Lithium ion battery scrap treatment method
The present invention relates to a method for treating lithium ion battery scrap containing Li, Ni, Co, Mn, Al, Cu and Fe, the method comprising carrying out a calcination step, a crushing step and a sieving step in this order, and after the steps, the method comprising: a leaching step of leaching the lithium ion battery scrap by adding it to an acidic solution to leave at least a part of Cu as a solid; a Fe/Al removal step comprising allowing a leached solution obtained in the leaching step to pass through a Fe removal process for separating and removing Fe by addition of an oxidizing agent and an Al removal process for separating and removing a part of Al by neutralization in any order; an Al/Mn extraction step of extracting and removing a residue of Al and Mn from a separated solution obtained in the Fe/Al removal step by solvent extraction; a Co recovery step of extracting and back-extracting Co from a first extracted solution obtained in the Al/Mn extraction step by solvent extraction and recovering the Co by electrolytic winning; a Ni recovery step of extracting and back-extracting, by solvent extraction, a part of Ni from a second extracted solution obtained by the solvent extraction in the Co recovery step and recovering the Ni by electrolytic winning; a Li concentration step of extracting and back-extracting, by solvent extraction, a residue of Ni and Li from a third extracted solution obtained by the solvent extraction in the Ni recovery step and repeating the operations of the extracting and the back-extracting to concentrate Li; and a Li recovery step of carbonating Li in a Li concentrated solution obtained in the Li concentration step to recover the Li as lithium carbonate.
1. A method for treating lithium ion battery scrap containing Li, Ni, Co, Mn, Al, Cu and Fe, the method comprising carrying out a calcination step, a crushing step and a sieving step in this order, and after the steps, the method comprising:
a leaching step of leaching the lithium ion battery scrap by adding it to an acidic solution to leave at least a part of Cu as a solid;
a Fe/Al removal step comprising allowing a leached solution obtained in the leaching step to pass through a Fe removal process for separating and removing Fe under a condition at pH of 3.0 to 4.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of 500 mV or more by addition of an oxidizing agent and an Al removal process for separating and removing a part of Al under a condition at pH of 4.0 to 6.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of −500 mV to 100 mV by neutralization in any order;
an Al/Mn extraction step of extracting and removing a residue of Al and Mn from a separated solution obtained in the Fe/Al removal step by solvent extraction;
a Co recovery step of extracting and back-extracting Co from a first extracted solution obtained in the Al/Mn extraction step by solvent extraction and recovering the Co by electrolytic winning;
a Ni recovery step of extracting and back-extracting, by solvent extraction, a part of Ni from a second extracted solution obtained by the solvent extraction in the Co recovery step and recovering the Ni by electrolytic winning;
a Li concentration step of extracting and back-extracting, by solvent extraction, a residue of Ni and Li from a third extracted solution obtained by the solvent extraction in the Ni recovery step and repeating the operations of the extracting and the back-extracting to concentrate Li; and
a Li recovery step of carbonating Li in a Li concentrated solution obtained in the Li concentration step to recover the Li as lithium carbonate.
2. The method according to claim 1 , wherein in the solvent extraction in the Ni recovery step, a carboxylic acid-based extracting agent is used for the second extracted solution.
3. The method according to claim 1 , further comprising a neutralization step of neutralizing the Li concentrated solution obtained in the Li concentration step and recovering a residue of the Ni, prior to the Li recovery step.
4. The method according to claim 3 , wherein in the neutralization step, a pH of the Li concentrated solution is within a range of from 10 to 13.
5. The method according to claim 1 , wherein the oxidizing agent used in the Fe removal process in the Fe/Al step contains Mn.
6. The method according to claim 1 , wherein in the leaching step, the acidic solution has a pH of from 0 to 2 and an oxidation-reduction potential (ORPvsAg/AgCl) of from −500 mV to 0 mV.
7. The method according to claim 1 , wherein in the Al/Mn extraction step, an extracting agent comprising a phosphate ester-based extracting agent and an oxime-based extracting agent is used for the separated solution.
8. The method according to claim 1 , wherein in the solvent extraction in the Co recovery step, a phosphonate ester-based extracting agent is used for the first extracted solution.
9. The method according to claim 1 , wherein in the solvent extraction in the Li concentration step, an extracting agent comprising 2-ethylhexyl 2-ethylhexylphosphonate or di-2-ethylhexylphosphoric acid is used.
10. The method according to claim 1 , wherein in the Li recovery step, the carbonating of Li is carried out by adding a carbonate salt to or blowing a carbon dioxide gas into the Li concentrated solution.
11. The method according to claim 1 , wherein in the Li recovery step, the lithium carbonate is subjected to repulp washing and the carbon dioxide gas is blown, and impurities are then removed by solid-liquid separation to purity the lithium carbonate.
12. A method for treating lithium ion battery scrap that contains Li, Co, Al, Cu and Fe and does not contain Ni, the method comprising carrying out a calcination step, a crushing step and a sieving step in this order, and after the steps, the method comprising:
a leaching step of leaching the lithium ion battery scrap by adding it to an acidic solution to leave at least a part of Cu as a solid;
a Fe/Al removal step comprising allowing a leached solution obtained in the leaching step to pass through a Fe removal process for separating and removing Fe under a condition at pH of 3.0 to 4.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of 500 mV or more by addition of an oxidizing agent and an Al removal process for separating and removing a part of Al under a condition at pH of 4.0 to 6.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of −500 mV to 100 mV by neutralization in any order;
an Al/Mn extraction step of extracting a residue of Al and Mn from a separated solution obtained in the Fe/Al removal step by solvent extraction;
a Co recovery step of extracting and back-extracting Co from a first extracted solution obtained in the Al/Mn extraction step by solvent extraction and recovering the Co by electrolytic winning;
a Li concentration step of extracting and back-extracting, by solvent extraction, Li from a second extracted solution obtained by the solvent extraction in the Co recovery step and repeating the operations of the extracting and the back-extracting to concentrate Li; and
a Li recovery step of carbonating Li in a Li concentrated solution obtained in the Li concentration step to recover the Li as lithium carbonate.
13. The method according to claim 12 , wherein the oxidizing agent used in the Fe removal process in the Fe/Al step contains Mn.
14. The method according to claim 12 , wherein in the leaching step, the acidic solution has a pH of from 0 to 2 and an oxidation-reduction potential (ORPvsAg/AgCl) of from −500 mV to 0 mV.
15. The method according to claim 12 , wherein in the Al/Mn extraction step, an extracting agent comprising a phosphate ester-based extracting agent and an oxime-based extracting agent is used for the separated solution.
16. The method according to claim 12 , wherein in the solvent extraction in the Co recovery step, a phosphonate ester-based extracting agent is used for the first extracted solution.
17. The method according to claim 12 , wherein in the solvent extraction in the Li concentration step, an extracting agent comprising 2-ethylhexyl 2-ethylhexylphosphonate or di-2-ethylhexylphosphoric acid is used.
18. The method according to claim 12 , wherein in the Li recovery step, the carbonating of Li is carried out by adding a carbonate salt to or blowing a carbon dioxide gas into the Li concentrated solution.
19. The method according to claim 12 , wherein in the Li recovery step, the lithium carbonate is subjected to repulp washing and the carbon dioxide gas is blown, and impurities are then removed by solid-liquid separation to purity the lithium carbonate.
20. A method for treating lithium ion battery scrap containing Li, Ni, Co, Mn, Al, Cu and Fe, the method comprising:
a leaching step of leaching the lithium ion battery scrap by adding it to an acidic solution to leave at least a part of Cu as a solid;
a Fe/Al removal step comprising allowing a leached solution obtained in the leaching step to pass through a Fe removal process for separating and removing Fe under a condition at pH of 3.0 to 4.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of 500 mV or more by addition of an oxidizing agent and an Al removal process for separating and removing a part of Al under a condition at pH of 4.0 to 6.0 and an oxidation-reduction potential (ORPvsAg/AgCl) of −500 mV to 100 mV by neutralization in any order;
an Al/Mn extraction step of extracting and removing a residue of Al and Mn from a separated solution obtained in the Fe/Al removal step by solvent extraction;
a Co recovery step of extracting and back-extracting Co from a first extracted solution obtained in the Al/Mn extraction step by solvent extraction and recovering the Co;
a Ni recovery step of extracting and back-extracting, by solvent extraction, a part of Ni from a second extracted solution obtained by the solvent extraction in the Co recovery step and recovering the Ni.