更多
基金The authors acknowledge financial support on this research from the ＂1000 talents program＂ of China （Zhi Sun）, and the National Natural Science Foundation of China （51425405）. This research was also supported by the National Science-Technology Support Program （2015 BAB02B05）.
文摘The rapid growth of lithium ion batteries （LIBs） for portable electronic devices and electric vehicles has resulted in an increased number of spent LIBs. Spent LIBs contain not only dangerous heavy metals but also toxic chemicals that pose a serious threat to ecosystems and human health. Therefore, a great deal of attention has been paid to the development of an efficient process to recycle spent LIBs for both economic aspects and environmental protection. In this paper, we review the state-of-the-art processes for metal recycling from spent LIBs, introduce the structure of a LIB, and summarize all available technologies that are used in different recovery processes. It is notable that metal extraction and pretreatment play impor- tant roles in the whole recovery process, based on one or more of the principles of pyrometallurgy, hydrometallurgy, biometallurgy, and so forth. By further comparing different recycling methods, existing challenges are identified and suggestions for improving the recycling effectiveness can be proposed.
基金Project (50804010) supported by the National Natural Science Foundation of China
文摘A two-step alkaline-acidic leaching process was conducted to separate the cryolite from spent pot lining and to purify the carbon. The influencing factors of temperature, time, and the ratio of liquid to solid in alkaline and acidic leaching were investigated. The results show that the recovery of soluble compounds of Na3AlF6 and Al2O3 dissolving into the solution during the NaOH leaching is 65.0%,and the purity of carbon reaches 72.7%. During the next step of HCl leaching, the recovery of soluble compounds of CaF2 and NaAl11O17 dissolving into the HCl solution is 96.2%, and the carbon purity increases to 96.4%. By mixing the acidic leaching solution and the alkaline leaching solution, the cryolite precipitates under a suitable conditions of pH value 9 at 70 °C for 2 h. The cryolite precipitating rate is 95.6%, and the purity of Na3AlF6 obtained is 96.4%.
基金Project (51078286) supported by the National Natural Science Foundation of ChinaProject (2008BAC46B02) supported by the National Key Technologies R&D Program of China+1 种基金Project (2011SQRL110) supported by the Excellent Youth Foundation of Anhui Education Department, ChinaProject (KJ2011z053) supported by the Natural Science Foundation of Anhui Education Department, China
文摘Cathode material of spent lithium-ion batteries was refined to obtain high value-added cobalt and lithium products based on the chemical behaviors of metal in different oxidation states. The active substances separated from the cathode of spent lithium-ion batteries were dissolved in H2SO4 and H2O2 solution, and precipitated as CoC2O4·2H2O microparticles by addition of （NH4）2C2O4. After collection of the CoC2O4·2H2O product by filtration, the Li2CO3 precipitates were obtained by addition of Na2CO3 in the left filtrate. The experimental study shows that 96.3% of Co （mass fraction） and 87.5% of Li can be dissolved in the solution of 2 mol/L H2SO4 and 2.0% H2O2 （volume fraction）, and 94.7% of Co and 71.0% of Li can be recovered respectively in the form of CoC2O4·2H2O and Li2CO3.
基金The National Natural Science Foundation of China for Distinguished Young Scholars(No.50225926 ,50425927) the Teaching and Research AwardProgramfor Outstanding Youth Teachers in Higher Education Institutions of MOE,China(TRAPOYT) in 2000 ,the Doctoral Foundation of Ministry of Education of China(No.20020532017) andthe Hi-Tech Research and Development Program(863) of China(No.2001AA644020 ,2003AA644010 and 2004AA649370)
文摘The spent mushroom compost of Lentinus edodes was used as a biosorbent for adsorbing cadmium, lead and chromium from solutions under batch conditions for the first time. Titration of the biomass revealed that it contained at least three types of functional groups. The Fourier transform infrared spectrometry showed that the carboxyl, phosphoryl, phenolic groups were the main groups. The simulated values of pK, and molar quantity were 5.00 and 0.44 mmol/g, 7.32 and 1.38 mmol/g, 10.45 and 1.44 mmol/g, respectively. The biosorption ability increased with pH in acid condition. When 10 mg/L biomass dosage was added in, there was no significant increment of metal uptake. The maximum uptake estimated with the Langmiur isotherm model were 833.33 mg/g for Cd（ Ⅱ ）, 1000.00 mg/g for Pb（ Ⅱ ） and 44.44 mg/g for Cr（ Ⅲ ）, respectively. All the results showed that vast potential sorption capacity was existed in the biomass for adsorbing these three kinds of metals studied.
基金financially supported by the National Natural Science Foundation of China(No.52173246)the 111 Project(B13013).
文摘The number of lithium-ion batteries(LIBs)is steadily increasing in order to meet the ever-growing demand for sustainable energy and a high quality of life for humankind.At the same time,the resulting large number of LIB waste certainly poses safety hazards if it is not properly disposed of and will seriously harm the environment due to its inherent toxicity due to the use of toxic substances.Moreover,the consumption of many scarce precious metal resources is behind the mass production of batteries.In the light of severe environmental,resources,safety and recycling problems,recycling spent LIBs have become an essential urgently needed action to achieve sustainable social development.This review therefore critically analyses the value and the need for recycling of spent LIBs from a variety of resources and the environment.A range of existing technologies for recycling and reusing spent LIBs,such as pretreatment,pyrometallurgy,hydrometallurgy,and direct recycled methods,is subsequently summarized exclusively.In addition,the benefits and problems of the methods described above are analyzed in detail.It also introduces recycling progress of other LIB components,such as anodes,separators,and electrolytes,as well as the high-value cathode.Finally,the prospects for recycling LIBs are addressed in four ways(government,users,battery manufacturers,and recyclers).This review should contribute to the development of the recycling of used LIBs,particularly in support of industrialization and recycling processes.
基金Project(51674298)supported by the National Natural Science Foundation of ChinaProject supported by Anhui Province Research and Development Innovation Program,China。
文摘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℃,and leaching time of 60 min.The activation energies of the leaching are determined to be 44.32,59.37 and 55.62 k J/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.
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“Transformational Technologies for Clean Energy and Demonstration,”Strategic Priority Research Program of the Chi-nese Academy of Sciences,Grant/Award Number:XDA21070300the National Natural Science Foundation of China,Grant/Award Numbers:51772301,21773264,21905286the China Postdoc-toral Science Foundation,Grant/Award Numbers:2017LH028,2017M620913。
文摘Lithium-ion batteries(LIBs)are booming in multiple fields due to a rapid devel-opment in the last decade.However,limited by operational lifespans,a grow-ing number of spent LIBs reaching the end of their lives are consequently faced with serious accumulation and descended to hazardous waste.Without proper disposal,the spent LIBs will inevitably cause negative influence on the ecol-ogy and undermine the sustainable manufacture of LIBs.The initial research of recycling strategies mainly focused on the optimization of metallurgical pro-cesses.Recently,the sustainability of the recycling process has attracted much more attention and become an important factor.Here,we summarize the recent progress of the spent LIBs recycling from a sustainable perspective,especially discussing the green innovations in recycling strategies for spent LIBs.Through this article,we expect to reveal the challenges and developing tendency of the recycling strategies and provide a guideline for future researches on process-ing spent LIBs and beyond,like the recycling of the solid-state lithium metal batteries.
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financially supported by Universitas Gadjah Mada partly through LPDP’s Molina Project fiscal year 2015 and partly by University Grant for Applied Research (PTUPT) 2018the support given by the Department of Earth Resource, Kyushu University for the research facilities provided during joint research in Sakura Science Project under Japan Science and Technology Agency
文摘Lithium and cobalt recovery from spent lithium-ion batteries(LIBs) is a major focus because of their increased production and usage. The conventional method for recycling spent LIBs using inorganic acids produces harmful byproducts. In this work, the leaching agent was substituted with a less expensive and more environmentally friendly alternative—acetic acid—and a mathematical model was developed to describe the kinetics of the recovery process. The variables used were the pH value, temperature, H_2O_2 concentration, and the solid-to-liquid(S/L) ratio. The mathematical model used was the shrinking core model, which was modified to accommodate an equilibrium reaction. The experimental results show that the rate of recovery of Li and Co over time was only affected by temperature. The leaching behaviors of Li and Co were found to oppose each other. An increase in temperature resulted in increased recovery of Li but decreased recovery of Co because of the product-favoring endothermic reaction of Li and the reactant-favoring exothermic reaction of Co. The product of Li has a lower entropy value than the reactant as a free-moving ion, whereas the product of Co leaching has a higher entropy value as a stiff crystal complex. Thus, temperature conditioning is a pivotal factor in the leaching of spent LIBs.
基金This work was supported by the International Science and Technology Cooperation Program of China(No.2016YFE0102200)SGCC’s Science&Technology Program(No.DG71-14-044).
文摘A simplistic and novel leaching process is developed to dispose spent lithium iron phosphate(LiFePO_(4))batteries.In this paper,oxalic acid is selected as a leaching reagent to recover lithium as a resource and remove phosphorus from LiFePO_(4) batteries,benefiting from its low natural effects.The physical properties of spent cathode materials(before leaching)and residues(after leaching)are identified by X-ray diffraction(XRD)and scanning electronic microscopy(SEM)with energy dispersive X-ray spectroscopy(EDS).The total amounts of Li and Fe are analyzed by inductively coupled plasma-atomic emission spectroscopy(ICP-AES).The process occurs under conditions of a 0.3 mol·L^(-1) oxalic acid concentration,a temperature of 80℃,a reaction time of 60 min and a solid/liquid ratio of 60 g·L^(-1).It can effectively precipitate92%ferrum in terms of FeC_(2)O_(4)·2H_(2)O from LiFePO4,with the leaching efficiency of Li achieving up to 98%.This method demonstrates a new strategy for dealing with spent lithium iron phosphate batteries with a low cost and low environmental impact.
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.
基金financially supported by the High-degree Talent Introduction Program of Guangdong Academy of Sciences(No.2017GDASCX-0841)the Science and Technology Program of Guangzhou(No.201607020021)+2 种基金the National Natural Science Foundation of China(No.51304055)the Innovative Platform Construction Program of Guangdong Academy of Sciences(No.2017GDASCX-0109)the Pearl River Nova Program of Guangzhou(No.201806010016)
文摘The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.
文摘With extensive use of lithium ion batteries （LIBs）, amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content （12%-21%） of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°Cfor 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N2H4·H2O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N2H4·H2O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H2SO4 and KMnO4 consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.
文摘Nanocrystalline Mn-Zn ferrites （Mno.GZno.4Fe204） with particle size of 12 nm were synthesized hydrotherreally using spent alkaline Zn-Mn batteries, and accompanied by a study of the influencing factors. The nanocrystals were examined by powder X-ray diffraction （XRD） for crystalline phase identification, and scanning electron microscopy （SEM） for grain morphology. The relationship between concentration of Fe（II）, Mn（II）, and Zn（II） and pH value was obtained through thermodynamic analysis of the Fe（II）-Mn（II）-Zn（II）-NaOH-H2O system. The results showed that all ions were precipitated completely at a pH value of 10-11. The optimal preparation conditions are： co-precipitation pH of 10.5, temperature of 200 ℃ and time of 9 h.
基金supported by the National Natural Science Foundation of China(51404297)
文摘The extraction of rare earths from acid leach solutions of spent nickel-metal hydride batteries using a primary amine ex- tractant of N 1923 was studied. The effects of feed pH, temperature, agitation rate and time on the extraction of rare earths, as well as stripping agent composition and concentration, phase ratio on the stripping were investigated. In addition, the extraction isotherm was determined. The pilot plant test results showed that the extraction of rare earths reached 99.98% after a five-stage counter current extraction. The mixed rare earths oxalates with the 99.77% purity of rare earth elements and impurity content less than 0.05% were obtained by the addition of oxalic acids in loaded strip liquors. The extractant exhibited good selectivity of rare earths over base metals of iron, nickel, copper and manganese.
基金supported by the National Natural Science Foundation of China(Nos.52173246,91963118,and 52102213)the Science Technology Program of Jilin Province(No.20200201066JC)。
文摘Due to the serious imbalance between demand and supply of lithium,lithium extraction from brine has become a research hotspot.With the demand for power lithium-ion batteries(LIBs)increased rapidly,a large number of spent LiFePO_(4)power batteries have been scrapped and entered the recycling stage.Herein,a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO_(4)powder without any treatment.Various electrochemical test results show that spent LiFePO_(4)electrode has appropriate lithium capacity(14.62 mg_(Li)/g_(LiFePO_(4))),excellent separation performance(α_(Li-Na)=210.5)and low energy consumption(0.768 Wh/g_(Li))in electrochemical lithium extraction from simulated brine.This work not only provides a novel idea for lithium extraction from brine,but also develops an effective strategy for recycling spent LIBs.The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.
