Tracing the origin of lithium in Li-ion batteries using lithium isotopes

Abstract

Rechargeable lithium-ion batteries (LIBs) play a key role in the energy transition to clean energy, powering electric vehicles, storing energy in renewable networks and helping to reduce emissions from the transport and energy sectors. The demand for lithium (Li) is expected to increase considerably in the near future, due to the growing need for clean energy technologies. The corollary is that consumer expectations will also grow in terms of guarantees about the origin of Li and efforts made to reduce the environmental and social impact potentially associated with its extraction. Today, the LIB industry supply chain is very complex, making it difficult for end users to ensure that Li comes from environmentally responsible sources. Using an innovative geochemical approach based on Li isotope analysis of raw and processed materials, we show that Li isotope “fingerprinting” is a useful tool for determining the origin of lithium in LIB. This lays the groundwork for a new method that ensures Li’s certification to LIB.

Introduction

Promoted as the “white oil” or “white gold” of the 21st century, lithium owes its remarkable economic success to its key role in the energy transition1. Historically, lithium has found wide use in the ceramic, glass, steel, and chemical industries, as well as in medicine to treat bipolar disorders. Recently, however, the lithium market has become dominated by lithium salts used in rechargeable batteries, which now consume ~65% of all lithium2.

Lithium ion battery (LIB) is the term used for a battery composed of multiple electrochemical cells, each of which has a positive electrode based on lithium metal oxide (cathode) and a negative electrode (anode, typically active material). graphitic carbon), electronically separated by a thin porous plastic film (i.e. a separator) containing the non-aqueous electrolyte solution (usually composed of LiPF6 as salt and organic carbonates as solvents) and electronic current collectors (usually Cu in the anode and Al at the cathode) that connect the electrochemical cell to an external circuit containing the load to be powered.

LIBs are widely used in portable electronic devices (tablets and mobile phones), and increasingly in cordless power tools, transportation applications (hybrid and electric vehicles, electric scooters, electric bicycles), and stationary energy storage for intermittent power sources. (solar or wind). ). The electrification of transport is becoming a top priority as part of the transition to a low-carbon future, in particular to meet the Paris climate agreement goals of reducing carbon emissions by more than a third by 20301 Several recent government initiatives incentivize or even force car owners to switch to electric: Norway will ban the sale of petrol cars by 2025, while the UK, Ireland, Germany and the Netherlands plan to do the same by 2030. and France by 20403. The recent EU plan to tackle global warming proposes to ban new internal combustion engines by 20354. Therefore, the demand for lithium will continue to increase as long as LIBs are the main source of energy for electric vehicles (VE). The annual amount of lithium required should increase by a factor of 44 by 2030 (considering a hypothesis of 0.8 million tons of lithium carbonate in 2030) compared to the production volumes of 2017, to meet new needs in the sector of mobility5.

Commercial LIB currently uses various cathode compositions, including ~5–10% lithium6 obtained from lithium salts (lithium carbonate or lithium hydroxide) and different proportions of other metals. The electrolyte, composed of lithium hexafluorophosphate (LiPF6) diluted in solvent (LiPF6/1 mol/L), contains a negligible amount of lithium compared to the cathode material. High-nickel cathode compounds, in particular lithium-nickel-manganese-cobalt oxide (Li(NiMnCo)O2 or NMC), are the most widely used cathode materials today for EV applications and stationary storage6. First generation LIB cathodes contained nickel-manganese-cobalt in a 1:1:1 ratio (often identified in industry jargon as NMC111 or NMC333). To increase the energy density, the Ni:Mn:Co ratio has been gradually changed from 1:1:1 to 5:3:2 to 6:2:2 to 8:1:1 to reduce the amount of Co required7. The increasing adoption of high-nickel content cathode compounds has led to increased use of lithium hydroxide, resulting in higher quality cathode materials with better cycle life and energy density8. According to previous studies6,9, NMC cathodes will account for 60-90% of annual battery demand by 2030, with the other types of battery cathodes being NCA (Nickel-Cobalt-Aluminum) and LFP (Lithium-Iron-Phosphate). ). In the coming years, the main evolution of LIB cathodes will concern the presence and amounts of cobalt, nickel, manganese, aluminum (NCA batteries) or phosphorous (LFP), but lithium will continue to be an indispensable component.

From a lithium point of view, the LIB manufacturing supply chain is complex and divided into many stages, including mining, refining and extractive metallurgy, cathode active material synthesis, battery cell manufacturing, and battery assembly. battery packs, which are commonly completed in different locations and countries.

Most of the mineral reserves are located in Chile (44%), Australia (22%), Argentina (9%), China (7%) and several other countries that represent the remaining 18%10. Lithium resources are mainly divided into three categories11: (1) Brine is the main source of lithium with about 60% of the identified global reserves. Among the brines, the salt flats in the “lithium triangle” of Bolivia, Argentina, Chile, and in the Qinghai province and the Tibetan region of China, contain most of the lithium brine reserves. (2) Hard rock lithium resources, ie lithium-rich pegmatite is the second largest source of lithium available. Recent estimates represent pegmatites around 30% of identified lithium reserves. Among the minerals containing lithium in pegmatites, spodumene (LiAlSi2O6) is the main economic mineral12. Lithium hard rock reserves are distributed throughout the world, the largest spodumene deposits are in Australia with significant deposits in Canada and China10. (3) Sediment-hosted deposits (sometimes erroneously generalized as “clay”) are the third source, accounting for less than 3% of global lithium resources. They are composed of hectorite (McDermitt, USA and Sonora, Mexico) and jadarite (Jadar, Serbia). So far, producing lithium from this source has been difficult and expensive, and so far no company has been able to produce commercial quantities from such deposits. In 2020, nearly half (47%) of global lithium production came from Australian hard rock deposits. Other major suppliers were Chile (21%), China (17%), Argentina (7%) and a group of countries including Zimbabwe, the US, Brazil and Portugal (7%)10.

After mining, the next step in the supply chain is refining and extractive metallurgy, processing and purification that transforms raw materials into high purity lithium hydroxide or carbonate. Global lithium refining capacity is concentrated in China, which supplies more than half (53%) of the world’s lithium salts, including the majority of lithium hard rock production13, while Chile (33%) and Argentina (11%) dominate lithium refining capacity from brine. operations8.

The production of active cathode materials, the manufacture of battery cells, and the assembly of battery packs as an end product are the other steps in LIB’s supply chain. Lithium metal oxide for the cathode active material is mainly produced by specialty chemical companies in China, Japan and South Korea, which supply 86% of the active material14. China is also a major player in lithium-ion cell manufacturing with 66% of global cell production; other suppliers are South Korea and the United States, with 13% each13. For electric vehicles, manufacturers design battery packs for specific models and tend to assemble them close to the vehicle assembly plant due to the cost of transporting large, heavy battery packs15. China is the largest producer of batteries for electric vehicles, followed by the United States and Germany5.

LIB’s life cycle does not stop there, and additional steps can take place. After use in electric vehicles, the life of LIBs can be extended by reusing them for less demanding applications, such as energy storage14. Even if this is not profitable today compared to primary resources, the lithium contained in the battery cells can be recycled and reused to make new cathodes.

Another complication in the LIB industry supply chain is the fact that each consumer company deals with multiple suppliers, each of which may deal with multiple sub-suppliers in multiple countries. For example, to supply a substantial part of its lithium needs, the US company Tesla has contracted directly with Ganfeng Lithium, a Chinese lithium mining and refining company (see Methods section), which has several subsidiaries involved in the industry. of lithium in Australia, China, Argentina, Mexico and Ireland16. The contract gives Tesla secure access to lithium, but in practice, the raw material goes through many other companies and processing steps before being made into a car. Panasonic and CATL, which assemble battery cells for Tesla, source active cathode material from various chemical companies (Sumitomo, BASF Toda, Beijing Easpring, Ecopro, Johnson Matthey)17, which in turn purchase lithium from various mining and refining companies. .

Due to this complex supply chain, ensuring that raw materials come from socially and environmentally responsible sources with a low carbon footprint is a difficult puzzle for end users. Although the lithium supply chain today is less problematic in terms of social and environmental risks than other battery metals, such as cobalt, lithium can be associated with various environmental and social impacts. With the growing demand for lithium, the environmental and social impacts of mining tend to increase.

In Argentina, indigenous communities denounce that lithium operations on their land threaten their survival and the exercise of their rights18. In Zimbabwe, where lithium exploitation is currently low (1%)10, illicit financial flows have already been identified in the lithium mining sector19. A recent study20 on the life cycle footprint of water scarcity showed that water use associated with lithium brine extraction in Chile and China, primarily through evaporative loss, can lead to a high risk of natural scarcity of fresh water for humans and nature.

Based on a comparative life cycle assessment21 between hard rock and brine lithium EV batteries, the environmental impact of hard rock lithium processing, dominated by traditional sulfuric acid processing and rock melting, is greater in terms of acidification and warming potential. A recent study showed that CO2 equivalent emissions from hard rock lithium hydroxide production in Australia and refining in China are up to three times higher than those from brine production in Chile and Argentina22. Another recent study, based on life cycle analysis of battery-grade lithium salts produced from Chilean brine and Australian spodumene processed in China, showed that lithium salt production from brine had lower greenhouse gas emissions. life-cycle greenhouse gases and freshwater consumption than lithium salts from rock-based lithium resources23.

Major automakers such as BMW Group, Tesla and Volvo have recently announced that they will increase the transparency of their electric vehicle battery supply chains and ensure responsible and sustainable sourcing of raw materials24,25. Some companies (BASF, Volkswagen, Fairphone) have started an association for sustainable lithium mining in Chile26. Automakers are also exploring the utility of blockchains to improve scrutiny of supply chains. A blockchain is the control of chain of custody systems, based on shipping documentation that is included in online databases, to enable real-time tracking of raw materials and electronic labeling. However, document-based traceability systems can be falsified and must be independently controlled and audited to provide credibility27.

We propose here an innovative geochemical approach based on analytical fingerprinting of lithium isotopes of raw and processed materials, to ensure the traceability of lithium in LIB. This method helps to verify and audit the blockchain, thus ensuring its control. It was developed for the coltan supply chain28 and, more recently, for native gold from French Guiana29. Lithium (Li) has two stable isotopes, 6Li and 7Li, with relative abundances of 7.6% and 92.4%, respectively. Isotope compositions of Li (δ7Li) are reported as classical notation of δ (parts per thousand, ‰) with the 7Li/6Li ratio relative to standard lithium (L-SVEC)30: δ7Li = [(7Li/6Li) shows /(7Li/6Li)std – 1] × 1000. The wide range of isotopic compositions of Li in natural samples, between −15‰ and +45‰31, provides a strong incentive to use δ7Li values ​​as a tool to ensure accuracy. traceability of lithium in LIB.

We first discuss the variability of Li isotope compositions between lithium deposits and in coexisting minerals. The effects of extractive and refining metallurgy, cathode active material synthesis, and battery fabrication on the intrinsic signatures of minerals are then analyzed and discussed. Finally, we discuss how Li isotope compositions can be used to ensure traceability and certification of lithium in LIB.

Results and discussion

The samples and analytical techniques we used are described below under Methods. Figure 1 shows the samples analyzed in this study with a known provenance. Supporting information is provided in the Supplementary Figures. 1 and 2, Supplementary Notes and data are listed in Supplementary Tables 1 and 2.

World mining production in 2020 comes from USGS data (2021)10, except for the United States, whose value is represented by production in 201816. Spodumene concentrates, lithium hydroxides and carbonates analyzed in this study with known deposits are shown, as well as lithium carbonate produced by Alfa Aeser in Argentina.

Isotope variability between lithium deposits and among coexisting ores

The Li isotope compositions of major deposits in China, Chile, Argentina, Bolivia, and Australia were taken from previous studies32,33,34,35,36,37,38,39,40,41 (Fig. 2). Their distribution in natural samples (spodumenes and brines) is shown in Supplementary Fig. 1.

Spodumenes from West Kunlun (China) and the Yilgarn and Pilbara cratons (Australia)32,33,34; and brines from the Qaidam Basin (China), Salar del Hombre Muerto, Salar de Olaroz, Salar de Pozuelos (Argentina), Salar de Atacama, Salar Grande, Salar de las Parinas, Salar de la Isla, Salar de Pedernales (Chile), and Salar de Uyuni (Bolivia)35,36,37,38,39,40,41. The error bars represent the 2σ associated with the δ7Li values. The isotopic compositions of the different Li deposits are shown by probability ellipses (confidence level p = 0.68). Data are shown with blue box plots for “Li triangle” salt flats (n = 103), China salt flat (n = 20) and pink box plots for hard rocks (n = 20). The vertical gray line labeled “UCC” represents the values ​​of the upper continental crust (UCC): 0 ± 4‰ (2σ)31.

For brines in South American salt flats in the “lithium triangle” of Bolivia (Salar de Uyuni), Argentina (Salar del Hombre Muerto, Salar de Olaroz, Salar de Ratones, Salar de Centenario, Salar de Pozuelos) and Chile (Salar de Atacama, Salar Grande, Salar de las Parinas, Salar de la Isla, Salar de Pedernales), the interquartile range (IQR) of the isotopic compositions of Li is from +7.9 to +11.3‰ with a median value of +9.8‰ (n = 103 )35 ,36,37,38,39,40. For brines from the Qaidam Basin in China, the IQR of the Li isotope compositions is between +16.1 and +31.4‰ with a mean value of +24.3‰ (n = 20)41. The origin of lithium in brine is variously explained by low-temperature rock weathering, hydrothermal leaching, or magmatic origin with subsequent evaporation. In such deposits, dissolved lithium commonly complexes with chloride as a LiCl42 species. General theoretical considerations suggest that lower coordination states and bond lengths should prefer the heavy isotope43. Under ambient P-T conditions, the quadruple coordination [Li(H2O)4]+ is the main group in aqueous fluids, while the Li coordination in most solids is higher31,44. The fractionation of Li isotopes in fluid-rock interactions, in particular rock weathering, results in a preferential fractionation of the heavier isotope (7Li) in fluids with a magnitude inversely correlated with temperature31,45. This behavior is consistent with low temperature leaching experiments on tuff, producing a leachate that is +5‰ enriched in 7Li relative to whole rock Li36. Furthermore, the Li isotope compositions of brines are also controlled by the incorporation of Li into secondary minerals, such as clays, removing the lighter isotope (6Li) from the sol. ution and enriching the water in 7Li (up to  + 10‰)31. Therefore, the Li isotope compositions of brines result from the mixing of waters derived from various rock reservoirs46 and fluid-rock interactions at different temperatures. Dissolved Li enrichment is co In agreement with literature data, which showed that δ7Li values ​​of brines from South America (Bolivia, Argentina, Chile) (+7.9 to +11.3‰, n = 103, IQR) and brines from China (+16.1 to +31.4‰, n = 20, IQR) are generally higher than the upper continental crust (UCC) values ​​(0 ± 4‰, 2σ) 31 (Fig. 2). While the δ7Li values ​​of the brines from the Qaidam Basin (China) are marked by a strong enrichment (+16.1 to +31.4‰, n = 20, IQR) compared to the brines from the “triangle of South American lithium” (+7.9 to +11.3‰, n = 103, IQR), the variability of the δ7Li values ​​in these latter brines is considerably greater than their differences (Fig. 2, Fig. S1).

For spodumenes in Australia (Yilgarn and Pilbara cratons) and China (West Kunlun), the IQR of Li isotope compositions is between −0.3 and +6.0‰, a mean value of +2.8‰ ( n = 20)32,33,34. The hard rock deposits, mostly lithium-rich granitic pegmatites, are interpreted as the product of fractional crystallization of an original granitic melt. Lithium is an important element in several minerals, such as amblygonite, bikitaite, eucryptite, lithiumophilite, lithiumphosphate, montebrasite, spodumene, and petalite in lithium-rich granitic pegmatites. Among them, spodumene is the most exploited on a commercial scale12. Ab initio density perturbation theory (DFT) experiments and calculations showed that, during pegmatite crystallization, 6Li preferentially occupies octahedral sites in the spodumene, while 7Li favors tetrahedral sites in the spodumene. granitic fusion44,47. Ab initio calculations by Liu et al.48 predicted that Li isotope fractionation in Li-rich minerals has a remarkable linear correlation with average Li–O bond lengths and Li coordination numbers; They showed that δ7Li values ​​in minerals were formed in the same crystallization stage from molten pegmatite in the order petalite>lithiophosphate>bikitaite>eucryptite>montebrasite>amblygonite>lithophyllite>spodumene. Therefore, in Li-rich granitic pegmatites, the δ7Li values ​​of spodumene are lower than those of petalite. This isotope depletion in spodumene is confirmed by data from the literature, which showed that spodumene δ7Li values ​​in major Australian and Chinese deposits are, in contrast to salt flats, of the same order of magnitude (−0, 3 to +6.0‰, n = 20, IQR) as UCC values ​​(0 ± 4‰, 2σ)31 (Fig. 2). as long as that the Li isotope compositions of spodumene from West Kunlun (China) are depleted in heavy isotopes (−1.3 to +1.4‰, n = 8, IQR) compared to Australian spodumene (+3 .8 and +9‰, n = 12, IQR), the variability of the δ7Li values ​​within the Australian deposits (Yilgarn and Pilbara cratons) is more important than the differences between them.

The Li isotope composition of lithium deposits is linked to the physicochemical conditions of mineral formation processes and varies within several tens of parts per thousand (Fig. 2). The different genesis of salt flats (supergene) and hard rock (magmatic) deposits explains why δ7Li values ​​of brines are generally higher (+7.9 to +11.3‰, n = 103, IQR and +16.1 to + 31.4‰, n = 20, IQR) than those of the spodumene deposits (−0.3 to 6.0‰, n = 20, IQR). This variation in δ7Li values ​​could discriminate a salar from a spodumene origin (see discussion below), but also between deposits of the same type (Australia versus China for hard rock, South America versus China for salars).

Effects of extractive and refining metallurgy, cathode active materials synthesis, and battery-cell manufacturing

The concentration, extraction or processing of the lithium contained in the deposits will affect its δ7Li value. In particular, industrial processes, involving chemical transformation with kinetic isotope effects and low recovery yield/high lithium loss, can induce significant isotope fractionation between industrial and natural samples. The LIB production chain includes several industrial processes: (i) The hard rock extractive metallurgical process begins with the production of a spodumene concentrate, increasing the lithium content by separating undesirable minerals from the ore through physical separation (comminution, flotation and magnetic separation)49. The concentrate is then calcined at >1000 °C, causing the rearrangement of α-spodumene to β-spodumene which readily dissolves in acid50. The traditional sulfuric acid process was first to efficiently extract lithium from spodumene in the 1950s (lithium yield 85-90% at the time) and was scaled up shortly thereafter (yield greater than 90%)11,12 . In this process, roasted β-spodumene is leached with sulfuric acid and mixed with sodium carbonate to precipitate lithium carbonate. A final step, the addition of calcium hydroxide, can be used to obtain lithium hydroxide from lithium carbonate50. The material used as the isotope standard, lithium carbonate L-SVEC, was purchased from Lithium Corporation of America (or American Lithium)30, prepared from Li ore (primarily spodumene) from the Foote Mine (Kings Mountain, North Carolina). North, USA) through traditional extraction. with sulfuric acid leaching https://www.americanlithiumcorp.com. Grégoire et al.51 showed that the Foote mine ore and derived carbonate have a similar Li isotope signature taking into account the uncertainty analytical, indicating that the sulfuric acid process does not cause Li isotope fractionation. As an alternative to the traditional process discussed above, Outotec and Keliber of Finland announced in early 2019 a new process, completely free of sulfate and acid, to produce lithium hydroxide directly from calcined β-spodumene52. After calcination, two-stage alkaline leaching (pressure leaching and conversion) produces a solution of hydroxide and analcime (NaAlSi2O6.H2O). Total lithium leach extraction yield from concentrates is 84% ​​to 94%52. Typical lithium processing impurities, Fe, Al, Ca, Mg and P, are then removed from solution by cation exchange resins with iminodiacetate or aminophosphonate (ion exchange purification). Finally, LiOH⋅H2O solidifies by preconcentration and vacuum crystallization. Figure 3 shows samples of spodumene, β-spodumene, analcime and lithium hydroxide concentrate provided by Keliber. In contrast to the US lithium product, the Finnish samples show strong partitioning between the spodumene concentrate and the produced lithium hydroxide (Δ7Lithium spodumene hydroxide concentrate = +5.5‰). Calcination does not cause isotopic fractionation, since spodumene concentrate and β-spodumene have the same lithium isotopic signature (Fig. 3). Regarding the leaching step, we can estimate the Li composition of the product with a Rayleigh model (Supplementary Fig. 2). Using the initial composition of δ7Li in the ores (+1.1‰), the analcime by-product δ7Li (−0.9‰), and the lithium leach extraction yield provided by Keliber (84% to 94%), the estimated values ​​of δ7Li they are between +1.3 and +1.5 ‰ for Li in solution (Fig. 3). This shows that the leaching does not lead to a significant fractionation of Li isotopes (Δ7LiLi+-β-concentrated + 0.2 to +0.4‰). Regarding the ion exchange purification, strong Li isotope fractionation occurs during ion exchange chromatography53. The heavy isotope 7Li passes through the exchange resin faster than 6Li, requiring 100% yield to avoid isotope fractionation in the eluent during the chemical preparation of Li31 (see Methods, below). We performed laboratory experiments to estimate the fractionation factor between Li+ and purified Li+ (eluent) due to purification by ca ion-exchange resins (see Supplementary Note for details). These experiments showed that even a 95% yield causes strong partitioning between Li+ and purified Li+ (Δ7Li purified Li+ -Li+ >+8‰). Regarding the crystallization process, since there is no change in the coordination number between Li in aqueous solution and Li hydroxide monohydrate (both tetrahedrally coordinated sites),54 this is not expected to result in significant fractionation. of the Li isotope.

Refining and extractive metallurgy (a) for hard rock-based lithium sources, with spodumene and lithium carbonate from American Lithium, and spodumene, β-spodumene, and lithium hydroxide concentrate from Keliber (this study). The δ7Li values ​​for Li+ (α = 1.0007, 1.0011; R = 84-94%) and purified Li+ (α = 1.055; R = 95–98%) are estimated as explained in the main text. bBrine-based lithium sources: Li-hydroxide and -carbonate from Leverton, SQM and Alpha Aesar (n = 5, this study). The blue box diagrams are the data from the Argentine salt flats (n = 58)35,36,38,39 and from the Chilean Atacama salt flat (n = 36)37,39,40. Synthesis of NMC active materials with NMC622 (n = 2) and NMC811 (n = 2) produced in this study from lithium carbonate (Li13, Li18) and hydroxide (Li01, Li17). Production of cell batteries with several pieces of cathode foils (n = 8) from the same NMC532 cell battery (this study). The error bars represent the 2σ associated with the δ7Li values.

(ii) Salar extractive metallurgy, that is, the production of lithium from brine, depends on its composition, volume and accessibility, as well as its suitability for local processing49. In the Salar de Atacama (Chile) and the Salar de Olaroz (Argentina), the process flow diagram used by the companies Rockwood, SQM and Orocobre is called the ‘Silver Peak’ method, where it was first developed in Nevada (USA). . USA) by Foote Mineral in the 1960s50. The brines are pumped to the surface to be concentrated by solar evaporation in ponds. This concentration causes the precipitation of sodium, potassium and magnesium chlorides50. Furthermore, in the Salar del Hombre Muerto (Argentina), lithium brine is first concentrated by ion absorption on polycrystalline alumina before solar evaporation50. However, a large loss of Li is observed due to the evaporated brine being trapped in the precipitated salts during evaporation, and the maximum recovery of Li from evaporation is ~80%55. The concentrated brine is then transferred to processing facilities where reagents are added to remove impurities and produce lithium compounds through precipitation/crystallization50. In the SQM process, the brine from the Salar de Atacama is drained from the evaporation ponds once the lithium concentration in the brine reaches ~6% Li, or the lithium chloride saturation point, and is transported to the plant. Salar del Carmen through trucks50. The brines are solvent extracted to remove boron, and sodium carbonate is added to precipitate and filter magnesium carbonate. The concentrated brine is then heated and reacted with additional sodium carbonate to precipitate lithium carbonate, which is filtered, washed and dried in a rotary dryer50. As a final step, Li carbonate can be converted to Li hydroxide by adding Ca hydroxide lcio. For the European market, this last stage takes place in processing plants in Russia50. The process used by Leverton on the Salar de Atacama brines is not described in the literature and Leverton does not disclose its processing information. However r, the δ7Li values ​​of the carbonates and hydroxides produced by SQM and Leverton from the brines of the Salar de Atacama are close to each other (Δ7LiSQM-Leverton + 1.0 to +1.4‰), which indicates that the metallurgical processes used may be similar. The δ7Li value of the carbonate produced in Argentina (+7.4‰) is slightly lower than the literature data for the brines of the Salar del Hombre Muerto, Salar de Olaroz, Salar de Ratones and Salar de Pozuelos (+7.6 at +11.3‰, n = 58 , IQR). The δ7Li values ​​of the carbonate (+11.9 to +13.3‰) and Li hydroxide (+12.7 to +13.7‰) produced by Leverton and SQM from the brines of the Salar de Atacama are slightly higher than those of the brines from the Salar de Atacama determined in previous studies (+9.6 to +11.4‰, n = 36, RIC) (fig. 3). This difference between the natural samples and the products may be due to the fact that the literature data is not representative of the brines exploited by salt producers, or to the fact that isotopic fractionation occurs during extraction, in particular during extraction. evaporation when Li losses are higher. This point shows the need to work in collaboration with salt producers to assess the importance of their products. The conversion of Li carbonate to Li hydroxide does not induce isotopic fractionation since the δ7Li values ​​for these products are close for the SQM and Leverton samples: Δ7Lihydroxide-carbonate + 0.4 to +0.8‰ (Fig. 3). Note that the δ7Li values ​​are also close for Li hydroxide and carbonate produced by Tianqi Lithium (China) (Fig. 4), reinforcing the hypothesis that the conversion of carbonate to hydroxide does not alter the Li isotope signature.

Spodumene concentrates (n = 3), lithium hydroxides (n = 11), lithium carbonates (n = 8), cathodic active materials (n = 5), cathodic sheets (n = 8). Also shown is lithium carbonate produced by American Lithium (L-SVEC)51. The error bars represent the 2σ associated with the δ7Li values. Data are shown with blue box plots for “Li triangle” salt flats (n = 103)35,36,37,38,39,40 and pink box plots for hard rocks (n = 20)32,33, 3. 4. The “hard rock domain” and “brine domain” defined in this study are shown by pink and blue shaded areas, respectively. The “domain of unknown origin” is shown by the white area between the two shaded areas.

(iii) The synthesis of the active material of the cathode. Producing batteries with a high energy density requires active materials with a high volume density. Coprecipitation synthesis is commonly used to produce dense lithium layered oxide materials with spherical particles. In such a synthesis, a mixture of nickel, cobalt, and manganese sulfates are dissolved in water in appropriate amounts to produce the target NMC. This sulfate solution and ammonium hydroxide solution are pumped together into a stirred tank reactor, with the addition of sodium hydroxide solution to maintain the reaction at basic pH. After a period of aging, the resulting precipitate is recovered by filtration. This first synthetic step leads to a mixed metal hydroxide, which is then mixed with a lithium salt. The resulting powder is calcined at high temperature to produce the active material (see Methods, below, for more details on the synthesis of NMC622 and NMC811). Figure 3 shows the δ7Li values ​​for active materials (NMC622 and NMC811) synthesized from lithium carbonate and hydroxide (Li01, Li13, Li17, Li18) for this study. Regardless of the type of NMC produced (NMC622 or NMC811) and the precursor used (Li hydroxide or Li carbonate), the δ7Li values ​​of the precursor and the product are similar considering the analytical uncertainty. The synthesis of the active material does not induce significant isotopic fractionation between the lithium salt and the active material.

(iv) The manufacture of battery cells. A cathode sheet consists of a current collector, typically aluminum foil, on which a fine powder of active material containing polyvinylidene difluoride (PVDF) and carbon black is deposited on two sides. The battery cell assembly consists of alternating sheets of anode, separator and cathode in a cell pack, filled with electrolyte. Since these steps do not involve any chemical transformation of the lithium contained in the active material, they cannot cause any significant isotopic fractionation between the active material and the cathode sheet. The Li isotope compositions of different sheets of the same battery cell, whether covered by electrolyte or not, are similar when analytical uncertainty is considered (Fig. 3). Such homogeneous composition indicates that a battery can be characterized by a single δ7Li value determined by spot analysis on a single sheet. The δ7Li value of this battery (+10.4 ± 0.4‰, 2σ) is in the same value range as Korean LIB (+8.5‰, +2.4‰, +3.1‰, + 12.6‰) analyzed by a previous study that evaluated the impact of anthropogenic input on the content of lithium in the environment57.

In conclusion, in addition to the sulfuric acid process, the extraction and purification processes discussed above tend to increase the δ7Li value of the produced salt compared to its initial/natural Li isotopic signature. The last complementary step of the lithium transformation chain (conversion of lithium carbonate to lithium hydroxide) does not introduce isotope fractionation. The other steps of battery manufacturing (cathode active material synthesis, battery cell manufacturing) also do not induce significant isotopic fractionation between lithium salts and the final product, which has a homogeneous composition of Li isotopes.

Assessing the geochemical traceability of lithium

Geochemical traceability is used to try to answer the question “What is the origin of unknown lithium?” by determining the origin (mine site, refining plant) of a material (ore, product) using measurable material properties and quantifiable. For that, the materials must have measurable compositions/properties that differ depending on their geological genesis or manufacture. Li isotope compositions of lithium deposits are related to the physicochemical conditions of mineral formation processes; differences in their genesis lead to higher values ​​of δ7Li for brines (+7.9 to +11.3‰ and +16.1 to +31.4‰) than for hard rock deposits (−0.3 to + 6.0‰). However, the extraction and purification processes, different from the traditional sulfuric acid process, tend to modify the initial/natural signature by increasing the δ7Li values ​​up to +5.5‰. Although such process-related fractionation tends to blur a sample’s link to its geological origin, it can also serve to differentiate lithium salts produced from minerals of similar origin, but whose extraction process may have an environmental or social impact. different. For example, this fractionation could discriminate lithium salts produced from spodumene using the traditional sulfuric acid process or using an alternative process without sulfuric acid, such as the Outotec and Keliber process.

Despite the uncertainty related to the process-related isotopic enrichment and the lack of data on the deposits, we can establish a first estimate of ranges of Li isotopic values ​​for which the probability that the Li salt belongs to hard rock or brine lithium sources is high. This first estimate will be refined as more data is acquired on the different deposits and the different extraction processes. For δ7Li values ​​below +6‰ (the third quartile of hard rock data), the probability that the sample was obtained from hard rock is high, while δ7Li values ​​above +11.3‰ (the third quartile of the “Li triangle” salar data, with values ​​for the Chinese salar being even higher) indicate a sample probably obtained from brine. However, samples with δ7Li values ​​between +6‰ and +11.3‰ fall in the “domain of unknown origin”. Considering samples from known reservoirs (Fig. 1), the three spodumene concentrates (Lithium from North America, Sayona and Keliber) are found within the “hard rock domain” and the four Li salts from the Atacama salt brines ( Leverton and SQM) are located within the “salt domain” (Fig. 4). Li hydroxide from Keliber and Li carbonate from Argentina fall into the “domain of unknown origin”. For the other salts, for which only the country of the last refining stage is known, there is heterogeneity of Li origin within the same country. For example, samples produced in Russia and the UK come from salt flats and hard rocks (Fig. 4). Ganfeng Lithium Carbonate of Li, which produces Li salts from spodumene concentrates from Australia and China, is in the “hard rock domain”, while Tianqi Lithium Products which has a more diversified supply (salt or spodumene), are found in the “hard rock domain”. domain of unknown origin.

As we saw that active material synthesis and battery cell fabrication do not induce significant isotopic fractionation, the ranges of Li isotopic values ​​stated above can be used as a first estimate to determine the origin of lithium in active materials and cathode foils. Of battery. . The δ7Li values ​​for active materials produced by TOB (China) are variable, even for materials produced in the same factory (NMC532 and NMC333) (Fig. 4). Except for TOB active materials NMC622 (in the “hard rock domain”) and NMC811 (in the “salt domain”), the other TOB samples and cathode sheets of the Korean battery manufacturer fall into the “domain of origin”. unknown”. These results show that the supply of lithium to the battery industry is based on economic criteria, with no preference for lithium based on hard rock or brine.

Although these results show that identifying the origin of an unknown lithium product is a challenging problem, the great diversity of Li isotopic signatures for secondary products demonstrates that δ7Li values, like a fingerprint, can be a useful tool to certify the product. origin of lithium in LIB.

Towards a methodological approach for certifying a responsible and sustainable lithium supply chain

Our analytical method, based on lithium isotope fingerprinting, can help control and certify the origin and trade of lithium production. It is an independent, reliable, and tamper-proof approach to auditing the document-based traceability system that end users (car manufacturers, consumer electronics companies, etc.) seek, answering the question: “Is lithium its declared origin??” Traded materials can be analyzed to provide additional credibility to document-based traceability systems with due diligence concepts for raw material supply chains Implementation of a lithium certification system will promote the development of a responsible, sustainable and stable supply of raw materials for batteries, guaranteeing the respect and protection of human rights and the conservation of the environment throughout the value chain The development of lithium certification is of vital importance, especially in the context of the political will to re-industrialize the production of batteries in Europe or the US, which defend sustainable battery manufacturing projects. Such certification would be in accordance with recent EU regulation for responsible and sustainable sourcing of various other raw materials, such as tin, tantalum, tungsten and gold, and consumer interest in sustainable products. The principle of this analytical method is the same as that used for the traceability of gold and coltan28,29, which verifies whether the product corresponds to its declared origin by comparing the sample in question with reference samples of known origin stored in a database. data. As the isotopic signature of Li is conserved from the lithium salt to the battery, it is possible to develop this control throughout the value chain.

Adoption of this approach will require guidelines for collecting reliable data on sample provenance and for a reference database with complete and up-to-date data on commercially available Li products. For this, reference samples of raw and processed materials must be collected from places worked by one or several companies during a certain period of time, such as a year. In particular, it should be checked whether samples produced by the same company from the same depot are more closely related to each other than samples produced by another company from a different depot. This approach is only possible if robust data on variations within the reservoir are available; In addition, the database must be active, as new ore bodies are exploited, new extraction sites are opened, and new mining/refining companies enter the market. The limitation of this approach will be overlaps in the Li product data from different places or salt producers. A specific statistical data evaluation strategy is needed to evaluate matches between unknown and reference samples from mining sites or processing plants declared as the source of the unknown sample.

Beyond this study, additional challenges in developing lithium certification will be to expand the database and assess the applicability of this approach to unconventional lithium sources (eg, geothermal waters, clay minerals) to support the future development of the global lithium supply chain.

Methods

Sample description

Samples of three spodumene concentrates were taken from mining companies in Finland (Keliber Oy) and Canada (North American Lithium, Sayona Québec). Keliber also supplied processed products: β-spodumene, analcime (NaAlSi2O6·H2O) and lithium hydroxide monohydrate (LiOH. H2O).

Keliber Oy (Keliber) operates spodumene deposits located in the province of Central Ostrobothnia (Finland)50 and produces battery-grade lithium hydroxide at its chemical plant https://www.keliber.fi/en/.

North American Lithium operates an open pit mine in La Corne (Abitibi, Québec, Canada) and plans to open a lithium carbonate plant http://na-lithium.com/.

Sayona Québec (Sayona) is a subsidiary of Sayona Mining, an emerging lithium miner with projects in Québec and Western Australia. In addition, it owns the Authier Lithium Project in Québec for the development of an open-pit spodumene mine https://www.sayonaquebec.com/.

We also analyzed eight samples of lithium carbonate (Li2CO3) and ten samples of lithium hydroxide monohydrate (LiOH.H2O) of battery grade purity (Li > 99.5%) from various chemical companies (Alfa Aeser, Acros Organics, Fluka , Sigma Aldrich, Fisher Chemical, Leverton) and from mining/refining companies that manufacture cathode active material. In particular, we analyzed lithium salts from three of the top five global producers of lithium chemicals (SQM, Ganfeng and Tianqi)8. We assume that the lithium carbonate produced by Alfa Aeser in Argentina (Li 11) was made from Argentine salt flats.

Leverton-Clarke (Leverton) operates a processing plant in Basingstoke, Hampshire, UK https://www.levertonlithium.com/; they produce lithium hydroxide and battery grade carbonate from the brine of the Salar de Atacama (personal communication).

Sociedad Química y Minera (SQM) extracts lithium brine from the Salar de Atacama in northern Chile. It is the world’s largest producer of lithium carbonate and one of the main producers of lithium hydroxide. SQM operates a lithium carbonate and hydroxide plant at the Salar del Carmen facilities in La Negra, near Antofagasta50. Lithium carbonate, supplied by SQM, is also transformed in processing plants in Russia into lithium hydroxide, which is mainly redistributed in the European market50.

Jiangxi Ganfeng Lithium (Ganfeng Lithium) operates a spodumene mine in China (Ningdu) and has a 50% equity interest in the Mt. Marion lithium mine in Western Australia50, as well as exclusive supply agreements with Pilbara Minerals (Pilgangoora and Height) in Australia http://www.ganfenglithium.com/about3_en.html. Ganfeng Lithium operates a number of subsidiaries, conducting lithium exploration in Ireland, Canada, Australia, Mexico, and Argentina, lithium processing in China, and lithium product trading in the Chinese and international markets50.

Sichuan Tianqi Lithium Industries (Tianqi Lithium) is a state-owned Chinese company that operates multiple lithium operations and projects, primarily in China and Australia. It owns a 51% stake in the Greenbushes mine in Western Australia50, is the largest producer of lithium ore concentrates and exploits brines from the Zhabuye salt lake on the Tibetan Plateau (China)58. Two Li processing plants are operated by Tianqi Lithium subsidiaries in China, in Sichuan and Jiangsu provinces. They produce lithium chemicals from imported Li products from a diversified supply base (salar or spodumene origin)50.

Xiamen TOB New Energy Technology (TOB) is a Chinese company specializing in the research and manufacture of lithium-ion batteries. Provides comprehensive battery production line equipment, materials and solutions for international companies and research institutions (BMW, Daimler-Benz, A123, SKC, MIT, IIT, etc.) https://www.tobmachine.com/company_d1, and produces cathode active materials, four of which (NMC333, NMC532, NMC622 and NMC811) were sampled. Samples NMC333 and NMC532 were produced at Factory A, while NMC622 and NMC811 were produced at two other factories (B and C).

For this study, we synthesized two types of active materials (NMC622 and NMC811) from lithium carbonate (Li13, Li18) and lithium hydroxide (Li01, Li17) at CEA LITEN (Commissariat à l’Energie Atomique et aux énergies Alternatives Laboratoire d’Innovation pour les Technologies des Energies nouvelles et les Nanomatériaux). The layered lithium oxide material was synthesized by coprecipitation using commercial sulfate reagents from Sigma Aldrich. In a standard synthesis, three different solutions containing all the reagents were prepared. The transition metal ion solution was obtained by dissolving NiSO4 6H2O (127.4 g for NMC622, 169.9 g for NMC811), MnSO4 H2O (27.3 g for NMC622, 13.7 g for NMC811) and CoSO4 7H2O (45.4 g for NMC622, 22.7 g for NMC811) in 400 g of water. The ammonium hydroxide solution was produced by mixing 150 g NH4OH (28% from Sigma Aldrich) in 233 g water, and the sodium hydroxide solution resulted from dissolving 81.6 g NaOH (from Sigma Aldrich) in 400 g of water. The transition metal ion solution and the ammonium hydroxide solution were pumped directly into the reactor, the pH being maintained at 11 during the synthesis by controlled injection of the hydroxide solution. After the introduction of the reactive solutions, the mixture was aged for 3 hours in the reactor, before recovery by filtration of nickel-manganese-cobalt hydroxides [Ni0.6Mn0.2Co0.2(OH)2 or Ni0.8Mn0 .1Co0.1(OH)2]. The product was washed several times with hot water to remove residual sodium and sulfate species, and finally the hydroxide was dried overnight in an oven at 80 °C. To obtain the final NMC material, the hydroxide was intimately mixed with an excess of lithium salt (3.3%) and the mixture was calcined at 850 °C for 24 h in air to produce NMC622, and at 925 °C for 12 h into oxygen to produce N MC811.

A large (30 × 9 cm) “automotive grade” prismatic battery cell from South Korea with an NMC532 cathode, containing 52 cathode sheets and 53 anode sheets, was also sampled.

Reagents and materials

All plastic and Teflon equipment for this study was acid cleaned before use. All acids were purified by sub-boiling distillation before use. The water was “Milli-Q” distilled water with a resistivity of 18.2 MΩ cm (Millipore®). AG 50 W − X12 (200–400 mesh) cation exchange resin and hydrogen from BioRad® were used for Li purification.

Sample preparation

The “automotive grade” battery cell was inaugurated at the EDF-LME (Électricité de France-Laboratoire des Matériels Electriques) R&D laboratory, after being fully discharged for safety reasons. Four cathode sheets (A, B, C, D) were selected to provide representative samples of the cell. Sheets A and B were rinsed with “Milli-Q” to remove any residual electrolyte, while sheets C and D were left untouched.

The samples were then prepared in the BRGM (Bureau de Recherches Géologiques et Minières) laboratory. Several 3 cm wide strips were cut from each sheet at different places with a ceramic chisel, and the front (A1, B1, C1, D1, A7, B3) or back (A8, B6, C6, D6) faces were carefully separated. it is scraped with a ceramic lancet so as not to damage the collector, made of aluminum foil. Approximately 200 mg of cathode active materials were calcined at 550 °C and dissolved in concentrated acids (HNO3, HClO4, HF, HCl) on a hot plate in the clean room. About 200 mg of spodumene concentrate and analcime were dissolved in concentrated acid using the same protocol. After drying, the residue was diluted in 0.5M HNO 3. About 200mg of lithium carbonate and hydroxide were also dissolved in 0.5M HNO 3 .

Lithium isotope analysis

Li concentrations were measured using an ICP-MS X Series II (Thermo Fisher Scientific) at the BRGM laboratory. A sample volume of ~100 ng Li was dried on a hot plate in the clean room. For the cathode active materials, the residue was dissolved in a mixture of 0.2 M HCl Lithium was separated from the matrix elements using an AG 50 W − X12 (200–400 mesh)59 resin, before drying and redissolve it in 0.5 M HNO3. To avoid Li isotope fractionation due to chemical purification, recovery of Li from this protocol was verified by analyzing an aliquot before and after chemical separation by ICP-MS: recoveries were consistently close to 100%. The other samples were directly dried and redissolved in 0.5 M HNO3 Total process blanks were measured to verify cleanup procedure; such blanks are generally less than 30 pg, which represents >0.03% of the mass of lithium analysed.

Lithium isotope compositions were measured at a concentration of 50 μg/L with a Thermo Fisher Scientific Neptune MC-ICP-MS, upgraded to ‘Neptune Plus’, at the BRGM laboratory, following the previously developed procedure59. The lithium isotope composition of each sample was expressed in δ notation relative to the mean value of the Li standard in parentheses (L-SVEC): δ7Li = [(7Li/6Li)sample/(7Li/6Li)std – 1] × 1000. The quality of the lithium isotope analyzes was controlled by periodic measurements of “in-house” standards, whose long-term reproducibility is 0.5‰ (2σ). The external reproducibility (2σ) reported in the various figures and tables was typically ±0.4‰, calculated by measuring the same sample multiple times over multiple analytical runs.

Data availability

All data generated or analyzed during this study is included in the Supplementary Information.

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Meixner, A., Alonso, R.N., Lucassen, F., Korte, L. & Kasemann, S. A. Lithium and Sr isotopic composition of salt deposits in the central Andes through space and time: the Salar de Pozuelos, Argentina. Miner. Deposits 57, 255–278 (2022).

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