The COOL-Process—A Selective Approach for Recycling Lithium Batteries

The global market of lithium-ion batteries (LIB) has been growing in recent years, mainly owed to electromobility. The global LIB market is forecasted to amount to $129.3 billion in 2027. Considering the global reserves needed to produce these batteries and their limited lifetime, efficient recycling processes for secondary sources are mandatory. A selective process for Li recycling from LIB black mass is described. Depending on the process parameters Li was recovered almost quantitatively by the COOL-Process making use of the selective leaching properties of supercritical CO2/water. Optimization of this direct carbonization process was carried out by a design of experiments (DOE) using a 33 Box-Behnken design. Optimal reaction conditions were 230 °C, 4 h, and a water:black mass ratio of 90 mL/g, yielding 98.6 ± 0.19 wt.% Li. Almost quantitative yield (99.05 ± 0.64 wt.%), yet at the expense of higher energy consumption, was obtained with 230 °C, 4 h, and a water:black mass ratio of 120 mL/g. Mainly Li and Al were mobilized, which allows for selectively precipitating Li2CO3 in battery grade-quality (>99.8 wt.%) without the need for further refining. Valuable metals, such as Co, Cu, Fe, Ni, and Mn, remained in the solid residue (97.7 wt.%), from where they are recovered by established processes. Housing materials were separated mechanically, thus recycling LIB without residues. This holistic zero waste-approach allows for recovering the critical raw material Li from both primary and secondary sources.

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Leaching Behavior Analysis of Valuable Metals from Lithium-Ion Batteries Cathode Material

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.775.419 ◽

2018 ◽

Vol 775 ◽

pp. 419-426 ◽

Cited By ~ 1

Author(s):

Wei Sheng Chen ◽

Hsing Jung Ho

Keyword(s):

Cathode Material ◽

Lithium Ion Batteries ◽

Acid Leaching ◽

Lithium Ion ◽

Activation Energies ◽

Mass Ratio ◽

Solid Mass ◽

Environmental Technology ◽

Valuable Metal ◽

Valuable Metals

The paper concerns an approach about using environmental technology and hydrometallurgical process to the recovery of valuable metal from waste cathode material produced during the manufacture of lithium-ion batteries. It is noteworthy that the content of nickel, manganese and cobalt from cathode material are in the extraordinary large proportion. In the acid leaching step, the essential effects of H2SO4 concentration, H2O2 concentration, leaching time, liquid-solid mass ratio and reaction temperature with the leaching percentage were investigated. The cathode material was leached with 2M H2SO4 and 10 vol.% H2O2 at 70 °C and 300 rpm using a liquid-solid mass ratio of 30 ml/g and the leaching efficiency of cobalt was 98.5%, lithium was 99.8%, nickel was 98.6% and manganese was 98.6% under optimum conditions. Kinetic study demonstrates the activation energies for those analyzed metals with Arrhenius equation and manifests the data with hybrid reaction control mechanism. The process was proved from activation energies ranged from 27.79 to 47.25 kJ/mol. Finally, the valuable metals will be leached in sulfuric acid effectively.

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Research on Synthesis Regularity of Epoxysuccinic Acid

Applied Mechanics and Materials ◽

10.4028/www.scientific.net/amm.316-317.942 ◽

2013 ◽

Vol 316-317 ◽

pp. 942-945

Author(s):

Qing He Gao ◽

Yi Can Wang ◽

Zhi Feng Hou ◽

Hui Juan Qian ◽

Yuan Zhang ◽

...

Keyword(s):

Hydrogen Peroxide ◽

Reaction Time ◽

Maleic Anhydride ◽

Reaction Temperature ◽

Raw Material ◽

Molar Ratio ◽

Mass Ratio ◽

Synthesis System ◽

Reaction Conditions ◽

Sodium Hydrate

The yield of epoxysuccinic acid was obtained by determining the content of unreacted maleic anhydride and tartaric acid as a by-product in synthesis system. This method could calculate the yield of epoxysuccinic acid precisely and overcome the disadvantage of obtaining inpure product by recrystallization method. Epoxysuccinic Acid was synthesized using maleic anhydride as raw material, hydrogen peroxide as oxidizer and tungstate as catalyst. The effects of reaction temperature, reaction time, ratio of materials, dosage of oxidizer and catalyst on epoxidation and hydrolysis reaction was investigated. The results showed that the yield of epoxysuccinic acid was 88% when the reaction conditions were as follows: reaction temperature 65°C, reaction time 1.5h, catalyst dosage 3%(based on mass of maleic anhydride), molar ratio of sodium hydrate to maleic anhydride 2:1, mass ratio of hydrogen peroxide to maleic anhydride 1:1.

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Pyrolysis of unsubstituted bicyclic hydrocarbons and gas oil

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19821838 ◽

1982 ◽

Vol 47 (7) ◽

pp. 1838-1847 ◽

Cited By ~ 6

Author(s):

Martin Bajus ◽

Jozef Baxa

Keyword(s):

Stainless Steel ◽

Elemental Sulphur ◽

Raw Material ◽

Gas Oil ◽

Mass Ratio ◽

Reaction Products ◽

Pyrolysis Products ◽

Reactor Material ◽

Tubular Reactors ◽

Stainless Steel Reactor

Pyrolysis of tetraline, decaline, 1,1'-bicyclohexane, cyclohexylbenzene and gas oil was studied in stainless steel and quartz flow tubular reactors at 780 and 800 °C, residence time 0.08 to 0.5 s and at the mass ratio of steam to the raw material changing from 0.5 to 1.5. The effect of reaction temperature, the mass ratio of steam to the raw material, reactor material and of the added elemental sulphur on the yields of individual reaction products is reported. Of bicyclic hydrocarbons, condensed hydrocarbons are more stable than those with noncondensed rings, cyclanoaromates being more stable than bicyclanes. Pyrolysis of gas oil in the stainless steel reactor yields greater amounts of ethylene, propylene, butadiene and smaller amounts of methane and ethane, compared to the pyrolysis carried out under identical conditions in the quartz reactor. Elemental sulphur increases the conversion of gas oil into gaseous pyrolysis products.

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A breakthrough method for the recycling of spent lithium-ion batteries without pre-sorting

Green Chemistry ◽

10.1039/d1gc02132j ◽

2021 ◽

Author(s):

Jialiang Zhang ◽

Guoqiang Liang ◽

Cheng Yang ◽

Juntao Hu ◽

Yongqiang Chen ◽

...

Keyword(s):

Lithium Ion Batteries ◽

Lithium Ion ◽

Mineral Resources ◽

Low Grade ◽

Valuable Metals

Inspired by the process of "metallurgy first and then beneficiation" for disposing low-grade and complex mineral resources, we proposed a breakthrough method to recover valuable metals from spent entire lithium-ion...

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Application of a cashew-based oxime in extracting Ni, Mn and Co from aqueous solution

Chemical and Biological Technologies in Agriculture ◽

10.1186/s40538-021-00236-5 ◽

2021 ◽

Vol 8 (1) ◽

Author(s):

Chi M. Phan ◽

Son A. Hoang ◽

Son H. Vu ◽

Hoang M. Nguyen ◽

Cuong V. Nguyen ◽

...

Keyword(s):

Organic Phase ◽

Extraction Efficiency ◽

Acidic Solution ◽

Lithium Ion ◽

Metal Extraction ◽

Economic Potential ◽

Cashew Nut ◽

Valuable Metals ◽

Loaded Organic Phase ◽

Cashew Nut Shell

Abstract Background Cashew nut shell is a by-product of cashew (Anacardium occidentale) production, which is abundant in many developing countries. Cashew nut shell liquor (CNSL) contains a functional chemical, cardanol, which can be converted into a hydroxyoxime. The hydroxyoximes are expensive reagents for metal extraction. Methods CNSL-based oxime was synthesized and used to extract Ni, Co, and Mn from aqueous solutions. The extraction potential was compared against a commercial extractant (LIX 860N). Results All metals were successfully extracted with pH0.5 between 4 and 6. The loaded organic phase was subsequently stripped with an acidic solution. The extraction efficiency and pH0.5 of the CNSL-based extractant were similar to a commercial phenol-oxime extractant. The metals were stripped from the loaded organic phase with a recovery rate of 95% at a pH of 1. Conclusions Cashew-based cardanol can be used to economically produce an oxime in a simple process. The naturally-based oxime has the economic potential to sustainably recover valuable metals from spent lithium-ion batteries. Graphic abstract

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Synergic Mechanisms on Carbon and Sulfur during the Selective Recovery of Valuable Metals from Spent Lithium-Ion Batteries

ACS Sustainable Chemistry & Engineering ◽

10.1021/acssuschemeng.0c08213 ◽

2021 ◽

Vol 9 (5) ◽

pp. 2271-2279

Author(s):

Ping Xu ◽

Chunwei Liu ◽

Xihua Zhang ◽

Xiaohong Zheng ◽

Weiguang Lv ◽

...

Keyword(s):

Lithium Ion Batteries ◽

Lithium Ion ◽

Selective Recovery ◽

Valuable Metals

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Separation and Efficient Recovery of Lithium from Spent Lithium-Ion Batteries

Metals ◽

10.3390/met11071091 ◽

2021 ◽

Vol 11 (7) ◽

pp. 1091

Author(s):

Eva Gerold ◽

Stefan Luidold ◽

Helmut Antrekowitsch

Keyword(s):

Lithium Ion Batteries ◽

Electric Vehicles ◽

Sodium Phosphate ◽

Room Temperature ◽

State Of The Art ◽

Potassium Phosphate ◽

Lithium Ion ◽

Rechargeable Batteries ◽

Raw Material ◽

Efficient Recovery

The consumption of lithium has increased dramatically in recent years. This can be primarily attributed to its use in lithium-ion batteries for the operation of hybrid and electric vehicles. Due to its specific properties, lithium will also continue to be an indispensable key component for rechargeable batteries in the next decades. An average lithium-ion battery contains 5–7% of lithium. These values indicate that used rechargeable batteries are a high-quality raw material for lithium recovery. Currently, the feasibility and reasonability of the hydrometallurgical recycling of lithium from spent lithium-ion batteries is still a field of research. This work is intended to compare the classic method of the precipitation of lithium from synthetic and real pregnant leaching liquors gained from spent lithium-ion batteries with sodium carbonate (state of the art) with alternative precipitation agents such as sodium phosphate and potassium phosphate. Furthermore, the correlation of the obtained product to the used type of phosphate is comprised. In addition, the influence of the process temperature (room temperature to boiling point), as well as the stoichiometric factor of the precipitant, is investigated in order to finally enable a statement about an efficient process, its parameter and the main dependencies.

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Forecast of International Trade of Lithium Carbonate Products in Importing Countries and Small-Scale Exporting Countries

Sustainability ◽

10.3390/su13031251 ◽

2021 ◽

Vol 13 (3) ◽

pp. 1251

Author(s):

Yichi Zhang ◽

Zhiliang Dong ◽

Sen Liu ◽

Peixiang Jiang ◽

Cuizhi Zhang ◽

...

Keyword(s):

International Trade ◽

Large Scale ◽

Prediction Method ◽

Lithium Ion ◽

Lithium Carbonate ◽

Raw Material ◽

Small Scale ◽

Trade Restrictions ◽

Energy Field ◽

Structure Of Trade

As the raw material of lithium-ion batteries, lithium carbonate plays an important role in the development of new energy field. Due to the extremely uneven distribution of lithium resources in the world, the security of supply in countries with less say would be greatly threatened if trade restrictions or other accidents occurred in large-scale exporting countries. It is of great significance to help these countries find new partners based on the existing trade topology. This study uses the link prediction method, based on the perspective of the topological structure of trade networks in various countries and trade rules, and eliminates the influence of large-scale lithium carbonate exporting countries on the lithium carbonate trade of other countries, to find potential lithium carbonate trade links among importing and small-scale exporting countries, and summarizes three trade rules: (1) in potential relationships involving two net importers, a relationship involving either China or the Netherlands is more likely to occur; (2) for all potential relationships, a relationship that actually occurred for more than two years in the period in 2009–2018 is more likely to occur in the future; and (3) potential relationships pairing a net exporter with a net importer are more likely to occur than other country combinations. The results show that over the next five to six years, Denmark and Italy, Netherlands and South Africa, Turkey and USA are most likely to have a lithium carbonate trading relationship, while Slovenia and USA, and Belgium and Thailand are the least likely to trade lithium carbonate. Through this study, we can strengthen the supply security of lithium carbonate resources in international trade, and provide international trade policy recommendations for the governments of importing countries and small-scale exporting countries.

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Preparation and Water Absorbency of Superabsorbent Kaolin/PAA-AM Composite

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.634-638.1968 ◽

2013 ◽

Vol 634-638 ◽

pp. 1968-1976 ◽

Cited By ~ 1

Author(s):

Shi Han Shen ◽

Yu Yu Zhang ◽

Tian Bin Li ◽

Qing Le Zeng

Keyword(s):

Composite Material ◽

Complex Structure ◽

Water Absorbency ◽

Solution Polymerization ◽

Mass Ratio ◽

Reaction Conditions ◽

Superabsorbent Composite ◽

Optimum Reaction ◽

The Fourier Transform ◽

Composite Variables

In this paper, a novel superabsorbent composite material based on acrylic acid (AA), acrylic amide (AM) and inorganic kaolin was synthesized via solution polymerization in aqueous medium with N,N’-methylene bisacrylamide (MBA) as crosslinker and potassium persulfate (KPS) as initiator. The effects of water absorbency of the composite variables, such as neutralization, kaolin concentration and MBA concentration, on the water absorbency were systematically optimized. Evidence of compositing was obtained by a comparison of the Fourier transform infrared spectra of the initial reactants with that of the superabsorbent composites, and its complex structure was confirmed with scanning electron microscope. The water absorbing mechanism was also discussed. The results indicated that the superabsorbent composite material was successfully synthesized and the optimum reaction conditions were as follows: the neutralization degree was 80%, the dosage of kaolin, crosslinker and initiator were 4%, 0.11%, and 0.9% respectively and the mass ratio of AA and AM was 3∶2. The optimum absorbency of the superabsorbent composite material in distilled water could reach 815.6g/g.

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