WO2024259612A1 - Procédé d'extraction de lithium basée sur une désintercalation électrochimique - Google Patents

Procédé d'extraction de lithium basée sur une désintercalation électrochimique Download PDF

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Publication number
WO2024259612A1
WO2024259612A1 PCT/CN2023/101575 CN2023101575W WO2024259612A1 WO 2024259612 A1 WO2024259612 A1 WO 2024259612A1 CN 2023101575 W CN2023101575 W CN 2023101575W WO 2024259612 A1 WO2024259612 A1 WO 2024259612A1
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WO
WIPO (PCT)
Prior art keywords
lithium
extraction
electrode
cathode
lithium extraction
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2023/101575
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English (en)
Chinese (zh)
Inventor
李爱霞
谢英豪
余海军
李长东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Publication date
Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to CN202380009671.1A priority Critical patent/CN117015623B/zh
Priority to PCT/CN2023/101575 priority patent/WO2024259612A1/fr
Priority to ARP240100272A priority patent/AR131783A1/es
Publication of WO2024259612A1 publication Critical patent/WO2024259612A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition

Definitions

  • CN102382984A discloses a method and device for separating magnesium and lithium from salt lake brine and enriching lithium.
  • the electrodialysis device is separated into two areas, a lithium salt chamber and a brine chamber, by an anion exchange membrane.
  • the brine chamber is filled with salt lake brine
  • the lithium salt chamber is filled with a supporting electrolyte solution that does not contain Mg 2+ ;
  • a conductive substrate coated with an ion sieve is placed in the brine chamber as a cathode;
  • a conductive substrate coated with a lithium-intercalated ion sieve is placed in the lithium salt chamber as an anode; under the drive of an external potential, the Li + in the brine in the brine chamber is embedded in the ion sieve to form a lithium-intercalated ion sieve, and the lithium-intercalated ion sieve in the lithium salt chamber releases Li + into the conductive solution and then returns to an ion sieve; the post-lithium-
  • the purpose of the present disclosure is to provide a method for electrochemical deintercalation and extraction of lithium, which can give full play to the adsorption performance of the material, reduce its capacity decay, and avoid the problem of capacity mismatch.
  • the present disclosure provides a method for electrochemical deintercalation and extraction of lithium, the method comprising the following steps:
  • step (3) removing the auxiliary electrode, using the lithium-poor electrode described in step (2) as the cathode, repeating the steps of one-step lithium extraction and two-step lithium extraction to perform multi-stage lithium extraction until
  • the disclosed embodiment divides the lithium extraction process into multiple stages. After the first stage of the lithium extraction process, the anode that has been completely de-lithiated is processed to convert the anode into a cathode, and an auxiliary electrode is connected to the anode, so that the anode in the first stage of the lithium extraction process is used as a cathode in the lithium-rich solution to perform a second-step lithium extraction reaction, so that it is converted from a lithium-rich state to a lithium-poor state again, and then the second stage of the lithium extraction reaction is performed, which can ensure that the anode and cathode capacities of the multi-stage lithium extraction process are matched.
  • the lithium-rich electrode adsorbs again after de-intercalation, and after the adsorption is completed, the solution can be replaced with pure Deintercalation of the lithium-rich solution can improve the purity and concentration of the lithium-rich solution and reduce the subsequent impurity removal and concentration steps.
  • the concentration of the salt solution in step (1) is 0.2-1 mol/L, for example, 0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L or 1 mol/L.
  • step (3) Remove the auxiliary electrode, use the lithium-poor electrode that has not completely absorbed lithium in step (2) as the cathode, repeat the steps of the one-step lithium extraction reaction and the two-step lithium extraction reaction, until the difference between the initial current value after the two-step lithium extraction treatment and the end current value before the treatment is less than 0.5% of the end current value before the treatment, do not repeat the auxiliary electrode treatment step, end the first multi-stage lithium extraction process, switch the cathode and cathode and perform multi-stage lithium extraction again, repeat the multi-stage lithium extraction 3 times, and obtain a lithium-rich solution.
  • the schematic diagram of the electrochemical deintercalation and lithium extraction process is shown in Figure 3.
  • the lithium-rich electrode in step (1) is The cathode chamber is transformed into a lithium-poor electrode, so it can re-adsorb lithium and transform into a lithium-rich electrode when used as a cathode.
  • the auxiliary electrode can be placed in the cathode chamber and connected to a 2V constant voltage power supply to perform a lithium extraction reaction. The reaction is suspended when the current is lower than 0.2mA.
  • Example 1 The only difference between this comparative example and Example 1 is that no auxiliary electrode is provided, and only a simple exchange of the positive and negative electrodes is performed. Other conditions and parameters are exactly the same as those in Example 1.
  • Chlorine gas can oxidize organic matter in the brine, reduce the viscosity of the brine, and the bubbles generated when chlorine gas is generated can stir the brine, making the solution components more evenly dispersed, thereby ultimately improving the lithium extraction efficiency of the next stage.
  • Example 1 By comparing Example 1 and Example 3, it can be seen that in the process of electrochemical deintercalation and lithium extraction described in the present invention, the voltage of the one-step lithium extraction will affect the lithium extraction effect.
  • the voltage of the one-step lithium extraction is controlled at 0.2-1.5V, and the lithium extraction effect is better. If the voltage of the one-step lithium extraction is too high, side reactions are likely to occur to produce chlorine gas, which reduces the lithium extraction efficiency. In addition, too high a voltage will also cause impurity ions to enter the lithium ion sieve, affecting the purity of the lithium-rich solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente divulgation concerne un procédé d'extraction de lithium basée sur une désintercalation électrochimique. Le procédé comprend les étapes suivantes consistant à : (1) injecter une solution de sel dans une chambre d'anode d'un dispositif d'extraction de lithium à base de désintercalation électrochimique, injecter de la saumure de lac salé dans une chambre de cathode de celle-ci, utiliser une électrode riche en lithium en tant qu'anode, utiliser une électrode pauvre en lithium en tant que cathode, appliquer une première tension pour effectuer une extraction de lithium primaire, et réaliser la suspension de la réaction lorsque le courant est inférieur à 0,2 mA ; (2) éliminer l'électrode pauvre en lithium, utiliser l'électrode riche en lithium en tant que cathode, utiliser une électrode auxiliaire en tant qu'anode, appliquer une seconde tension pour effectuer une extraction secondaire au lithium, et réaliser une suspension de la réaction lorsque le courant est inférieur à 0,2 mA ; et (3) retirer l'électrode auxiliaire, à l'aide de l'électrode pauvre en lithium en tant que cathode, répéter les étapes d'extraction de lithium primaire et d'extraction de lithium secondaire pour effectuer une extraction de lithium à étages multiples jusqu'à ce que la relation soit satisfaite : a-b < 1%, terminer la première extraction de lithium à étages multiples, réaliser l'extraction de lithium à étages multiples après commutation de l'anode et de la cathode, et répéter l'extraction de lithium à étages multiples n fois pour obtenir une solution riche en lithium. Le procédé divulgué par la présente divulgation peut pleinement exercer les performances d'adsorption de matériaux, réduit l'atténuation de capacité de ceux-ci, et évite le problème de désadaptation entre les capacités.
PCT/CN2023/101575 2023-06-21 2023-06-21 Procédé d'extraction de lithium basée sur une désintercalation électrochimique Ceased WO2024259612A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202380009671.1A CN117015623B (zh) 2023-06-21 2023-06-21 一种电化学脱嵌提锂的方法
PCT/CN2023/101575 WO2024259612A1 (fr) 2023-06-21 2023-06-21 Procédé d'extraction de lithium basée sur une désintercalation électrochimique
ARP240100272A AR131783A1 (es) 2023-06-21 2024-02-05 Método de extracción de litio por desintercalación / intercalación electroquímica

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/101575 WO2024259612A1 (fr) 2023-06-21 2023-06-21 Procédé d'extraction de lithium basée sur une désintercalation électrochimique

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WO2024259612A1 true WO2024259612A1 (fr) 2024-12-26

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CN (1) CN117015623B (fr)
AR (1) AR131783A1 (fr)
WO (1) WO2024259612A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118176327A (zh) * 2023-12-20 2024-06-11 广东邦普循环科技有限公司 一种锂的电化学提取装置及方法
CN118389851B (zh) * 2024-04-01 2026-03-31 广东邦普循环科技有限公司 一种三明治结构电极及其电化学提锂应用
CN118479435B (zh) * 2024-05-15 2025-12-16 江苏大学 一种用于电化学提锂的磷酸锰改性锰酸锂复合电极及其制备方法与应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5954935A (en) * 1994-05-30 1999-09-21 Forschuugszentrum Julich GmbH Electrolytic cell arrangement for the deionization of aqueous solutions
CN102382984A (zh) * 2011-07-04 2012-03-21 中南大学 一种盐湖卤水镁锂分离及富集锂的方法和装置
CN202181336U (zh) * 2011-07-04 2012-04-04 中南大学 一种盐湖卤水镁锂分离及富集锂的装置
CN106823816A (zh) * 2016-12-19 2017-06-13 天齐锂业股份有限公司 废旧锂电池正极材料中锂的电化学回收方法
CN109267086A (zh) * 2018-10-30 2019-01-25 吉首大学 一种盐湖卤水中镁/锂分离及富集锂的装置及方法
CN111592018A (zh) * 2020-06-11 2020-08-28 孟元 从盐湖卤水中分离并提取锂的绿色生产方法
CN115159550A (zh) * 2022-08-26 2022-10-11 江苏特丰新材料科技有限公司 一种盐湖卤水循环提锂工艺及装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115818801B (zh) * 2022-12-20 2024-07-19 中南大学 一种从盐湖卤水中提取锂的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5954935A (en) * 1994-05-30 1999-09-21 Forschuugszentrum Julich GmbH Electrolytic cell arrangement for the deionization of aqueous solutions
CN102382984A (zh) * 2011-07-04 2012-03-21 中南大学 一种盐湖卤水镁锂分离及富集锂的方法和装置
CN202181336U (zh) * 2011-07-04 2012-04-04 中南大学 一种盐湖卤水镁锂分离及富集锂的装置
CN106823816A (zh) * 2016-12-19 2017-06-13 天齐锂业股份有限公司 废旧锂电池正极材料中锂的电化学回收方法
CN109267086A (zh) * 2018-10-30 2019-01-25 吉首大学 一种盐湖卤水中镁/锂分离及富集锂的装置及方法
CN111592018A (zh) * 2020-06-11 2020-08-28 孟元 从盐湖卤水中分离并提取锂的绿色生产方法
CN115159550A (zh) * 2022-08-26 2022-10-11 江苏特丰新材料科技有限公司 一种盐湖卤水循环提锂工艺及装置

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AR131783A1 (es) 2025-04-30
CN117015623A (zh) 2023-11-07
CN117015623B (zh) 2025-07-29

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