A method for one-step efficient separation of lithium from multi-element lithium battery electrode waste

Abstract

The application discloses a method for one-step efficient separation of lithium from multi-element lithium battery electrode waste, which comprises the following steps: the multi-element lithium battery electrode waste is at least one of positive electrode waste and negative electrode waste, and the multi-element lithium battery contains at least one of nickel, cobalt and manganese elements; S1, one-step separation of lithium, inorganic acid, leaching aid and reducing agent are added into the multi-element lithium battery electrode waste powder, stirring leaching is carried out, reaction is carried out at a certain temperature for a certain time, and a reaction completed slurry is obtained; S2, filtration and washing, the reaction completed slurry is filtered and washed, a lithium ion concentration of 10-30 g / L rich lithium solution and a residue are obtained; the application realizes one-step efficient separation of lithium and elements such as nickel, cobalt and manganese, breaks through the production barrier between waste lithium battery recycling and nickel, cobalt and manganese smelting, improves the high recovery rate of lithium, and reduces the comprehensive unit cost of nickel, cobalt and manganese recovery.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of battery waste resource recycling, and particularly relates to a method for one-step efficient separation of lithium from multi-element lithium battery electrode waste. BACKGROUND

[0002] With the development of the new energy automobile industry, the market demand for lithium batteries is expanding, and the demand for lithium carbonate as the main raw material for power batteries has also increased significantly in recent years. On the one hand, with the vigorous development of the electric vehicle industry, the supply and demand contradiction of lithium metal raw materials needed for power battery production will be more prominent; on the other hand, the valuable metals such as lithium, cobalt and nickel in power batteries have high content and many toxic / harmful compounds. If a large number of retired power batteries cannot be safely disposed of and utilized, it will cause waste of resources and serious environmental pollution problems.

[0003] The current conventional method for recycling and processing lithium battery positive (negative) electrode waste containing one or several elements of nickel, cobalt and manganese is a full leaching method. Specifically, sulfuric acid and other inorganic acids are used, and hydrogen peroxide or sodium pyrosulfite is used as a reducing agent to make lithium, nickel, cobalt, manganese, copper and aluminum all enter the solution. The leaching solution is purified, and nickel, cobalt and manganese are separated by extraction to obtain sulfate products, and the raffinate is recovered for lithium. The disadvantages of this process are long process flow, high cost, complex extraction and separation process of nickel, cobalt and manganese, and low lithium content in the raffinate, resulting in low lithium recovery rate.

[0004] Relatively speaking, the one-step efficient separation of lithium / selective lithium extraction method is to separate lithium from nickel, cobalt and manganese by technical means, and the lithium recovery process is short and simple. According to different technical means, it can be divided into three different lithium separation processes: reduction roasting, acid roasting and full wet method.

[0005] The reduction roasting method destroys the original structure to realize the separation process of lithium, nickel, cobalt and manganese. For example, Chinese patent CN112374511B reports that the graphite and adhesive in waste ternary battery black powder are used as reducing agents to destroy the structure of ternary materials by self-reduction phase transformation through roasting, and carbonated water leaching is used to convert lithium carbonate into lithium bicarbonate which is easy to leach in water, thereby realizing one-step efficient separation of lithium. Chinese patent CN10872648 reports that hydrogen is used as a reducing agent to realize structure transformation by fluidized reduction roasting, and the reduced powder is leached to obtain lithium hydroxide solution, thereby realizing the separation of lithium, nickel, cobalt and manganese.

[0006] The acid roasting method destroys the original structure to realize one-step efficient separation of lithium. For example, Chinese patent CN116516174A provides a method of adding water-soluble iron salt and inorganic acid mixture for roasting, and the roasting product is leached in water to obtain a lithium-rich solution and separate lithium from nickel, cobalt and manganese.

[0007] The selective lithium extraction process by full wet method, such as the Chinese patent CN109022793A, adds an oxidizing agent to oxidize the low-valence ions of nickel, cobalt and manganese in the ternary positive electrode material into high-valence compounds, so that the crystal structure is destroyed, lithium enters the solution in the form of ions, and nickel, cobalt and manganese exist in the form of slag, realizing the purpose of one-step efficient separation of lithium.

[0008] The above one-step efficient separation of lithium / selective lithium extraction method or the reduction / acid roasting treatment-wet process or the full wet process realizes the separation of lithium from most of nickel, cobalt and manganese by controlling the process conditions to preferentially leach lithium into the solution and most of nickel, cobalt and manganese into the slag, realizes the purpose of separating lithium from most of nickel, cobalt and manganese, and has a short lithium recovery process and simple process. However, the roasting treatment-wet process still has problems such as large investment in heat treatment equipment, high operating cost, great safety and environmental protection pressure, and low one-step efficient lithium separation leaching rate. The full wet process has problems such as low lithium enrichment concentration in the leaching solution, incomplete separation of nickel, cobalt and manganese, and further improvement of lithium leaching rate, recovery rate and lithium / nickel, cobalt and manganese separation efficiency.

[0009] The above one-step efficient separation of lithium / selective lithium extraction process has great defects in aspects of production line investment, production cost, safety and environmental protection, and production efficiency, and therefore is not widely used in industrial production.

[0010] At present, in China, the capacity of MHP (nickel-cobalt hydroxide intermediate product produced by mineral products) hydrometallurgical production line is large, and the comprehensive unit cost of nickel, cobalt and manganese recovery is low. The wet metallurgical production line for recovering lithium batteries containing one or several elements of nickel, cobalt and manganese generally has small capacity, high comprehensive cost of nickel and cobalt recovery, and low comprehensive recovery rate of lithium less than 80%, which is not economical. After the application of the present application, lithium is preferentially separated, and the (carbon) slag containing one or several elements of nickel, cobalt and manganese can be directly integrated into the existing MHP hydrometallurgical production line to recover nickel, cobalt and manganese, the production cost of nickel, cobalt and manganese will be reduced, the recovery rate of lithium will be improved, and the economic benefit will be improved.

[0011] At present, in foreign countries, with the rapid development of lithium batteries containing one or several elements of nickel, cobalt and manganese, especially ternary lithium batteries as the power of new energy vehicles, Europe and the United States will scrap lithium batteries as a kind of high-value waste, and formulate relevant bills to establish lithium battery recycling industry chain. The European local battery recycling industry enterprise Umicore company in Belgium uses pyrometallurgical process to recover lithium batteries, but the production line construction cost is high, the operating cost is high, and the lithium recovery rate is less than 50%, so this technology is not suitable for new lithium battery recycling projects; some projects directly introduce the production process of nickel, cobalt and manganese lithium full dissolution-extraction recovery of nickel, cobalt and manganese-recovery of lithium, because the relevant professionals have withdrawn from the whole production-research line for a long time, there are no engineers and first-line technicians for extraction production of wet nickel, cobalt and manganese separation and purification, it is difficult to realize continuous production, and similar projects are not very successful.

[0012] In summary, the nickel-cobalt-manganese smelting project is aimed at recovering nickel and cobalt, and the comprehensive cost of recovering nickel is relatively low. When lithium-containing and nickel-cobalt battery waste enters the system as raw material, lithium is recovered as a by-product, and the recovery efficiency is very low. The special lithium battery recycling project considers comprehensive recovery of lithium, nickel, cobalt and manganese. Although the existing production process has a lithium recovery process, there are still problems of low lithium recovery rate and high comprehensive recovery cost of nickel and cobalt. SUMMARY

[0013] Therefore, it is necessary to develop a new method for one-step efficient separation of lithium from various lithium battery positive (negative) electrode waste containing one or more of nickel, cobalt and manganese elements on the market, which has short process, low equipment investment and low production cost, and can realize full and effective separation of lithium, nickel, cobalt and manganese (carbon). Therefore, the present application provides a method for one-step efficient separation of lithium from multi-element lithium battery electrode waste.

[0014] The scheme of the present application is:

[0015] A method for one-step efficient separation of lithium from multi-element lithium battery electrode waste, comprising the following steps:

[0016] The multi-element lithium battery electrode waste is at least one of positive electrode waste and negative electrode waste, and the multi-element lithium battery contains at least one of nickel, cobalt and manganese elements;

[0017] S1, one-step separation of lithium

[0018] An inorganic acid, a leaching aid and a reducing agent are added to the multi-element lithium battery electrode waste powder, stirred and leached, reacted at a certain temperature for a certain time, and a reaction completed slurry is obtained;

[0019] S2, filtration and washing

[0020] The reaction completed slurry is filtered and washed to obtain a lithium ion concentration of 10-30 g / L of a lithium-rich solution and a residue.

[0021] As a preferred technical scheme, the waste in S1 is a mixture of one or more of electrode waste produced by crushing and sorting of batteries and electrode pieces and positive electrode material production waste;

[0022] The battery is one or more of a lithium nickel cobalt manganese oxide battery, a lithium cobalt oxide battery, a lithium nickel oxide battery, a lithium manganese oxide battery and a lithium nickel cobalt aluminum oxide battery;

[0023] The electrode waste produced by the electrode sheet crushing and separation is one or more of the electrode waste produced by the lithium nickel cobalt manganese oxide electrode sheet crushing and separation, the electrode waste produced by the lithium cobalt oxide electrode sheet crushing and separation, the electrode waste produced by the lithium nickel oxide electrode sheet crushing and separation, the electrode waste produced by the lithium manganese oxide electrode sheet crushing and separation, and the electrode waste produced by the lithium nickel cobalt aluminum oxide electrode sheet crushing and separation; the electrode waste produced by the electrode sheet crushing and separation includes the positive electrode waste produced by the electrode sheet crushing and separation and the negative electrode waste produced by the electrode sheet crushing and separation.

[0024] The positive electrode material production waste is one or more of the lithium nickel cobalt manganese oxide positive electrode material production waste, the lithium cobalt oxide positive electrode material production waste, the lithium nickel oxide positive electrode material production waste, the lithium manganese oxide positive electrode material production waste, and the lithium nickel cobalt aluminum oxide positive electrode material production waste.

[0025] As a preferred technical solution, the reducing agent is added after the addition of the inorganic acid and the leaching aid in S2; there is no special requirement for the addition sequence of the inorganic acid and the leaching aid, but they cannot be premixed and then added.

[0026] As a preferred technical solution, the inorganic acid in S2 is one or more of a mixture of sulfuric acid, hydrochloric acid, and nitric acid.

[0027] The reducing agent in S2 is one or more of sodium pyrosulfite, sodium dithionate, hydrogen peroxide, glucose, soluble starch, ferrous sulfate, sodium sulfite, and sodium thiosulfate.

[0028] The leaching aid in S2 is one or more of citric acid, malonic acid, acetylacetone, oxalic acid, ascorbic acid, tartaric acid, salicylic acid, and EDTA.

[0029] As a preferred technical solution, the mass ratio of the multi-element lithium battery electrode waste in the slurry of S2 to the inorganic acid is 1:0.05-0.6.

[0030] As a preferred technical solution, the mass ratio of the multi-element lithium battery electrode waste in the slurry of S2 to the reducing agent is 1:0.1-1.0.

[0031] As a preferred technical solution, the mass ratio of the multi-element lithium battery electrode waste in the slurry of S2 to the leaching aid is 1:0.5-3.0.

[0032] As a preferred technical solution, the solid-liquid ratio of the leaching reaction solution in the operating conditions in S2 is 2-6:1.

[0033] As a preferred technical solution, the reaction time in the operating conditions of S2 is 1h-8h; the reaction endpoint pH value in the operating conditions of S2 is 1.5-4.0; and the reaction temperature in the operating conditions of S2 is 40℃-100℃.

[0034] Due to the adoption of the above technical solution, a method for one-step efficient separation of lithium from multi-element lithium battery electrode waste material is provided, which comprises the following steps: the multi-element lithium battery electrode waste material is at least one of positive electrode waste material and negative electrode waste material, and the multi-element lithium battery contains at least one of nickel, cobalt and manganese elements; S1, one-step lithium separation, adding inorganic acid, leaching aid and reducing agent to the multi-element lithium battery electrode waste material powder, stirring and leaching, reacting at a certain temperature for a certain time to obtain a reaction completed slurry; S2, filtering and washing, filtering and washing the reaction completed slurry to obtain a lithium ion concentration of 10-30 g / L of lithium-rich solution and residue. The lithium extraction residue is nickel-cobalt-manganese (carbon) residue, which can be used as raw material for producing nickel, cobalt and manganese salts. A simpler way is to enter the existing nickel-cobalt-manganese wet extraction production line as raw material.

[0035] Working principle:

[0036] The slurry of the method under the acidic condition, under the joint action of the reducing agent and the aid, dissociates the phase and structure of the electrode material, the dissociated lithium ions react with the inorganic acid to form a water-soluble lithium salt solution; and part of the high-valence nickel, cobalt and manganese ions in the positive electrode material are converted into low-valence state and form insoluble low-valence compounds to remain in the nickel-cobalt-manganese residue, so as to achieve the purpose of lithium preferential leaching and complete separation from nickel, cobalt and manganese.

[0037] Compared with the prior art, the technical solution has the following technical advantages or positive effects:

[0038] 1. The raw material of the method has strong adaptability, and one or a mixture of several of the positive (negative) electrode waste material, positive electrode material production waste material and the like produced by crushing and sorting of nickel-cobalt-manganese lithium, lithium cobaltate, lithium nickelate, lithium manganese, lithium cobalt aluminum and the like can be used as the raw material in the technical solution;

[0039] 2. The method achieves the purpose of one-step efficient separation of lithium and effective separation of nickel, cobalt and manganese, and the lithium leaching rate can reach more than 95%, and the nickel, cobalt and manganese leaching rate is less than 3%. The leaching solution has good quality, the lithium concentration can reach 10-30 g / L, and the concentration of other metal impurities is very low; the lithium recovery rate of lithium carbonate product reaches more than 90%, which can be large-scale industrialized application, and provides a new idea for efficient and economical recycling of lithium battery positive (negative) electrode waste material containing one or several of nickel, cobalt and manganese elements;

[0040] 3. The method is a new process of full wet method, which has low production line investment, low production cost, obvious safety and environmental protection advantages and high production efficiency. The lithium recovery process is self-contained, which is convenient for front-end processing in the existing lithium / nickel-cobalt-manganese production system, and various lithium battery positive (negative) electrode waste materials containing one or several of nickel, cobalt and manganese elements in the market are used as new production raw materials for processing.

[0041] 4. After applying this invention, the lithium-rich solution can be used to produce lithium products (battery-grade lithium carbonate, battery-grade lithium chloride, and battery-grade lithium hydroxide, etc.) on-site. The product contains one or more (carbon) slags containing nickel, cobalt, and manganese elements, which can be recycled into nickel-cobalt smelting enterprises through pyrometallurgical or hydrometallurgical processes.

[0042] 5. This invention achieves efficient one-step separation of lithium and nickel, cobalt and manganese, breaking down the production barriers between waste lithium battery recycling and nickel, cobalt and manganese smelting. It improves the high recovery rate of lithium while reducing the overall unit cost of nickel, cobalt and manganese recycling, and has global promotion significance.

[0043] 6. This invention is environmentally friendly, with a short lithium extraction process, simple operation, and a self-contained lithium recovery system that is easy to use. It can efficiently and selectively separate lithium and nickel, cobalt, and manganese from battery waste through a one-step leaching process, allowing them to enter their respective production systems to obtain their respective products, thus avoiding mutual interference. Attached Figure Description

[0044] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0045] This invention provides a one-step, highly efficient method for separating lithium from waste lithium-ion battery electrodes. To facilitate understanding of the technical means, inventive features, objectives, and effects of this invention, specific embodiments are described below to further illustrate the invention.

[0046] Example 1

[0047] Waste nickel-cobalt-manganese lithium-ion batteries were crushed and sorted to obtain positive and negative electrode waste powder (main components and contents: Li 4.32%, Ni 20.0%, Co 8.5%, Mn 9.7%, Cu 1.5%, Al 0.5%, C 32.5%). This powder was then slurried with dilute sulfuric acid solution at a liquid-to-solid ratio of 2:1, with the mass ratio of sulfuric acid to the positive and negative electrode waste powder being 37.55%. Leaching aids tartaric acid and ascorbic acid were continuously added at 80℃, with a mass ratio of 6:4, and the total amount of leaching aids was 2.0 times the mass of the positive and negative electrode waste powder. Then, sodium metabisulfite, a reducing agent, was added, with the amount of reducing agent being 0.1 times the mass of the positive and negative electrode waste powder. The reaction was stirred for 8 hours, and the final pH value was controlled at 3.0. Solid-liquid separation yielded a lithium-rich solution and nickel-cobalt-manganese slag.

[0048] The concentrations of the lithium-rich solution were determined to be Li 21.0 g / L, Ni 0.05 g / L, Co 0.01 g / L, Mn 0.4 g / L, Cu 0.3 g / L, and Al 0.05 g / L. Based on the concentrations of each ion in the solution, the leaching rates were calculated to be 97.22% for lithium, 0.05% for Ni, 0.02% for Co, and 0.08% for Mn.

[0049] The lithium-rich solution, i.e. lithium sulfate leaching solution, is heated to 90°C, and solid sodium hydroxide is added to adjust the pH value of the solution to be greater than 11, and the reaction is carried out for 4 hours. The lithium in the leaching solution remains in an ionic state, while the impurities such as nickel, cobalt, manganese, copper and aluminum form solids and enter the impurity-removing residue. The liquid and solid are separated to obtain the impurity-removed solution. The prepared 300 g / L sodium carbonate solution is heated to 90°C, and then slowly added into the 90°C impurity-removed solution, and the reaction is carried out for 2 hours. The solution is centrifuged to obtain industrial-grade lithium carbonate.

[0050] The lithium-rich residue is slurried by adding water at a liquid-solid ratio of 3:1, and concentrated sulfuric acid is added. The solution is heated to 90°C, and the reaction is carried out for 4 hours. Nickel, cobalt and manganese are converted into a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, which is separated from the negative electrode carbon. The mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate can be used to produce various nickel, cobalt and manganese salt products according to requirements.

[0051] Example 2

[0052] The lithium nickel cobalt manganese oxide production waste powder (main components and contents: Li 6.54%, Ni 29.63%, Co 12.5%, Mn 11.7%) is slurried by adding hydrochloric acid solution at a liquid-solid ratio of 3:1, and the mass ratio of hydrochloric acid to waste powder is 30.0%. The leaching aid citric acid is added at 80°C for reaction for 2 hours, and the leaching amount is 2.3 times the mass of the waste powder. The reducing agent is hydrogen peroxide, and the reducing agent amount is 0.25 times the mass of the waste powder. The stirring reaction is carried out for 6 hours, and the reaction end point pH value is controlled to be 1.5-2.0. The solid-liquid separation obtains a lithium-rich solution and a nickel cobalt manganese residue.

[0053] The concentration of the lithium-rich solution is Li 21.36 g / L, Ni 0.08 g / L, Co 0.05 g / L and Mn 0.8 g / L. According to the concentration of each ion in the solution, the leaching rate of lithium is 98.00%, the leaching rate of Ni is 0.08%, the leaching rate of Co is 0.12%, and the leaching rate of Mn is 2.05%.

[0054] The lithium-rich solution is purified to remove a small amount of residual nickel, cobalt, manganese and other impurity ions in the solution for subsequent preparation of lithium carbonate products.

[0055] Example 3

[0056] The lithium nickel cobalt manganese oxide waste negative electrode powder (main components and contents: Li 6.35%, Ni 25.63%, Co 12.5%, Mn 11.7%, Al 1.5%) is slurried by adding sulfuric acid solution at a liquid-solid ratio of 4:1, and the mass ratio of sulfuric acid to waste negative electrode powder is 60.0%. The leaching aid EDTA is continuously added at 90°C, and the leaching aid amount is 0.6 times the mass of the waste negative electrode powder. Then, the reducing agent sodium dithionite is added, and the reducing agent amount is 0.15 times the mass of the waste negative electrode powder. The stirring reaction is carried out for 6 hours, and the reaction end point pH value is controlled to be 4.0. The solid-liquid separation obtains a lithium-rich solution and a nickel cobalt manganese residue.

[0057] The concentration of the lithium-rich solution is Li 15.55 g / l, Ni 0.05 g / L, Co 0.05 g / L, Mn 0.5 g / L, and Al 0.05 g / L. According to the ion concentration in the solution, the leaching rate of lithium is 98.00%, the leaching rate of Ni is 0.06%, the leaching rate of Co is 0.12%, the leaching rate of Mn is 1.28%, and the leaching rate of Al is 1.0%.

[0058] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese in the solution, for subsequent preparation of lithium carbonate products.

[0059] Example 4

[0060] The lithium nickel cobalt aluminate waste powder (main components and contents: Li 6.3%, Ni 10.22%, Co 43.05%, Al 1.23%) is uniformly stirred with the leaching aid EDTA, and the amount of the leaching aid is 1.6 times the mass of the waste powder; a nitric acid solution is added to make a slurry with a liquid-solid ratio of 6:1, and the mass ratio of the nitric acid to the waste powder is 20.0%; a reducing agent glucose is added at 75°C, and the amount of the reducing agent is 0.35 times the mass of the waste powder; the stirring reaction is carried out for 8 h, and the pH value at the end point of the reaction is controlled to be 4.0; and the lithium-rich solution and nickel cobalt manganese residue are obtained through solid-liquid separation.

[0061] The concentration of the lithium-rich solution is Li 10.34 g / l, Ni 0.05 g / L, Co 0.05 g / L, Mn 0.6 g / L, and Al 0.08 g / L. According to the ion concentration in the solution, the leaching rate of lithium is 98.00%, the leaching rate of Ni is 0.08%, the leaching rate of Co is 0.02%, the leaching rate of Mn is 1.18%, and the leaching rate of Al is 1.1%.

[0062] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese in the solution, for subsequent preparation of lithium carbonate products.

[0063] Example 5

[0064] The lithium nickelate waste powder (main components and contents: Li 6.8%, Ni 57.8%) is added to water hydrochloric acid solution to make a slurry with a liquid-solid ratio of 4.5:1, and the amount of the hydrochloric acid is 50% of the amount of the lithium nickelate waste powder; a leaching aid salicylic acid is added to stir and leach for 2.5 h at 90°C, and the amount of the leaching aid is 1.85 times the mass of the lithium nickelate waste powder; a reducing agent soluble starch is added, and the amount of the reducing agent is 0.4 times the mass of the lithium nickelate waste powder; the stirring reaction is carried out for 1.5 h, and the pH value at the end point of the reaction is controlled to be 4.0; and the lithium-rich solution and nickel cobalt manganese residue are obtained through solid-liquid separation.

[0065] The concentration of the lithium-rich solution was Li 14.84 g / L, Ni 0.5 g / L. According to the ion concentration in the solution, the leaching rate of Li was 98.00%, and the leaching rate of Ni was only 0.31%.

[0066] The lithium-rich solution was purified to remove a small amount of impurity ions such as nickel in the solution for subsequent preparation of lithium carbonate products.

[0067] Example 6

[0068] The lithium-rich solution was purified to remove a small amount of impurity ions such as nickel in the solution for subsequent preparation of lithium carbonate products.

[0069] The concentration of the lithium-rich solution was Li 10.78 g / L, Mn 1.5 g / L. According to the ion concentration in the solution, the leaching rate of Li was 98.02%, and the leaching rate of Mn was only 1.18%.

[0070] The lithium-rich solution was purified to remove a small amount of impurity ions such as nickel in the solution for subsequent preparation of lithium carbonate products.

[0071] Example 7

[0072] The lithium-rich solution was purified to remove a small amount of impurity ions such as nickel in the solution for subsequent preparation of lithium carbonate products.

[0073] The concentration of the lithium-rich solution was Li 13.85 g / L, Co 1.5 g / L. According to the ion concentration in the solution, the leaching rate of Li was 98.28%, and the leaching rate of Co was 1.22%.

[0074] The lithium-rich solution was purified to remove a small amount of impurity ions such as nickel in the solution for subsequent preparation of lithium carbonate products.

[0075] Example 8

[0076] The lithium nickel cobalt manganese oxide waste powder (main components and contents: Li 6.25%, Ni 11.22%, Co 44.05%) is slurried with a liquid-solid ratio of 2.5:1 with a nitric acid solution, and the amount of nitric acid used is 30% of the mass of the lithium nickel cobalt manganese oxide waste powder; at 90°C, the leaching aids salicylic acid and oxalic acid, and the reducing agent soluble starch are continuously added, the amount of salicylic acid and oxalic acid (1:1) added is 1.75 times the mass of the lithium nickel cobalt manganese oxide waste powder, and the amount of soluble starch added is 0.55 times the mass of the lithium nickel cobalt manganese oxide waste powder, and the stirring leaching is carried out for 6h, and the reaction endpoint pH value is controlled at 3.0, and the solid-liquid separation obtains a lithium-rich solution and a nickel cobalt manganese residue.

[0077] The concentration of the lithium-rich solution is Li 24.6g / L, Co 1.5g / L, and Ni 0.05g / L, and according to the ion concentrations in the solution, the leaching rate of Li is 98.40%, the leaching rate of Co is 0.85%, and the leaching rate of Ni is 0.12%.

[0078] The lithium-rich solution is purified to remove a small amount of residual nickel cobalt and other impurity ions in the solution for subsequent preparation of lithium carbonate products.

[0079] Example 9

[0080] The lithium manganese cobalt oxide mixed waste powder (main components and contents: Li 5.68%, Co 33.7%, Mn 20.18%) is slurried with a liquid-solid ratio of 3:1 with water, and sulfuric acid, the leaching aid acetylacetone and salicylic acid, and the reducing agent ferrous sulfate are sequentially added. The amount of sulfuric acid used is 0.15% of the mass of the lithium manganese cobalt oxide mixed waste powder; the leaching aids salicylic acid and acetylacetone (1:1) are 0.85 times the mass of the lithium manganese cobalt oxide mixed waste powder; the reducing agent ferrous sulfate is 0.35 times the mass of the lithium manganese cobalt oxide mixed waste powder; at 80°C, the stirring leaching is carried out for 5h, and the solid-liquid separation obtains a lithium-rich solution and a nickel cobalt manganese residue.

[0081] The concentration of the lithium-rich solution is Li 18.75g / L, Co 0.8g / L, and Mn 1.05g / L, and according to the ion concentrations in the solution, the leaching rate of Li is 99.00%, the leaching rate of Co is 0.72%, and the leaching rate of Mn is 1.56%.

[0082] The lithium-rich solution is purified to remove a small amount of residual cobalt manganese and other impurity ions in the solution for subsequent preparation of lithium carbonate products.

[0083] Example 10

[0084] The mixed waste powder of lithium manganate and nickel-cobalt-manganese acid lithium (main components and contents: Li 4.95%, Ni 20.26%, Co 4.59%, Mn 20.07%) is slurried with sulfuric acid solution at a liquid-solid ratio of 2:1, the sulfuric acid dosage is 0.3% of the mass of the mixed waste powder, and the leaching aid citric acid and the reducing agent sodium hyposulfite are continuously added at 80°C, the addition amount of citric acid is 1.8 times of the mass of the mixed waste powder of lithium manganate and nickel-cobalt-manganese acid lithium, the addition amount of sodium hyposulfite is 0.1%, and the reaction endpoint pH is controlled at 4.0, and the lithium-rich solution and nickel-cobalt-manganese residue are obtained by solid-liquid separation.

[0085] The concentration of the lithium-rich solution is Li 24.35 g / L, Ni 0.08 g / L, Co 0.04 g / L, and Mn 1.05 g / L, and according to the ion concentration in the solution, the leaching rate of Li is 98.37%, the leaching rate of Co is 0.17%, the leaching rate of Ni is 0.1%, and the leaching rate of Mn is 1.05%.

[0086] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution for subsequent preparation of lithium carbonate products.

[0087] Example 11

[0088] The mixed waste powder of lithium manganate, lithium cobaltate and nickel-cobalt acid lithium (main components and contents: Li 5.96%, Ni 15.77%, Co 20.81%, Mn 12.53%) is first mixed with the leaching aid malonic acid, and the leaching aid dosage is 2.8 times of the mass of the mixed waste powder of lithium manganate, lithium cobaltate and nickel-cobalt acid lithium; sulfuric acid and nitric acid solution is added to slurry at a liquid-solid ratio of 3.5:1, and the sulfuric acid and nitric acid dosages are 20% and 10% of the mass of the mixed waste powder of lithium manganate, lithium cobaltate and nickel-cobalt acid lithium, respectively. The reaction is carried out at 80°C for 3h, and then the reducing agent hydrogen peroxide is slowly added and reacted for 3h, and the addition amount of hydrogen peroxide is 0.15 times of the mass of the mixed waste powder of lithium manganate, lithium cobaltate and nickel-cobalt acid lithium; the reaction endpoint pH is controlled at 1.5, and the lithium-rich solution and nickel-cobalt-manganese residue are obtained by solid-liquid separation.

[0089] The concentration of the lithium-rich solution is Li 16.78 g / L, Ni 0.08 g / L, Co 0.1 g / L, and Mn 1.05 g / L, and according to the ion concentration in the solution, the leaching rate of Li is 98.54%, the leaching rate of Co is 0.18%, the leaching rate of Ni is 0.18%, and the leaching rate of Mn is 2.93%.

[0090] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution for subsequent preparation of lithium carbonate products.

[0091] Example 12

[0092] The mixed waste powder of lithium cobaltate and lithium nickel cobalt manganese acid black powder (main components and contents: Li 4.54%, Ni 10.85%, Co 31.6%, Mn 4.71%) is mixed with ascorbic acid, the amount of ascorbic acid is 1.5 times the mass of the mixed waste powder of lithium cobaltate and lithium nickel cobalt manganese acid black powder, water is added to make a slurry with a liquid-solid ratio of 3:1, sulfuric acid is slowly added at 90°C and stirred for leaching for 1.5h, the amount of sulfuric acid added is 0.60 times the mass of the mixed waste powder of lithium cobaltate and lithium nickel cobalt manganese acid black powder; then the reducing agent sodium thiosulfate is added for reaction for 4.5h, the amount of reducing agent added is 0.35 times the mass of the mixed waste powder of lithium cobaltate and lithium nickel cobalt manganese acid black powder, and the pH of the reaction endpoint is controlled at 2.5, to obtain a lithium-rich solution and a nickel cobalt manganese residue after solid-liquid separation.

[0093] The concentration of the lithium-rich solution is Li 15.01g / L, Ni 0.05g / L, Co 0.1g / L, and Mn 0.15g / L, and according to the ion concentrations in the solution, the leaching rate of Li is 99.18%, the leaching rate of Co is 0.13%, the leaching rate of Ni is 0.15%, and the leaching rate of Mn is 0.96%.

[0094] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution, for subsequent preparation of lithium carbonate products.

[0095] Example 13

[0096] The mixed waste powder of lithium manganate, lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt aluminate and lithium nickel cobalt manganese acid (main components and contents: Li 5.8%, Ni 10.85%, Co 25.63%, Mn 8.71%, Al 0.5%) is added with water to make a slurry with a liquid-solid ratio of 5:1, a 40% hydrochloric acid solution is slowly added at 95°C, and leaching aid EDTA is added at the same time, and stirred for leaching for 3.5h, wherein the amount of EDTA added is 2.2 times the mass of the mixed waste powder of lithium manganate, lithium cobaltate, lithium nickelate, lithium nickel cobaltate, lithium nickel cobalt aluminate and lithium nickel cobalt manganese acid; then the reducing agent glucose is added for reaction for 3.5h, the amount of glucose added is 0.3 times the mass of the mixed waste powder, and the pH of the reaction endpoint is controlled at 3.5, to obtain a lithium-rich solution and a nickel cobalt manganese residue after solid-liquid separation.

[0097] The concentration of the lithium-rich solution is Li 11.41g / L, Ni 0.05g / L, Co 0.1g / L, Mn 0.15g / L, and Al 0.03g / L, and according to the ion concentrations in the solution, the leaching rate of Li is 98.36%, the leaching rate of Co is 0.58%, the leaching rate of Ni is 0.20%, the leaching rate of Mn is 0.85%, and the leaching rate of Al is 3.0%.

[0098] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution, for subsequent preparation of lithium carbonate products.

[0099] Example 14

[0100] The positive and negative electrode waste powder (main components and contents: Li 4.24%, Ni 12.85%, Co 35.6%, Mn 5.71%, C 28.7%, Cu 3.0%, Al 0.55%) and malonic acid obtained by crushing and sorting waste lithium cobalt oxide and lithium nickel cobalt manganese oxide batteries were mixed, the amount of malonic acid was 2.0 times the mass of the positive and negative electrode waste powder, water was added to prepare a slurry at a liquid-solid ratio of 3:1, sulfuric acid was slowly added under stirring at 85°C for leaching for 1.5h, the amount of sulfuric acid added was 0.60 times the mass of the positive and negative electrode waste powder; then the reducing agent sodium thiosulfate was added for reaction for 4.5h, the amount of reducing agent added was 0.35 times the mass of the positive and negative electrode waste powder, and the pH at the end point of the reaction was controlled to be 2.5-3.0, to obtain a lithium-rich solution and a nickel-cobalt-manganese carbon residue after solid-liquid separation.

[0101] The concentration of the lithium-rich solution was Li 13.91g / L, Ni 0.03g / L, Co 0.1g / L, Mn 0.15g / L, Cu 0.3g / L, and Al 0.05g / L, and according to the concentrations of the ions in the solution, the leaching rate of Li was 98.42%, the leaching rate of Co was 0.08%, the leaching rate of Ni was 0.07%, and the leaching rate of Mn was 0.78%.

[0102] The lithium-rich solution was purified to remove a small amount of nickel, cobalt, manganese and other impurity ions remaining in the solution for subsequent preparation of lithium carbonate products.

[0103] Example 15

[0104] The positive and negative electrode waste powder (main components and contents: Li 3.54%, Ni 9.85%, Co 5.6%, Mn 20.71%, C 26.7%, Cu 3.5%, Al 1.55%) and ascorbic acid obtained by crushing and sorting waste lithium manganese oxide and lithium nickel cobalt manganese oxide batteries were mixed, the amount of ascorbic acid was 2.5 times the mass of the positive and negative electrode waste powder; water was added to prepare a slurry at a liquid-solid ratio of 3:1, hydrochloric acid was slowly added under stirring at 90°C for leaching for 3.5h, the amount of hydrochloric acid added was 0.60 times the mass of the positive and negative electrode waste powder; then the reducing agent soluble starch was added for reaction for 4.5h, the amount of reducing agent added was 0.35 times the mass of the positive and negative electrode waste powder, and the pH at the end point of the reaction was controlled to be 3.5, to obtain a lithium-rich solution and a nickel-cobalt-manganese carbon residue after solid-liquid separation.

[0105] The concentration of the lithium-rich solution is Li 11.65 g / L, Ni 0.01 g / L, Co 0.01 g / L, Mn 0.15 g / L, Cu 0.5 g / L, and Al 0.08 g / L. According to the ion concentration in the solution, the leaching rate of Li is 98.70%, the leaching rate of Co is 0.05%, the leaching rate of Ni is 0.05%, and the leaching rate of Mn is 0.26%.

[0106] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution, for subsequent preparation of lithium carbonate products.

[0107] Example 16

[0108] The positive and negative mixed waste powder (main components and contents: Li 3.67%, Ni 19.85%, Co 12.6%, Mn 15.71%, C 30.7%, Cu 2.5%, and Al 1.15%) obtained by crushing and sorting waste lithium cobalt oxide, lithium manganese oxide and nickel cobalt manganese oxide batteries is slurried with sulfuric acid solution at a liquid-solid ratio of 3:1, tartaric acid is slowly added as a leaching aid under stirring at 95°C for 3.5h, the addition amount of tartaric acid is 1.67 times the mass of the mixed waste powder; then the reducing agent sodium thiosulfate and soluble starch are added and the reaction is continued for 4.5h, the addition amount of the reducing agent is 0.35 times the mass of the mixed waste powder, and the reaction endpoint pH is controlled at 1.5-3.5, to obtain a lithium-rich solution and a nickel-cobalt-manganese carbon residue after solid-liquid separation.

[0109] The concentration of the lithium-rich solution is Li 12.00 g / L, Ni 0.04 g / L, Co 0.02 g / L, Mn 0.17 g / L, Cu 0.35 g / L, and Al 0.08 g / L. According to the ion concentration in the solution, the leaching rate of Li is 98.10%, the leaching rate of Co is 0.05%, the leaching rate of Ni is 0.06%, and the leaching rate of Mn is 0.33%.

[0110] The lithium-rich solution is purified to remove a small amount of impurity ions such as nickel, cobalt and manganese remaining in the solution, for subsequent preparation of lithium carbonate products.

[0111] The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for one-step high-efficiency separation of lithium from multi-element lithium battery electrode waste, characterized in that, The method comprises the following steps: The multi-element lithium battery electrode waste is positive electrode waste or a mixture of positive electrode waste and negative electrode waste, and the multi-element lithium battery contains at least one of nickel, cobalt and manganese elements; S1, one-step separation of lithium An inorganic acid, a leaching aid and a reducing agent are added to the multi-element lithium battery electrode waste powder, the mixture is stirred and leached, and the mixture is reacted at a certain temperature for a certain time to obtain a reaction completed slurry; S2, filtration and washing The reaction completed slurry is filtered and washed to obtain a lithium ion concentration of 10-30 g / L of a lithium-rich solution and a residue; The reducing agent is added after the inorganic acid and the leaching aid are added in S1, and the order of adding the inorganic acid and the leaching aid has no special requirement, but they cannot be premixed and then added; The inorganic acid is one or a mixture of more than one of sulfuric acid, hydrochloric acid and nitric acid; The reducing agent is one or more than one of sodium pyrosulfite, sodium dithionate, hydrogen peroxide, glucose, soluble starch, ferrous sulfate, sodium sulfite and sodium thiosulfate; The leaching aid is one or more than one of citric acid, malonic acid, acetylacetone, oxalic acid, ascorbic acid, tartaric acid, salicylic acid and EDTA; The pH value of the reaction end point in the operation condition of S1 is 1.5-4.0; The mass ratio of the multi-element lithium battery electrode waste to the inorganic acid in S1 is 1:0.05-0.6; The mass ratio of the multi-element lithium battery electrode waste to the reducing agent in S1 is 1:0.1-1.0; The mass ratio of the multi-element lithium battery electrode waste to the leaching aid in S1 is 1:0.5-3.0; The solid-liquid ratio of the leaching reaction liquid in the operation condition of S1 is 2-6:1; The reaction time in the operation condition of S1 is 1 h-8 h, and the reaction temperature in the operation condition of S1 is 40°C-100°C.

2. The method for one-step high-efficiency separation of lithium from multi-element lithium battery electrode waste according to claim 1, characterized in that: The waste in S1 is one or both of electrode waste produced by crushing and sorting of electrode sheets and positive electrode material production waste; The electrode waste produced by crushing and sorting of electrode sheets is one or more than one of electrode waste produced by crushing and sorting of lithium nickel cobalt manganese oxide electrode sheets, electrode waste produced by crushing and sorting of lithium cobalt oxide electrode sheets, electrode waste produced by crushing and sorting of lithium nickel oxide electrode sheets, electrode waste produced by crushing and sorting of lithium manganese oxide electrode sheets and electrode waste produced by crushing and sorting of lithium nickel cobalt aluminum oxide electrode sheets; the electrode waste produced by crushing and sorting of electrode sheets includes positive electrode waste produced by crushing and sorting of electrode sheets and negative electrode waste produced by crushing and sorting of electrode sheets; The positive electrode material production waste is one or more than one of lithium nickel cobalt manganese oxide positive electrode material production waste, lithium cobalt oxide positive electrode material production waste, lithium nickel oxide positive electrode material production waste, lithium manganese oxide positive electrode material production waste and lithium nickel cobalt aluminum oxide positive electrode material production waste.

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