Preferentially selective extraction of lithium from spent LiCoO_(2)cathodes by medium-temperature carbon reduction roasting

Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.

Effects of conductive agent type on lithium extraction from salt lake brine with LiFePO_(4) electrodes

Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.

A review of lithium extraction from natural resources

Lithium is considered to be the most important energy metal of the 21st century.Because of the development trend of global electrification,the consumption of lithium has increased significantly over the last decade,and it is foreseeable that its demand will continue to increase for a long time.Limited by the total amount of lithium on the market,lithium extraction from natural resources is still the first choice for the rapid development of emerging industries.This paper reviews the recent technological developments in the extraction of lithium from natural resources.Existing methods are summarized by the main resources,such as spodumene,lepidolite,and brine.The advantages and disadvantages of each method are compared.Finally,reasonable suggestions are proposed for the development of lithium extraction from natural resources based on the understanding of existing methods.This review provides a reference for the research,development,optimization,and industrial application of future processes.

Lithium extraction from hard rock lithium ores(spodumene,lepidolite,zinnwaldite,petalite):Technology,resources,environment and cost

Lithium production in China mainly depends on hard rock lithium ores,which has a defect in resources,environment,and economy compared with extracting lithium from brine.This paper focuses on the research progress of extracting lithium from spodumene,lepidolite,petalite,and zinnwaldite by acid,alkali,salt roasting,and chlorination methods,and analyzes the resource intensity,environmental impact,and production cost of industrial lithium extraction from spodumene and lepidolite.It is found that the sulfuric acid method has a high lithium recovery rate,but with a complicated process and high energy consumption;alkali and chlorination methods can directly react with lithium ores,reducing energy consumption,but need to optimize reaction conditions and safety of equipment and operation;the salt roasting method has large material flux and high energy consumption,so require adjustment of sulfate ratio to increase the lithium yield and reduce production cost.Compared with extracting lithium from brine,extracting lithium from ores,calcination,roasting,purity,and other processes consume more resources and energy;and its environmental impact mainly comes from the pollutants discharged by fossil energy,9.3-60.4 times that of lithium extracted from brine.The processing cost of lithium extraction from lepidolite by sulfate roasting method is higher than that from spodumene by sulfuric acid due to the consumption of high-value sulfate.However,the production costs of both are mainly affected by the price of lithium ores,which is less competitive than that of extracting lithium from brine.Thus,the process of extracting lithium from ores should develop appropriate technology,shorten the process flow,save resources and energy,and increase the recovery rate of related elements to reduce environmental impact and improve the added value of by-products and the economy of the process.

Engineering Multi‑field‑coupled Synergistic Ion Transport System Based on the Heterogeneous Nanofluidic Membrane for High‑Efficient Lithium Extraction

The global carbon neutrality strategy brings a wave of rechargeable lithium‐ion batteries technique development and induces an ever-growing consumption and demand for lithium(Li).Among all the Li exploitation,extracting Li from spent LIBs would be a strategic and perspective approach,especially with the low energy consumption and eco-friendly membrane separation method.However,current membrane separation systems mainly focus on monotonous membrane design and structure optimization,and rarely further consider the coordination of inherent structure and applied external field,resulting in limited ion transport.Here,we propose a heterogeneous nanofluidic membrane as a platform for coupling multi-external fields(i.e.,lightinduced heat,electrical,and concentration gradient fields)to construct the multi-field-coupled synergistic ion transport system(MSITS)for Li-ion extraction from spent LIBs.The Li flux of the MSITS reaches 367.4 mmol m^(−2)h^(−1),even higher than the sum flux of those applied individual fields,reflecting synergistic enhancement for ion transport of the multi-field-coupled effect.Benefiting from the adaptation of membrane structure and multi-external fields,the proposed system exhibits ultrahigh selectivity with a Li^(+)/Co^(2+)factor of 216,412,outperforming previous reports.MSITS based on nanofluidic membrane proves to be a promising ion transport strategy,as it could accelerate ion transmembrane transport and alleviate the ion concentration polarization effect.This work demonstrated a collaborative system equipped with an optimized membrane for high-efficient Li extraction,providing an expanded strategy to investigate the other membrane-based applications of their common similarities in core concepts.

Classification and mineralization of global lithium deposits and lithium extraction technologies for exogenetic lithium deposits

A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous novel lithium resources. Given the presence of varied classification criteria for lithium resources presently, this study further ascertained and classified the lithium resources according to their occurrence modes, obtaining 10 types and 5 subtypes of lithium deposits(resources) based on endogenetic and exogenetic factors. As indicated by surveys of Cenozoic exogenetic lithium deposits in China and abroad,the formation and distribution of the deposits are primarily determined by plate collision zones, their primary material sources are linked to the anatectic magmas in the deep oceanic crust, and they were formed primarily during the Miocene and Late Paleogene. The researchers ascertained that these deposits,especially those of the salt lake, geothermal, and volcanic deposit types, are formed by unique slightly acidic magmas, tend to migrate and accumulate toward low-lying areas, and display supernormal enrichment. However, the material sources of lithium deposits(resources) of the Neopaleozoic clay subtype and the deep brine type are yet to be further identified. Given the various types and complex origins of lithium deposits(resources), which were formed due to the interactions of multiple spheres, it is recommended that the mineralization of exogenetic lithium deposits(resources) be investigated by integrating tectono-geochemistry, paleoatmospheric circulation, and salinology. So far, industrialized lithium extraction is primarily achieved in lithium deposits of the salt lake, clay, and hard rock types. The lithium extraction employs different processes, with lithium extraction from salt lake-type lithium deposits proving the most energy-saving and cost-effective.

Li^+ extraction/insertion reaction with Mg_2Mn_(0.5)Ti_(0.5)O_4 inverse spinel in the aqueous phase

An inverse spinel-type metal oxide, magnesium-manganese-titanium oxide （Mg2Mn0.5Ti0.5O4）, were prepared using the coprecipitation/thermal crystallization method. The extraction/insertion reaction with this material was investigated by X-ray, saturation capacity of exchange, pH titration, and distribution coefficient （Kd） measurement. The acid treatments of Mg2Mn0.5Ti0.5O4 caused Mg^2＋ extractions of more than 81%, whereas the dissolutions of Mn^4＋ and Ti^4＋ were less than 10%. The experimental results proved that the acid-treated sample has a capacity of exchange 56 mg·g^-1 for Li^＋ in the solution. The chemical analysis showed that the Li^＋ extraction/insertion progressed mainly by ion-exchange mechanism and surface adsorption.

Aqueous Zn-MnO_(2) battery: Approaching the energy storage limit with deep Zn^(2+) pre-intercalation and revealing the ions insertion/extraction mechanisms

Rechargeable aqueous zinc ion batteries(AZIBs)were considered as one of the most promising candidates for large-scale energy storage due to the merits of high safety and inexpensiveness.As AZIBs cathode material,Mn O_(2)possesses great merits but was greatly hindered due to the sluggish diffusion kinetic of Zn^(2+) during electrochemical operations.Herein,deep Zn^(2+) ions intercalatedδ-Mn O_(2)(Zn-Mn O_(2))was achieved by the in situ electrochemical deposition route,which significantly enhanced the diffusion ability of Zn^(2+) due to the synergistic effects of Zn^(2+) pillars and structural H;O.The resultant Zn-Mn O_(2)based AZIBs delivers a record capacity of 696 m Ah/g(0.5 m Ah/cm^(2))based on the initial mass loading,which is approaching the theoretical capacity of Mn O_(2)with a two-electrons reaction.In-situ Raman studies reveal highly reversible Zn^(2+)ions insertion/extraction behaviors and here the Zn-Mn O_(2)plays the role of a container during the charge–discharge process.Further charge storage mechanism investigations point out the insertion/extraction of Zn^(2+) and H^(+) coincides,and such process is significantly facilitated results from superior interlayered configurations of Zn-Mn O_(2)The excellent electrochemical performance of Zn-Mn O_(2)achieved in this work suggests the deep ions pre-intercalation strategy may aid in the future development of advanced cathodes for AZIBs.

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part I: LiMn_2O_4 and LiCo_(0.5)Ni_(0.5)O_2

Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materiaIs on electrochemical Li insertion/extraction performance was discussed. These two transition metal oxides belong to onegroup that the crystallinity of these oxides affects to the performance.

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part Ⅱ: TiO_2, V_2O_5 and MoO_3

Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and showed a wide range of crystallinity. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materials on electrochemical Li insertion/extraction pedermance was discussed. These three transition metal oxides were classified as one group on the basis of whether the crystallinity of these oxides affects to the performance or not; LiMn_2O_4 and LiCo_(0.5)O_2 belongs to the former group and TiO_2, V_2O_5 and MoO_3 to the latter.

Review on Li-insertion/extraction Mechanisms of LiFePO4 Cathode Materials

The work distills the main mechanisms during the lithium insertion/extraction of LiFePO_4 cathode materials. The "diffusion-controlled" and "phase-boundary controlled" mechanism are especially illustrated. Meanwhile, some recent observation and analyses by in-situ or in operando on the Li-insertion/extraction of LiFePO_4 are summarized and prospected.

Extraction of lithium from salt lake brine by aluminum-based alloys

Salt lake brine was reacted with activated aluminum-based alloys and lithium was precipitated.The effects of aluminum-based alloys on precipitating lithium were investigated and the reasonable alloy used to extract lithium from brine was obtained.The effects of the mole ratio of Al to Li and Ca content of Al-Ca alloy,the initial concentration of lithiumion ion in solution,reaction temperature and reaction time on the adsorption rate of lithium were studied,and the optimized process parameters were determined.The results show that the mole ratio of Al to Li and Ca content of Al-Ca alloy and reaction temperature have great influences on the precipitation rate of lithium.The precipitation rate of lithium reaches 94.6% under the optimal condition,indicating that Al-Ca alloy is suitable for the extraction of lithium from salt lake brine.

Recovery of Li_(2)CO_(3)and FePO_(4)from spent LiFePO_(4)by coupling technics of isomorphic substitution leaching and solvent extraction

Efficient and low-cost recycling of spent lithium iron phosphate(LiFePO_(4),LFP)batteries has become an inevitable trend.In this study,an integrated closed-loop recycling strategy including isomorphic substitution leaching and solvent extraction process for spent LFP was proposed.An inexpensive FeCl_(3)was used as leaching agent to directly substitute Fe^(2+)from LFP.99%of Li can be rapidly leached in just 30 min,accompanied by 98%of FePO_(4)precipitated in lixivium.The tri-n-butyl phosphate(TBP)-sulfonated kerosene(SK)system was applied to extract Li from lixivium through a twelve-stage countercurrent process containing synchronous extraction and stepwise stripping of Li^(+)and Fe^(3+).80.81%of Li can be selectively enriched in stripping liquor containing 3.059 mol·L^(-1)of Li^(+)under optimal conditions.And the Fe stripping liquor was recovered for LFP re-leaching,of which,Fe^(2+)was oxidized to Fe^(3+)by appropriate H_(2)O_(2).Raffinate and lixivium were concentrated and entered into extraction process to accomplished closeloop recycling process.Overall,the results suggest that more than 99%of Li was recovered.FeCl_(3)holding in solution was directly regenerated without any pollutant emission.The sustainable mothed would be an alternative candidate for total element recycling of spent LFP batteries with industrial potential.

Highly efficient extraction of lithium from salt lake brine by LiAl-layered double hydroxides as lithium-ion-selective capturing material

The extraction of lithium from salt lake brine in the Chinese Qaidam Basin is challenging due to its high Mg/Li and Na/Li ratios. Herein, we utilized a reaction-coupled separation technology to separate sodium and lithium ions from a high Na/Li ratio brine(Na/Li = 48.7, w/w) and extracted lithium with Li Al-layered double hydroxides(Li Al-LDHs). The Li Al-LDHs act as lithium-ion-selective capturing materials from multication brines. That is, the lithium ions selectively enter the solid phase to form Li Al-LDHs, and the sodium ions are still retained in the liquid phase. This is because the lithium ions can be incorporated into the structural vacancies of LiAl-LDHs, whereas the sodium ions cannot. The effects of reaction conditions on lithium loss and separation efficiency were investigated at both the nucleation and the crystallization stage, e.g., the nucleation rotating speed, the Li/Al molar ratio, the crystallization temperature and time, and co-existing cations. The lithium loss is as low as 3.93% under optimal separation conditions.The sodium ions remained in the solution. Consequently, an excellent Na/Li separation efficiency was achieved by this reaction-coupled separation technology. These findings confirm that LiAl-LDHs play a critical function in selectively capturing lithium ions from brines with a high Na/Li ratio, which is useful for the extraction of lithium ions from the abundant salt lake brine resources in China.

Optimization of an innovative approach involving mechanical activation and acid digestion for the extraction of lithium from lepidolite

The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. There- fore, this study optimized an innovative process, which does not require a high-temperature calcination step, for lithium extraction from le- pidolite. Mechanical activation and acid digestion were suggested as crucial process parameters, and experimental design and re- sponse-surface methodology were applied to model and optimize the proposed lithium extraction process. The promoting effect of amorphi- zation and the formation of lithium sulfate hydrate on lithium extraction yield were assessed. Several factor combinations led to extraction yields that exceeded 90%, indicating that the proposed process is an effective approach for lithium recovery.

Preparation and adsorption performance of multi-morphology H_(1.6)Mn_(1.6)O_(4) for lithium extraction

In this paper,a lithium-ion sieve(LIS)with different morphologies,such as rod-like(LIS-R),spherical(LIS-S),flower-like(LIS-F),and three-dimensional macroporous-mesoporous(LIS-3D),was prepared by hydrothermal synthesis,solid reaction,and hard-template synthesis.The results showed that the LIS with different morphologies presented great differences in specific surface area,pore volume,adsorption selectivity,and structure stability.LIS-3D with highest specific surface area and pore volume displayed the maximum adsorption capacity and adsorption rate,but the stability of LIS-3D was poor because of the manganese dissolution.By comparison,LIS-S has the best structural stability while maintaining a satisfactory adsorption capacity(35.02 mg·g^(-1))and adsorption rate.The LIS-S remained about 90%of the original adsorption capacity after five cycles of adsorption-desorption process.In addition,in the simulated brine system(the magnesium to lithium ratio of 400),the LIS-S exhibited the highest selectivity(α_(Mg)^(Li))of 425.14.In sum,the LIS-S with good morphology is a potential adsorbent for lithium extraction from brine.

Extraction of Lithium from Salt Lake Brine using N523-TBP Mixture System

In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.

Extraction of Lithium from Brine Containing High Concentration of Magnesium by Tri-n-Butyl Phosphate Dissolved in Kerosene

Tri-n-butyl phosphate（TBP）dissolved in kerosene was chosen as extractant for lithium from a modelbrine having high magnesium-to-lithium ratio and ferric chloride was added to the system.The influences of con-tact time,concentration of the extractant,concentrations of some salts(Mg2+, Na+,K+)in the solution,acid-ity of hydrochloric acid and extraction temperature on the exttaction of lithium with TBP-kerosene system werestudied.The suitable extraction conditions were found to be:contact time not any less than 20min;at 20-25C;[Fe+3]/[Li+]about 1.5-2.0;TBP concentration 50%-70%;[MgCl2]exceeding 3 mol·L-1;pH about 2;while most sodium and potassium salts in the aqueous phase should be removed before the extraction.

Great Breakthrough Achieved in Extraction of Lithium from Brine with High Magnesium to Lithium Ratios

With the worldwide rise in electric vehicles, the demand for lithium batteries is increasing day by day. In 2015, China＇s new energy vehicles developed rapidly, and the price of lithium carbonate rose from fifty or sixty thousand yuan per ton to 150 thousand yuan. In the past, lithium was often extracted from spodumene （LiAlSi2O6）, which is time consuming, laborious and expensive. Over the past decade, abundant lithium has been discovered in brackish and salt water lakes, which is an important way to obtain lithium resources.

Aqueous electrochemical delithiation of cathode materials as a strategy to selectively recover lithium from waste lithium-ion batteries

Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.