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A closed loop process for recycling spent lithium ion batteries
Abstract
As lithium ion (Li-ion) batteries continue to increase their market share, recycling Li-ion batteries will become mandatory due to limited resources. We have previously demonstrated a new low temperature methodology to separate and synthesize cathode materials from mixed cathode materials. In this study we take used Li-ion batteries from a recycling source and recover active cathode materials, copper, steel, etc. To accomplish this the batteries are shredded and processed to separate the steel, copper and cathode materials; the cathode materials are then leached into solution; the concentrations of nickel, manganese and cobalt ions are adjusted so NixMnyCoz(OH)(2) is precipitated. The precipitated product can then be reacted with lithium carbonate to form LiNixMnyCozO2. The results show that the developed recycling process is practical with high recovery efficiencies (similar to 90%), and 1 ton of Li-ion batteries has the potential to generate $5013 profit margin based on materials balance.
... In the recovery of metals from the material obtained after mechanical pretreatment and physical separation processes, inorganic acids such as H2SO4 [56], HCI [71], and HNO3 [72], organic acids [73] such as oxalic acid [74], formic acid and malic acid [75], and alkaline (NaOH) reagents are used in the development of leaching processes. In addition, ascorbic acid is also suggested as a reducing agent in leaching with glycine, which is an amino acid. ...
... Therefore, Co 3+ needs to be reduced to Co 2+ to increase the leaching efficiency. For this purpose, a wide variety of reductants including H2O2 [56], [71], [82]- [85], Na2S2O3 [28], NaHSO3 [47], [86[-[88] and Na2S2O5 [89] are used. Figure 3. Recovery of metals from lithium-ion batteries by hydrometallurgical methods [2]. ...
... Pregnant leach solutions are treated to reject impurities such as Cu, Fe, Al and Mn through precipitation by using NaOH or CaCO3 [36], [56]. Precipitation of metals from leaching solutions is a relatively easy and simple process. ...
Wastes with high metal content are an important secondary source. Utilisation of these wastes is important offering environmental and economic advantages as well as the conservation of natural resources. Due to the widespread use of portable electrical and electronic devices (mobile phones, laptops, video cameras, etc.) and electric cars, the consumption of lithium and cobalt, which are used as main components in lithium-ion batteries/batteries (LIB), has increased. Because LIBs contain lithium (1.5-7%), cobalt (5-20%), manganese (15-20%), copper (8-10%), aluminium (5-8%), and nickel (5-10%), they are considered as an important secondary source. Industrially, mechanical pretreatment, pyrometallurgical and hydrometallurgical methods as alone or in combination are used to recover metals from waste LIBs. After mechanical pretreatment and physical separation processes, hydrometallurgical methods, including solution purification, precipitation and solvent extraction methods, are used after leaching with inorganic such as H2SO4, HCI and HNO3 or organic acids. In this study, processes for recovery of metals from LIBs are discussed with a critical review of studies carried out on this. In addition, flowsheets of industrial applications for lithium/cobalt recovery in the world are presented. Yüksek metal içeriklerine sahip olan atıklar önemli bir ikincil kaynak konumundadırlar. Bu atıkların değerlendirilmesi, çevresel ve ekonomik avantajlarının yanı sıra doğal kaynakların korunması açısından da önemlidir. Taşınabilir elektrikli ve elektronik cihazların (cep telefonları, dizüstü bilgisayarlar, video kameralar vb.) ve elektrikli otomobillerin yaygınlaşmasına bağlı olarak bunların temel bileşeni olan lityum-iyon pillerde/bataryalarda (LIB) kullanılan lityum ve kobalt tüketimleri de artmıştır. LIB'ler, lityum (%1,5-7), kobalt (%5-20), manganez (%15-20), bakır (%8-10), alüminyum (%5-8) ve nikel (%5-10) gibi metalleri içermesinden dolayı önemli bir ikincil kaynak olarak değerlendirilmektedirler. Atık LIB'lerden metallerin geri kazanımında endüstriyel olarak mekanik ön-işlem, pirometalurjik, hidrometalurjik veya bunların birleşimden oluşan yöntemler kullanılmaktadır. Mekanik ön-işlem ve fiziksel ayırma işlemlerinden sonra H2SO4, HCI ve HNO3 gibi inorganik ya da organik asitlerle liç sonrası çözelti saflaştırma, çöktürme ve solvent ekstraksiyon yöntemlerini içeren hidrometalurjik yöntemler kullanılmaktadır. Bu çalışmada, LIB'lerden metallerin geri kazanım prosesleri ve yapılmış farklı çalışmalar tartışılmıştır. Ayrıca, Dünya'da lityum/kobalt kazanımının gerçekleştirildiği endüstriyel uygulamalardan akım şemaları sunulmuştur.
... Magnetic separation based on spent LIB types could be used in different steps. After vibration screening, magnetic separation has been frequently utilised in the LIB recycling process to remove Fe-containing components like steel casing fragments (steel coating) and Al-Cu electrodes from the other parts [33,35,43,44,57,70,105]. In other words, the cathode, which comprised the active components (lithium manganese oxide, nickel manganese cobalt oxide, and lithium cobalt oxide) and the Al-Cu current collector, could be recovered from the anode, the steel casings, and the plastic packaging [18]. ...
... They indicated that the minimum suspension velocities declined with particle size (for smaller particles), and the separation could be done at a relatively low airflow rate [52]. Other gravity separation methods include air-based separation methods such as heavy liquid (using a heavy organic liquid such as tribromomethane or [105,[114][115][116] can also be utilised for processing materials even below 0.5 mm. Gravity separation would be feasible since graphite density is different from LiCoO 2 . ...
... Some investigations have presented a complete flowsheet for recycling the spent LIB batteries [25,33,43,52,58,68,100,110,113,123]. Gratz et al. (2014) proposed a process that involves crushing the material using two steps (shearing and impact crushing) followed by discharging. The discharged material is then classified into three fractions based on size. ...
Since soon a huge amount of the spent lithium-ion batteries (LIBs) will end up in landfills, their recycling would be essential in reducing potential environmental issues and covering the raised lithium demands. Therefore, recycling LIBs has turned into a hot research topic. While essential developments in our understanding of recycling LIBs have been achieved, a fully optimised flowsheet design, to some extent, remained the in-house know-how of manufacturing plants. Pretreatment (physical separation), as an initial step, unquestionably affects the performance of the entire recycling process of the spent LIBs. Nevertheless, surprisingly no detail was provided through investigations for each step of the physical separation processes applied for recycling spent LIBs based on the published reports. To tackle these issues, this work analyzed approximately all the possible pretreatment processes involved in the safe recycling of LIBs. Detailed assessments of these investigations indicated that several critical points did not consider or reported through original and reviewed research for recycling LIBs. The process optimisation, metallurgical responses of various pretreatment steps, particle size limitation of different pretreatment methods, magnetic, specific gravity, and surface properties of cathode and anode materials, and several other essential variables did not consider or reported through various investigations. Addressing these gaps will pave the way for the design and operation of the recycling LIBs flowsheet.
... The spent battery was immersed in water and stirred for 30 min to achieve a full discharge [102]. The same method was adapted by Gratz et al. (2014) to achieve a comparably similar discharge rate [103]. Thirdly, in some studies, cryogenic discharge has been used to drain the remaining charge of the LIB. ...
... The spent battery was immersed in water and stirred for 30 min to achieve a full discharge [102]. The same method was adapted by Gratz et al. (2014) to achieve a comparably similar discharge rate [103]. Thirdly, in some studies, cryogenic discharge has been used to drain the remaining charge of the LIB. ...
... In a practical approach, as aqueous salt affects the quality and the quantity of the recoveries, less corrosive or non-corrosive salt would be ideal for discharging the LIB as well as receiving stable products. In contrast, using corrosive salts can even lead to the production of HF after the contamination of trace amounts of water with electrolyte material [101,103]. In addition, discharge of LIB using ohmic discharging needs further optimization to determine its discharging rates and economic performances. ...
The search for global CO2 net zero requires adapting transport vehicles to an electrification system for electric vehicles. In addition, the consumption of electric devices, and consequently batteries, has risen over the years. In order to achieve a circular economy, the spent batteries must be recycled. In this review, the recent literature about Lithium-ion Battery (LIB) recycling was thoroughly examined to propose a decentralized line where different types of LIBs can be pretreated. Different treatment possibilities and segments to include in a common line were identified and discussed. Crushing, density separation, drying, second crushing step, heating with CaO, vibro-sieving, washing and flotation-based separation were distinguished as the best segments to include in the mentioned order. As the conclusion, a new design that can be incorporated in an industrial pretreatment line before metallurgical steps is proposed for recycling of LIBs.
... Nowadays, lithium-ion batteries (LIBs) have been broadly applied in electronic products and electric vehicles (EV), mostly due to their high energy density and long cycling life [1][2][3][4][5]. The global yield of LIBs reached 259.5 GW h in 2020, which is expected to exceed 1135.4 and 6486.6 GW h by 2025 and 2030, respectively [6]. As is well known, the large-scale manufacturing of LIBs has resulted in a shortage of nickel and cobalt resources [7]. ...
... The F concentration detected in the leaching solution was 0.91 g L −1 , which was further regulated to 0.60, 0.30, and 0 g L −1 , respectively, through the removal of F employing active zirconia adsorption [25], in order to investigate the effect of F on material regeneration. Meanwhile, the concentration of TMs (TM = Ni + Co + Mn) in the leaching solution was adjusted to 2.0 mol L −1 with a Ni:Co: Mn ratio of 9:0.5:0.5 by adding NiSO 4 , CoSO 4 , and MnSO 4 [6]. ...
Recycling of spent lithium-ion batteries (LIBs) has raised wide concerns vis-à-vis resource value and environmental protection. Benefiting from the short process and high added value of the recycled products, the regeneration of cathode materials from spent LIBs is a popular approach. However, due to the lack of studies on fluorine (F) migration and the impact thereof on recycled materials, F control relies on deep removal and becomes a considerable challenge, limiting the generation of high-quality cathode materials. Herein, the migration-transformation behaviors of F are investigated in the integrated pyrolysis-leaching-regeneration process of spent LIBs. It is indicated that 45.71% of the amount of F is released into the atmosphere during pyrolysis and some amount of F in the leaching solution is adsorbed into coprecipitated precursors through coordination with metal ions and then regularly entering the lattices of the regenerated LiNi0.9Co0.05Mn0.05O2. Regarding the effects of F on the regenerated LiNi0.9Co0.05Mn0.05O2, a moderate F concentration (approximately 0.30 g L−1) in the leaching solution can boost the regenerated LiNi0.9Co0.05Mn0.05O2 material’s cycling stability (the capacity retention of 95.7% after 100 cycles at 1 C), due to the stabilizing effect of F-doping on the regenerated material’s structure. This study reveals the migration-transformation mechanisms of F during the recycling of spent LIB and provides a rational in-situ F-doping strategy for the regeneration of LiNi0.9Co0.05Mn0.05O2.
... Closed-loop recycling can consist of two different methods: hydro-metallurgy, where metals are leached from the active material in order to form their salts, or pyro-metallurgy, where the cells are consumed in a furnace and a metal alloy of the most valuable metals is obtained. However, these methods are arguably financially limited, as only a fraction the original value of the pack, around 10% can be re-obtained [18,19]. Closed-loop recycling methods are ideally suited to processing material that is low-value, such as LMO and NCA, a chemistry that is becoming obsolete, or the active material is simply too degraded to be directly recycled. ...
... A number of methods for closed-loop recycling have been demonstrated [18,19]. The main barrier to their widespread adoption is that many of these processes are very chemistry-specific and would potentially struggle to efficiently work with the several different types of battery chemistries that are either already on the market or which may be coming down the R&D pipeline [20]. ...
The recycling of lithium-ion batteries presents challenges due to the complex composition of waste streams generated by current processes. Achieving higher purity levels, particularly in the reclamation of aluminium metal and transition metal black mass, is essential for improved valorisation. In this study, we propose a high-efficiency, low-energy, and environmentally friendly method using organic acids to separate cathodic black mass from the aluminium current collector. The acids selected in this study all show >86% peeling efficiency with acetic acid showing 100% peeling efficiency of black mass from the current collector. The recovered materials were subjected to X-ray diffraction, electron microscopy, and elemental analysis techniques. We show that oxalic-acid-treated material exhibited two distinct active material components with a minimal change in mass ratio compared to the untreated material. We show by elemental analysis of the leachates that the majority of critical materials were retained in the black mass and limited aluminium was leached during the process, with almost 100% of Al recovery achieved. This methodology enables the production of high-purity concentrated aluminium and critical metal feedstocks (Mn, Co, Ni, and Li) for further hydro-metallurgical processes, upcycling of the cathode material, and direct recycling. The proposed approach offers significant potential for enhancing valorization in lithium-ion battery recycling, facilitating efficient separation and optimal recovery of valuable metals.
... Eric et al. used a simple and low-cost precipitation method to remove almost 99 % Cu impurities by adjusting pH to 6.47. 8 However, selective precipitation of Cu was challenging as a significant amount of Mn, Ni, and Co were co-precipitated. Hence, new methods to selectively separate specific metal ions for cost-effective and facile extraction are always sought. ...
... Other Cu removal methods from LiB waste include solvent extractions, electrodeposition, or ion exchange. [8][9][10] Peng et al. reported Cu removal from LiB waste using a multi-step process: electrodeposition followed by the extraction of the remaining Cu using N902 organic extractant. 10 However, current Cu removal methods from LiB waste are either expensive, multi-step complicated processes, or methods with low selectivity. ...
Elemental sulfur (S8) is an abundant and inexpensive by-product of petroleum refining. Polymeric sulfur is thermodynamically unstable and depolymerizes back to S8 with time, which limits its applications and causes...
... It is reported that 4,000 tons of spent LIBs contain 1,100 tons of heavy metals and more than 200 tons of toxic electrolytes [7]. The value of one ton of LIBs is 7708 USD, 6101 dollars of which is related to their cathodes [8]. In fact, the most expensive constituent of the battery is the materials present in its cathode [9]. ...
... The precipitation of insoluble jarosite, which is an acid production process, occurred simultaneously with the hydrolysis reactions (reactions 3 to 5) [34,38]. (8) where M=K + , Na + , Ag + , NH 4 + , or H 3 O + . The extraction process of Co is a combination of acid dissolution and oxidation-reduction processes. ...
Recycling spent lithium-ion batteries is important from an environmental perspective and metals worthiness. In this study, an ultrasonic-assisted bioleaching process was developed to recycle valuable metals from spent lithium-ion batteries using bacterial supernatant of Acidithiobacillus ferrooxidans. The results showed that 13% Co, 42% Mn, 25% Ni, and 57% Li were extracted after 24 hours from 10 g/L pulp density without ultrasonication. Ultrasonication with a power of 203.5 W for 30 minutes with intervals of 1 hour enhanced the metal extraction and reduced bioleaching time; 19% Co, 50% Mn, 34% Ni, and 67% Li were extracted after 12 hours from 10 g/L pulp density. This study also investigated the effect of ultrasound on the growth of the pure culture of Acidithiobacillus ferrooxidans. Results indicated that a 10-minute daily application of ultrasonic waves with a power of 203.5 W was optimal for bacterial growth. The results of metals extraction and morphological, structural, and elemental analyses of the battery powder before and after the bioleaching process proved that the application of ultrasound effectively enhanced metal extraction and reduction of bioleaching time as well as the growth of Acidithiobacillus ferrooxidans.
... However, the efficiency of direct recycling highly relies on the state of health of LiB, which limits its commercialization (Clemens & Slater, 2013). (Gratz et al., 2014) figured out that LiB recycling technologies are in their nascent stages, grappling with challenges like high costs and environmental concerns. ...
In light of the burgeoning electric vehicle (EV) market, the demand for lithium-ion batteries (LiBs) is on the rise. However, the supply of materials essential for LiBs is struggling to keep pace, posing a significant challenge in meeting the surging market demand. This study offers a viable solution to bolster the dependability of the material supply chain by prioritizing material suppliers who are deeply committed to sustainable practices and performance. We have developed a comprehensive system for evaluating sustainable performance, encompassing three vital dimensions: economic, social and environmental contexts. Then, we introduced a pioneering approach known as the multi-criteria material supplier selection (MCMSS) methodology which amalgamates multi-criteria decision-making techniques with artificial intelligence to effectively generate sustainability performance of suppliers and identify the most suitable supplier, out of all alternatives. Eventually, the supply of four key materials of LiBs is used as illustrative examples to verify the feasibility and rationality of the proposed MCMSS. This work carries significant implications for overseeing the LiB material industry. The MCMSS model offers a solution for the government to establish a comprehensive material supplier database to intelligently supervise the activities of material suppliers and foster collaboration between upstream and downstream enterprises within the LiB industry.
... Traditionally, most recycling strategies have targeted the recovery of valuable metals such as Li and Co separately, aiming to yield pure singlemetal salts as products used for battery precursors or other applications (Peeters et al., 2022;Yao et al., 2018). Some studies have instead focused on developing a closed-loop recovery strategy to generate new cathode material or obtain battery precursors from end-of-life LIB batteries (Chan et al., 2021;Gratz et al., 2014;Verma et al., 2023;Zhou et al., 2021), aiming to streamline the recycling process and reduce the need for separate metal recovery steps. Reactive crystallization or chemical precipitation, evaporative crystallization as well as solvent extraction are usually needed to recover metals from leachate after the leaching or dissolution step . ...
... In addition, recycling is favorable for low carbon footprint and a net reduction in greenhouse gas emissions compared to direct mining from natural resources (Ciez and Whitacre, 2019). A closed-loop system for recycling battery metals should be soon achieved (Gratz et al., 2014). In practice, there are many limiting factors, such as customer behavior, regulation, collection rates, battery design, and thermodynamics for separation and recycling technologies (Reck and Graedel, 2012;Thompson et al., 2020;Bird et al., 2022). ...
Tremendous efforts are being made toward electrification of the transport sector. Accordingly, next-generation recycling technologies to tackle the large volumes of spent batteries must be urgently innovated. Herein, ionic liquids and the promising ionometallurgy that can overcome some issues of traditional recycling methods are discussed. Ionic liquids-mediated recovery of metals from spent batteries represents a sustainable strategy, featured with new fundamental chemistries. The opportunities for regeneration and reuse of ionic liquids are promising toward a cost-levelized recycling process. The unique chemical environment of ionic liquids also allows the development of coupled electrochemical procedures and upcycling. Future development requires the assessment of continuous operation and holistic process efficiency, technoeconomic and environmental aspects.
... Many recent works have revealed the use of hydrometallurgical process as one of the most efficient processes for recycling of spent LiBs. Gratz et al. (2014) reported the use of sulfuric acid leaching for the recovery of Ni, Mn and Co from the cathode active materials (Ni 0.33 Mn 0.33 Co 0.33 (OH) 2 ) [15]. Li et al. (2011) disclosed the use of nitric acid leaching for the recovery of cobalt [16]. ...
... Recycling facilities need to follow set standards for battery handling, transportation, and recycling, to avoid environmental damage and legal issues [56,57]. Battery recycling faces several challenges including complex battery chemistries, increased volume of used batteries, safety concerns, insufficient infrastructure, environmental implications, and achieving high material recovery rates [54,58]. Overcoming these challenges requires collaborative efforts from researchers, industries, and governments. ...
The pressing requirement to combat climate change and reduce greenhouse gas emissions has catalyzed the development of sustainable mobility solutions. This review presents a detailed analysis of the environmental issues associated with traditional transportation systems, highlighting the significant role of sustainable mobility in addressing these challenges. Important strategies, including electric vehicles (EVs), mass transit, active transportation, and innovative mobility options, are examined. The review accentuates the necessity to cultivate more habitable communities, diminish emissions, enhance air quality, elevate energy efficiency, and contribute to a prosperous future through the adoption of sustainable mobility. The transition to sustainable transportation necessitates comprehensive policies, enabling regulations, and public participation. The creation and implementation of sustainable mobility strategies, the promotion of cleaner products and methods, and the fostering of collaboration across various sectors are pivotal roles for governments, legislators, and stakeholders. Additionally, public awareness campaigns and educational programs can drive behavioral changes and encourage the adoption of sustainable mobility solutions.
... Scalability of the process primarily depends on the cost of the chemicals utilized, safety, and toxicity of the reagents employed in the extraction process. 23,24 A cost-effective, energy efficient process with minimal generation of effluent is imperative for successful industrialization of the recycling process. Hence, a consolidated and critical view on the lab-scale procedures and processes should be accompanied by the developments. ...
... The typical procedure of this approach involves a first shredding stage, the external case is eliminated via magnetic segregation. This is followed by fine crushing and sieving to separate organic materials and current collector foils from the active leachable powder (Gratz et al., 2014). After crushing and sieving, copper foil, aluminum foil, plastics, etc., mostly exist in coarse particles (Zhou et al., 2010) as they tend to be curled than shredded. ...
Lithium-ion batteries (LIBs) with high power density are commonly used in electric vehicles and portable electronic devices. Their applications have been soaring in recent years resulting in an increasing number of used LIBs. Spent LIBs containing heavy metals and toxic hazardous are becoming a severe threat to the environment and human health which must be addressed properly. Recycling is an option for end-of-life LIBs, which not only prevents the pollution of toxic components but also saves natural sources. This paper introduces battery structures and gives an overview of the current state of waste LIBs and their recycling status. Moreover, recent advancements in hydrometallurgy, pyrometallurgy, and direct recycling at both research and industrial levels are deeply analyzed. This document can serve as a useful reference resource for researchers or engineers, who might profit from applying the concept to the examples summarized in the comprehensive review paper.
... The ReCell project applied a wet magnetic technique to separate the mixture of virgin cathode materials with a >90% efficiency. 75 Although the initial results are promising, the cost-effectiveness of the approach at a large scale is unexplored. Density-based classiers single out materials based on their movements in response to the eld of gravity. ...
The advent of lithium-ion battery technology in portable electronic devices and electric vehicle applications results in the generation of millions of hazardous e-wastes that are detrimental to the ecosystem. A proper closed-loop recycling protocol reduces the environmental burden and strengthens a country with resource sustainability, circular economy, and the provision of raw materials. However, to date, only 3% of spent LIBs have been recycled. The recycling efficiency can be further increased upon strong policy incentives by the government and legislative pressure on the collection rate. This review sheds light on the pretreatment process of end-of-life batteries that includes storage, diagnosis, sorting, various cell discharge methods (e.g., liquid medium, cryogenic and thermal conditioning, and inert atmosphere processing), mechanical dismantling (crushing, sieving, sequential, and automated segregation), and black mass recovery (thermally and solvent leaching). The advantage of the stagewise physical separation and practical challenges are analyzed in detail. Disassembling the battery module pack at the cell level with the improved technology of processing spent batteries and implementing artificial intelligence-based automated segregation is worth it for high-grade material recovery for battery applications. Herein, we outline an industry-viable mechanochemical separation process of electrode materials in a profitable and ecofriendly way to mitigate the energy demand in the near future.
... Magnetic, eddy current, electrostatic, gravity separation, and froth flotation can be used to classify the comminution products, which were previously only classified on the basis of their grain size. Further processing is not discussed in this contribution as the focus is primarily on the hydrometallurgical processing of the obtained fine fraction [5,14]. ...
The recycling of lithium-ion batteries (LIBs) is currently an important topic in the fields of research and industry. New developments for the recovery of valuable metals from spent LIBs show a clear trend towards hydrometallurgical concepts. In this context, pre-treatment in particular plays an essential role. If organic compounds remain in the material or if the cathode and anode materials are insufficiently separated from the conductor foils, this can lead to massive process complications in the subsequent hydrometallurgical processes. The chair of Non-ferrous Metallurgy is developing and testing the adaptation and improvement of the recycling possibilities of used lithium-ion batteries for subsequent hydrometallurgical processing. Particular attention is paid to the use of synergy effects and the interaction of treatment and metallurgical processes as this combination is the only way to find an efficient and economical way to recover valuable metals. For this purpose, the comparison of different aggregates for the optimal preparation of the active material from spent lithium-ion batteries for subsequent further processing is carried out. By improving the overall processes, the recovery rates for the valuable metals contained, such as cobalt, nickel, and lithium, can be significantly increased, the metallurgical processes be optimised and the raw material cycle be closed. This is a significant contribution to environmental and climate protection, especially in view of the criticality of the elements mentioned. Due to the demand for a holistic solution for the long-term supply of the European Union with critical raw materials through recycling, a significant optimisation in the field of recovering valuable metals from used lithium-ion batteries can be realised.
... Great efforts have been undertaken for the recycling of spent LIBs and some processes have been commercialized as the Umicore process, the Sony-Sumitomo process, the Toxco process, and the Recupyl process (Xu et al., 2008;Zeng et al., 2014;Gratz et al., 2014;Thompson et al., 2020). Generally, there are three main technologies employed for metal recycling from spent LIBs consisting of pyrometallurgy, hydrometallurgy, and biometallurgy (Asadi et al., 2020;Zhang et al. 2020). ...
Smelting reduction of spent lithium-ion batteries (LIBs) produces metallic alloys containing Co, Ni, Cu, Mn, and Fe. Finding suitable reagents in terms of efficiency, economics, and friendly environment for the dissolution of these metals from the alloys is very important for the recovery process of the metals. In this work, the employment of ferric chloride solution for the dissolution of the metals from the alloys was studied. The effect of parameters like FeCl3 concentration, temperature, time, and pulp density on the leaching efficiency of metals was investigated. Our results indicate that ferric ions in the leaching solutions act as oxidizing agents for the dissolution of the metals, while chloride anions as ligands for the formation of the complexes of the dissolved metal ions. The best conditions for the dissolution of full metals were 0.7 mol/L FeCl3, 12.5 g/L pulp density, 22oC, and 30 min. In comparison with HCl or H2SO4 leaching agents, ferric chloride shows some advantages like a decrease in the dosage of acids and oxidizing agents, fast reaction kinetics, and low energy consumption. With its advantages, ferric chloride solution is considered a potential leaching agent in the recovery process of valuable metals from spent LIBs.
... According to the life cycle assessment (LCA) of the LIB, production of 1 Wh storage capacity of LIB is linked to a cumulative energy demand of 328 Wh and emission of 110 gCO 2 eq of greenhouse gas (GHG) (Peters et al., 2017). The total cost for the production of one ton of LIB is US$ 77,708, and among the various components, the cost of the cathode material (e.g., LiCoO 2 , US$ 2,946) is higher than other parts (Gratz et al., 2014) (Supplementary Figure 3). Due to considerable progress on LIB research and developments, the price of LIB is gradually decreasing, e.g., from 3.17 $/Wh in 1991 to 0.28 $/Wh in 2005 (Vanitha and Balasubramanian, 2013). ...
Spent lithium-ion batteries (LIBs) are increasingly generated due to their widespread use for various energy-related applications. Spent LIBs contain several valuable metals including cobalt (Co) and lithium (Li) whose supply cannot be sustained in the long-term in view of their increased demand. To avoid environmental pollution and recover valuable metals, recycling of spent LIBs is widely explored using different methods. Bioleaching (biohydrometallurgy), an environmentally benign process, is receiving increased attention in recent years since it utilizes suitable microorganisms for selective leaching of Co and Li from spent LIBs and is cost-effective. A comprehensive and critical analysis of recent studies on the performance of various microbial agents for the extraction of Co and Li from the solid matrix of spent LIBs would help for development of novel and practical strategies for effective extraction of precious metals from spent LIBs. Specifically, this review focuses on the current advancements in the application of microbial agents namely bacteria (e.g., Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans ) and fungi (e.g., Aspergillus niger ) for the recovery of Co and Li from spent LIBs. Both bacterial and fungal leaching are effective for metal dissolution from spent LIBs. Among the two valuable metals, the dissolution rate of Li is higher than Co. The key metabolites which drive the bacterial leaching include sulfuric acid, while citric acid, gluconic acid and oxalic acid are the dominant metabolites in fungal leaching. The bioleaching performance depends on both biotic (microbial agents) and abiotic factors (pH, pulp density, dissolved oxygen level and temperature). The major biochemical mechanisms which contribute to metal dissolution include acidolysis, redoxolysis and complexolysis. In most cases, the shrinking core model is suitable to describe the bioleaching kinetics. Biological-based methods (e.g., bioprecipitation) can be applied for metal recovery from the bioleaching solution. There are several potential operational challenges and knowledge gaps which should be addressed in future studies to scale-up the bioleaching process. Overall, this review is of importance from the perspective of development of highly efficient and sustainable bioleaching processes for optimum resource recovery of Co and Li from spent LIBs, and conservation of natural resources to achieve circular economy.
... As a result, the transition metals are precipitated together with Cu at much lower pH values than expected. [111,112]. ...
Today’s rapid increase in lithium-ion battery (LIBs) applications exacerbates a voluminous rise of spent LIBs. Furthermore, manufacturing LIB cathode materials demands valuable metals depleting from the earth crust. Efficient routes are urgently needed to address these problems for upcycling cathode materials from spent LIBs into precursors for manufacturing new LIB cathode materials. Hydrometallurgy is a popular method for extracting metal from spent LIB cathode materials, wherein precipitation processes serve as the foundation for obtaining metal salts. However, the resulting precipitate metal salts are often inferior in yield and quality, limiting their use as precursors for resynthesizing new LIB cathode materials. This review is dedicated to untangling the individual challenges in the precipitation processes, identifying the root causes, and their effects on the quality and yield of the precursors. Based on the problem cause-effect correlation, enhancement strategies, research design guidelines, and future perspectives are highlighted to improve the precipitation processes and the precursor quality and yield for LIB cathode material resynthesis.
... However, conventional inorganic acids are liable to generate hazardous gases such as Cl 2 , SO 3 , and NO x , which threaten the environment and human health and are difficult to manage (Chen et al., 2016;Nayaka et al., 2016). Organic acids (e.g., citric acid , malic acid (Li (Gratz et al., 2014;Gu-Chun et al., 2011;He et al., 2018;Jingu Kang et al., 2010;Meshram et al., 2015;Sandhya et al., 2016;Shuva and Kurny, 2013;Weng et al., 2013;Yang and Xi, 2016;Zhang et al., 2018c;Zhu et al., 2012)). et al., 2013), aspartic acid , ascorbic acid , and organic aqua regia (Lin et al., 2021)), although weaker than inorganic acids, are gaining popularity because they are more thermally stable, have smaller environmental impacts and good recyclability, and can produce strong chelates with heavy metals. ...
Electrifying transportation through the large-scale implementation of electric vehicles (EVs) is an effective route for mitigating urban atmospheric pollution and greenhouse gas emissions and alleviating petroleum-derived fossil fuel reliance. However, huge dumps of spent lithium-ion batteries (LIBs) have emerged worldwide as a consequence of their extensive use in EVs. With the increasing shortage in LIB raw materials, the recycling of spent LIBs has become a fundamental part of a sustainable approach for energy storage applications, considering the potential economic and environmental benefits. In this mini-review, we will provide a state-of-the-art overview of LIB recycling processes (e.g., echelon utilization, pretreatment, valuable metal leaching and separation). We then discuss the sustainability of current LIB recycling processes from the perspectives of life cycle assessment (LCA) and economic feasibility. Finally, we highlight the existing challenges and possibilities of LIB recycling processes and provide future directions that can bridge the gap between proof-of-concept bench demonstrations and facility-scale field deployments through mutual efforts from academia, industry, and government. It is expected that this review could provide a guideline for enhancing spent LIB recycling and facilitating the sustainable development of the field.
... Therefore, the leachate contains a mixture of various metal ions, such as Li + , Co 2+ , Ni 2+ , Mn 2+ , and Fe 3+ . In order to separate various metal components from the leachate, metal ions are precipitated by stepwise addition of alkali, oxalate, or carbonate (Gratz et al. 2014;Verma et al. 2019), or by electrodeposition . Finally, the regeneration of cathode materials can be accomplished by hydrothermal synthesis or calcination (Yang et al. 2017;Zhao et al. 2020). ...
In modern societies, the accumulation of vast amounts of waste Li-ion batteries (WLIBs) is a grave concern. Bioleaching has great potential for the economic recovery of valuable metals from various electronic wastes. It has been successfully applied in mining on commercial scales. Bioleaching of WLIBs can not only recover valuable metals but also prevent environmental pollution. Many acidophilic microorganisms (APM) have been used in bioleaching of natural ores and urban mines. However, the activities of the growth and metabolism of APM are seriously inhibited by the high concentrations of heavy metal ions released by the bio-solubilization process, which slows down bioleaching over time. Only when the response mechanism of APM to harsh conditions is well understood, effective strategies to address this critical operational hurdle can be obtained. In this review, a multi-scale approach is used to summarize studies on the characteristics of bioleaching processes under metal ion stress. The response mechanisms of bacteria, including the mRNA expression levels of intracellular genes related to heavy metal ion resistance, are also reviewed. Alleviation of metal ion stress via addition of chemicals, such as spermine and glutathione is discussed. Monitoring using electrochemical characteristics of APM biofilms under metal ion stress is explored. In conclusion, effective engineering strategies can be proposed based on a deep understanding of the response mechanisms of APM to metal ion stress, which have been used to improve bioleaching efficiency effectively in lab tests. It is very important to engineer new bioleaching strains with high resistance to metal ions using gene editing and synthetic biotechnology in the near future.
... While the addition of Fe can be considered as an issue for downstream purification, the mM amounts added, and the final redox state (Fe 2+ ) have demonstrated to have no interference with separation processes such as ion exchange . pH driven precipitation is commonly used to remove metal impurities in which the pH of the leachate rather than Fe concentration plays a more important role in chemical consumption (Ghassa et al., 2021;Gratz et al., 2014). KOH is not involved in the leachate but is used as anolyte electrolyte for the electrochemical process, generating O 2 as the only product. ...
The manufacturing of lithium-ion batteries (LIB) requires critical materials such as cobalt (Co) and lithium (Li) that are essential for clean-energy products including electric vehicles. Because of their rapidly increasing demand and limited supply, the recycle and reuse of these materials from end-of-life LIB have garnered a lot of interest. Electrochemical leaching has emerged as a sustainable method to extract critical materials out of LIB, so life cycle assessment was conducted to compare the environmental impacts with traditional peroxide-based leaching and another emerging technology-SO 2-based leaching. The results showed that electrochemical leaching reduces the global warming potential (GWP) by 80%− 87% compared to peroxide-based leaching due to a lower acid consumption, avoidance of hydrogen peroxide, and regeneration of reducing agent iron (II) sulfate and compares well with SO 2-based leaching in most impact categories. The analysis suggested renewable energy can further reduce the environment footprint of electrochemical leaching.
... The separation method based on the particle size of the crushed product is one of the most commonly used in LIBs recycling [101]. Traditionally, the milled LIBs scrap can be divided into three groups according to their size: <0.25 mm fraction rich in graphite and cathode active material, 0.25-2 mm fraction containing Al and Cu, and coarse fraction with Al and other components [100]. ...
Due to the accumulation of waste mobile devices, the increasing production of electric vehicles, and the development of stationary energy storage systems, the recycling of end-of-life Li-ion batteries (EOL LIBs) has recently become an intensively emerging research field. The increasing number of LIBs produced accelerates the resources' depletion and provokes pollution. To prevent this, the global communities are concerned with expanding and improving the LIBs recycling industry, whose biggest problems are either large gaseous emissions and energy consumption or toxic reagents and low recycling yields. These issues are most likely solvable by upgrading or changing the core recycling technology, introducing effective benign chemicals, and reducing cathode losses. In this review, we analyze and discuss various LIB recycling approaches, emphasizing cathode processing. After a brief introduction (LIB's design, environmental impact, commercialized processes), we discuss the technological aspects of LIB's pretreatment, sorting and dissolving of the cathode, separation of leached elements, and obtaining high-purity materials. Covering the whole LIB recycling line, we analyze the proven and emerging approaches and compare pyrometallurgy, hydrometallurgy, and cathode's direct restoration methods. We believe that the comprehensive insight into the LIB recycling technologies made here will accelerate their further development and implementation in the large-scale battery industry.
... Solvent extraction utilizes toxic chemicals and complex process routes; thus, selective precipitation requires further investigative exploration, as a possible alternative to solvent extraction, in order to assess the viability and effectiveness of the selective precipitation process route for metal recovery, as well as to further pursue and develop a recycling process that could easily be scaled up from laboratory scale to pilot scale and ultimately industrial scale [18,24,134,136]. Solvent extraction, however, requires the use of toxic organic chemicals as well as complicated experiment sub-process routes [21,82,134,137]. ...
The recycling of spent lithium-ion batteries (Li-ion Batteries) has drawn a lot of interest in recent years in response to the rising demand for the corresponding high-value metals and materials and the mounting concern emanating from the detrimental environmental effects imposed by the conventional disposal of solid battery waste. Numerous studies have been conducted on the topic of recycling used Li-ion batteries to produce either battery materials or specific chemical, metal or metal-based compounds. Physical pre-treatment is typically used to separate waste materials into various streams, facilitating the effective recovery of components in subsequent processing. In order to further prepare the recovered materials or compounds by applying the principles of materials chemistry and engineering, a metallurgical process is then utilized to extract and isolate pure metals or separate contaminants from a particular waste stream. In this review, the current state of spent Li-ion battery recycling is outlined, reviewed, and analyzed in the context of the entire recycling process, with a particular emphasis on hydrometallurgy; however, electrometallurgy and pyrometallurgy are also comprehensively reviewed. In addition to the comprehensive review of various hydrometallurgical processes, including alkaline leaching, acidic leaching, solvent (liquid-liquid) extraction, and chemical precipitation, a critical analysis of the current obstacles to process optimization during Li-ion battery recycling is also conducted. Moreover, the energy-intensive nature of discussed recycling process routes is also assessed and addressed. This study is anticipated to offer recommendations for enhancing wasted Li-ion battery recycling, and the field can be further explored for commercialization.
... 4 Numerous researches had been done on the recycling or remanufacturing of power LIBs. [5][6][7] However, according to circular energy storage's report, LIBs utilized in portable devices account for 80% of the total EOL LIBs for recycling in the year 2019, since more than 90% of power batteries went through cascade utilization process before being recycled. Here, we recycled the typical EOL LIBs utilized in portable devices, especially mobile phones and laptops, and remanufactured LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material from the leaching solution for the production of power batteries. ...
The boom of the electric vehicle industry significantly aggravates the demand for lithium-ion batteries (LIBs), especially the ternary cathode materials, however, the majority of end-of-life (EOL) LIBs on the market are batteries utilized in customer electronics. Here, we utilized the mixed EOL LIBs from cell phones and laptops to manufacture the LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode material. A feasible, high efficiency (99.98% Co, 99.98% Ni, 99.99% Mn, and 99.99% Li), and ultra-fast leaching of EOL LIB cathodes was achieved. Thermodynamic calculations suggested that the coordination number, coordination species concentrations, and fractions have significant effects on the apparent activation energy and the equilibrium of the leaching reactions. The remanufactured NCM622 cathode material demonstrated a well-ordered layered hexagonal structure with a low Li+/Ni2+ mixing ratio, which facilitated reliable reversible capacity, low polarization, high rate capabilities (163.8 mA h g-1), and capacity retention ratio (94.3%).
The lithium-ion batteries (LIBs) have been widely equipped in electric/hybrid electric vehicles (EVs/HEVs) and the portable electronics due to their excellent electrochemical performances. However, a large number of retired LIBs that consist of toxic substances (e.g., heavy metals, electrolytes) and valuable metals (e.g., Li, Co) will inevitably flow into the waste stream, and their incineration or landfill treatment will cause severe risks to ecosystem and human beings. The sustainable and efficient treatment or recycling of valuable resources from spent LIBs should be fully recognized for environmental and resource security. As one of the most important processes for spent LIBs recycling, the pretreatment is an indispensable step, which is directly related to the subsequent metal extraction and separation processes. Although considerable progresses have been made regarding the pretreatment technologies, there are few summarized reports concerning critical processes of spent LIBs recycling, especially combination of currently available recycling technologies with industrialized applications during pretreatments. Therefore, comprehensive review of the current prevailing pretreatment technologies in laboratory to existing scale-up applications is quite necessary to reveal cutting-edge development in the field of pretreatment. In this review, the current pretreatment technologies are systematically categorized and introduced, along with critical discussions. This review focused on the various options for pretreatment processes itself, instead of general spent LIBs recycling technologies without the focused topics that have been sophisticatedly reviewed by previous studies. Here, the deactivation, discharge, dismantling, separation, liberation of active material and electrolyte treatment have been summarized with the in-depth discussion of the technology development and current status of each category. Finally, current states of industrial development are also reviewed and discussed for the development of efficient and environmentally friendly recycling technologies for future applications. This review tends to present a focused topic concerning the pretreatment of spent LIBs to potential readers with a comprehensive illustration of the development on both cutting-edge technologies and scale-up applications.
Advancement in energy storage technologies is closely related to social development. However, a significant conflict has arisen between the explosive growth in battery demand and resource availability. Facing the upcoming large-scale disposal problem of spent lithium-ion batteries (LIBs), their recycling technology development has become key. Emerging direct recycling has attracted widespread attention in recent years because it aims to 'repair' the battery materials, rather than break them down and extract valuable products from their components. To achieve this goal, a profound understanding of the failure mechanisms of spent LIB electrode materials is essential. This review summarizes the failure mechanisms of LIB cathode and anode materials and the direct recycling strategies developed. We systematically explore the correlation between the failure mechanism and the required repair process to achieve efficient and even upcycling of spent LIB electrode materials. Furthermore, we systematically introduce advanced in situ characterization techniques that can be utilized for investigating direct recycling processes. We then compare different direct recycling strategies, focussing on their respective advantages and disadvantages and their applicability to different materials. It is our belief that this review will offer valuable guidelines for the design and selection of LIB direct recycling methods in future endeavors. Finally, the opportunities and challenges for the future of battery direct recycling technology are discussed, paving the way for its further development.
A recycling process is proposed in which spent cathode materials and Al foil are leached by low-concentration acids, then Al is selectively precipitated, finally the lithium iron phosphate material is synthesized by a one-step hydrothermal synthesis.
Currently, the main drivers for developing Li‐ion batteries for efficient energy applications include energy density, cost, calendar life, and safety. The high energy/capacity anodes and cathodes needed for these applications are hindered by challenges like: (1) aging and degradation; (2) improved safety; (3) material costs, and (4) recyclability. The present review begins by summarising the progress made from early Li‐metal anode‐based batteries to current commercial Li‐ion batteries. Then discusses the recent progress made in studying and developing various types of novel materials for both anode and cathode electrodes, as well the various types of electrolytes and separator materials developed specifically for Li‐ion battery operation. Battery management, handling, and safety are also discussed at length. Also, as a consequence of the exponential growth in the production of Li‐ion batteries over the last 10 years, the review identifies the challenge of dealing with the ever‐increasing quantities of spent batteries. The review further identifies the economic value of metals like Co and Ni contained within the batteries and the extremely large numbers of batteries produced to date and the extremely large volumes that are expected to be manufactured in the next 10 years. Thus, highlighting the need to develop effective recycling strategies to reduce the levels of mining for raw materials and prevention of harmful products from entering the environment through landfill disposal.
With an ever-increasing demand for energy, there is a proportionate increase in energy storage devices, among which batteries hold the key to the energy transition. Globally, batteries constitute the fastest-growing energy storage technology that is playing a key role in the transport sector electrification leading to rising demand for LIBs. However, there is a substantial need for innovation that will help mitigate the environmental effects of the production and use of LIBs—such as energy use, mineral extraction, and chemical processing. The battery value chain can be seen as an exceptional sustainable value creation opportunity wherein sustainability depends in part on the ability to reuse and recycle batteries. A typical LIB battery serves in electric vehicles (EVs) for about 5–10 years and needs to be replaced when they reach ~ 20% capacity loss. At this stage, the fate of the battery follows one of the routes—disposal, reuse/repurpose/remanufacture (3R) or recycle. However, a major obstacle for car and battery manufacturers to invest in second life, or to otherwise take advantage of the reuse market, is that they in many cases do not have control over the batteries. On the other hand, recycling LIBs holds tremendous potential owing to the recirculation of materials i.e., closed-loop recycling needed for battery manufacturing promoting sustainability. This review will enable readers to devise processes that contribute to closing the loop of the EV LIBs value chain from an industrial perspective as well as critically understand the current state and future of battery recycling.
Graphical Abstract
Lithium (Li)‐based batteries are gradually evolving from the liquid to the solid state in terms of safety and energy density, where all solid‐state Li‐metal batteries (ASSLMBs) are considered the most promising candidates. This was demonstrated by the Bluecar electric vehicle produced by the Bolloré Group, which is utilized in car‐sharing services in several cities worldwide. Despite impressive progress in the development of ASSLMBs, their avenues for recycling them remain underexplored, and combined with the current explosion of spent Li‐ion batteries, they should attract widespread interest from academia and industry. Here, we analyze the potential challenges of recycling ASSLMBs as compared to Li‐ion batteries and summarize and analyze the current progress and prospects for recycling ASSLMBs. Drawing on the lessons learned from Li‐ion battery recycling, it is important to design sustainable recycling technologies before ASSLMBs gain widespread market adoption. We also highlighted a battery‐recycling‐oriented design for ASSLMBs to promote the recycling rate and maximize profitability. Finally, future research directions, challenges, and prospects are outlined to provide strategies for achieving sustainable development of ASSLMBs.
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Bu çalışmada atık lityum-iyon pil katot malzemesinin nitrik asit çözeltisinde çözülerek metalik malzemeler ile grafitin geri kazanım koşulları belirlenmiştir. Yapılan çalışmada atık Li-iyon katot malzemesi farklı molaritelere sahip nitrik asit çözeltisinde liç edilmiş ve metallerin çözünme verimi araştırılmıştır. Çözünme verimini etkileyen katı-sıvı oranı, çözünme süresi, H2O2 katkısı parametrelerinin çözünme verimi üzerindeki etkisi incelenmiştir. Yapılan incelemeler sonucunda en uygun çözme koşullarının 2 saat liç süresi, 100 g/L katı-sıvı oranı ve 3M nitrik asit çözeltisi olduğu tespit edilmiştir. H2O2 katkısının incelendiği 2M nitrik asit çözeltisinde H2O2 katkısının olumlu etkisinin olmasına karşılık yeterli çözünme verimine ulaşılamadığı görülmüştür.
The extensive use of lithium-ion batteries (LIBs) has generated a huge amount of their wastes. As waste, LIBs can be used as a source for valuable metals such as lithium, cobalt, manganese, and nickel. Like the ores of these metals, their values are recognized as raw material. This can ultimately help bring down the cost of LIB production while reducing their harmful environmental impacts. As a result, recycling has become a major opportunity for industrialists and a challenge to environmentalists all across the globe. Researchers have explored various methods to recover cobalt and lithium precious metals from worn out batteries. This review provides an overview of the recent technological solutions on the recovery from waste LIBs using organic acids-based hydrometallurgical processes concerning chemical reactions, structures, and leaching efficiency with different organic acids. Subsequently, the advantages of organic acids over inorganic acid have also been discussed with an emphasis on possible complex formations during the recovery process. At last, the potent role of process variables: reductant concentration, reaction time, temperature, solid:liquid ratio, and concentration of complexing agent during the Co and Li leaching has been discussed along with prospects in this research area.
The rechargeable lithium ion (Li-ion) battery market was $11.8 billion in 2011 and is expected to increase to $50 billion by 2020. With developments in consumer electronics as well as hybrid and electric vehicles, Li-ion batteries demand will continue to increase. However, Li-ion batteries are not widely recycled because currently it is not economically justifiable (in contrast, at present more than 97% lead-acid bat-teries are recycled). So far, no commercial methods are available to recycle Li-ion batteries with different cathode chemistries economically and efficiently. Considering our limited resources, environmental impact, and national security, Li-ion batteries must be recycled. A new low temperature methodology with high efficiency is proposed in order to recycle Li-ion batteries economically and thus commercially feasible regardless of cathode chemistry. The separation and synthesis of cathode materials (the most valuable material in Li-ion batteries) from the recycled components are the main focus of this study. The results show that the developed recycling process is practical with high recovery efficiencies, and that it is viable for commercial adoption.
Lithium cobalt oxide, LiCoO2, has been the most widely used cathode material in commercial lithium ion batteries. Nevertheless, cobalt has economic and environmental problems that leave the door open to exploit alternative cathode materials, among which LiNix
CoyMn1 − x − y
O2 may have improved performances, such as thermal stability, due to the synergistic effect of the three ions. Recently, intensive effort has been directed towards the development of LiNix
Coy
Mn1 − x − y
O2 as a possible replacement for LiCoO2. Recent advances in layered LiNix
CoyMn1 − x − y
O2 cathode materials are summarized in this paper. The preparation and the performance are reviewed, and the future promising cathode materials are also prospected.
A new aging model for Lithium Ion batteries is proposed based on theoretical models of crack propagation. This provides an exponential dependence of aging on stress such as depth of discharge. A measure of stress is derived from arbitrary charge and discharge histories to include mixed use in vehicles or vehicle to grid operations. This aging model is combined with an empirical equivalent circuit model, to provide time and state of charge dependent charge and discharge characteristics at any rate and temperature. This choice of model results in a cycle life prediction with few parameters to be fitted to a particular cell.
Lithium batteries are characterized by high specific energy, high efficiency and long life. These unique properties have made lithium batteries the power sources of choice for the consumer electronics market with a production of the order of billions of units per year. These batteries are also expected to find a prominent role as ideal electrochemical storage systems in renewable energy plants, as well as power systems for sustainable vehicles, such as hybrid and electric vehicles. However, scaling up the lithium battery technology for these applications is still problematic since issues such as safety, costs, wide operational temperature and materials availability, are still to be resolved. This review focuses first on the present status of lithium battery technology, then on its near future development and finally it examines important new directions aimed at achieving quantum jumps in energy and power content.
Technological improvements in rechargeable solid-state batteries are being driven by an ever-increasing demand for portable electronic devices. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. We present a brief historical review of the development of lithium-based rechargeable batteries, highlight ongoing research strategies, and discuss the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems.
Researchers must find a sustainable way of providing the power our modern lifestyles demand.
Acid leach liquors from spent lithium-ion batteries that use lithium cobalt dioxide (LiCoO2) as a cathode active material contain valuable metals such as cobalt and lithium, as well as common metals such as aluminum and copper. The objective of this study was to develop a hydrometallurgical process that provides a degree of high selectivity between aluminum, cobalt, copper, and lithium from acidic sulfate media.The results from batch experiments showed that a selective hydroxide precipitation approach was not suitable because a significant amount of cobalt was coprecipitated with aluminum and/or copper hydroxides. In contrast, batch experiments and the subsequent data analysis indicated that the sequence of solvent extraction circuits using PC-88A, Acorga M5640, and tri-n-octylamine (TOA) extractants effectively separates four metals of interest. In the first circuit of the proposed process, copper was selectively extracted by Acorga M5640 at pH 1.5–2.0. Aluminum, cobalt, and lithium remained in the aqueous phase. In the second circuit, aluminum was selectively extracted by PC-88A at pH 2.5–3.0. For separation of the remaining cobalt and lithium, Acorga M5640 provided higher cobalt selectivity (separation factor could not be accurately obtained due to negligible lithium extraction) compared to PC-88A (βCo, 90%/Li = 350 at pH 4.5) and PC-88A/TOA (βCo, 90%/Li = 1,170 at pH 5.4). However, the stripping efficiency of cobalt from the Acorga M5640 organic phase was found to be low (less than 10%). Therefore, the PC-88A/TOA mixed extractant rather than Acorga M5640 is a suitable choice for the separation of cobalt and lithium.
In cooperation with the industrial project partners ACCUREC Recycling and UVR-FIA a recycling process specially dedicated to portable Li-ion batteries was developed combining a mechanical pretreatment with hydro- and pyrometallurgical process steps. Therefore not only the recovery of cobalt but also the recovery of all other battery components, especially of lithium was of interest. Besides the characterization and evaluation of all generated metallic material fractions, the focus of the research work was the development of a pyrometallurgical process step in an electric arc furnace for the carbo-reductive melting of the fine fraction extracted from spent Li-ion batteries. This fine fraction mainly consists of the cobalt and lithium containing electrode material. Since a selective pyrometallurgical treatment of the fine fraction for producing a cobalt alloy has not been done before, the proof of feasibility was the main aim.
"full paper existing"
Spherical Li[Ni0.8Co0.2−xMnx]O2 (x = 0, 0.1) with phase-pure and well-ordered layered structure have been synthesized by heat-treatment of spherical [Ni0.8Co0.2−xMnx](OH)2 and LiOH·H2O precursors. The structure, morphology, electrochemical properties, and thermal stability of Li[Ni0.8Co0.2−xMnx]O2 (x = 0, 0.1) were studied. The average particle size of the powders was about 10–15 μm and the size distribution was narrow due to the homogeneity of the metal hydroxide [Ni0.8Co0.2−xMnx](OH)2 (x = 0, 0.1). The Li[Ni0.8Co0.2−xMnx]O2 (x = 0, 0.1) delivered a discharge capacity of 197–202 mAh g−1 and showed excellent cycling performance. Compared to Li[Ni0.8Co0.2]O2, Li[Ni0.8Co0.1Mn0.1]O2 exhibited greater thermal stability resulting from improved structural stability due to Mn substitution.
LiNi0.5Mn0.3Co0.2O2 and LiNi0.5Mn0.3Co0.2O1.98S0.02 were prepared using a simple combustion method. Surface coating was carried out by the sol–gel method using LiNi0.5Mn0.3Co0.2O2, LiNi0.5Mn0.3Co0.2O1.98S0.02, and LiNiPO4. Physical properties of the synthesized materials were measured by XRD, SEM, and TEM. Electrochemical performance was assessed by measuring parameters such as charge and discharge capacity, cycling performance, rate capability, EIS testing, and the XANES. Sulfur-doped cathode material conferred improved cycling performance compared with LiNi0.5Mn0.3Co0.2O2 and had a low capacity decrease after 50 cycles. LiNiPO4 provided an enhancement of rate capability for discharging at 0.1–5 C. In addition, the 3 wt% LiNiPO4-coated LiNi0.5Mn0.3Co0.2O1.98S0.02 cathode material had improved cycling performance, rate capability, and EIS testing results compared with the other samples. The rate capability and cycling performance of LiNi0.5Mn0.3Co0.2O2 cathode material for lithium ion batteries have been enhanced by the stabilization of the surface of cathode with a LiNiPO4 coating and sulfur doping.
In this research, we studied the first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V. Properties, such as valence state of the transition metals and crystallographic features, were analyzed by X-ray absorption spectroscopy and X-ray and neutron diffractions. Especially, two plateaus observed around 3.75 and 4.54 V were investigated by ex situ X-ray absorption spectroscopy. XANES studies showed that the oxidation states of transition metals in Li[Ni1/3Co1/3Mn1/3]O2 are mostly Ni2+, Co3+ and Mn4+. Based on neutron diffraction Rietveld analysis, there is about 6% of all nickel divalent (Ni2+) ions mixed with lithium ions (cation mixing). Meanwhile, it was found that the oxidation reaction of Ni2+/Ni4+ is related to the lower plateau around 3.75 V, but that of Co3+/Co4+ seems to occur entire range of x in Li1−x[Ni1/3Co1/3Mn1/3]O2. Small volume change during cycling was attributed to the opposite variation of lattice parameter “c” and “a” with charging–discharging.
Reductive leaching of LiCoO2 from spent lithium ion battery was investigated in terms of reaction variables. The leaching efficiency of LiCoO2 increased with increasing temperature, and concentration of HNO3, but with decreasing solid/liquid (S/L) ratio. Li and Co from LiCoO2 were leached over 95% with the addition of 1.7 vol.% H2O2 as a reducing agent. This is due to the reduction of Co3+ to Co2+ which can be readily dissolved. The dissolution rates of Co and Li were inversely proportional to their respective concentrations in the solution. Apparent activation energies of 12.5 and 11.4 kcal/mol were obtained for Co and Li, respectively. This indicates that the dissolution of LiCoO2 is controlled by surface chemical reaction.
The crystal chemistry and electrochemical performance of the layered LiNi0.5−yCo0.5−yMn2yO2 and LiCo0.5−yMn0.5−yNi2yO2 oxide cathodes for 0 ≤ 2y ≤ 1 have been investigated. Li2MnO3 impurity phase is observed for Mn-rich compositions with 2y > 0.6 in LiNi0.5−yCo0.5−yMn2yO2 and 2y < 0.2 in LiCo0.5−yMn0.5−yNi2yO2. Additionally, the Ni-rich compositions encounter a volatilization of lithium at the high synthesis temperature of 900 °C. Compositions around 2y = 0.33 are found to be optimum with respect to maximizing the capacity values and retention. The rate capabilities are found to bear a strong relationship to the cation disorder in the layered lattice. Moreover, the evolution of the X-ray diffraction patterns on chemically extracting lithium has revealed the presence of Li2MnO3 phase in addition to the layered phase for the composition LiNi0.25Co0.25Mn0.5O2 with an oxidation state of manganese close to 4+, which results in a large anodic peak at around 4.5 V due to the extraction of both lithium and oxygen.
The low-heating solid-state method has been adopted to synthesize LiNi1/3Co1/3Mn1/3O2 materials. The final product, with homogeneous phase and smooth crystals indicated by XRD and SEM results, can be synthesized at 700°C, much lower than the synthesis temperatures of co-precipitation method. The reaction process and microstructure of precursor has been investigated by IR spectrum. By comparative studies with the mixture of CH3COOLi and (Ni, Co, Mn)(C2O4), it is testified that the precursor is homogeneous, rather than a mixture. The decomposition process and the reaction energy have been studied to investigate the reaction mechanism of the precursor when heated at high temperature. The as-synthesized LiNi1/3Co1/3Mn1/3O2 exhibits excellent electrochemical properties, exhibiting initial specific capacity of 167mAhg−1 with stable cyclic performance.
The structure of the coprecipitated precursor to the positive electrode material,
(NMC), is typically synthesized via a coprecipitation reaction and assumed to be
or
. The coprecipitation reaction and its products are not thoroughly understood. Here, pure phase
is synthesized in the presence of aqueous ammonia, yielding dense and spherical particles.
was found to readily oxidize in air, especially during heating. The obtained product was analyzed with powder X-ray diffraction
and thermogravimetric analysis. The results indicate that
undergoes oxidation to the oxyhydroxide phase,
. Heating also resulted in an increase in tap density of the oxyhydroxide; the final tap density of the material was found
to be
.
A novel process was conducted with experiments which separated and recovered metal values such as Co, Mn, Ni and Li from the cathode active materials of the lithium-ion secondary batteries. A leaching efficiency of more than 99% of Co, Mn, Ni and Li could be achieved with a 4 M hydrochloric acid solution, 80 °C leaching temperature, 1 hour leaching time and 0.02 gml− 1 solid-to-liquid ratio. For the recovery process of the mixture, firstly the Mn in the leaching liquor was selectively reacted and nearly completed with a KMnO4 reagent, the Mn was recovered as MnO2 and manganese hydroxide. Secondly, the Ni in the leaching liquor was selectively extracted and nearly completed with dimethylglyoxime. Thirdly, the aqueous solution in addition to the 1 M sodium hydroxide solution to reach pH = 11 allowed the selective precipitation of the cobalt hydroxide. The remaining Li in the aqueous solution was readily recovered as Li2CO3 precipitated by the addition of a saturated Na2CO3 solution. The purity of the recovery powder of lithium, manganese, cobalt and nickel was 96.97, 98.23, 96.94 and 97.43 wt.%, respectively.
LiNi1−x−yCoxMnyO2 (0≤x≤0.5, 0≤y≤0.3) were prepared by heating Ni1−x−yCoxMny(OH)2 and LiNO3 in flowing oxygen for 10 h at 550°C, followed by another heating at 750°C. The XRD patterns of LiNi1−x−yCoxMnyO2 (0≤x≤0.5, 0≤y≤0.3) samples with different x and y values show a pure phase of layered hexagonal structure. The lattice parameters a, c and the unit cell volume are found to decrease with increasing x in LiNi1−xCoxO2. The partial substitution of Ni by Co and Mn as in LiNi1−xCoxO2 and LiNi1−yCo0.2MnyO2 has a positive effect on lithium stoichiometry. However, lithium deficiency is still found after a prolonged thermal treatments (24 h). Among the doped materials synthesized, LiNi0.8Co0.2O2 and LiNi0.7Co0.2Mn0.1O2 have shown the best characteristics in terms of initial capacity and cycle life.
After reviewing the status of the lithium battery waste treatment and, in particular, outlining the technical and practical aspects of this operation, we describe some preliminary activity in progress in our laboratory mainly directed to the development and evaluation of a multi-step recycling process. Although this process is still in an exploratory phase, the preliminary results obtained in our laboratory suggest that the process may be of some practical interest since it gives promises of obtaining a good recovery of the battery components by rather efficient and easily achievable operations.
This paper describes a new recycling process of metal values from spent lithium-ion batteries (LIBs). After the dismantling of the spent batteries steel crusts, the leaching of battery internal substances with alkaline solution and the dissolving of the residues with H2SO4 solution were carried out. Then mass cobalt was chemically deposited as oxalate, and Acorga M5640 and Cyanex272 extracted the small quantities of copper and cobalt, respectively. Lithium was recovered as deposition of lithium carbonate. It is shown that about 90% cobalt was deposited as oxalate with less than 0.5% impurities, and Acorga M5640 and Cyanex272 were efficient and selective for the extraction of copper and cobalt in sulfate solution. Over 98% of the copper and 97% of the cobalt was recovered in the given process. In addition, the waste solution was treated innocuously, and LiCoO2 positive electrode material with good electrochemical performance was also synthesized by using the recovered compounds of cobalt and lithium as precursors. The process is feasible for the recycling of spent LIBs in scale-up.
The purpose of this paper is to review the current status of the recycling technologies of spent lithium-ion secondary batteries. It introduced the structure and components of the lithium-ion secondary batteries, summarized all kinds of single recycling processes from spent lithium-ion secondary batteries and presented some examples of typical combined recycling processes. Also, the problems and prospect of the studies of their recycling technologies have been put forward.
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