WO2021160239A1 - Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses - Google Patents

Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses Download PDF

Info

Publication number
WO2021160239A1
WO2021160239A1 PCT/EP2020/053293 EP2020053293W WO2021160239A1 WO 2021160239 A1 WO2021160239 A1 WO 2021160239A1 EP 2020053293 W EP2020053293 W EP 2020053293W WO 2021160239 A1 WO2021160239 A1 WO 2021160239A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
electrode
dissolved
ions
aqueous lithium
Prior art date
Application number
PCT/EP2020/053293
Other languages
English (en)
Inventor
Yousef M. Alyousef
Radwan ALRASHEED
Saad AL JILIL
Felix HIPPAUF
Thomas Abendroth
Holger Althues
Stefan Kaskel
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
King Abdulaziz City Of Science And Technology Kacst
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., King Abdulaziz City Of Science And Technology Kacst filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority to PCT/EP2020/053293 priority Critical patent/WO2021160239A1/fr
Publication of WO2021160239A1 publication Critical patent/WO2021160239A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Definitions

  • the present invention relates to a method and an apparatus for the extraction of lithium from aqueous lithium sources which contain dissolved lithium, carbonate, calcium and/or magnesium ions.
  • Seawater is available in virtually unlimited supply. It thus is a promising source of lithium despite its low concentration in lithium of approximately 0.17 ppm.
  • Saline waste waters offer the advantage of an increased lithium concentration due to their prior processing. Brines of desalination plants or zero liquid discharge plants or produced waters of gas or oil extrac tion wells are particularly attractive as sources of lithium since they are readily available and high in lithium compared to seawater. The recovery of pure lithium from aqueous lithium sources, however, is challenging due to the presence of different anions and cations in these sources.
  • anions and cations set off parasitic side-reactions or produce undesired chemical species which may degrade the electrodes.
  • a major problem are anions and cations, such as sodium, calcium, potassium, magnesium, chloride, bromide, carbonate or sulphate, which form insoluble compounds at the surfaces of the electrodes.
  • Such deposits act as diffusion barriers to lithium ions at the surface of the electrodes and impair the uptake and the release of lithium at the electrodes.
  • the electrodes presently available are very fragile and less resistant to harsh chemical treatments, the removal of solid deposits from the electrodes is cumbersome, if at all possible, and frequently causes severe damage to the electrodes.
  • the low chemical resistance of the electrodes also places limits on the salinity of aqueous lithium sources to be processed. Hence such lithium recovery processes are currently neither long term stable nor efficient.
  • the present invention is therefore based on the object to overcome these disadvantages by providing a method and an apparatus for an efficient and long term stable lithium extraction from aqueous lithium sources containing dissolved lithium, carbonate, calcium and/or magnesium.
  • a method for extracting lithium from an aqueous lithium source comprises the step of pre-treating an aqueous lithium source containing dissolved lithium ions Li + , dissolved carbonate ions C0 3 2 , dissolved calcium ions Ca 2+ and/or dissolved magnesium ions Mg 2+ by mixing the aqueous lithium source with a scale inhibitor, and the step of electrochemically extracting the dissolved lithium ions Li + from the pre-treated aqueous lithium source in an electrochemical cell which comprises in a housing: a working electrode, a counter electrode and the pre-treated aqueous lithium source as an electro lyte.
  • the working electrode of the electrochemical cell comprises a lithium storage material, a binder and an electrically conductive additive.
  • the scale inhibitor is configured to inhibit the formation of solid carbonate compounds, in particular calcium carbonate, magnesium carbonate and lithium carbonate, in the aqueous lithium source.
  • the dissolved lithium Li + ions of the pre-treated aqueous lithium source are intercalated, i.e. extracted by intercalation, into the lithium storage material of the working electrode.
  • the described method thus allows a highly selective and efficient extraction of Li + ions from aqueous lithium sources despite a high concentration of other anions and cations in the aqueous lithium source.
  • the method may be easily implemented in existing industrial sites and may be used to produce high purity lithium solutions, which may, for example, be used for the production of lithium battery components.
  • the method may be conducted with aqueous lithium sources which exhibit a salinity of more than BO g/l, more than 100 g/l or more than 200 g/l.
  • salinity refers to the total amount of salts dissolved as ions in the aqueous lithium source.
  • a saline solution is meant to be regarded as an aqueous lithium source if the saline solution has a concentration of dissolved lithium ions Li + of at least 0.3 mg/I, preferably at least 10 mg/I, most prefera bly at least 30 mg/I.
  • Aqueous lithium sources may, for example, be provided from sea water or saline industrial waste waters, in particular from brines of desalination or zero liquid discharge plants or produced waters of gas or oil production plants.
  • intercalation and deintercalation refer to the reversible insertion and removal of lithium ions Li + into and from the crystal structure of a lithium storage material.
  • the lithium storage material may be selected from the group of lithium iron phosphates, e.g. LiFeP0 4 , lithium cobalt oxides, e.g. LiCo0 2 , lithium nickel oxides, e.g. LiNi0 2 , lithium nickel cobalt oxides, e.g. LiNii_ x Co x 0 2 , lithium manganese oxides, e.g. LiMn 2 0 4 , lithium nickel manga nese cobalt oxides, e.g. LiNii/ 3 Coi/3Mni/ 3 0 2 , and/or lithium nickel cobalt aluminium oxides, e.g. LiNi 0 .85Co 0 .iAlo.o50 2 .
  • Binders are materials which enhance the cohesion between the lithium storage material and the electrically conductive additive in the working electrodes. Binders are typically made of materials which are chemically and electrochemically inert in the aqueous lithium source.
  • the binder may for example comprise or consist of fibrils. It may preferably be a fibrillated binder in which a material has been formed into fibrils during the fabrication of the working electrode.
  • Suitable materials for binders may for example be chosen from the group of fluoropolymers, e.g. polyvinylidene fluoride (PVDF) and/or polytetrafluoroethylene (PTFE) or from the group of rubbers, e.g. NBR and/or SBR.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • fibril may refer to an elongated filament with an aspect ratio of more than 10, preferably more than 50.
  • the length of filaments may be in the range between 0.2 pm and 500 pm, while their diameter may be in a range between 2 nm and 1 pm.
  • An electrically conductive additive is a material which exhibits an electrical conductivity of more than 10 6 S/m at a temperature of 20 °C.
  • the electrically conductive additive and/or the binder may be finely dispersed in the working electrode.
  • the electrically conductive additive may be an electrochemically inactive carbon material, for example selected from carbon black, porous carbons, carbon nanotubes, graphene, graphite, carbon fibres or mixtures thereof.
  • Carbon nanotubes may be single-walled or multi-walled carbon nanotubes (MWCNTs), e.g. with a length in the range from 0.1 pm to 1000 pm, and a diameter in the range from 0.1 nm to 100 nm.
  • the pre-treatment of the aqueous lithium source with scale-inhibitors does not involve any complex, environmentally harmful, energy- and/or time consuming processing steps or equipment, such as evaporators, crystallization chambers, filters or pumps. It can be easily implemented in a batch, cyclic or a continuous feed stream mode of the aqueous lithium source and does not require any extreme temperatures or harsh pH-regimes.
  • the intercalation of the lithium ions may thus be con ducted in a modest pH-range between 6 and 9 in which the lithium storage material exhibits a high efficiency, while the electrode is consistently pro tected against carbonate scaling.
  • the pre-treatment with scale- inhibitors may be highly selective to calcium and/or magnesium carbonate.
  • undesired lithium compounds may be suppressed and as a result a high amount of dissolved lithium ions remains available for the extraction into the working electrode. This is of particular importance if lithium is to be extracted from aqueous lithium sources with a low content of lithium.
  • Scale inhibitors of the group of organic polymers further offer the great advantage of a good environmental compatibility. If used appropriately, tedious post-treatments for the deposition of the delithiated aqueous lithium source may be avoided.
  • scale inhibitors of the group of organophos- phorus scale inhibitors and/or the group of organic polymer scale inhibitors may be blended together, preferably at ratios between 0.4 to 1.0 relative to each other.
  • the described method may be conducted with a working electrode which exhibits a porosity of at least 50 %, more preferably a porosity of at least 55 %.
  • a high porosity increases the active surface area of the electrode and thus significantly enhances the diffusion and uptake of lithium during the lithium extraction.
  • Film electrodes and/or electrodes with porosities of 50 % or more may be achieved with fibrillated binders, which may for example comprise or consist of PTFE fibrils, and carbon nanotubes as electrically conductive additive in the working electrode.
  • the fibrils and the carbon nanotubes act as highly efficient binder and may enhance both the chemical and the mechanical stability of the working electrode.
  • the working electrode may be a dry-film electrode.
  • an electrode is meant to be regarded a dry-film electrode if the electrode is fabricated in a solvent-free dry-film process in which a film electrode is formed from particulate dry electrode materials without the use of solvents.
  • dry and solvent-free electrode materials i.e. the lithium storage material, the binder and the electrically conductive additive
  • dry and solvent-free electrode materials may be mixed and homogenised in a mortar to form a dry and solvent-free powder mixture.
  • the mixture may be heated and rolled out to a dry and solvent-free film forming the dry-film electrode.
  • the binder e.g. PTFE
  • fibrillated meaning that fibrils are formed in the fabrication of the electrode.
  • These fibrils are an efficient binder in the dry-film electrode.
  • the lithium extraction method may be conducted with dry- film electrodes that are non-toxic and fabricated without any aggressive or environmentally harmful solvents, the environmental performance of the lithium extraction may be improved appreciably. This particularly holds, when multiple working electrodes are used to up-scale the method to an industrial scale, e.g. for the post-processing of waste water from desalination plants, zero liquid discharge plants, gas production plants or oil production plants.
  • the extraction of lithium may for example be performed with a working electrode that comprises spinel-type lithium manganese (III, IV) oxide LiMn 2 0 4 as lithium storage material.
  • Spinel-type lithium manganese (III, IV) oxide LiMn 2 0 4 is a very promising lithium storage material since it allows a highly selective and reversible electrochemical extraction of lithium ions within the electrochemical stability window of aqueous lithium sources and exhibits a good environmental compatibility. Hence the postprocessing of the delithiated aqueous lithium source may be reduced.
  • the working electrode may further comprise polytetrafluoroethyl- ene (PTFE) fibrils as binder and multi-walled carbon nanotubes (MWCNTs) as electrically conductive additive.
  • PTFE polytetrafluoroethyl- ene
  • MWCNTs multi-walled carbon nanotubes
  • the working electrode may for example comprise 85 weight-% to 95 weight-% LiMn 2 0 4 , 2 weight-% to 5 weight-% PTFE fibrils and 3 weight-% to 10 weight-% MWCNTs.
  • These working elec trodes display an excellent chemical and electrochemical stability in harsh chemical environments and may be operated in the electrochemical stability window of pre-treated aqueous lithium sources without irreversible structural changes. They may exhibit a prolonged-lifetime even if they are employed as film electrodes and/or highly porous electrodes in concentrated aqueous lithium sources.
  • the extraction method is highly selective to lithium, it may be used to produce high purity lithium solutions of at least 99.99 % purity, which may be metallised to high purity lithium metal.
  • the high selectivity of the electro chemical extraction step results from the intercalation of lithium ions Li + into the lithium storage material in the working electrode.
  • the redox reactions at the working electrode may take place within the electrochemical stability window of the aqueous lithium source, avoiding the formation of hydrogen or oxygen gas.
  • the stability window ranges from 2.5 V to 3.8 V for pure water on a Li/Li + potential scale and may range from 2 V to 5 V in saline solutions on a Li/Li + potential scale.
  • the dissolved lithium ions Li + may thus be extracted from the pre-treated aqueous lithium source at a working potential of the working electrode in a range between 2.5 V and 3.8 V on a Li/Li + potential scale, possibly in a range between 2 V and 5 V on a Li/Li + potential scale.
  • the lithium ions may be recovered from the working electrode into an aqueous recovery solution, for example a lithium chloride or a lithium hydroxide solution, by reversing the electrochemical cell polarity, wherein the working potential of the working electrode remains within the stability window of water.
  • the counter electrode may be an activated or inert carbon electrode, a graphite electrode, an Ag/AgCI electrode, an electrode based on the Prussian blue structure or a noble metal electrode.
  • the counter electrode may preferably be a non-porous electrode, i.e. an electrode which is manufactured from a non-porous material, in order to avoid the co adsorption of lithium at the counter electrode.
  • the counter electrode may be an inert redox electrode, which merely acts as an electron donor and acceptor in an electrochemical water splitting reaction, such as electrodes comprising glassy carbon, platinum or titanium.
  • Electrodes do not absorb or discharge anions or cations of the aqueous lithium source and are chemically inert in the pre-treated aqueous lithium source. Hence they are very durable and show a long-term stable performance without any additional means of protection or requirements to the ionic composition of the electrolyte.
  • a lithium-recovery unit comprises an electrochemical cell and a mixing unit.
  • the electrochemical cell of the lithium-recovery unit comprises in a housing: a working electrode, a counter electrode and an electrolyte; wherein the working electrode comprises a lithium storage material, binder and an electrically conductive additive.
  • the mixing unit is configured to mix an aqueous lithium source comprising dissolved lithium ions Li + , dissolved carbonate ions C0 3 2 , dissolved calcium ions Ca 2+ and/or dissolved magnesium ions Mg 2+ with a scale inhibitor, wherein the scale inhibitor is configured to inhibit the formation of solid carbonate compounds, in particular calcium and/or magnesium carbonate, in the aqueous lithium source.
  • the mixing unit is further configured to supply the aqueous lithium source mixed with the scale inhibitor as an electrolyte to the electrochemical cell.
  • the electrochemi cal cell is configured to electrochemically intercalate the dissolved lithium ions Li + from the electrolyte into the lithium storage material of the working electrode.
  • Mixing refers to combining the aqueous lithium source and the scale inhibitor to a homogeneous liquid.
  • the scale inhibitor is preferably added to the aqueous lithium source before or during the nucleation stage of the crystal growth of carbonates in the aqueous lithium source.
  • the mixing unit may be separate from the lithium-recovery unit but may in some embodiments be integrated into the electrochemical cell. Mixing may be achieved by stirring and/or by diffusive mixing which may reduce the nucleation sites of calcite crystals in the aqueous lithium source, e.g. by releasing the scale inhibitor at multiple locations in the aqueous lithium source.
  • the lithium-recovery unit described is set up to carry out the described method, that is the described method can be carried out in particular with the lithium-recovery unit described.
  • An exemplary embodiment of the invention is illustrated in the drawing and will be explained below with reference to figures 1 to 5.
  • the singular forms “a”, “an” and “the” include plural referents unless the context indicates otherwise.
  • the terms “a” (or “an”), as well as the terms “one or more,” and “at least one” can be used interchangeably.
  • Fig. 1 illustrates in a schematic diagram an example of a method for extract ing lithium from an aqueous lithium source in a lithium-recovery unit
  • Fig. 2 displays scanning electron microscopy images of a working elec trode of a of a lithium-recovery unit without (left image) and with (right image) scale inhibitors
  • Fig. 3 displays the capacity retention of a working electrode of a lithium- recovery unit without and with scale inhibitors
  • Fig. 4 displays the cyclovoltammogram of an electrochemical cell of a lithium-recovery unit with scale inhibitors
  • Fig. 5 displays discharging/charging voltage curves of an electrochemical cell of a lithium-recovery unit with scale inhibitors.
  • FIG. 1 illustrates in a schematic diagram an example of a method for extracting lithium from an aqueous lithium source in a lithium-recovery unit.
  • an aqueous lithium source 5 which contains dissolved lithium ions Li + , dissolved carbonate ions C0 3 2 ⁇ , dissolved calcium ions Ca 2+ and/or dissolved magnesium ions Mg 2+ is pre-treated SI by mixing the aqueous lithium source 5 with a scale inhibitor 5a.
  • the scale inhibitor 5a is configured to inhibit the formation of solid carbonate compounds, in particu lar calcium carbonate, magnesium carbonate and lithium carbonate, in the aqueous lithium source 5.
  • the dissolved lithium ions Li + are electrochemically extracted S2 from the pre-treated aqueous lithium source 5, 5a in an electro chemical cell which comprises in a housing 1: a working electrode 3, a counter electrode 4 and the pre-treated aqueous lithium source 5, 5a as an electrolyte separating the working electrode 3 and the counter electrode 4 from each other.
  • the working electrode 3 comprises a lithium storage material, a binder and an electrically conductive additive.
  • the dissolved lithium ions Li + are electrochemically extracted S2 from the pre-treated aqueous lithium source 5, 5a in the electrochemical cell by intercalating the dissolved lithium Li + ions into the lithium storage material of the working electrode 3 (cathode).
  • the aqueous lithium source 5 is a waste water brine of a desalination plant with a concentration of dissolved lithium ions Li + of 0.3 mg/I.
  • the lithium extraction method may also be conducted with other aqueous lithium sources 5, in particular aqueous lithium sources 5 with a salinity of more than 30 g/l, more than 100 g/l or even more than 200 g/l and a concentration of dissolved lithium ions Li + of at least 0.3 mg/I, preferably at least 10 mg/I, most preferably at least 30 mg/I.
  • the scale inhibitor 5a may be chosen from the groups of organophosphorus scale inhibitors, in particular from the group of water soluble polymers of phosphonic acid, e.g. aminotrimethylene phosphonic acid (ATMP), ethyl- enediamine-tetramethylene phosphonic acid (EDTMP), diethylenetriamine- pentamethylene phosphonic acid (DETPMP), bis(hexamethylene) triamine- pentamethylene phosphonic acid) (BHMT), pentaethylenehexamine octakis- methylene phosphonic acid (PEHOMP), l-hydroxyethylidene-1,1- diphosphonic acid (HEDP) or phosphino-carboxylic acids (PCA), and/or the group of organic polymer scale inhibitors, including water soluble polymers of maleic anhydride, maleic acid, acrylic acid, methacryclic acid and/or copoly mers thereof, e.g.
  • ATMP aminotrimethylene phosphonic acid
  • a pre-treatment with the scale inhibitors 5a may easily be implemented without negative effects on the lithium intercalation and deintercalation at the working electrode 3. Further more, the scale inhibitors 5a are very efficient and may be applied in small quantities of typically less than 10 mg/I of the aqueous lithium source 5.
  • a dosage of 8 mg/I aqueous lithium source 5 of a non toxic hydrolyzed poly(maleic anhydride) has been used as a scale inhibitor 5a to stabilize the performance of the working electrode 3.
  • scale inhibi tors 5a of the group of organophosphorus scale inhibitors and the group of organic polymer scale inhibitors may exhibit different inhibition mechanisms, they may be blended together for a synergistically enhanced inhibition efficiency. Satisfactory results may for example be attained with the blend of scale inhibitors 5a summarized in table 1.
  • Table 1 Scale inhibitors for the extraction of lithium from aqueous lithium sources 5 in the temperature range from 15 °C to 60 °C
  • the working electrode 3 comprises spinel-type lithium manganese (III, IV) oxide LiMn 2 0 4 as lithium storage material, polytetrafluoroethylene (PTFE) fibrils as binder and multi-walled carbon nanotubes (MWCNTs) as electrically conductive additive, for example 85 % to 95 % LiMn 2 0 4 , 2 % to 5 % PTFE fibrils and 3 % to 10 % MWCNTs by weight.
  • LiMn 2 0 4 exhibits a good thermal stability compared to other lithium storage materials. It is chemically and electrochemically stable within the electro chemical stability window of aqueous lithium sources 5 and environmental compatible.
  • thermoly, mechanically and chemically durable working electrode 3 which may be configured as porous and/or thin film electrode for aqueous lithium sources 5 which may be pre-treated with scale inhibitors 5a without any damage to the working electrode.
  • the lithium storage material may be selected from the group of lithium iron phosphates, lithium cobalt oxides, lithium nickel oxides, lithium nickel cobalt oxides, lithium nickel manganese cobalt oxides and/or lithium nickel cobalt aluminium oxides
  • the binder may be selected from the group of fluoropolymers including polyvi- nylidene fluoride (PVDF) or from the group of rubbers, preferably NBR and or SBR
  • the electrically active additive may be selected of the group of electrochemically inactive carbon materials including carbon black, porous carbons, carbon nanotubes, graphene, graphite, carbon fibres or mixtures thereof.
  • the working electrode 3 in the example of figure 1 is a dry-film electrode with a film thickness of 231 pm, a density of 1.9 g/cm 3 and a porosity of 55 %. It has been laminated onto a current collector electrode 3a, e.g. a platinum chip, using an electrically conductive adhesion promoter.
  • the counter electrode 4 may be an activated or inert carbon electrode, a graphite electrode, an Ag/AgCI electrode, an electrode based on the Prussian Blue structure or a noble metal electrode.
  • a mesh of non-porous platinized titanium is utilized as an inert redox counter electrode.
  • Inert redox counter electrodes provide and remove electrons in an electrochemical water splitting reaction without absorbing or discharging anions or cations of the aqueous lithium source. They may therefore be operated independently of a specific composition or specific ionic species in the electrolyte of the electro chemical cell, i.e. in the pre-treated aqueous lithium source.
  • the pre-treated aqueous lithium source 5, 5a in the electrochemical cell may be replaced by an aqueous recovery solution, e.g. an aqueous lithium chloride or lithium hydroxide solution, and the extracted lithium ions may be electrochemically recovered from the working electrode 3 to the recovery solution by reversing the electrochemical cell polarity.
  • an aqueous recovery solution e.g. an aqueous lithium chloride or lithium hydroxide solution
  • the extracted lithium ions may be electrochemically recovered from the working electrode 3 to the recovery solution by reversing the electrochemical cell polarity.
  • the working potential of the working electrode 3 may, like in the case of the intercalation (discharging), remain within the electrochemical stability window of the aqueous recovery solution, in the example of figure 1 in the range between 2.5 V and 3.8 V on a Li/Li + potential scale.
  • the coloumbic efficiency (ratio of discharge capacity to charge capacity) of the working electrode 3 may thus be stabilised above 90 % for more than 50 extraction and
  • Figures 2 and 3 display scanning electron microscopy images and capacity retention results of the working electrode 3 of a lithium recovery unit as described in the example of figure 1.
  • scale inhibitors 5a Without scale inhibitors 5a, the surface of the working electrode 3 is blocked by micrometer-sized crystals, as can be seen in the left image of figure 2.
  • Energy-dispersive X-ray spectroscopy revealed that the crystals are mainly based on calcium and magnesium. The crystals act as a diffusion barrier to lithium ions and lower the capacity retention of the working electrode 3 shown in figure 3 (full square symbols).
  • With the scale inhibitors 5a the growth and/or deposition of such crystals may be suppressed, as seen in the right image of figure 2, and a long term stable capacity retention may be achieved as shown in figure 3 (open triangular symbols).
  • Figures 4 and 5 display a cyclovoltammogram and discharging/charging voltage curves of an electrochemical cell of a lithium recovery unit described in the example of figure 1.
  • the cyclovoltammogram in figure 4 and the discharging/charging voltage curves of figure 5 reveal that the scale inhibi tors 5a enable reversible two-fold phase changes in the lithium storage material during the intercalation and deintercalation of lithium without any parasitic electrochemical reactions of the scale inhibitors 5a.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé et un appareil pour extraire du lithium d'une source aqueuse de lithium comprenant les étapes de prétraitement (S1) d'une source aqueuse de lithium (5) contenant des ions lithium dissous Li+, des ions carbonate dissous C03 2-, des ions calcium dissous Ca2+ et/ou des ions magnésium dissous Mg2+, en mélangeant la source aqueuse de lithium (5) avec un inhibiteur de tartre (5a), l'inhibiteur de tartre (5a) étant configuré pour inhiber la formation de composés carbonatés solides dans la source aqueuse de lithium (5), et l'extraction électrochimique (S2) des ions lithium dissous Li+ dans une cellule électrochimique qui comprend dans un boîtier (1) une électrode de travail (3), une contre-électrode (4) et la source de lithium aqueuse prétraitée (5, 5a) en tant qu'électrolyte ; l'électrode de travail (3) comprenant un matériau de stockage du lithium, un liant et un additif électriquement conducteur, et les ions lithium dissous Li+ étant intercalés à partir de la source de lithium aqueuse prétraitée (5, 5a) dans le matériau de stockage du lithium de l'électrode de travail (3).
PCT/EP2020/053293 2020-02-10 2020-02-10 Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses WO2021160239A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/053293 WO2021160239A1 (fr) 2020-02-10 2020-02-10 Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/053293 WO2021160239A1 (fr) 2020-02-10 2020-02-10 Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses

Publications (1)

Publication Number Publication Date
WO2021160239A1 true WO2021160239A1 (fr) 2021-08-19

Family

ID=69528850

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/053293 WO2021160239A1 (fr) 2020-02-10 2020-02-10 Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses

Country Status (1)

Country Link
WO (1) WO2021160239A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114436376A (zh) * 2022-01-31 2022-05-06 浙江佰辰低碳科技有限公司 一种以mof衍生碳纳米管阵列为基底原位生长普鲁士蓝类似物的电极材料及其制备方法
WO2024164415A1 (fr) * 2023-02-09 2024-08-15 广东邦普循环科技有限公司 Matériau d'électrode positive modifié, feuille d'électrode d'extraction de lithium électrochimique, son procédé de préparation et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198081A (en) * 1991-03-04 1993-03-30 Japan As Represented By Director General Of Agency Of Industrial Science And Technology Method and electrode for electrochemical recovery of lithium value from aqueous solution
EP2851454A1 (fr) * 2012-05-16 2015-03-25 SNU R&DB Foundation Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée
CN109440132A (zh) * 2018-10-17 2019-03-08 武汉大学 一种流动式电化学提锂体系
KR20190069693A (ko) * 2017-12-12 2019-06-20 주식회사 셀젠 리튬이온 흡착 및 탈착용 전극모듈의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5198081A (en) * 1991-03-04 1993-03-30 Japan As Represented By Director General Of Agency Of Industrial Science And Technology Method and electrode for electrochemical recovery of lithium value from aqueous solution
EP2851454A1 (fr) * 2012-05-16 2015-03-25 SNU R&DB Foundation Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée
KR20190069693A (ko) * 2017-12-12 2019-06-20 주식회사 셀젠 리튬이온 흡착 및 탈착용 전극모듈의 제조방법
CN109440132A (zh) * 2018-10-17 2019-03-08 武汉大学 一种流动式电化学提锂体系

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114436376A (zh) * 2022-01-31 2022-05-06 浙江佰辰低碳科技有限公司 一种以mof衍生碳纳米管阵列为基底原位生长普鲁士蓝类似物的电极材料及其制备方法
WO2024164415A1 (fr) * 2023-02-09 2024-08-15 广东邦普循环科技有限公司 Matériau d'électrode positive modifié, feuille d'électrode d'extraction de lithium électrochimique, son procédé de préparation et son utilisation

Similar Documents

Publication Publication Date Title
Trócoli et al. Optimized lithium recovery from brines by using an electrochemical Ion‐Pumping process based on λ‐MnO2 and nickel hexacyanoferrate
Chen et al. Dual-ions electrochemical deionization: a desalination generator
Kasiri et al. Mixed copper-zinc hexacyanoferrates as cathode materials for aqueous zinc-ion batteries
Zhou et al. Progress in electrochemical lithium ion pumping for lithium recovery
Lee et al. Highly selective lithium recovery from brine using a λ-MnO 2–Ag battery
Chen et al. Chemical coupling constructs amorphous silica modified LiNi0. 6Co0. 2Mn0. 2O2 cathode materials and its electrochemical performances
Zhao et al. Semi-continuous electrochemical extraction of lithium from brine using CF-NMMO/AC asymmetric hybrid capacitors
US20140076734A1 (en) Method and electrochemical device for low environmental impact lithium recovery from aqueous solutions
Lawagon et al. Li1− xNi0. 5Mn1. 5O4/Ag for electrochemical lithium recovery from brine and its optimized performance via response surface methodology
US8663844B2 (en) Rechargeable zinc ion battery
CN101783419B (zh) 一种可充电的锌离子电池
Cho et al. Effects of CeO2 coating uniformity on high temperature cycle life performance of LiMn2O4
US9199850B2 (en) Method of fabricating LiFePO4 cathode electroactive material by recycling, and LiFePO4 cathode electroactive material, LiFePO4 cathode, and lithium secondary battery fabricated thereby
TW201001784A (en) Sodium ion based aqueous electrolyte electrochemical secondary energy storage device
WO2013134114A2 (fr) Procédé et appareil pour l'extraction d'énergie et de métal à partir d'électrodes à eau de mer
Niu et al. An electrically switched ion exchange system with self-electrical-energy recuperation for efficient and selective LiCl separation from brine lakes
WO2021160239A1 (fr) Procédé et appareil pour l'extraction de lithium à partir de sources de lithium aqueuses
Usui et al. Novel composite thick-film electrodes consisted of zinc oxide and silicon for lithium-ion battery anode
Tan et al. Reduced Lattice Constant in Al‐Doped LiMn2O4 Nanoparticles for Boosted Electrochemical Lithium Extraction
Song et al. Progress and challenges of Prussian blue analogs for potassium-ion batteries: a perspective on redox-active transition metals
Gu et al. Particle size control and electrochemical lithium extraction performance of LiMn2O4
Zhang et al. Cross-linked PVDF-b-PAA composite binder enhanced LiMn2O4/C film based electrode for selective extraction of lithium from brine with a high Mg/Li ratio
Son et al. Seawater battery desalination with sodium-intercalation cathode for hypersaline water treatment
WO2021160240A1 (fr) Procédé et appareil d'extraction électrochimique de lithium à partir de sources de lithium aqueuses
CN105489884B (zh) 化学还原氧化石墨烯/镁改善镍钴锰酸锂电化学性能的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20704520

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20704520

Country of ref document: EP

Kind code of ref document: A1