Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid

Highly selective separation of vanadium over iron from stone coal by oxalic acid leaching

Physical treatment and chemical treatment of spent lithium-ion battery were studied in our research team. Especially we developed two types of acidic leaching for crushed powders containing LiCoO2 of spent lithium ion battery. One of them is sulfuric acid leaching with H2O2 as a reducing agent. The leaching rates of cobalt, lithium and the other metals were above 99 % at the condition of 2 M H2SO4, 10 vol. % H2O2, 75°C, 300 rpm agitation speed, 250 g/5L solid liquid ratio and 75 minutes reaction time. And the other leaching process is the oxalic acid leaching. In this process more than 99% of Li and less than 1% of Co were dissolved at the condition of 3M oxalic acid, 80°C reaction temperature, 300rpm agitation speed, 50g/L initial solid/liquid ratio and 90min extraction time. Each process has its advantage and disadvantage. In sulfuric acid leaching, leaching reagent is very cheap and cobalt could be recovered into cobalt hydroxide. On the other hand, oxalic acid is more expensive than sulfuric acid but lithium could be dissolved selectively. Also cobalt could be recovered into cobalt oxalate and it could be changed into cobalt oxide after heat treatment. In order to select the effective recycling process, recovery rate and purity of cobalt hydroxide and cobalt oxalate were compared and it was investigated which process was more environment-friendly and economical.

Recovery of lithium from oxalic acid leachate produced from black mass of spent electric vehicle Li-ion batteries

How has external knowledge contributed to lithium-ion batteries for the energy transition?

The electrification of transport systems is essential for improved city air quality and reduced noise, may also contribute to enhanced energy security and decreased greenhouse gas emissions. The key enabler of the large-scale uptake of electric vehicles (EVs) are improved lithium-ion batteries (LIBs), offering higher mass specific energies, volumetric energy densities, potential differences and energy efficiencies. Most LIBs used in automotive applications combine nickel-cobalt-manganese (NCM) oxide cathodes with graphite (Gr) anodes intercalating lithium ions from organic electrolyte solutions of lithium salts. Two widely reported modifications include increasing the nickel content in cathodes and introducing silicon-graphite (SiGr) composite anodes, enabling increased energy storage capacities. Technological developments in EVs and LIBs have triggered a growing interest in using Life Cycle Assessment (LCA) to quantify the environmental burdens of electrified mobility (Ellingsen et al., 2014; Kim et al., 2016). Figure 1 compares the global warming potential (GWP) (kg CO2-eq. (battery kW h)- 1) of battery manufacturing at different locations, for reports that allowed the production footprint to be distinguished. The indication that despite the higher coal intensity in its electricity mix, China’s LIB manufacturing has a lower GWP production footprint than other regions is counter-intuitive and raises the need for more detailed analysis. An important additional aim of this work is to consider whether the high environmental burdens of producing LIBs can be counter-balanced by extended EV use periods and the parameters that affect these. Since nickel-rich cathodes and silicon-based anodes are considered the most promising modifications for next-generation LIBs in the near-term, their combined environmental performance is studied. This paper reports on the development of a detailed unit process-based Life Cycle Inventory model, built to assess the production of current and future NCM batteries in China. The definition of the studied product system and LCI model is followed by the introduction of four different battery production scenarios, which were developed to assess the impacts of producing batteries in China, study the introduction of silicon in anodes and examine the effects of two novel cathode chemistries with increased nickel content (NCM622, NCM811). A detailed presentation of the production phase impacts is provided, based on the ReCiPe 1.08 Midpoint characterisation method. The production phase analysis is complemented by the development of a gate-to-gate model, assessing the environmental impact of using a LIB in a passenger vehicle in China. The results indicate that the GWP of producing a LIB in China is 250 kg CO2-eq (battery kW h)-1, which is 40% higher than previously estimated (Ellingsen et al., 2014) and significantly higher than earlier reported values for China (Hao et al., 2017; Yu et al., 2018). The mismatch with the latter two studies is due to the fundamentally different assumptions made when modelling the production phase. This work provides the means to make sensible comparisons, using the same model and assumptions, and accurately benchmark the performance of different scenarios. It is shown that copper production for anode current collectors makes the most important contribution towards all human toxicity and ecotoxicity categories, with the next most important contribution coming from nickel sulfate production for mixed metal oxide cathodes. Furthermore, the manufacturing of next-generation LIBs is estimated to have a slightly increased impact intensity on a per battery pack basis, with the increased nominal energy capacity effectively reducing the impacts on a per kW h basis. The use of LIBs in China primarily affects the GWP, as a result of the high coal intensity of the local electricity mix. References Amarakoon, S., Smith, J., Segal, B., 2013. Application of life-cycle assessment to nanoscale technology: Lithium-ion batteries for electric vehicles. No. EPA 744-R-12-001. Ellingsen, L.A.W., Majeau-Bettez, G., Singh, B., Srivastava, A.K., Valøen, L.O., Strømman, A.H., 2014. Life Cycle Assessment of a Lithium-Ion Battery Vehicle Pack. J. Ind. Ecol. 18, 113–124. Hao, H., Mu, Z., Jiang, S., Liu, Z., Zhao, F., 2017. GHG Emissions from the production of lithium-ion batteries for electric vehicles in China. Sustain. 9. Kim, H.C., Wallington, T.J., Arsenault, R., Bae, C., Ahn, S., Lee, J., 2016. Cradle-to-Gate Emissions from a Commercial Electric Vehicle Li-Ion Battery: A Comparative Analysis. Environ. Sci. Technol. 50, 7715–7722. Majeau-Bettez, G., Hawkins, T.R., StrØmman, A.H., 2011. Life cycle environmental assessment of lithium-ion and nickel metal hydride batteries for plug-in hybrid and battery electric vehicles. Environ. Sci. Technol. 45, 4548–4554. Yu, A., Wei, Y., Chen, W., Peng, N., Peng, L., 2018. Life cycle environmental impacts and carbon emissions: A case study of electric and gasoline vehicles in China. Transp. Res. Part D Transp. Environ. 65, 409–420. Figure 1

The closure of Tank 16H will require removal of material from the annulus of the tank. Samples from Tank 16H annulus were characterized and tested to provide information to evaluate various alternatives for removing the annulus waste. The analysis found all four annulus samples to be composed mainly of Si, Na, and Al and lesser amounts of other elements. The XRD data indicate quartz (SiO{sub 2}) and sodium aluminum nitrate silicate hydrate (Na{sub 8}(Al{sub 6}Si{sub 6}O{sub 24})(NO{sub 3}){sub 2}.4H{sub 2}O) as the predominant crystalline mineral phases in the samples. The XRD data also indicate the presence of crystalline sodium nitrate (NaNO{sub 3}), sodium nitrite (NaNO{sub 2}), gibbsite (Al(OH){sub 3}), hydrated sodium bicarbonate (Na{sub 3}H(CO{sub 3}){sub 2}.2H{sub 2}O), and muscovite (KAl{sub 2}(AlSi{sub 3}O{sub 10})(OH){sub 2}). Based on the weight of solids remaining at the end of the test, the water leaching test results indicate 20-35% of the solids dissolved after three contacts with an approximately 3:1 volume of water at 45 C. The chemical analysis of the leachates and the XRD results of the remaining solids indicate sodium salts of nitrate, nitrite, sulfate, and possibly carbonate/bicarbonate make up the majority of the dissolved material. The majority of these salts were dissolved in the first water contact and simply diluted with each subsequent water contact. The water leaching removed large amounts of the uranium in two of the samples and approximately 1/3 of the {sup 99}Tc from all four samples. Most of the other radionuclides analyzed showed low solubility in the water leaching test. The oxalic acid leaching test result indicate approximately 34-47% of the solids in the four annulus samples will dissolve after three contacts with an approximately 3:1 volume of acid to solids at 45 C. The same sodium salts found in the water leaching test comprise the majority of dissolved material in the oxalic acid leaching test. However, the oxalic acid was somewhat more effective in dissolving radionuclides than the water leach. In contrast to the water leaching results, most constituents continued to dissolve during subsequent cycles of oxalic acid leaching. The somewhat higher dissolution found in the oxalic acid leaching test versus the water leaching test might be offset by the tendency of the oxalic acid solutions to take on a gel-like consistency. The filtered solids left behind after three oxalic acid contacts were sticky and formed large clumps after drying. These two observations could indicate potential processing difficulties with solutions and solids from oxalic acid leaching. The gel formation might be avoided by using larger volumes of the acid. Further testing would be recommended before using oxalic acid to dissolve the Tank 16H annulus waste to ensure no processing difficulties are encountered in the full scale process.

Purpose: Lithium-ion batteries that are commonly used in electric vehicles and plug-in electric hybrid vehicles cannot be simply discarded at the end of vehicle application due to the materials of which they are composed. In addition the US Department of Energy has estimated that the cost per kWh of new lithium-ion batteries for vehicle applications is four times too high, creating an economic barrier to the widespread commercialization of plug-in electric vehicles. (USDOE 2014). Thus, reducing this cost by extending the application life of these batteries appears to be necessary. Even with an extension of application life, all batteries will eventually fail to hold a charge and thus become unusable. Thus environmentally safe disposition must be accomplished. Addressing these cost and environmental issues can be accomplished by remanufacturing end of vehicle life lithium ion batteries for return to vehicle applications as well as repurposing them for stationary applications such as energy storage systems supporting the electric grid. In addition, environmental safe, “green” disposal processes are required that include disassembly of batteries into component materials for recycling. The hypotheses that end of vehicle application remanufacturing, repurposing, and recycling are each economic are examined. This assessment includes a forecast of the number of such batteries to ensure sufficient volume for conducting these activities. Design/methodology/approach: The hypotheses that end of vehicle application remanufacturing, repurposing, and recycling are economic are addressed using cost-benefit analysis applied independently to each. Uncertainty is associated with all future costs and benefits. Data from a variety of sources are combined and reasonable assumptions are made. The robustness of the results is confirmed by sensitivity analysis regarding each key parameter. Determining that a sufficient volume of end of vehicle application lithium-ion batteries will exist to support remanufacturing, repurposing, and recycling involves estimating a lower bound for the number of such batteries. Based on a variety of forecasts for electric vehicle and plug-in hybrid electric vehicle production, a distribution of life for use in a vehicle, and the percent recoverable for further use, three projections of the number of end of vehicle applications batteries for the time period 2010 to 2050 are developed. The lower bound is then the minimum of these three forecasts. Multiple forecasts based on multiple sources of information are used to help reduce uncertainty associated with finding the lower bound, which is particularly important given the short time such vehicles have been in use. Findings: The number of lithium-ion batteries becoming available annually for remanufacturing, recycling and repurposing is likely to exceed 3,000,000 between 2029 and 2032 as well as reaching 50% of new vehicle demand between 2020 and 2033. Thus, a sufficient number of batteries will be available. Cost benefit analysis shows that remanufacturing is economically feasible, saving approximately 40% over new battery use. Repurposing is likewise economically feasible if research and development costs for new applications are less than $82.65 per kWh for upper bound sales price of $150.00 per kWh. For a lower bound in R&D expenses of $50 per kWh, the lowest economic sales price is $114.05 per kWh. Recycling becomes economically feasible only if the price of lithium salts increases to $98.60 per kg due to a shortage of new lithium, which is possible but perhaps not likely, with increasing demand for lithium-ion batteries. Research limitations/implications: The demand for lithium-ion batteries for vehicle applications through 2050 has a high degree of uncertainty. Repurposing applications are currently not fully developed and recycling processes are still evolving. There is a high degree of uncertainty associated with the cost-benefit analysis. Practical implications: Lithium-ion batteries are a major cost component of an electric vehicle and a plug-in electric hybrid vehicle. One way of reducing this cost is to develop additional uses for such batteries at the end of vehicle application as well as an environmentally friendly method for recycling battery components as an alternative to destruction and disposal. Social implications: The use of lithium-ion batteries in vehicles as opposed to fossil fuels is consistent with the guiding principles of sustainability in helping to meet current needs without compromising the needs and resources of future generations. Reusing entire lithium-ion batteries or recycling the materials of which they are composed further reinforces the sustainability of the use of lithium-ion batteries. Originality/value: The results show that a sufficient number of batteries to support remanufacturing, repurposing, and recycling will be available. Remanufacturing is shown to be economically feasible. Repurposing is shown to be feasible under reasonable conditions on design and development. Recycling will likely not be economically feasible in isolation but will eventually be necessary for all batteries. Thus, the costs of recycling must be assigned to original vehicle use, remanufacturing and repurposing applications Furthermore, this effort integrates information from a wide variety of sources to show the economic feasibility of end of vehicle application uses for lithium-ion batteries.

The use of lithium-ion batteries has increased due to the large number of portable devices and electric vehicles that are considered environmentally friendly. The cathode is one of the electrodes that have an important role in ion delivery in lithium-ion batteries. Ni-rich Nickel Manganese Cobalt (NMC) is one of the most frequently used cathodes. The increasing demand for lithium-ion batteries has also led to an increase in the use of nickel as a cathode material, so that other sources of nickel are needed. The use of nickel recovered from a spent nickel catalyst can be a solution for alternative sources of nickel. Spent nickel catalyst is one of the hazardous and toxic wastes, so this recovery process can reduce the amount of catalyst waste. Nickel is extracted from a spent nickel catalyst using the acid leaching method. The acid used is 2M lactic acid with various solid/liquid ratios. Spent nickel catalyst leaching was carried out at 80°C for3 hours. At the same time, the synthesis of NMC 811 material used the co-precipitation method with oxalic acid as the precipitant. Based on the results obtained, the variation of the ratio that produces the highest leaching efficiency is 20 grams/L. The obtained NMC material has high peaks at two theta 15-20° and 40-46°. The morphology of the NMC 811 material is agglomerated with a homogeneous shape and inhomogeneous size. Based on the charge discharge test on the battery, the battery capacity obtained reached 119 mAh.

<span lang="EN-US">Lithium ion batteries have been widely applied in portable electronic devices and electric vehicles as high-density energy storage. The significant consumption of lithium ion batteries is outweighed by the threat to the environment of battery waste. Recovery of valuable metals contained in lithium ion batteries, such as Cu foil, is one of the efforts to overcome environmental pollution due to copper metal. The hydrometallurgical method is used in the recovery process, which includes leaching using nitric acid and precipitation using oxalic acid. The material obtained was copper oxide (CuO), which was analyzed using XRD, SEM-EDX, and FTIR to determine the characteristics of the sample. XRD analysis showed that the crystallinity of CuO was in accordance with the database. SEM images confirm the presence of agglomeration and inhomogeneous particle distribution in the samples. FTIR analysis confirmed the formation of the CuO phase, and the EDX results showed the purity of the sample, which consisted of Cu and O elements. Based on the research, CuO was successfully produced from the recovery of Cu Foil waste.</span>

Compared to the traditional electrochemical power source, lithium ion batteries (LIBs) have the advantages of higher energy density, longer life, and absence of any memory effect, and thus have attracted widespread research interest around the world. After Sony Inc. invented and produced the first commercial 18650 cell, many domestic and international research centers and companies have promoted the industrialization of LIBs. With the development of LIB technology, its application scope has extended from traditional consumer electronics to the new energy vehicles (NEVs) and energy storage fields. NEVs include pure electric vehicles (PEVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs). LIBs have been the main driving force for PEVs to date, and their cathode technology development process has had three generations, i.e., the first using LiCoO2, the second using LiMn2O4 and LiFePO4, and the third generation using Li(NixCoyMn1-x-y)O2. With the development of cathode and anode materials with higher capacities and the increased reliability of LIB safety technology (including separators with higher temperature resistance, electrolytes with higher voltage resistance, and other protection methods), cells with higher energy densities and longer lives can be developed and applied in the future. These improvements will enable PEVs to travel longer distances, which is the most critical issue to customers. This paper provides a review of the development status of the power battery industry and an analysis of the direction of LIB technology with respect to the following:(1) the cathode/anode materials used, including the higher Ni content in Li(NixCoyMn1-x-y)O2, along with its structural modification, and the stability of silicon and improvements in its efficiency and cycle life; (2) the design technology, including the electrode and structure designs developed using simulation technology, theoretical modeling, and experimental methods based on Taguchi design; and (3) advances in process technology, including mixing and coating processes. Based on the above information, a clear picture of the technical direction was provided for LIBs in the PEV field.

Emerging trends in sustainable battery chemistries

This study investigates the environmental and technical challenges associated with the production, use, and recycling of lithium-ion batteries (LIBs), which are critical components in consumer electronics and electric vehicles (EVs). As the demand for LIBs continues to grow, the concerns related to the mining and processing of key materials like lithium, cobalt, nickel, and manganese are also increasing. The extraction and refining processes for these metals are energy-intensive and produce significant environmental impacts, including greenhouse gas emissions, toxic waste, and resource depletion. The review emphasizes the need for improved re-cycling technologies and sustainable practices to mitigate the environmental footprint of LIBs and secure a more sustainable supply chain for the future of clean energy storage solutions. This study also analyzes LIB components to assess the presence of environmentally hazardous metals and compounds. Advanced analytical techniques like X-ray fluorescence (XRF), inductively coupled plasma–optical emission spectroscopy (ICP-OES), and Fourier transform infrared (FTIR) spectroscopy revealed significant leaching of toxic elements and PFAS from battery parts, underscoring the environmental and health risks associated with improper disposal. The findings highlight the urgent need for improved recycling methods to mitigate these risks and enhance the sustainability of LIB use.

A moving urban mine: The spent batteries of electric passenger vehicles

Drive circuitry of an electric vehicle enabling rapid heating of the battery pack at low temperatures.

Guest Editorial for Special Issue: Design, Modeling and Control of Electric Vehicles: Selected papers from IEEE Vehicle Power and Propulsion Conference (VPPC 2015)