TWI286850B - A recycling means for scrap lithium batteries - Google Patents

Abstract

This patent provides a recycling means for scrap lithium batteries. In this patent, the remained electricity of lithium battery will be discharged first. Then, the battery will be mechanically cut and manually dismantled. The potion which contains lithium and cobalt will be leached by HCL for two hours to dissolve the lithium, cobalt, nickel and aluminum into solution. The pH of this solution will be adjusted to 8 by NaOH to precipitate the cobalt, nickel and aluminum ions. By filtration, the lithium ions can be separated from the precipitates. By adding the saturated NaCO3 into the lithium solution, the lithium ions can be recovered as the powder of LiCO3. The precipitate can be dissolved by H2SO4 with a pH at 2. Then, by adding the ammonia water to adjust its pH into 8 to precipitate the aluminum ions. After the filtration, the pH of filtrate was adjusted to 4.3 by adding the H2SO4. And the final solution was put into an electric wining device at 55 DEG C to recover the metals of cobalt and nickel as a precipitate at the stainless plate.

Description

1286850 I. Description of the Invention (1) [Technical Field] The inventors of the present invention have studied their own concerns, and finally provided the present invention to provide a lithium-ion battery resource for recycling and to cut and separate a lithium-ion battery without causing high heat. After the iron outer film (plastic) and the negative electrode (mainly recycled for final treatment or sent to the other part of the clock, the positive part of the cobalt, the ratio of solid to solid is 3g / i〇〇mi, can dissolve the bell Recovery of the recovery rate of 9 g · 7%) Adjusting the p Η value of the impregnation solution to eight ions will produce gelation precipitation, and only remove cobalt (C 〇), aluminum, and the ratio of the solution is 1: 5 (When the temperature is 9 5 °C, stir the content of 9 0 · 7 % of lithium carbonate (Co), aluminum (a 1 ), nickel pickling and adjust the p Η value to 2, so that the ammonia adjustment ρ Η is eight The filter can remove the aluminum-containing (A 1 ) pickling liquid and reuse the sulfuric acid to recover the ρ 电解. The cathode is not engaged in the relevant industry for many years of experience, and can not be born, its primary purpose is in the method, The waste clock battery is discharged, cut and cut, and its The part of the waste shell can be sent to the smelting plant; the part containing copper, carbon, etc. can be recovered by the resource recovery plant, and is immersed in hydrochloric acid with a concentration of 4 · 0 、, 'at 70 ° C At the temperature of the impregnation, the second rate reaches 9 6 · 4 %, and the cobalt is impregnated. Then, with sodium hydroxide (N a 〇Η , the cobalt, aluminum, and nickel residual lithium ions in the impregnation solution are dissolved in the impregnation. In the liquid, the (A 1 ), nickel (N i ) gelling immersion liquid / saturated sodium carbonate solution), one hour, can be obtained as the original positive electrode lithium starch; another filtered, the resulting containing aunt (N i) the gel, first dissolved in the liquid phase with sulfuric acid, then added aluminum ions to gel precipitation, at this time through the gel, and finally adjust the filtered value to 4 · 3 and then pour Electrolytic tank rust steel sheet, anode is platinum sheet, using constant

1286850 V. INSTRUCTIONS (2) The warm water bath keeps the electrolyte at 5 5 °C, and after applying the current of χ · 5 a / dy for eight hours, the cobalt and nickel metal will be deposited on the cathode stainless steel sheet. The cobalt content of the original positive cobalt content of 8 2 .i 〇% and the nickel content of 72.23% of nickel are obtained, and the purity of the deposited metal/face obtained by electrolysis is 9 8 · 14%. [Previously, such as the bell (C, will be the accident and the lithium explosion due to charge and discharge of the invention of the invention of the waste of the invention), generally discarded Li), u), etc. Contact hazard; this, how to, the battery, the invention of the clock ionic dicobalt (C 〇, these gold into serious pollution; and the waste caused by lithium gold to water or empty to provide a recycling waste clock price metal back to the secondary battery中),绍 (If it is not properly dyed, the formation of a lithium battery is a precipitation, the lithium in the gas in the use of lithium discharge technology and contains a variety of valuable metals (such as A ", nickel (N i), good treatment It can arbitrarily discard the problem of pollution that is difficult to make up, and it is very likely that it will cause a fire or a small metal such as a shell, a sink, a pickling, a cobalt, etc., when it is repeatedly disposed of in a waste lithium battery. The method of the research process is to stimulate the present invention. Please refer to the first figure, the present invention provides a method for recycling waste battery resources, and the waste clock battery 1 (the internal structure thereof is referred to Annex I) The internal residual power is exhausted, and then cut by a machine that does not generate high heat 2

V. Description of invention (3) Waste lithium battery 1 cuts off the separated outer shell 3 parts; benefits 0 0m), dissolves and dissolves back into the filter and is completely immersed (Co precipitation (1 dissolved 3) dissolved 8 2) Use concentration 1 to obtain the liquid p Η in the dissolution yield, and aluminum. Refer to the impregnation solution, liquid, and 9 in the amount of 9 0. The waste lithium battery 1 cutting and separating wire can be sent to the smelting plant. 3 1 Recycling Final treatment 4 1 or delivery, if there is a significant electrolyte, it can act to produce fluorination | bow Shen Dian, and part of the 'send to the smelting plant 5 C 〇) where the positive electrode 6 part, and the separator 4 ( Plastic material) to the other resource recycling plant 4 2 can be, back to I] add calcium ions and the electrolyte = the negative electrode 5 (mainly containing copper, carbon, etc. = 1 treatment, as for lithium (L i ), Hongbei 5 ancient (4 · 〇Ν 7 〇 ° C temperature recovery rate reached 9 9 · 7 immersion liquid followed by a value of eight ( (A 1 ), as shown in the third figure, at this time When the volume ratio of liquid to 15 °C is satisfied, 7% of the carbonic acid is impregnated, 7 and the solid-liquid ratio is 3 g / working degree for two hours, which can make lithium (L soil 9 6 · 4 %, cobalt (C 0 Dip ^ % (see the second figure), with the sodium hydroxide 8 (Na〇H) transferred to see Annex II), the cobalt (N i ) ion in the impregnation will produce a gel Show), and only the lithium (L i ) ion 8 is left with saturated sodium carbonate (N a 2 C〇• 5 (snap or saturated sodium carbonate solution for one hour to obtain the original acid clock powder) 8 3 (See the fourth picture

Is it filtered to contain cobalt (c 〇 ), aluminum (A 1 ), nickel N? Acid pickling 9 adjusts the P Η value to two, so that the metal contained in it is stored in the liquid phase, and then added ammonia water to adjust the ρ Η value is 1286850

V. INSTRUCTIONS (4) VIII. Let the solution A 1 ) glue 9 2 p Η 9 9 3 , which makes the electrolyte temperature of the current dense powder 9 4 after drying can be used in the positive nickel content of cobalt metal Decrement f i of the condensate, the value of the adjustment of the cathode for the degree of retention of eight small will be deposited to account for 7 2 · purity for the double ion sink and finally to 4 · after the steel at 5 5, at the cathode original positive 2 3 % 9 8· Purpose (Ding, this will filter 3, after the film, Yang ° C, pass the gu (not the beginning of the iron content, 14%, see the acid after the pouring into the electrode to fix the Co) on-chip ( 8 2· and electricity, and the fifth filter will remove the washing liquid and resolve the inside of the tank to take the piece 'Using constant 1 · 5 A / , nickel (N i see Annex 1 0 % of the cobalt obtained, To the waste map shown in the figure. Aluminum (using sulfuric acid electrolysis back to the warm water bath dm2) of the gold three), and the original nickel metal source regeneration

[Embodiment] The present invention provides a method for recycling a waste lithium battery resource. After discharging the waste lithium battery, the machine is cut by a machine that does not generate high heat, and lithium (L 1 ^, cobalt (C 〇) is located. The positive electrode portion is immersed at a high temperature by a high concentration of hydrochloric acid, and then the sodium hydroxide (Na〇H) is used to adjust the p Η value of the immersion liquid to the cobalt (◦ 0 ) in the octalysis solution. Aluminum (a 1 ) and nickel (N i ) ions will produce a gelation sink, and only lithium ions will be dissolved in the impregnation solution. At this time, the surface (C 〇), I Lu (A 1 ), and nickel are removed by filtration. The gelation of N i ) is fully stirred at a solution ratio of 1:5 (impregnation/saturated sodium carbonate solution) at 95 ° C to obtain a lithium content of the original cathode of 9 0 · 7 % carbonic acid clock powder; another filter containing the beginning (C 〇), | Lu (a 1 ), nickel (ni)

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1286850 Washing with sulfuric acid in the liquid phase, removing the acid containing aluminum, p Η value of the cathode is not maintained after the temperature, cobalt can obtain the original amount of 7 2 · 2 is 9 8 · 1 and the immersion is added to the glue The condensate is adjusted to 5 5 °C of rust steel sheet, 4% of 3% of nickel-gold positive electrode, and the enthalpy value is 2, so that the enthalpy value is VIII. At this time, the filtered acid washing liquid is put into the electrolytic cell to be used. Constant temperature water 1 · 5 A / dm 10% cobalt on the cathode stainless steel sheet and the high purity found in the deposited metal. Inventive Note (5) Gellings, completely dissolved and filtered, can reuse sulfur Electrolytic recovery, the bath makes the current of the electrolyte 2 eight, after drying, the original positive nickel contains its recorded purity starting metal. The liquid is adjusted to adjust the P ammonia water to adjust P, and finally the 4 · 3 back is poured, the anode is platinum, and the fixed genus will be deposited at the content of 8 2 · nickel is electrolyzed, that is, after electrolysis, the present invention is more apparent. Listed as follows: v, health and compatibility, it is best to 1, to avoid waste lithium battery pollution environment. 3f to waste resource recycling 3. Safe and progressive. 1 4 H and industry (4) value. In summary, the invention of the invention p法: the law to apply for 'pray, • Bureau of UaC application requirements' 专利 patent rights, real sense of virtue. - To Be Ming Zhong, and to give the invention 1286850

1286850

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Claims (1)

1286850 Sixth, the patent application scope of the waste f battery resource regeneration method, its main feature is: the waste will be cut by the high heat machine to separate, ^ ^ m ^ Taikoo, ") where the positive part, by high Concentration of hydrochloric acid, impregnated at two temperatures, and then use M (N a 〇Η ) 氢氧化 hydroxide to adjust the ρ Η value of the immersion liquid to the cobalt (c 〇), aluminum ϋ丄 八 in the eight immersion solution: U1)·The child will produce a gelation precipitate' and only the lithium ions will remain in the secondary liquid. At this time, the cobalt (c 〇), ), nickel (N i ) gel is removed by filtration and in solution. The ratio is 丄:, 夺, main / saturated sodium carbonate solution), 9 in the case of sufficient mixing, (^ 2 to account for the original positive lithium content of 9 〇. 7 % of lithium carbonate powder; (c 0 ), aluminum (A 丨), nickel · gel, & pickled with sulfuric acid and adjust the dipping solution pw 1丄: completely dissolved in the liquid phase [addition of ammonia to adjust Pd; filtered Remove the aluminum-containing gel, and finally: this $ again with sulfuric acid to adjust the ρ Η value to 4 · 3 de 5 = after the pickling liquid electrolytic recovery 'its yin For stainless steel [anode is platinum::= bath in the tank to keep the temperature of the electrolyte at 5 5 t, pass through to fix, ^ after using the constant temperature water 2 for eight hours, the abbreviated metal will sink dm, after drying Obtaining the original cathode cobalt content of 8 2 on the ^ stainless steel sheet f positive cathode nickel content 7 2 2 2 % of the nickel obtained by electrolysis of 〇β? cobalt and the purity of the 3 genera is Μ]... ;:ί Page 13 1286850 IV. Summary of Chinese Invention (Invention Name: Recycling Method of Waste Battery Resource) Wu, (a 444 7 waste machine is separated from normal salt hydrogen, the representative figure of this case is: the first figure, the representative symbol of the representative figure of the case Brief description of the lithium battery cutter cutting shell lysing plant off-film final treatment resource recovery plant extreme smelting plant acid soaking sodium oxide (N a 〇Η ) Lu, English abstract (invention name · · a recycling means for scrap lithium Batteries will be adjusted to 8 by NaOH to precipitate the cobalt, nickel and aluminum ions. By filtration, the lithium ions can be separated from the precipitates. By adding the saturated NaC03 into the lithium solution, the lithium ions can be recovered as the Powder of L i C03. The precipitate can be dissoved by H2S04 with a pH at 2 . Then, by adding the ammonia water to adjust its pH into 8 1286850 IV. Summary of Chinese Invention (Invention Name: Recycling Method for Waste Battery Resource) 8 8 8 4 • Lithium (L i ) ion • Saturated sodium carbonate solution • Lithium carbonate powder pickling • Ammonia • Sulfuric acid • Electrolytic recovery • Inclusion ( Co), nickel (Ni) metal powder, English invention summary (invention name: a recycling means for scrap lithium batteries) to precipitate the aluminum ions. After the filtration, the pH of filtrate was adjusted to 4 by adding the H2S04. And the final solution was put into an electric wining device at 55OC to recover the metals of cobalt and nickel as a precipitate at the stainless plate.