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CN-122003292-A - Lithium recovery device, multi-chamber lithium recovery device, and lithium recovery method

CN122003292ACN 122003292 ACN122003292 ACN 122003292ACN-122003292-A

Abstract

In a lithium recovery device (1), a treatment tank (7) is divided into 3 chambers by an ion conductive membrane (31) and a lithium ion conductive electrolyte membrane (2) in the order of chambers (11, 12, 13), a power source (5) is connected between electrodes (41, 42) in the chambers (11, 13) provided at both ends with the 1 st electrode chamber (11) side as the positive electrode, water (S1) is contained in the 1 st electrode chamber (11), a nonaqueous solution (FS) of Li is contained in a Li supply chamber (12), and an aqueous solution (RS) of Li is contained in the Li recovery chamber (13). When a voltage is applied by a power supply (5), H + moves from water (S1) to a Li-containing nonaqueous solution (FS) through an ion conductive membrane (31), and in the Li-containing nonaqueous solution (FS) supplied with H + , li + moves to a lithium ion conductive electrolyte membrane (2) and Li + in the lithium ion conductive electrolyte membrane (2) moves to a Li-recovering aqueous solution (RS) in order to maintain charge balance.

Inventors

  • SASAKI KAZUYA
  • NIIMURA MASATO

Assignees

  • 国立大学法人弘前大学

Dates

Publication Date
20260508
Application Date
20240927
Priority Date
20230929

Claims (18)

  1. 1. A lithium recovery device having a treatment tank, a lithium ion conductive electrolyte membrane, a1 st ion conductive membrane, a1 st electrode, a 2 nd electrode, and a power supply, wherein, The treatment tank is formed by separating a1 st chamber, a2 nd chamber and a3 rd chamber in sequence; the lithium ion conductive electrolyte membrane partitions the processing tank into the 1 st chamber and the 2 nd chamber; the 1 st ion conductive membrane divides the processing tank into the 2 nd chamber and the 3 rd chamber; The 1 st electrode is disposed in the 3 rd chamber; The 2 nd electrode is provided in a chamber of an end portion of the processing bath opposite to the 3 rd chamber; the positive electrode of the power supply is connected with the 1 st electrode, the negative electrode is connected with the 2 nd electrode, The method is characterized in that lithium ions are moved from a non-aqueous solution containing lithium ions accommodated in the 2 nd chamber to water or an organic solvent accommodated in the 1 st chamber, The 1 st ion conductive film conducts at least one of cations other than lithium ions and anions that are water-soluble and contained in the nonaqueous solution, Water is contained in the 3 rd chamber.
  2. 2. The lithium recovery device according to claim 1, wherein, And a2 nd ion conductive membrane which divides the treatment tank into the 1 st chamber and the 4 th chamber and does not conduct lithium ions, The 2 nd electrode is disposed in the 4 th chamber, Water is contained in the 4 th chamber.
  3. 3. A lithium recovery device having a treatment tank, a lithium ion conductive electrolyte membrane, a 2 nd ion conductive membrane, a1 st electrode, a 2 nd electrode, and a power supply, wherein, The treatment tank is formed by separating a2 nd chamber, a1 st chamber and a3 rd chamber in sequence; the lithium ion conductive electrolyte membrane partitions the processing tank into the 1 st chamber and the 2 nd chamber; The 2 nd ion conducting membrane separates the treatment tank into the 1st chamber and the 3 rd chamber and does not conduct lithium ions; The 1 st electrode is disposed in the 2 nd chamber; The 2 nd electrode is disposed in the 3 rd chamber; the positive electrode of the power supply is connected with the 1 st electrode, the negative electrode is connected with the 2 nd electrode, The method is characterized in that lithium ions are moved from a non-aqueous solution containing lithium ions accommodated in the 2 nd chamber to water or an organic solvent accommodated in the 1 st chamber, Water is contained in the 3 rd chamber, Water is further contained in the 2 nd chamber.
  4. 4. A lithium recovery device according to claim 2 or 3, wherein, An organic solvent is contained in the 1 st chamber, An aqueous solution in which anions soluble in the organic solvent are dissolved is stored in a chamber of the processing bath in which the 2 nd electrode is provided, The 2 nd ion conducting membrane conducts the anion.
  5. 5. The lithium recovery device according to claim 1, wherein, An organic solvent is contained in the 1 st chamber, The power supply applies a voltage such that the potential of the 2 nd electrode is equal to or lower than the lithium ion reduction potential.
  6. 6. The lithium recovery device according to any one of claim 1 to 4, wherein, The power supply is formed by sequentially connecting a1 st power supply and a 2 nd power supply in series from the positive side, And a 3 rd electrode connected to the negative electrode of the 1 st power supply, separated from the 2 nd electrode, and disposed in contact with or facing the 1 st chamber side surface of the lithium ion conductive electrolyte membrane, In the 1 st chamber, water or an organic solvent in which anions are dissolved is contained.
  7. 7. A lithium recovery method for moving lithium ions contained in a nonaqueous solution contained in a 2 nd chamber to water or an organic solvent contained in the 1 st chamber in a treatment tank partitioned into the 1 st chamber and the 2 nd chamber by a lithium ion conductive electrolyte membrane, The treatment tank is further partitioned into a2 nd chamber and a 3 rd chamber by a1 st ion conductive membrane, the 1 st ion conductive membrane is configured to conduct at least one of cations other than lithium ions and anions that are soluble in water and contained in the nonaqueous solution, water is contained in the 3 rd chamber, And a voltage is applied between the 1 st electrode and the 2 nd electrode by a power supply connected so that the 1 st electrode is positive, the 1 st electrode is provided in the 3 rd chamber, and the 2 nd electrode is provided in a chamber of an end portion of the processing bath opposite to the 3 rd chamber.
  8. 8. A lithium recovery method for moving lithium ions contained in a nonaqueous solution contained in a 2 nd chamber to water or an organic solvent contained in the 1 st chamber in a treatment tank partitioned into the 1 st chamber and the 2 nd chamber by a lithium ion conductive electrolyte membrane, Water is further contained in the 2 nd chamber, And a voltage is applied between the 1 st electrode and the 2 nd electrode by a power supply connected so that the 1 st electrode is positive, the 1 st electrode is provided in the 2 nd chamber, and the 2 nd electrode is provided in a chamber of an end portion of the processing bath opposite to the 2 nd chamber.
  9. 9. The method for recovering lithium according to claim 7 or 8, wherein, The treatment tank is further divided into a1 st chamber and a4 th chamber by a2 nd ion conducting membrane which does not conduct lithium ions, The 2 nd electrode is disposed in the 4 th chamber, Water is contained in the 4 th chamber.
  10. 10. The method for recovering lithium according to claim 9, wherein, An organic solvent is contained in the 1 st chamber, An aqueous solution in which anions soluble in the organic solvent are dissolved is stored in a chamber of the processing bath in which the 2 nd electrode is provided, The 2 nd ion conducting membrane conducts the anion.
  11. 11. The method for recovering lithium according to claim 7 or 8, wherein, An organic solvent is contained in the 1 st chamber, The power supply applies a voltage such that the potential of the 2 nd electrode is equal to or lower than the lithium ion reduction potential.
  12. 12. The method for recovering lithium according to any one of claim 7 to 10, wherein, In the 1 st chamber, water or an organic solvent in which anions are dissolved is contained, The power supply is formed by sequentially connecting a1 st power supply and a 2 nd power supply in series from the positive side, And a 3 rd electrode connected to the negative electrode of the 1 st power supply, wherein the 3 rd electrode is separated from the 2 nd electrode and is disposed in contact with or in opposition to the 1 st chamber side surface of the lithium ion conductive electrolyte membrane.
  13. 13. A multi-chamber lithium recovery device is characterized by comprising a lithium ion conductive electrolyte membrane, a1 st ion conductive membrane, a 2 nd ion conductive membrane, a treatment tank, a1 st electrode, a 2 nd electrode and a power supply, wherein, The lithium ion conductive electrolyte membrane has 2 or more; the 1 st ion conductive membrane is disposed on the one end side of the lithium ion conductive electrolyte membrane disposed 1 st from the one end side; the 2 nd ion conductive film is disposed between the lithium ion conductive electrolyte films, and does not conduct lithium ions; The treatment tank is divided into more than 5 chambers by the 1 st ion conducting membrane, the lithium ion conducting electrolyte membrane and the 2 nd ion conducting membrane; the 1 st electrode is arranged in the chamber of the one end formed by the separation of the treatment tank; the 2 nd electrode is arranged in the chamber at the other end; the positive electrode of the power supply is connected with the 1 st electrode, the negative electrode is connected with the 2 nd electrode, Water is contained in the chamber of the one end of the treatment tank, In the adjacent 2 chambers partitioned by the lithium ion conductive electrolyte membrane, lithium ions are moved from the non-aqueous solution containing lithium ions stored at the one end side to water stored at the other end side.
  14. 14. A multi-chamber lithium recovery device according to claim 13, wherein, And a2 nd ion conductive membrane that separates the processing bath between the 1 st lithium ion conductive electrolyte membrane and the 2 nd electrode disposed from the other end side, Water is contained in a chamber at the other end of the treatment tank partitioned by the 2 nd ion conductive membrane.
  15. 15. A multi-chamber lithium recovery device according to claim 13 or 14, wherein, The power supply is formed by sequentially connecting a1 st power supply and a 2 nd power supply in series from the positive side, And a3 rd electrode connected to the negative electrode of the 1 st power supply, separated from the 2 nd electrode, and disposed in contact with or facing the surface of the 1 st lithium ion conductive electrolyte membrane disposed from the other end side.
  16. 16. A lithium recovery method for moving lithium ions from a non-aqueous solution containing lithium ions stored in one of adjacent 2 chambers partitioned by a lithium ion conductive electrolyte membrane to water stored in the other in a treatment tank partitioned into 5 chambers or more by the ion conductive membrane and the lithium ion conductive electrolyte membrane alternately arranged from one end side, The ion conductive membranes disposed between the lithium ion conductive electrolyte membranes do not conduct lithium ions, Water is contained in the chamber of the one end of the treatment tank, A voltage is applied between a 1 st electrode provided in the chamber at one end of the processing bath and a 2 nd electrode provided in the chamber at the other end of the processing bath, by a power source connected so that the 1 st electrode is positive, Lithium ions are moved from the non-aqueous solution containing lithium ions stored in the one end side of the adjacent 2 chambers to water stored in the other end side.
  17. 17. The method for recovering lithium according to claim 16, wherein, The treatment tank is partitioned by an ion conductive membrane that does not conduct lithium ions and is disposed between the 1 st lithium ion conductive electrolyte membrane and the 2 nd electrode from the other end side, Water is contained in a chamber of the other end of the treatment tank partitioned by the ion conductive membrane.
  18. 18. The method for recovering lithium according to claim 16 or 17, wherein, The power supply is formed by sequentially connecting a1 st power supply and a 2 nd power supply in series from the positive side, And a 3 rd electrode connected to the negative electrode of the 1 st power supply, wherein the 3 rd electrode is separated from the 2 nd electrode and is in contact with or arranged opposite to the surface of the 1 st lithium ion conductive electrolyte membrane arranged from the other end side.

Description

Lithium recovery device, multi-chamber lithium recovery device, and lithium recovery method Technical Field The present invention relates to a lithium recovery device and a lithium recovery method for selectively recovering lithium ions from a nonaqueous solution. Background Lithium (Li) is a highly demanded resource as a raw material for fuel and the like of a lithium ion secondary battery or a nuclear fusion reactor, and a collection method which can be stably supplied and is inexpensive is demanded. As a stable supply source of Li, there is sea water or the like dissolved in the form of cationic Li +. In addition, since lithium ion secondary batteries mainly contain Li as lithium cobaltate (LiCoO 2) or the like in the positive electrode, an inexpensive recovery technique for recovering from a battery (waste battery) that is discarded due to battery life or the like is desired. Although adsorption has been conventionally used as a recovery technique for recovering Li from sea water or the like, as a method with more excellent selectivity, a recovery method using an electrodialysis method using an electrolyte membrane having lithium ion conductivity has been developed (for example, patent documents 1 to 3 and non-patent document 1). An example of a Li recovery method using the electrodialysis method described in patent document 1 and the like will be described with reference to fig. 25. The lithium recovery device 101 is configured such that a processing tank 107 is partitioned into a Li supply chamber 112 and a Li recovery chamber 113 by a lithium ion conductive electrolyte membrane (hereinafter, electrolyte membrane) 2, and a power supply 105 is connected to the electrode 141 as a positive electrode between the electrode 141 in the Li supply chamber 112 and the electrode 142 in the Li recovery chamber 113. The Li supply chamber 112 is filled with an aqueous Li-containing solution SW such as seawater as a Li source, and the Li recovery chamber 113 is filled with an aqueous Li recovery solution RS such as pure water. In the Li-containing aqueous solution SW, lithium ions (Li +) and other metal ions (M n+), hydrogen ions (H +), and hydroxide ions (OH -), and other anions, such as chloride ions (Cl -), sulfate ions (SO 42-), and the like, are dissolved. When a voltage is applied by the power supply 105, in the Li-containing aqueous solution SW in the Li supply chamber 112, the reaction of the following formula (1) occurs in the vicinity of the electrode 141 to generate oxygen (O 2), and the reaction of the following formula (2) occurs on the surface of the electrolyte membrane 2. In the case where the Li-containing aqueous solution SW contains Cl -, chlorine gas (Cl 2) is further generated in the vicinity of the electrode 141. On the other hand, in the aqueous Li-recovering solution RS in the Li-recovering chamber 113, the reaction of the following formula (3) occurs on the front surface (back surface) of the electrolyte membrane 2, and the reaction of the following formula (4) occurs in the vicinity of the electrode 142, thereby generating hydrogen gas (H 2). In the formulae, lithium ions (Li +) contained in the electrolyte membrane 2 (electrolyte) are represented as Li + (electrolyte), and other ions (Li +、H+、OH-) are represented as ions dissolved in an aqueous solution. The following formula (2) represents a reaction in which Li + in the solution moves into the electrolyte membrane 2, and the following formula (3) represents a reaction in which Li + in the electrolyte membrane 2 moves into the solution. As a result, li + is moved from the Li-containing aqueous solution SW to the Li-recovering aqueous solution RS through the electrolyte membrane 2 by using the electrochemical potential difference of Li + contained in each of the Li-containing aqueous solution SW, the electrolyte membrane 2 and the Li-recovering aqueous solution RS. Since the size of the lattice defect site of the electrolyte membrane 2 is small, the metal ion M n+ such as Na +、Ca2+ having a larger diameter than Li + is not transmitted. Therefore, li + selectively moves from the Li-containing aqueous solution SW to the Li-recovery aqueous solution RS, and an aqueous solution of Li + (lithium hydroxide aqueous solution) can be obtained in the Li-recovery chamber 113. [ Chemical formula 1] [ Prior Art literature ] [ Patent literature ] Patent document 1 Japanese patent application laid-open No. 6233877 Patent document 2 Japanese patent laid-open publication No. 2019-141807 Patent document 3 International publication No. 2022/239864 [ Non-patent literature ] Non-patent literature 1:Kunugi S.,Inaguma Y.,Itoh M.,"Electrochemical recovery and isotope separation of lithium ion employing lithium ion conductive perovskite-type oxides", Solid State Ionics, Vol. 122, Issues 1-4, pp. 35-39, July 1999 Disclosure of Invention [ Problem to be solved by the invention ] In the Li recovery method using the electrodialysis method, electrons e - are re