Electrochemical Methods for Lithium Recovery: A Comprehensive and Critical Review

Due to the ubiquitous presence of lithium‐ion batteries in portable applications, and their implementation in the transportation and large‐scale energy sectors, the future cost and availability of lithium is currently under debate. Lithium demand is expected to grow in the near future, up to 900 ktons per year in 2025. Lithium utilization would depend on a strong increase in production. However, the currently most extended lithium extraction method, the lime‐soda evaporation process, requires a period of time in the range of 1–2 years and depends on weather conditions. The actual global production of lithium by this technology will soon be far exceeded by market demand. Alternative production methods have recently attracted great attention. Among them, electrochemical lithium recovery, based on electrochemical ion‐pumping technology, offers higher capacity production, it does not require the use of chemicals for the regeneration of the materials, reduces the consumption of water and the production of chemical wastes, and allows the production rate to be controlled, attending to the market demand. Here, this technology is analyzed with a special focus on the methodology, materials employed, and reactor designs. The state‐of‐the‐art is reevaluated from a critical perspective and the viability of the different proposed methodologies analyzed.

[1]  F. La Mantia,et al.  Lithium recovery from diluted brine by means of electrochemical ion exchange in a flow-through-electrodes cell , 2020 .

[2]  Seunghyun Kim,et al.  Rapid and selective lithium recovery from desalination brine using an electrochemical system. , 2019, Environmental science. Processes & impacts.

[3]  Yuliang Cao,et al.  Highly Selective and Pollution-Free Electrochemical Extraction of Lithium by a Polyaniline/Lix Mn2 O4 Cell. , 2019, ChemSusChem.

[4]  Hern Kim,et al.  Li Ni0.5Mn1.5O4/Ag for electrochemical lithium recovery from brine and its optimized performance via response surface methodology , 2019, Separation and Purification Technology.

[5]  F. La Mantia,et al.  Effect of Current Density and Mass Loading on the Performance of a Flow-Through Electrodes Cell for Lithium Recovery , 2019, Journal of The Electrochemical Society.

[6]  Jian Zhi,et al.  Controlling the sustainability and shape change of the zinc anode in rechargeable aqueous Zn/LiMn2O4 battery , 2018, Energy Storage Materials.

[7]  Yunfeng Song,et al.  Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques , 2018, Separation and Purification Technology.

[8]  G. Kasiri,et al.  Phase transformation of copper hexacyanoferrate (KCuFe(CN)6) during zinc insertion: Effect of co-ion intercalation , 2018, Journal of Power Sources.

[9]  V. Flexer,et al.  Lithium recovery from brines: A vital raw material for green energies with a potential environmental impact in its mining and processing. , 2018, The Science of the total environment.

[10]  Hern Kim,et al.  Li1−Ni0.33Co1/3Mn1/3O2/Ag for electrochemical lithium recovery from brine , 2018, Chemical Engineering Journal.

[11]  V. Flexer,et al.  Sustainable Electrochemical Extraction of Lithium from Natural Brine for Renewable Energy Storage , 2018 .

[12]  Z. Ji,et al.  Self-Assembly of Free-Standing LiMn2O4-Graphene Flexible Film for High-Performance Rechargeable Hybrid Aqueous Battery , 2018, Materials.

[13]  M. Fan,et al.  A Self-Supported λ-MnO2 Film Electrode used for Electrochemical Lithium Recovery from Brines. , 2018, ChemPlusChem.

[14]  Barbara Tomaszewska,et al.  Lithium capturing from geothermal water by hybrid capacitive deionization , 2018, Desalination.

[15]  Yu Han,et al.  Prussian Blue Analogs for Rechargeable Batteries , 2018, iScience.

[16]  E. Calvo,et al.  Effect of the electrode potential on the surface composition and crystal structure of LiMn2O4 in aqueous solutions , 2018 .

[17]  M. Winter,et al.  Performance and cost of materials for lithium-based rechargeable automotive batteries , 2018 .

[18]  B. Moyer,et al.  Lithium Recovery from Aqueous Resources and Batteries: A Brief Review , 2018 .

[19]  E. Ventosa,et al.  An innovative multi-layer pulsed laser deposition approach for LiMn2O4 thin film cathodes , 2018 .

[20]  Z. Ji,et al.  Development of recovering lithium from brines by selective-electrodialysis: Effect of coexisting cations on the migration of lithium , 2018 .

[21]  Seonghwan Kim,et al.  Electrochemical lithium recovery and organic pollutant removal from industrial wastewater of a battery recycling plant , 2018 .

[22]  Seonghwan Kim,et al.  Electrochemical Lithium Recovery with a LiMn2O4–Zinc Battery System using Zinc as a Negative Electrode , 2018 .

[23]  A. Ludwig,et al.  Effect of Pt and Au current collector in LiMn2O4 thin film for micro-batteries , 2018, Nanotechnology.

[24]  Hongbin Cao,et al.  A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries , 2018 .

[25]  J. John,et al.  Lithium-enriched polypyrrole as a prospective cathode material for Li-ion cells , 2018, Ionics.

[26]  F. J. Williams,et al.  Electrochemical impedance spectroscopy study of the LixMn2O4 interface with natural brine , 2017, Journal of Electroanalytical Chemistry.

[27]  F. J. Williams,et al.  Sustainable Selective Extraction of Lithium Chloride from Natural Brine Using a Li1-xMn2O4 Ion Pump , 2018 .

[28]  Influence of Hydrodynamics on the Lithium Recovery Efficiency in an Electrochemical Ion Pumping Separation Process , 2017 .

[29]  Yufeng Wu,et al.  An overview of recycling and treatment of spent LiFePO4 batteries in China , 2017 .

[30]  Young Ho Kim,et al.  Selective lithium recovery from aqueous solution using a modified membrane capacitive deionization system , 2017 .

[31]  Meng Zhao,et al.  Study on lithium extraction from brines based on LiMn2O4/Li1-xMn2O4 by electrochemical method , 2017 .

[32]  M. Armand,et al.  A review on hexacyanoferrate-based materials for energy storage and smart windows: challenges and perspectives , 2017 .

[33]  M. Fehse,et al.  High Specific Power Dual-Metal-Ion Rechargeable Microbatteries Based on LiMn2O4 and Zinc for Miniaturized Applications. , 2017, ACS applied materials & interfaces.

[34]  Pankaj K Choubey,et al.  Advance review on the exploitation of the prominent energy-storage element Lithium. Part II: From sea water and spent lithium ion batteries (LIBs) , 2017 .

[35]  L. Nghiem,et al.  Lithium extraction from Chinese salt-lake brines: Opportunities, challenges, and future outlook , 2017 .

[36]  E. Ventosa,et al.  Ultrafast Dischargeable LiMn2O4 Thin-Film Electrodes with Pseudocapacitive Properties for Microbatteries. , 2017, ACS applied materials & interfaces.

[37]  Eric N. Guyes,et al.  A one-dimensional model for water desalination by flow-through electrode capacitive deionization , 2017, ArXiv.

[38]  R. Huggins Review—A New Class of High Rate, Long Cycle Life, Aqueous Electrolyte Battery Electrodes , 2017 .

[39]  S. Vigneswaran,et al.  Mining valuable minerals from seawater: a critical review , 2017 .

[40]  F. L. Mantia,et al.  Optimized Lithium Recovery from Brines by using an Electrochemical Ion‐Pumping Process Based on λ‐MnO2 and Nickel Hexacyanoferrate , 2017 .

[41]  Z. Ji,et al.  Preliminary study on recovering lithium from high Mg2+/Li+ ratio brines by electrodialysis , 2017 .

[42]  B. Swain Recovery and recycling of lithium: A review , 2017 .

[43]  J. Slack,et al.  Cobalt: Chapter F of critical mineral resources of the United States - Economic and environmental geology and prospects for future supply , 2017 .

[44]  A. Ludwig,et al.  Synthesis of nanostructured LiMn2O4 thin films by glancing angle deposition for Li-ion battery applications , 2016, Nanotechnology.

[45]  Pu Chen,et al.  Binder-free flexible LiMn 2 O 4 /carbon nanotube network as high power cathode for rechargeable hybrid aqueous battery , 2016 .

[46]  G. Guan,et al.  A novel electroactive λ-MnO2/PPy/PSS core–shell nanorod coated electrode for selective recovery of lithium ions at low concentration , 2016 .

[47]  Zhengcheng Zhang,et al.  Advanced hybrid battery with a magnesium metal anode and a spinel LiMn2O4 cathode. , 2016, Chemical communications.

[48]  Xinghua Liang Structural and Properties of LiNi0.5Mn1.5O4-δ and LiNi0.5Mn1.5O4 Spinels: A first-Principles Investigation , 2016 .

[49]  Jin-Young Lee,et al.  Advance review on the exploitation of the prominent energy-storage element: Lithium. Part I: From mineral and brine resources , 2016 .

[50]  Kian Ping Loh,et al.  High-performance NaFePO4 formed by aqueous ion-exchange and its mechanism for advanced sodium ion batteries , 2016 .

[51]  E. Calvo,et al.  Surface Chemistry and Lithium-Ion Exchange in LiMn2O4 for the Electrochemical Selective Extraction of LiCl from Natural Salt Lake Brines , 2016 .

[52]  Yi Cui,et al.  Manganese-cobalt hexacyanoferrate cathodes for sodium-ion batteries , 2016 .

[53]  F. L. Mantia,et al.  Lithium recovery by means of electrochemical ion pumping: a comparison between salt capturing and selective exchange , 2016, Journal of physics. Condensed matter : an Institute of Physics journal.

[54]  E. Calvo,et al.  A LiMn2O4-Polypyrrole System for the Extraction of LiCl from Natural Brine , 2016 .

[55]  W. Guo,et al.  Research progress on design strategies, synthesis and performance of LiMn2O4-based cathodes , 2015 .

[56]  Feng Wu,et al.  Structural and Electrochemical Study of Hierarchical LiNi(1/3)Co(1/3)Mn(1/3)O2 Cathode Material for Lithium-Ion Batteries. , 2015, ACS applied materials & interfaces.

[57]  Shumei Dou Review and prospects of Mn-based spinel compounds as cathode materials for lithium-ion batteries , 2015, Ionics.

[58]  F. La Mantia,et al.  Nickel hexacyanoferrate as suitable alternative to Ag for electrochemical lithium recovery. , 2015, ChemSusChem.

[59]  Xinping Ai,et al.  High-Performance Olivine NaFePO4 Microsphere Cathode Synthesized by Aqueous Electrochemical Displacement Method for Sodium Ion Batteries. , 2015, ACS applied materials & interfaces.

[60]  Donghyuk Jang,et al.  Deciphering the thermal behavior of lithium rich cathode material by in situ X-ray diffraction technique , 2015 .

[61]  J. Choi,et al.  An Electrochemical Cell for Selective Lithium Capture from Seawater. , 2015, Environmental science & technology.

[62]  Mamadou S Diallo,et al.  Mining Critical Metals and Elements from Seawater: Opportunities and Challenges. , 2015, Environmental science & technology.

[63]  Y. Sung,et al.  Lithium recovery from brine using a λ-MnO2/activated carbon hybrid supercapacitor system. , 2015, Chemosphere.

[64]  Xinhua Zhao,et al.  Lithium extraction from seawater by manganese oxide ion sieve MnO2·0.5H2O , 2015 .

[65]  F. La Mantia,et al.  An aqueous zinc-ion battery based on copper hexacyanoferrate. , 2015, ChemSusChem.

[66]  Ahmad Azmin Mohamad,et al.  Advances of aqueous rechargeable lithium-ion battery: A review , 2015 .

[67]  H. Gasteiger,et al.  Review—Electromobility: Batteries or Fuel Cells? , 2015 .

[68]  Hongbin Zhao,et al.  Enhancing rate performance of LiMn2O4 cathode in rechargeable hybrid aqueous battery by hierarchical carbon nanotube/acetylene black conductive pathways , 2015, Ionics.

[69]  Synthesis and electrochemical investigation of nanosized LiMn2O4 as cathode material for rechargeable hybrid aqueous batteries , 2014 .

[70]  B. D. Pandey,et al.  Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review , 2014 .

[71]  M. Park,et al.  Recyclable composite nanofiber adsorbent for Li+ recovery from seawater desalination retentate , 2014 .

[72]  S. Franger,et al.  Insights on the electrode/electrolyte interfaces in LiFePO4 based cells with LiAl(Al) and Li(Mg) anodes , 2014 .

[73]  M. Ranjbar,et al.  Recovery of lithium from Urmia Lake by a nanostructure MnO2 ion sieve , 2014 .

[74]  F. L. Mantia,et al.  Selectivity of a lithium-recovery process based on LiFePO4. , 2014, Chemistry.

[75]  K. Ooi,et al.  Lithium recovery from salt lake brine by H2TiO3. , 2014, Dalton transactions.

[76]  Xinxing Liang,et al.  Effect of Na+ on Li extraction from brine using LiFePO4/FePO4 electrodes , 2014 .

[77]  J. A. Milton,et al.  Selective lithium extraction from brines by chemical reaction with battery materials , 2014 .

[78]  K. Ooi,et al.  Synthesis of Iron-Doped Manganese Oxides with an Ion-Sieve Property: Lithium Adsorption from Bolivian Brine , 2014 .

[79]  Lingyun Liu,et al.  A review of blended cathode materials for use in Li-ion batteries , 2014 .

[80]  Yitai Qian,et al.  Uniform LiNi1/3Co1/3Mn1/3O2 hollow microspheres: Designed synthesis, topotactical structural transformation and their enhanced electrochemical performance , 2013 .

[81]  T. Hoshino Development of technology for recovering lithium from seawater by electrodialysis using ionic liquid membrane , 2013 .

[82]  Mikael Höök,et al.  Lithium availability and future production outlooks , 2013 .

[83]  Shuying Sun,et al.  Synthesis and Adsorption Properties of Li1.6Mn1.6O4 Spinel , 2013 .

[84]  Robert U. Ayres,et al.  Lithium: Sources, Production, Uses, and Recovery Outlook , 2013 .

[85]  S. Dou,et al.  Cathode materials for next generation lithium ion batteries , 2013 .

[86]  J. Morales,et al.  On the limited electroactivity of Li2NiTiO4 nanoparticles in lithium batteries , 2013 .

[87]  Kai Zhu,et al.  Aqueous rechargeable lithium batteries as an energy storage system of superfast charging , 2013 .

[88]  T. Hoshino Preliminary studies of lithium recovery technology from seawater by electrodialysis using ionic liquid membrane , 2013 .

[89]  Yung-Eun Sung,et al.  Highly selective lithium recovery from brine using a λ-MnO2-Ag battery. , 2013, Physical chemistry chemical physics : PCCP.

[90]  Lili Liu,et al.  LiMn2O4 nanotube as cathode material of second-level charge capability for aqueous rechargeable batteries. , 2013, Nano letters.

[91]  Xinxing Liang,et al.  Electrochemical behavior of Li+, Mg2+, Na+ and K+ in LiFePO4/ FePO4 structures , 2013 .

[92]  Xinxing Liang,et al.  Li extraction from high Mg/Li ratio brine with LiFePO4/FePO4 as electrode materials , 2013 .

[93]  Zhibing Zhang,et al.  Synthesis of Li+ adsorbent (H2TiO3) and its adsorption properties , 2013 .

[94]  F. L. Mantia,et al.  Batteries for lithium recovery from brines , 2012 .

[95]  Lili Liu,et al.  An aqueous rechargeable lithium battery of excellent rate capability based on a nanocomposite of MoO3 coated with PPy and LiMn2O4 , 2012 .

[96]  Philippe Poggi,et al.  Assessment of world lithium resources and consequences of their geographic distribution on the expected development of the electric vehicle industry , 2012 .

[97]  Björn A. Sandén,et al.  The time dimension and lithium resource constraints for electric vehicles , 2012 .

[98]  S. Franger,et al.  Influence of the lithium salt electrolyte on the electrochemical performance of copper/LiFePO4 composites , 2012 .

[99]  Yi Cui,et al.  A desalination battery. , 2012, Nano letters.

[100]  Yusong Zhu,et al.  Nano LiMn2O4 as cathode material of high rate capability for lithium ion batteries , 2012 .

[101]  Lixia Yuan,et al.  Revisit of Polypyrrole as Cathode Material for Lithium-Ion Battery , 2012 .

[102]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[103]  W. Qin,et al.  Extraction Equilibria of Lithium with Tributyl Phosphate in Three Diluents , 2011 .

[104]  Yi Cui,et al.  Batteries for efficient energy extraction from a water salinity difference. , 2011, Nano letters.

[105]  Philippe Moreau,et al.  Structure and Stability of Sodium Intercalated Phases in Olivine FePO4 , 2010 .

[106]  Xin Jia,et al.  Electrochemical Performance of the LiNi1 / 3Co1 / 3Mn1 / 3O2 in Aqueous Electrolyte , 2010 .

[107]  Julián Morales,et al.  Cycling-induced stress in lithium ion negative electrodes: LiAl/LiFePO4 and Li4Ti5O12/LiFePO4 cells , 2010 .

[108]  J. Morales,et al.  A LiFePO4-Based Cell with Li x ( Mg ) as Lithium Storage Negative Electrode , 2009 .

[109]  E. Rodríguez-Castellón,et al.  Effect of C and Au additives produced by simple coaters on the surface and the electrochemical properties of nanosized LiFePO4 , 2009 .

[110]  Demetrios Anglos,et al.  Mechanisms of the laser plume expansion during the ablation of LiMn2O4 , 2009 .

[111]  P. Novák,et al.  Influence of the substrate material on the properties of pulsed laser deposited thin Li1+xMn2O4−δ films , 2009 .

[112]  Tingfeng Yi,et al.  A review of recent developments in the surface modification of LiMn2O4 as cathode material of power lithium-ion battery , 2009 .

[113]  Yuping Wu,et al.  An aqueous electrochemical energy storage system based on doping and intercalation: Ppy//LiMn2O4. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[114]  N. Sinha,et al.  Electrochemical conversion of LiMn2O4 to MgMn2O4 in aqueous electrolytes , 2008 .

[115]  P. Bruce,et al.  A Stoichiometric Nano-LiMn2O4 Spinel Electrode Exhibiting High Power and Stable Cycling , 2008 .

[116]  A. Wokaun,et al.  Laser-produced plasma ion characteristics in laser ablation of lithium manganate , 2007 .

[117]  Xianming Wu,et al.  The effect of thickness on the properties of solution-deposited LiMn2O4 thin films , 2007 .

[118]  I. Belharouak,et al.  Comparative study of different crystallographic structure of LiNi0.5Mn1.5O4−δ cathodes with wide operation voltage (2.0–5.0 V) , 2007 .

[119]  Tsutomu Ohzuku,et al.  Solid-State Chemistry and Electrochemistry of LiCo1 ∕ 3Ni1 ∕ 3Mn1 ∕ 3O2 for Advanced Lithium-Ion Batteries III. Rechargeable Capacity and Cycleability , 2007 .

[120]  Li Lu,et al.  Comparative study of LiMn2O4 thin film cathode grown at high, medium and low temperatures by pulsed laser deposition , 2006 .

[121]  M. Manickam,et al.  Redox behavior and surface characterization of LiFePO4 in lithium hydroxide electrolyte , 2006 .

[122]  Gerbrand Ceder,et al.  A Combined Computational/Experimental Study on LiNi1/3Co1/3Mn1/3O2 , 2003 .

[123]  J. Amarilla,et al.  The Role of Carbon Black in LiMn2O4-Based Composites as Cathodes for Rechargeable Lithium Batteries , 2001 .

[124]  J. Akimoto,et al.  Single crystal X-ray diffraction study of the spinel-type LiMn2O4 , 2000 .

[125]  Emmanuel Haro-Poniatowski,et al.  Growth of LiMn2O4 thin films by pulsed-laser deposition and their electrochemical properties in lithium microbatteries , 2000 .

[126]  Tao Zheng,et al.  The elevated temperature performance of the LiMn2O4/C system: Failure and solutions , 1999 .

[127]  T. Richardson,et al.  Characterization of pulsed laser-deposited LiMn2O4 thin films for rechargeable lithium batteries , 1998 .

[128]  K. Striebel,et al.  Cyclic voltammetry of pulsed laser deposited Li{sub x}Mn{sub 2}O{sub 4} thin films , 1998 .

[129]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[130]  P. Novák,et al.  Electrochemically Active Polymers for Rechargeable Batteries. , 1997, Chemical reviews.

[131]  E. Uhlemann,et al.  Selective Extraction of Lithium Chloride from Brines , 1993 .

[132]  Y. Miyai,et al.  Electrochemical Recovery of Lithium Ions in the Aqueous Phase , 1993 .

[133]  Y. Miyai,et al.  Selective electroinsertion of lithium ions into a platinum/.lambda.-manganese dioxide electrode in the aqueous phase , 1991 .

[134]  Y. Miyai,et al.  Topotactic lithium(1+) insertion to .lambda.-manganese dioxide in the aqueous phase , 1989 .

[135]  J. J. Fritz Thermodynamic properties of chloro-complexes of silver chloride in aqueous solution , 1985 .

[136]  John B. Goodenough,et al.  Lithium insertion into manganese spinels , 1983 .

[137]  A. E. Torma,et al.  Lithium chloride extraction by n-butanol , 1978 .

[138]  Alan Caruba,et al.  THE SOCIETY OF NAVAL ARCHITECTS AND MARINE ENGINEERS. , 1978 .

[139]  J. Newman,et al.  Electrochemical Removal of Silver Ions from Photographic Fixing Solutions Using a Porous Flow‐Through Electrode , 1977 .

[140]  R. Houghton,et al.  A comparison of the performance of electrochemical reactor designs in the treatment of dilute solutions , 1974 .

[141]  D. Kaplan Process for the Extraction of Lithium from Dead Sea Solutions , 1963 .