WO2024250154A1 - Bain électrolytique à membrane céramique pour extraire du lithium à partir d'un lac salé au moyen d'une désintercalation électrique, et dispositif et procédé d'électrolyse pour l'extraction de lithium à partir d'un lac salé au moyen d'une désintercalation électrique - Google Patents

Bain électrolytique à membrane céramique pour extraire du lithium à partir d'un lac salé au moyen d'une désintercalation électrique, et dispositif et procédé d'électrolyse pour l'extraction de lithium à partir d'un lac salé au moyen d'une désintercalation électrique Download PDF

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WO2024250154A1
WO2024250154A1 PCT/CN2023/098367 CN2023098367W WO2024250154A1 WO 2024250154 A1 WO2024250154 A1 WO 2024250154A1 CN 2023098367 W CN2023098367 W CN 2023098367W WO 2024250154 A1 WO2024250154 A1 WO 2024250154A1
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lithium
electrode
ceramic membrane
deintercalation
electro
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PCT/CN2023/098367
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English (en)
Chinese (zh)
Inventor
李爱霞
谢英豪
余海军
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/098367 priority Critical patent/WO2024250154A1/fr
Priority to CN202380009315.XA priority patent/CN117043365B/zh
Priority to ARP240101178A priority patent/AR132643A1/es
Publication of WO2024250154A1 publication Critical patent/WO2024250154A1/fr
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • the present disclosure relates to the technical field of lithium extraction from salt lakes, and in particular to a ceramic membrane electrolytic cell for electro-deintercalation of lithium from salt lakes, and an electrolytic device and method for electro-deintercalation of lithium from salt lakes.
  • Methods for extracting lithium from salt lake brine include evaporation crystallization, electrodialysis, extraction, precipitation, adsorption and ion exchange.
  • the extraction method is easy to operate, highly selective, and conducive to industrial production, but the large amount of organic reagents used will corrode equipment and pollute the environment.
  • the adsorption method is cost-effective and efficient, but the permeability and solubility of the adsorbent are poor, and a large amount of acidic solution is required, resulting in the generation of a large amount of waste liquid, which limits its industrial application.
  • Traditional lithium extraction methods have problems such as high cost, high energy consumption, and low separation efficiency.
  • electro-deintercalation is considered to be a salt lake lithium extraction technology with great development potential due to its good selectivity, high recovery rate, and no pollution.
  • the LiFePO 4 /FePO 4 "rocking chair" structure electrode system is used to achieve simultaneous extraction and recovery of lithium on different electrodes.
  • salt lake brine contains multiple cations such as Na + , K + , Mg 2+ , which will inevitably participate in the electrochemical reaction and embed into the electrode material, which not only reduces the purity of lithium ions, but also reduces the exchange capacity of the electrode for lithium.
  • the purpose of the present disclosure includes providing a ceramic membrane electrolytic cell for extracting lithium from salt lakes by electro-deintercalation.
  • the purpose of the present disclosure includes providing an electrolysis device for extracting lithium from salt lakes through electro-deintercalation.
  • the present disclosure also aims to provide a method for extracting lithium from salt lakes by electro-deintercalation.
  • the present disclosure provides a ceramic membrane electrolytic cell for extracting lithium from a salt lake by electro-deintercalation, which includes a bottom wall and multiple side walls, wherein the multiple side walls are connected to the bottom wall to form a trough-like structure, and both the bottom wall and the side walls are made of lithium ion conductor ceramic materials.
  • the lithium ion conductor ceramic material includes lithium zirconium oxide or lithium titanium oxide.
  • the method for preparing the ceramic membrane electrolyzer includes:
  • the lanthanum zirconium oxide or lanthanum titanium oxide and the lithium source are mixed and ground evenly to obtain a mixed material, and the mixed material is pre-sintered and then cooled to room temperature to obtain a pre-sintered material;
  • the green blank is sintered to obtain the ceramic membrane electrolytic cell.
  • the lanthanum zirconium oxide or the lanthanum titanium oxide and the lithium source are ball-milled at a rotation speed of 150-200 r/min for 2-3 hours to obtain a mixed material.
  • the pre-sintering includes heating the temperature to 800-1000° C. at a heating rate of 3-7° C./min, keeping the temperature for 3-5 hours, and then cooling the temperature to room temperature in the furnace.
  • the pre-sintered material is ball-milled again at a rotation speed of 150-200/min for 2-3 hours to obtain the mother powder.
  • sintering the green billet comprises: heating the temperature to 1200-1400° C. at a heating rate of 3-7° C./min, keeping the temperature for 8-12 minutes, and then cooling with the furnace.
  • the bottom wall and the side wall are both film-like structures with a thickness of 1-10 mm.
  • the thickness of the bottom wall and the side wall is 1-5 mm.
  • the present disclosure provides an electrolytic device for extracting lithium from a salt lake through electro-deintercalation, which comprises the ceramic membrane electrolytic cell described in the above embodiment.
  • the electrolysis device for extracting lithium from a salt lake by electro-deintercalation also includes an outer electrolysis cell, a cation exchange membrane, a first electrode, and a second electrode.
  • the cation exchange membrane vertically divides the outer electrolysis cell into a cathode chamber and an anode chamber.
  • the ceramic membrane electrolytic cell is placed in the cathode chamber.
  • One of the first electrode and the second electrode is provided in the ceramic membrane electrolytic cell, and the other of the first electrode and the second electrode is provided in the anode chamber.
  • the first electrode is a lithium-intercalated electrode.
  • the method for preparing the lithium-intercalated electrode comprises:
  • the electrode active material, conductive carbon black, PVDF and N-methylpyrrolidone are mixed and ground into a slurry, the slurry is coated on a current collector, and dried to obtain a lithium extraction electrode;
  • the lithium extraction electrode is placed in a NaCl solution to de-lithiate and form a lithium insertion electrode.
  • the masses of the conductive carbon black, the PVDF and the N-methylpyrrolidone are 5-15%, 10-15% and 150-200% of the mass of the electrode active material, respectively.
  • the current collector includes a titanium mesh, a carbon fiber cloth, a carbon fiber felt, a porous carbon substrate, or a titanium plate, and the thickness of the current collector is 0.1-2 mm.
  • a voltage of 1-1.2 V is applied during the delithiation, the concentration of the NaCl solution is 0.4-0.6 mol/L, and the delithiation time is 4-10 h.
  • the second electrode is an inert electrode.
  • the second electrode is placed in a 0.4-0.6 mol/L LiCl solution for cyclic voltammetry scanning activation before use.
  • the present disclosure provides a method for extracting lithium from a salt lake by electro-deintercalation, which is carried out using the electrolysis device for extracting lithium from a salt lake by electro-deintercalation as described in the above embodiment.
  • the cathode chamber is filled with brine
  • the anode chamber and the ceramic membrane electrolyzer are both filled with water.
  • the first electrode is inserted into the ceramic membrane electrolyzer as a cathode
  • the second electrode is inserted into the anode chamber as an anode.
  • a voltage is applied to both ends of the first electrode and the second electrode to perform electrolytic lithium extraction.
  • the lithium ions in the brine are embedded in the first electrode to obtain a lithium-rich electrode.
  • the brine is replaced with a recovery liquid, and a reverse voltage is applied.
  • the lithium-rich electrode serves as an anode and the second electrode serves as a cathode.
  • the lithium ions in the lithium-rich electrode are released into the recovery liquid to enrich the lithium in the brine in the recovery liquid.
  • the brine includes one or more of sulfate brine, chloride brine and carbonate brine.
  • the concentration of impure cations in the brine is greater than 200 g/L.
  • the water includes at least one of pure water, high-purity water, ultrapure water, deionized water, distilled water and double-distilled water.
  • the recovery liquid is a 40-60 mmol/L lithium chloride solution.
  • the voltage applied to both ends of the first electrode and the second electrode is 1.5-4.5V.
  • the time for electrolysis to extract lithium is 0.5-3h.
  • the beneficial effects of the present invention include:
  • the lithium ion conductor ceramic membrane is a lithium solid lithium-containing compound with the ability to conduct lithium rapidly.
  • the holes contained in its crystal structure are just enough for lithium ions to pass through, and it has a preferential permeability to Li + .
  • the present invention forms a ceramic membrane electrolytic cell by using the lithium ion conductor ceramic membrane as the bottom wall and the side wall, so that the ceramic membrane electrolytic cell has the effect of preferentially permeating Li + .
  • the ceramic membrane electrolytic cell provided by the present invention can be arranged in the brine of an electrolytic device for extracting lithium from a salt lake by electro-deintercalation. Water is added to the ceramic membrane electrolytic cell, and a lithium-intercalated electrode is placed therein as a cathode.
  • the Li + in the brine moves toward the cathode, preferentially passes through the ceramic membrane electrolytic cell and is separated from other impurity cations, and is initially enriched in the water, which is beneficial to reducing the influence of impurity cations on the electro-deintercalation process.
  • the preparation method of the lithium ion ceramic membrane is simple, easy to mass produce, and has low cost.
  • the cathode produces hydrogen under the action of the electric field, and lithium ions preferentially pass through the ceramic.
  • the membrane electrolyzer enters the water and embeds the electrode under the action of the electric field.
  • the solution of the ceramic membrane electrolyzer is a lithium-containing aqueous solution.
  • the coexisting impurity cations in the solution of the ceramic membrane electrolyzer are less, and the viscosity of the solution is lower than that of the brine. Therefore, lithium can be extracted at a higher potential without the occurrence of impurity ions embedded in the electrode, thereby improving the purity of the recovered lithium and the exchange capacity of the electrode for lithium extraction, thereby improving the efficiency of lithium extraction.
  • the rate of lithium ion transport from brine to the ceramic membrane electrolyzer across the membrane can be increased, further improving the efficiency of lithium extraction and shortening the lithium extraction time.
  • the generation of chlorine can be avoided when extracting lithium at a high potential, the anode undergoes hydrolysis to produce oxygen, and the generated hydrogen ions enter the brine through the cation exchange membrane, increasing the acidity of the brine, and avoiding the formation of impurities such as magnesium hydroxide during the lithium extraction process, which are precipitated on the lithium ion ceramic membrane to hinder the passage of lithium ions.
  • FIG1 is a diagram showing the working principle of the method for extracting lithium from salt lakes by electro-deintercalation provided in the present invention.
  • Icons 100 - electrolytic device for extracting lithium from salt lakes by electro-deintercalation; 101 - ceramic membrane electrolytic cell; 102 - electrolytic outer cell; 103 - cation exchange membrane; 104 - first electrode; 105 - second electrode.
  • any values of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
  • the present disclosure provides a ceramic membrane electrolytic cell, which can be used in preparing an electrolytic device for extracting lithium from a salt lake through electro-deintercalation.
  • the ceramic membrane electrolyzer includes a bottom wall and a plurality of side walls, the plurality of side walls are connected to the bottom wall to form a trough-like structure, and the bottom wall and the side walls are both made of lithium ion conductor ceramic materials.
  • the bottom wall and the side walls in the present disclosure are both thin-film-shaped.
  • the lithium ion conductor ceramic membrane is a membrane structure that can be used as a partition membrane between the cathode chamber and the anode chamber.
  • the present disclosure innovatively prepares the lithium ion conductor ceramic membrane into a trough-shaped structure to form a ceramic membrane electrolytic cell, and places the ceramic membrane electrolytic cell in brine.
  • the lithium ion conductor ceramic material includes a garnet type ceramic material or a Li 3x La 2/3-x TiO type ceramic material.
  • the garnet type ceramic material is made of lithium zirconium oxide, and the Li 3x La 2/3-x TiO type ceramic material is made of lithium titanium oxide.
  • the preparation method of the ceramic membrane electrolyzer includes:
  • Lanthanum zirconium oxide or lanthanum titanium oxide and a lithium source are mixed and ground evenly to obtain a mixed material, and the mixed material is pre-sintered and then cooled to room temperature to obtain a pre-sintered material.
  • the lanthanum zirconium oxide is specifically lanthanum oxide and zirconium oxide
  • the lanthanum titanium oxide is specifically lanthanum oxide and titanium oxide
  • the lithium source can be, for example, lithium hydroxide
  • the mass fractions of lithium hydroxide, lanthanum oxide and zirconium oxide are 10-30%: 40-60%: 20-40% respectively
  • the mass fractions of lithium hydroxide, lanthanum oxide and titanium oxide are 10-30%: 40-60%: 20-40% respectively.
  • the lanthanum zirconium oxide or lanthanum titanium oxide and the lithium source are ball milled at a speed of 150-200r/min for 2-3h to obtain a mixed material.
  • the pre-sintering includes heating to 800-1000°C at a heating rate of 3-7°C/min, keeping the temperature for 3-5 hours and then cooling to room temperature with the furnace.
  • the ball milling speed can be, for example, any one of 150, 160, 170, 180, 190, 200 r/min, or a range value between any two of them;
  • the ball milling time can be, for example, any one of 2, 2.2, 2.5, 2.7, 2.8, 3 h, or a range value between any two of them;
  • the pre-sintering heating rate can be, for example, any one of 3, 4, 5, 6, 7 ° C/min, or a range value between any two of them;
  • the pre-sintering temperature can be, for example, any one of 800, 850, 900, 950, 1000 ° C, or a range value between any two of them;
  • the pre-sintering holding time can be, for example, any one of 3, 3.5, 4, 4.5, 5 h, or a range value between any two of them.
  • the pre-sintered material is ball-milled again at a rotation speed of 150-200 r/min for 2-3 hours to obtain a mother powder of a lithium ion conductor ceramic material.
  • the rotation speed of the pre-sintered material for ball milling again is, for example, any one of 150, 160, 170, 180, 190, 200 r/min or a range between any two of them;
  • the ball milling time can be, for example, any one of 2, 2.2, 2.5, 2.7, 2.8, 3 h or a range between any two of them.
  • the sintering of the green blank includes: heating to 1200-1400°C at a heating rate of 3-7°C/min, keeping the temperature for 8-12 minutes and then cooling with the furnace.
  • the thickness of the prepared lithium ion conductor ceramic membrane is 1-10mm, and the thickness of the lithium ion conductor ceramic membrane is 1-5mm.
  • the heating rate of sintering can be, for example, any one of 3, 4, 5, 6, 7 ° C / min or a range between any two of them;
  • the sintering temperature can be, for example, any one of 1200, 1250, 1300, 1350, 1400 ° C or a range between any two of them;
  • the sintering holding time can be, for example, 8, 9, 10, 11, 12 minutes. Either one or a range of values between any two.
  • the present disclosure also provides an electrolytic device 100 for extracting lithium from a salt lake by electro-deintercalation.
  • the electrolytic device 100 for extracting lithium from a salt lake also includes an electrolytic outer cell 102, a cation exchange membrane 103, a first electrode 104 and a second electrode 105.
  • the cation exchange membrane 103 vertically divides the electrolytic outer cell 102 into a cathode chamber and an anode chamber.
  • the ceramic membrane electrolytic cell 101 is placed in the cathode chamber, and brine is contained in the cathode chamber.
  • the anode chamber and the ceramic membrane electrolytic cell 101 are both filled with water.
  • One of the first electrode 104 and the second electrode 105 is provided in the ceramic membrane electrolytic cell 101, and the other of the first electrode 104 and the second electrode 105 is provided in the anode chamber.
  • the preparation method of the lithium-intercalated electrode comprises:
  • the mass of conductive carbon black, PVDF and N- methylpyrrolidone is 5-15%, 10-15% and 150-200 % of the mass of the electrode active material, respectively.
  • the current collector includes titanium mesh, carbon fiber cloth, carbon fiber felt, porous carbon substrate or titanium plate, and the thickness of the current collector is 0.1-2mm.
  • the lithium-extracting electrode is placed in a NaCl solution to de-lithiate and form a lithium-intercalated electrode.
  • the voltage applied during delithiation is any one of 1, 1.1, and 1.2 V or a range between any two of them; the concentration of the NaCl solution is any one of 0.4, 0.5, and 0.6 mol/L or a range between any two of them; and the delithiation time is any one of 4, 5, 6, 7, 8, 9, and 10 h or a range between any two of them.
  • the inert electrode includes but is not limited to an activated carbon electrode, a platinum electrode and a graphite electrode. Before use, the second electrode is placed in a 0.4-0.6 mol/L LiCl solution for cyclic voltammetry scanning activation.
  • the present disclosure also provides a method for extracting lithium from a salt lake by electro-deintercalation, which is performed using the electrolysis device 100 for extracting lithium from a salt lake by electro-deintercalation according to the above embodiment.
  • the method for extracting lithium from a salt lake by electro-deintercalation includes filling a cathode chamber with brine, filling an anode chamber and a ceramic membrane electrolytic cell 101 with water, inserting a first electrode 104 as a cathode into the ceramic membrane electrolytic cell 101, and inserting a second electrode 105 as an anode into the anode chamber, applying a voltage (1.5-4.5V) to both ends of the first electrode 104 and the second electrode 105 for electrolytic lithium extraction for 0.5-3h, and during the electrolytic lithium extraction, lithium ions in the brine are intercalated into the first electrode 104 to obtain a lithium-rich electrode, and after the lithium extraction process is completed, the brine is replaced with a recovery liquid (40-60mmol/L lithium chloride solution), and a reverse voltage is applied, the lithium-rich electrode is used as an anode, and the second electrode 105 is used as a cathode, and the lithium ions in the lithium-rich electrode are de
  • the voltage applied to the first electrode 104 and the second electrode 105 is 1.5, 2, 2.5
  • the voltage of the electrolytic lithium extraction device is any one of 3, 3.5, 4, and 4.5 V or any range between two of them; the time for electrolytic lithium extraction is any one of 0.5, 0.8, 1, 1.5, 2, 2.5, and 3 h or any range between two of them.
  • salt lake brine contains Na + , K + , Mg 2+ and other cations coexisting, it is inevitable that they will participate in the electrochemical reaction and be embedded in the electrode material.
  • the degree of the coexisting cations embedding the electrode reaction depends on the electrode potential in the actual electrolyte solution and the concentration of the coexisting cations in the brine.
  • Most of China's salt lakes are high magnesium-lithium ratio salt lakes, and the concentration of lithium ions is low.
  • the electrode potential is usually increased during the electro-deintercalation and lithium extraction.
  • the embedding potential order of cations in the brine is ER , Li + > ER , Na + > ER , Mg2+ > ER , K + , so it is mainly sodium ions and magnesium ions in the brine that have a greater impact on the embedding of lithium ions, and other impurity cations are mainly adsorbed on the electrode surface to affect the embedding of lithium. For this reason, it is necessary to control the concentration of impurity cations in the brine, especially the concentration of sodium ions and magnesium ions, resulting in a small range of brines targeted.
  • the method for extracting lithium from salt lakes by electro-deintercalation provided in the present disclosure can be used for brine with a coexisting cation concentration greater than 200 g/L. It can be seen that the concentration requirement of coexisting impurity cations in the brine applicable to the present disclosure is lower, which greatly expands the scope of application of the method for extracting lithium from salt lakes by electro-deintercalation.
  • the lithium ion conductor ceramic membrane is a lithium solid lithium-containing compound with the ability to conduct lithium rapidly.
  • the holes contained in its crystal structure are just enough for lithium ions to pass through, and it has a preferential permeability to Li + .
  • the present disclosure forms a ceramic membrane electrolytic cell by using the lithium ion conductor ceramic membrane as the bottom wall and the side wall, so that the ceramic membrane electrolytic cell has the effect of preferentially permeating Li + .
  • the ceramic membrane electrolytic cell provided by the present disclosure can be arranged in the brine of the electrolysis device 100 for extracting lithium from a salt lake by electro-deintercalation. Water is added to the ceramic membrane electrolytic cell, and a lithium-intercalated electrode is placed therein as a cathode.
  • the Li + in the brine moves toward the cathode, preferentially passes through the ceramic membrane electrolytic cell and is separated from other impurity cations, and is initially enriched in the water, which is beneficial to reducing the influence of impurity cations on the electro-deintercalation process.
  • the preparation method of the lithium ion ceramic membrane is simple, easy to mass produce, and low in cost.
  • the solution of the ceramic membrane electrolytic cell is a lithium-containing aqueous solution.
  • impurity cations there are fewer coexisting impurity cations in the solution of the ceramic membrane electrolytic cell, and the viscosity of the solution is lower than that of the brine.
  • lithium extraction can be carried out at a higher electric potential without the occurrence of impurity ions embedded in the electrode, thereby improving the purity of the recovered lithium and the lithium extraction exchange capacity of the electrode, thereby improving the efficiency of lithium extraction.
  • the rate of cross-membrane transport of lithium ions from brine to the ceramic membrane electrolytic cell can be increased, further improving the lithium extraction efficiency and shortening the lithium extraction time.
  • the anode chamber is water, and a cation exchange membrane is used to separate the anode chamber from the brine.
  • the production of chlorine can be avoided when extracting lithium.
  • Hydrolysis occurs at the anode to produce oxygen, and the generated hydrogen ions enter the brine through the cation exchange membrane, increasing the acidity of the brine and avoiding the formation of impurities such as magnesium hydroxide during the lithium extraction process that precipitate on the lithium ion ceramic membrane and hinder the passage of lithium ions.
  • This embodiment provides a method for extracting lithium from a salt lake by electro-deintercalation, which comprises the following steps:
  • LiFePO4 active material, conductive carbon black and PVDF are added to N-methylpyrrolidone and repeatedly ground into a slurry, the slurry is coated on a titanium mesh, and dried to obtain a lithium extraction electrode.
  • the mass of conductive carbon black, PVDF and N-methylpyrrolidone is 10%, 12% and 150% of the mass of the electrode active material, respectively.
  • Electrode activation The prepared lithium extraction electrode was placed in a 0.5 mol/L NaCl solution at a voltage of 1.1 V to delithiate for 7 h to form a lithium-intercalated FePO 4 electrode.
  • the activated carbon electrode was activated by cyclic voltammetry scanning in a 0.5 mol/L LiCl solution.
  • the mother powder was placed in an electrolytic cell-shaped mold and pressed into a blank.
  • the blank was subjected to secondary sintering, heated to 1300°C at 5°C/min, kept warm for 10 minutes, and then cooled with the furnace to obtain LLTO with a thickness of 3mm.
  • the outer electrolytic cell is vertically divided into a cathode chamber and an anode chamber by a cation exchange membrane.
  • the cathode chamber is filled with brine
  • the anode chamber and the ceramic membrane electrolytic cell are both filled with pure water.
  • the ceramic membrane electrolytic cell is placed in the cathode chamber, and the lithium extraction electrode is placed in the ceramic membrane electrolytic cell as the cathode, and the activated carbon is placed in the anode chamber as the anode, as shown in Figure 1.
  • composition of the brine is: 0.35 g/L Li, 105.65 g/L Na, 107.97 g/L Mg, 8.45 g/L K, 2.76 g/L Ca, 10.54 g/L SO42- .
  • Lithium extraction by electrolysis A voltage of 3 V was applied to both ends of the electrodes for electrolysis for 1.5 h. During the lithium extraction by electrolysis, the lithium ions in the brine were embedded in the first electrode to obtain a lithium-rich electrode LiFePO 4 . After the lithium extraction process was completed, the brine was replaced with a recovery solution (50 mmol/L lithium chloride solution) and a reverse voltage was applied. The LiFePO 4 electrode was used as the anode and the activated carbon electrode was used as the cathode. After 1.5 h of electrolysis, the lithium ions in the electrode material were released into the recovery solution.
  • This embodiment provides a method for extracting lithium from a salt lake by electro-deintercalation, which comprises the following steps:
  • LiFePO4 active material, conductive carbon black and PVDF are added to N-methylpyrrolidine
  • the ketone is repeatedly ground into a slurry, the slurry is coated on a titanium mesh, and dried to obtain a lithium extraction electrode.
  • the mass of conductive carbon black, PVDF and N-methylpyrrolidone is 15%, 10% and 200% of the mass of the electrode active material respectively.
  • Electrode activation The prepared lithium extraction electrode was placed in a 0.5 mol/L NaCl solution at a voltage of 1.2 V to delithiate for 4 h to form a lithium-intercalated FePO 4 electrode, and the activated carbon electrode was activated by cyclic voltammetry scanning in a 0.5 mol/L LiCl solution.
  • the mother powder was placed in an electrolytic cell-shaped mold and pressed into a blank.
  • the blank was subjected to secondary sintering, heated to 1300°C at 5°C/min, kept warm for 10 minutes, and then cooled with the furnace to obtain LLTO with a thickness of 5mm.
  • the outer electrolytic cell is vertically divided into a cathode chamber and an anode chamber by a cation exchange membrane.
  • the cathode chamber is filled with brine
  • the anode chamber and the ceramic membrane electrolytic cell are both filled with pure water.
  • the ceramic membrane electrolytic cell is placed in the cathode chamber, and the lithium extraction electrode is placed in the ceramic membrane electrolytic cell as the cathode, and the activated carbon is placed in the anode chamber as the anode, as shown in Figure 1.
  • composition of the brine is: 0.35 g/L Li, 105.65 g/L Na, 107.97 g/L Mg, 8.45 g/L K, 2.76 g/L Ca, 10.54 g/L SO42- .
  • a voltage of 4.5 V is applied to both ends of the electrode for electrolysis for 0.5 h, and then the brine is replaced with a recovery liquid and a reverse voltage is applied.
  • the LiFePO4 electrode serves as the anode and the activated carbon electrode serves as the cathode. After electrolysis for 0.5 h, the lithium ions in the electrode material are released into the recovery liquid.
  • This embodiment provides a method for extracting lithium from a salt lake by electro-deintercalation, which comprises the following steps:
  • LiFePO4 active material, conductive carbon black and PVDF are added to N-methylpyrrolidone and repeatedly ground into a slurry, the slurry is coated on a titanium mesh, and dried to obtain a lithium extraction electrode.
  • the mass of conductive carbon black, PVDF and N-methylpyrrolidone is 5%, 15% and 150% of the mass of the electrode active material, respectively.
  • Electrode activation The prepared lithium extraction electrode was placed in a 0.5 mol/L NaCl solution at a voltage of 1.0 V to delithiate for 10 h to form a lithium-intercalated FePO 4 electrode, and the activated carbon electrode was activated by cyclic voltammetry scanning in a 0.5 mol/L LiCl solution.
  • the mother powder was placed in an electrolytic cell-shaped mold and pressed into a blank.
  • the blank was sintered twice, heated to 1300°C at 5°C/min, kept at this temperature for 10 minutes, and then cooled with the furnace to obtain LLTO with a thickness of 1mm.
  • the outer electrolytic cell is vertically divided into a cathode chamber and an anode chamber by a cation exchange membrane.
  • the cathode chamber is filled with brine
  • the anode chamber and the ceramic membrane electrolytic cell are both filled with pure water.
  • the ceramic membrane electrolytic cell is placed in the cathode chamber, and the lithium extraction electrode is placed in the ceramic membrane electrolytic cell as the cathode, and the activated carbon is placed in the anode chamber as the anode, as shown in Figure 1.
  • composition of the brine is: 0.35 g/L Li, 105.65 g/L Na, 107.97 g/L Mg, 8.45 g/L K, 2.76 g/L Ca, 10.54 g/L SO42- .
  • a voltage of 1.5 V is applied to both ends of the electrode for electrolysis for 3 h, and then the brine is replaced with a recovery liquid, and a reverse voltage is applied.
  • the LiFePO4 electrode is used as the anode and the activated carbon electrode is used as the cathode. After electrolysis for 3 h, the lithium ions in the electrode material are released into the recovery liquid.
  • This embodiment provides a method for extracting lithium from a salt lake by electro-deintercalation, which comprises the following steps:
  • LiFePO4 active material, conductive carbon black and PVDF are added to N-methylpyrrolidone and repeatedly ground into a slurry, the slurry is coated on a titanium mesh, and dried to obtain a lithium extraction electrode.
  • the mass of conductive carbon black, PVDF and N-methylpyrrolidone is 10%, 12% and 150% of the mass of the electrode active material, respectively.
  • Electrode activation The prepared lithium extraction electrode was placed in a 0.5 mol/L NaCl solution at a voltage of 1.1 V to delithiate for 7 h to form a lithium-intercalated FePO 4 electrode, and the activated carbon electrode was activated by cyclic voltammetry scanning in a 0.5 mol/L LiCl solution.
  • the mother powder was placed in an electrolytic cell-shaped mold and pressed into a blank.
  • the blank was subjected to secondary sintering, heated to 1200°C at 5°C/min, kept warm for 25 minutes, and then cooled with the furnace to obtain LLZO with a thickness of 3mm.
  • the outer electrolytic cell is vertically divided into a cathode chamber and an anode chamber by a cation exchange membrane.
  • the cathode chamber is filled with brine
  • the anode chamber and the ceramic membrane electrolytic cell are both filled with pure water.
  • the ceramic membrane electrolytic cell is placed in the cathode chamber, and the lithium extraction electrode is placed in the ceramic membrane electrolytic cell as the cathode, and the activated carbon is placed in the anode chamber as the anode, as shown in Figure 1.
  • composition of the brine is: 0.35 g/L Li, 105.65 g/L Na, 107.97 g/L Mg, 8.45 g/L K, 2.76 g/L Ca, 10.54 g/L SO42- .
  • a voltage of 3 V is applied to both ends of the electrode for electrolysis for 1.5 h, and then the brine is replaced with a recovery liquid and a reverse voltage is applied.
  • the LiFePO4 electrode serves as the anode and the activated carbon electrode serves as the cathode. After electrolysis for 1.5 h, the lithium ions in the electrode material are released into the recovery liquid.
  • This embodiment is substantially the same as Embodiment 1, except that, in this embodiment, the electrode active material is LiMn 2 O 4 , the prepared lithium-intercalated electrode is a lithium-intercalated Mn 2 O 4 electrode, and the second electrode is a platinum electrode.
  • the electrode active material is LiMn 2 O 4
  • the prepared lithium-intercalated electrode is a lithium-intercalated Mn 2 O 4 electrode
  • the second electrode is a platinum electrode.
  • This embodiment is substantially the same as Embodiment 1, except that, in this embodiment, the electrode active material is LiNi x Co y Mn z O 2 , the prepared lithium-intercalated electrode is a lithium-intercalated Ni x Co y Mn z O 2 electrode, and the second electrode is a graphite electrode.
  • the electrode active material is LiNi x Co y Mn z O 2
  • the prepared lithium-intercalated electrode is a lithium-intercalated Ni x Co y Mn z O 2 electrode
  • the second electrode is a graphite electrode.
  • This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the thickness of the bottom wall and the side wall of the ceramic membrane electrolytic cell used is 5 mm.
  • This embodiment is basically the same as Embodiment 1, except that, in this embodiment, the thickness of the bottom wall and the side wall of the ceramic membrane electrolytic cell used is 8 mm.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, no ceramic membrane electrolytic cell is used for lithium extraction, that is, step (3) in Example 1 is omitted, and in steps (4) and (5), the cathode lithium-intercalated LiFePO4 is directly inserted into the brine, and a voltage of 3 V is applied across the electrodes for electrolysis for 1.5 h to extract lithium.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, no ceramic membrane electrolytic cell is used for lithium extraction, that is, step (3) in Example 1 is omitted, and in steps (4) and (5), the cathode lithium-intercalated LiFePO4 is directly inserted into the brine, and a voltage of 1 V is applied across the electrodes for electrolysis for 1.5 h to extract lithium.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, the step (5) in Example 1 is applied to both ends of the electrode. The applied voltage is replaced with 1.2V.
  • Example 1 The difference between this comparative example and Example 1 is that the ceramic membrane electrolytic cell used in this comparative example adopts Li 9 SiAlO 8 material.
  • Example 1 The difference between this comparative example and Example 1 is that the thickness of the bottom wall and the side wall of the ceramic membrane electrolytic cell used in this comparative example is 15 mm.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, the pure water contained in the anode chamber in step (4) of Example 1 is replaced with 50 mmol/L lithium chloride solution.
  • the ceramic membrane electrolyzer prepared using the lithium ion ceramic membrane is placed in the cathode chamber and The brine in the cathode chamber is separated from the electrolyte (water) in the ceramic membrane electrolytic cell, so lithium can be extracted at a higher potential.
  • the recovery rate of lithium ions reaches more than 92%, the purity of lithium ions reaches more than 95%, and the exchange capacity of lithium ions reaches more than 29.5 mg (Li) / g (LiFePO 4 ).
  • the lithium ion purity, recovery rate and electrode exchange capacity are significantly improved.
  • Comparative Example 2 reduces the lithium extraction voltage, but the lithium ion concentration, purity and electrode adsorption of the recovered liquid are better than those of Comparative Example 1, but are still significantly worse than those of Example 1. This may be because, as the electrode potential increases, the coexisting impurity cations in the brine are more easily embedded in the electrode, which not only reduces the purity of lithium ions, but also reduces the exchange capacity of the electrode for lithium. Therefore, when lithium extraction is not performed using a ceramic membrane electrolyzer, lithium extraction can only be performed at a lower potential, while Example 1 of the present application can perform lithium extraction at a higher potential, which is beneficial to improving the lithium extraction efficiency. At the same time, it can also avoid the coexisting impurity cations in the brine from being embedded in the electrode, thereby improving the purity of lithium ions and the electrode adsorption.
  • the present disclosure provides a ceramic membrane electrolytic cell, which is made of lithium ion conductor ceramic material, and the lithium ion conductor ceramic material is a lithium solid lithium-containing compound with the ability to conduct lithium rapidly.
  • the holes contained in its crystal structure can just allow lithium ions to pass through, and it has a preferential permeability to Li + .
  • the present disclosure forms a ceramic membrane electrolytic cell by using a lithium ion conductor ceramic membrane as a bottom wall and a side wall, so that the ceramic membrane electrolytic cell has the effect of preferentially permeating Li + .
  • the ceramic membrane electrolytic cell provided by the present disclosure can be arranged in the brine of an electrolysis device 100 for extracting lithium from a salt lake by electro-deintercalation.
  • Li + in the brine moves toward the cathode, preferentially passes through the ceramic membrane electrolytic cell and is separated from other impurity cations, and is initially enriched in pure water, thereby reducing the influence of impurity cations on the electro-deintercalation process.
  • the preparation method of the lithium ion ceramic membrane is simple, easy to mass produce, and low in cost.
  • the cathode Under the action of the electric field, the cathode produces hydrogen, and at the same time, the lithium-ion ceramic membrane electrolyzer enters the water and embeds Into the electrode, at this time, the solution of the ceramic membrane electrolyzer is a lithium-containing aqueous solution, the coexisting impurity cations in the solution of the ceramic membrane electrolyzer are less, and the viscosity of the solution is lower than that of the brine, so lithium can be extracted at a higher potential, and the impurity ions will not be embedded in the electrode, which improves the purity of the recovered lithium, and at the same time improves the exchange capacity of the electrode for lithium extraction, thereby improving the efficiency of lithium extraction.
  • the solution of the ceramic membrane electrolyzer is a lithium-containing aqueous solution, the coexisting impurity cations in the solution of the ceramic membrane electrolyzer are less, and the viscosity of the solution is lower than that of the brine, so lithium can be extracted at a higher potential, and the
  • the rate of lithium ion transport from brine to the ceramic membrane electrolyzer across the membrane can be increased, further improving the efficiency of lithium extraction and shortening the lithium extraction time.
  • the generation of chlorine can be avoided when extracting lithium at a high potential, the anode undergoes hydrolysis to produce oxygen, and the generated hydrogen ions enter the brine through the cation exchange membrane, increasing the acidity of the brine, and avoiding the formation of impurities such as magnesium hydroxide during the lithium extraction process.
  • Precipitation on the lithium ion ceramic membrane hinders the passage of lithium ions.
  • the present disclosure provides a ceramic membrane electrolytic cell, which is prepared from a lithium ion conductor ceramic material, and the lithium ion conductor ceramic material is a lithium solid lithium-containing compound with the ability to conduct lithium rapidly.
  • the holes contained in its crystal structure can just allow lithium ions to pass through, and it has a preferential permeability to Li + .
  • the present disclosure forms a ceramic membrane electrolytic cell by using a lithium ion conductor ceramic membrane as a bottom wall and a side wall, so that the ceramic membrane electrolytic cell has the effect of preferentially permeating Li + .
  • the ceramic membrane electrolytic cell provided by the present disclosure can be arranged in the brine of an electrolysis device for extracting lithium from a salt lake by electro-deintercalation.
  • Li + in the brine moves toward the cathode, preferentially passes through the ceramic membrane electrolytic cell and is separated from other impurity cations, and is initially enriched in pure water, thereby reducing the influence of impurity cations on the electro-deintercalation process.
  • the preparation method of the lithium ion ceramic membrane is simple, easy to mass produce, and low in cost.
  • the cathode produces hydrogen, and at the same time, the lithium ion ceramic membrane electrolyzer enters the water and embeds the electrode under the action of the electric field.
  • the solution of the ceramic membrane electrolyzer is a lithium-containing aqueous solution.
  • the coexisting impurity cations in the solution of the ceramic membrane electrolyzer are less, and the viscosity of the solution is lower than that of the brine. Therefore, lithium can be extracted at a higher potential without the situation of impurity ions being embedded in the electrode, thereby improving the purity of the recovered lithium and the exchange capacity of the electrode for lithium extraction, thereby improving the efficiency of lithium extraction.
  • the rate of lithium ion transport from brine to the ceramic membrane electrolyzer across the membrane can be increased, further improving the efficiency of lithium extraction and shortening the time of lithium extraction.
  • the generation of chlorine can be avoided when extracting lithium at a high potential, the anode undergoes hydrolysis to produce oxygen, and the generated hydrogen ions enter the brine through the cation exchange membrane, increasing the acidity of the brine, and avoiding the formation of impurities such as magnesium hydroxide during the lithium extraction process, which are precipitated on the lithium ion ceramic membrane to hinder the passage of lithium ions.

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  • Electrolytic Production Of Metals (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente divulgation concerne le domaine technique de l'extraction de lithium à partir d'un lac salé, et fournit un bain électrolytique à membrane céramique pour extraire du lithium d'un lac salé au moyen d'une désintercalation électrique, ainsi qu'un dispositif et un procédé d'électrolyse pour l'extraction de lithium à partir d'un lac salé au moyen d'une désintercalation électrique. Dans la présente divulgation, une membrane céramique conductrice d'ions lithium est utilisée en tant que paroi inférieure et paroi latérale, de manière à former un bain électrolytique à membrane céramique, de telle sorte que le bain électrolytique à membrane céramique a pour effet d'imprégner de manière préférentiellement sélective Li+. Le bain électrolytique à membrane céramique selon la présente divulgation peut être disposé dans une saumure d'un dispositif d'électrolyse pour extraire le lithium d'un lac salé au moyen d'une désintercalation électrique ; de l'eau est ajoutée au bain électrolytique à membrane céramique ; une électrode à lithium intercalé est placée en tant que cathode à l'intérieur ; et Li+ dans la saumure se déplace vers la cathode sous l'action d'un champ électrique, est de préférence séparé vis-à-vis d'autres cations d'impuretés au moyen du bain électrolytique à membrane céramique et est préalablement enrichi en eau pure, ce qui permet de réduire l'influence des cations d'impuretés sur le processus de désintercalation électrique. Le procédé de préparation d'une membrane céramique lithium-ion est simple et facile à mettre en œuvre pour une production à grande échelle, et présente un faible coût.
PCT/CN2023/098367 2023-06-05 2023-06-05 Bain électrolytique à membrane céramique pour extraire du lithium à partir d'un lac salé au moyen d'une désintercalation électrique, et dispositif et procédé d'électrolyse pour l'extraction de lithium à partir d'un lac salé au moyen d'une désintercalation électrique Ceased WO2024250154A1 (fr)

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CN202380009315.XA CN117043365B (zh) 2023-06-05 2023-06-05 一种电脱嵌盐湖提锂用陶瓷膜电解槽、电脱嵌盐湖提锂的电解装置和方法
ARP240101178A AR132643A1 (es) 2023-06-05 2024-05-08 Baño de electrólisis de membrana cerámica, dispositivo de electrólisis y método para la extracción de litio desde lagos salados, por medio de desintercalación / intercalación electroquímica

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