Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery
View Patent ↗Disclosed are a recovery for a metaloxidic cathodic active material for a lithium ion secondary battery and a synthesis thereof by the recovery method, wherein the recovery method includes (a) dissolving a cathodic active material from a waste lithium ion secondary battery using sulfuric acid solution containing sulfurous acid gas to generate a solution containing metal ions, (b) injecting sodium hydroxide solution and ammonia solution in the solution containing the metal ions to fabricate an electrode active material precursor, and (c) filtrating the active material precursor, followed by drying and grinding, thus to fabricate a solid-state cathodic active material precursor, and the synthesis method is achieved by mixing the electrode active material precursor fabricated according to the recovery method with lithium carbonate or lithium hydroxide, followed by heat treatment, to generate a metaloxidic cathodic active material.
1. A method for recovering metaloxidic cathodic active material for a lithium ion secondary battery comprising:
(a) dissolving a ternary or binary cathodic active material from a waste lithium ion secondary battery using sulfuric acid solution containing sulfurous acid gas to generate a solution containing metal ions; and
(b) injecting sodium hydroxide solution and ammonia solution in the solution containing the metal ions to fabricate an electrode active material precursor;
wherein the concentration of the ternary or binary cathodic active material within the solution containing the metal ions is in the range of 10 to 50 g/L;
wherein the concentration of the sulfuric acid solution is in the range of 0.5 to 2M, and the sulfurous acid gas contained in the sulfuric acid solution is in a saturated state;
wherein step (a) is performed at room temperature within 1 hour;
wherein in step (b), the ammonia solution in the range of 6 to 13 M is added to adjust the coprecipitation rate with maintaining pH in the range of 8 to 14 and a temperature in the range of 30 to 70° C.; and
wherein in step (b), the concentration of metal ions in the solution containing the metal ions is in the range of 1 to 6M, and the sodium hydroxide solution is injected at a concentration twice as high as the metal ion concentration of the solution containing the metal ions.
2. The method of claim 1 , further comprising (c) filtrating the active material precursor, followed by drying and grinding, thus to fabricate a solid-state cathodic active material precursor.
3. A method for preparing an electrode active material precursor of ternary or binary cathodic active material, consisting of:
(a) dissolving a ternary or binary cathodic active material from a waste lithium ion secondary battery using sulfuric acid solution containing sulfurous acid gas to generate a solution containing metal ions; and
(b) injecting sodium hydroxide solution and ammonia solution in the solution containing the metal ions to fabricate the electrode active material precursor,
wherein the concentration of the ternary or binary cathodic active material within the solution containing the metal ions is in the range of 10 to 50 g/L;
wherein the concentration of the sulfuric acid solution is in the range of 0.5 to 2 M and the sulfurous acid gas contained in the sulfuric acid solution of step (a) is in a saturated state;
wherein the step (a) is performed at room temperature within 1 hour;
wherein the ammonia solution in the range of 6 to 13 M is added to adjust the coprecipitation rate with maintaining pH in the range of 8 to 14 and a temperature in the range of 30 to 70° C.; and
wherein in step (b), the concentration of metal ions in the solution containing the metal ions is in the range of 1 to 6 M, and the sodium hydroxide solution is injected at a concentration twice as high as the metal ion concentration of the solution containing the metal ions.