Method for separating and recycling valuable metal in waste ternary lithium battery positive electrode material based on eutectic solvent

Abstract

The invention discloses a method for separating and recycling valuable metals in a waste ternary lithium battery positive electrode material based on a deep eutectic solvent. The method comprises the following steps: mixing a deep eutectic solvent with a ternary lithium battery positive electrode material, leaching, and collecting nickel-rich precipitate and leachate after solid-liquid separation; wherein the eutectic solvent is composed of a leaching agent and a solvent; the leaching agent is choline chloride and tartaric acid. The nickel in the ternary lithium battery can be specifically precipitated on the basis of the synthesized deep eutectic solvent, the nickel element is preferentially separated out, and then valuable metals including cobalt, manganese and lithium are obtained through a step-by-step precipitation method. The eutectic solvent system has the advantages that the leaching temperature is low, the dynamic time is short, the nickel precipitation efficiency is high, the cobalt and manganese leaching efficiency is close to 100% and the like, and the method is short in needed process, flexible and diversified in export product and high in adjustability and has wide application value in the aspect of separating and recycling valuable metal in batteries.

Description

Technical Field

[0001] The present invention relates to the field of recycling waste lithium-ion battery materials, and more specifically, to a method for separating and recycling valuable metals in waste ternary lithium battery positive electrode materials based on a low eutectic solvent. Background Art

[0002] Energy shortage and environmental pollution have seriously restricted the sustainable development of my country's economy and society. The "carbon neutrality" and "carbon peak" goals proposed by the Chinese government have put the comprehensive development of the new energy industry on the fast track. Lithium-ion batteries (LIBs) are the main energy source for new energy vehicles. After long-term use, the structure of the battery electrode materials will be destroyed, and the battery performance will decline until it is retired and scrapped. Recycling and reusing waste LIBs can not only prevent batteries from causing damage to the environment, but also alleviate the shortage of domestic battery resources and reduce the pressure on battery production capacity.

[0003] At present, the recycling process of waste batteries is mainly based on wet extraction. This process transfers the solid metal in the electrode material to the liquid in an acidic or alkaline solution, and then separates the metal ions in the solution through solvent extraction, chemical precipitation, adsorption, electrochemistry and other technologies. However, the existing technical means mainly focus on the synchronous separation of elements in the positive electrode material, which is not only complicated to operate but also causes the entrainment loss of metal elements. In addition, the existing recycling process mostly uses strong inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. In order to strengthen the leaching process, a large amount of reducing agents such as hydrogen peroxide and sodium hyposulfite are used. During the leaching process, obvious acid mist will be generated, which will cause serious corrosion to equipment and factory buildings and cause physical damage to front-line operators. Therefore, in order to achieve effective leaching and recovery of metals, it is necessary to find a more green and economical alternative solvent.

[0004] In recent years, a new type of "green solvent" - deep eutectic solvents (DESs) has the advantages of cheap and easy raw materials, simple preparation, stable physicochemical properties, adjustable structural properties, good conductivity, non-volatility, non-flammability, biodegradability, etc., and it has good solubility for most metal oxides. It is considered to be a promising battery recovery leaching agent that can replace inorganic and organic acids. However, the existing deep eutectic solvent system composition is relatively simple, and the hydrogen bond donors are mainly concentrated in urea, malic acid, lactic acid, acetamide, sulfonic acid compounds, etc., and no new hydrogen bond donors have been developed. In addition, the disclosed deep eutectic solvents have a long reaction kinetic time and a high reaction temperature when used to recover metal elements in ternary lithium batteries.

[0005] Therefore, it is necessary to achieve efficient, clean and selective recovery of valuable metals in multi-element batteries under the premise of exploring new low-eutectic solvent systems. Summary of the invention

[0006] Based on the above defects, the first object of the present invention is to provide an application of a low eutectic solvent in the recovery of nickel from waste ternary lithium battery positive electrode materials. The present invention uses a new low eutectic solvent system to recover nickel from waste ternary lithium battery positive electrode materials, achieving efficient separation of nickel from cobalt, manganese and lithium, and has mild leaching conditions, low pollution, low cost, and a simple entire process flow, with good social and economic benefits.

[0007] The second object of the present invention is to provide a method for separating and recovering valuable metals in the positive electrode materials of waste ternary lithium batteries. The method uses a new low eutectic solvent system to separate and recover valuable metals in the positive electrode materials of waste ternary lithium batteries. In the first step, nickel is separated first, and then valuable metals including manganese, cobalt and lithium are obtained by a step-by-step precipitation method. The method provided by the present invention can produce a variety of export products, has the advantages of strong adjustability, high precipitation efficiency, simple steps, short process, green environmental protection, low cost, etc., and has a wide range of application value in separating and recovering valuable metals in batteries.

[0008] In order to achieve the above first object, the present invention adopts the following technical scheme:

[0009] The invention discloses an application of a low eutectic solvent in recycling nickel in waste ternary lithium battery positive electrode materials, wherein the low eutectic solvent is mixed with the ternary lithium battery positive electrode material, leached, and after solid-liquid separation, the nickel-rich precipitate and the leachate are collected;

[0010] Wherein, the deep eutectic solvent consists of a leaching agent and a solvent;

[0011] The leaching agents are choline chloride and tartaric acid.

[0012] In previous studies on low eutectic solvent systems, researchers mainly focused on the efficient precipitation of nickel from the positive electrode materials of ternary lithium batteries, emphasizing the high precipitation efficiency of nickel, and did not pay too much attention to the leaching efficiency of other metals such as cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The leaching efficiency of cobalt and manganese is generally at the level of 96-98%, which also leads to 2-4% of cobalt and manganese being precipitated together with nickel, which is not conducive to the subsequent use of recovered nickel. Based on this problem, the present invention develops a new low eutectic solvent system. It is found through experimental data calculation that it has a high nickel precipitation efficiency (more than 95%) and cobalt and manganese leaching efficiency (both close to 100%), and lithium is not completely leached from the positive electrode materials of ternary lithium batteries due to the solubility of the low eutectic solvent system. After inductively coupled plasma emission spectrometer (ICP) testing, the lithium content in the calcined nickel oxide is only about 4%, which shows that the low eutectic solvent system achieves efficient separation of nickel and cobalt, manganese and lithium, reduces the loss of cobalt, manganese and lithium, and thus ensures the purity of the recovered nickel, which is very beneficial for subsequent use.

[0013] Further, choline chloride and tartaric acid are effective components of the deep eutectic solvent, and the dosage relationship of the choline chloride and tartaric acid should be controlled. When the molar ratio of choline chloride to tartaric acid is 1:10-10:1, the nickel precipitation efficiency is high, the cobalt, manganese and lithium leaching efficiency is high, and the nickel can be separated first. Preferably, when the molar ratio of choline chloride to tartaric acid is 1:2-2:1, the nickel precipitation and the leaching of cobalt, manganese and lithium are more favorable. For example, the molar ratio of choline chloride to tartaric acid can be 2:1, 3:2, 1:1, 2:3, 1:2, and the like.

[0014] Furthermore, since the leaching agent formed by choline chloride and tartaric acid has a high viscosity, it is difficult to use or separate the solid and liquid subsequently, and nickel-rich precipitates are easily adhered. Therefore, during the preparation of the low eutectic solvent, a solvent such as water or ethanol is added to improve the fluidity of the leaching agent and reduce its viscosity. The amount of solvent added is 5-10wt% of the mass of the leaching agent.

[0015] Further, the solid-liquid ratio of the ternary lithium battery positive electrode material to the low eutectic solvent is 10-100 g / L. Exemplarily, the solid-liquid ratio of the ternary lithium battery positive electrode material to the low eutectic solvent can be 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L, etc., or an interval formed by any two point values.

[0016] Furthermore, the leaching temperature is 60-120°C, and the leaching time is 10-240 min; preferably, the leaching temperature is 80-120°C, and the leaching time is 40-90 min.

[0017] Furthermore, the stirring speed is controlled to be 200-1000 rpm during the leaching process.

[0018] Furthermore, the positive electrode material of the ternary lithium battery includes but is not limited to LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2、LiNi 0.5 Co 0.2 Mn 0.3 O2、LiNi 0.6 Co 0.2 Mn 0.2 O2 and LiNi 0.8 Co 0.1 Mn 0.1 Any one or more of O2.

[0019] Furthermore, the positive electrode material of the ternary lithium battery is prepared by the following pretreatment process:

[0020] After the waste ternary lithium-ion battery is completely discharged, the battery is disassembled to obtain an aluminum foil containing positive electrode active material, and the positive electrode active material on the aluminum foil is ultrasonically stripped to obtain the positive electrode material of the ternary lithium battery.

[0021] Furthermore, after obtaining the nickel-rich precipitate, it is necessary to wash, dry and calcine it to finally obtain nickel oxide;

[0022] Among them, the selected washing reagent is anhydrous ethanol;

[0023] The selected drying condition is drying at a temperature of 50-80°C;

[0024] The controlled calcination temperature is 400-800°C and the calcination time is 1-3h.

[0025] In order to achieve the above second purpose, the present invention adopts the following technical solutions:

[0026] On the basis of the above, the present invention continues to develop a method for separating and recovering valuable metals in waste ternary lithium battery positive electrode materials. The method can first separate nickel from the ternary lithium battery positive electrode material through a low eutectic solvent. This process is the same as the technical solution provided in the first purpose, and then obtain valuable metals including manganese, cobalt and lithium through a step-by-step precipitation method, which specifically includes the following steps:

[0027] 1) mixing choline chloride and tartaric acid, adding a solvent, and preparing a deep eutectic solvent;

[0028] 2) adding the positive electrode material of the ternary lithium battery into the low eutectic solvent for leaching, separating the solid and the liquid after the leaching is completed, and collecting the primary leachate and the nickel-rich precipitate;

[0029] 3) adding ammonium oxalate to the primary leachate, collecting the secondary leachate and the cobalt-rich precipitate after solid-liquid separation;

[0030] 4) adding sodium hydroxide to the secondary leachate, collecting the tertiary leachate and manganese-rich precipitate after solid-liquid separation;

[0031] 5) Add soda ash to the tertiary leaching solution and collect the lithium-rich precipitate.

[0032] Further, choline chloride and tartaric acid are effective components of the deep eutectic solvent, and the dosage relationship of the choline chloride and tartaric acid should be controlled. When the molar ratio of choline chloride to tartaric acid is 1:10-10:1, the nickel precipitation efficiency is high, the cobalt, manganese and lithium leaching efficiency is high, and the nickel can be separated first. Preferably, when the molar ratio of choline chloride to tartaric acid is 1:2-2:1, the nickel precipitation and the leaching of cobalt, manganese and lithium are more favorable. For example, the molar ratio of choline chloride to tartaric acid can be 2:1, 3:2, 1:1, 2:3, 1:2, and the like.

[0033] Further, the amount of the added solvent is 5-10 wt % of the total mass of choline chloride and tartaric acid; illustratively, the solvent may be water or ethanol.

[0034] Furthermore, the positive electrode material of the ternary lithium battery includes but is not limited to LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2、LiNi 0.5 Co 0.2 Mn 0.3 O2、LiNi 0.6 Co 0.2 Mn 0.2 O2 and LiNi 0.8 Co 0.1 Mn 0.1 Any one or more of O2.

[0035] Furthermore, in step 2), the leaching temperature is 60-120° C., and the leaching time is 10-240 min; preferably, the leaching temperature is 80-120° C., and the leaching time is 40-90 min.

[0036] Furthermore, the stirring speed is controlled to be 200-1000 rpm during each leaching process.

[0037] Furthermore, in step 3), the molar ratio of ammonium oxalate to cobalt is 1:1-1.5.

[0038] Furthermore, the leaching conditions in step 3) are: reacting at 40-60° C. for 30-120 min at a pH of 1-3.

[0039] Further, in step 4), sodium hydroxide is added to raise the pH of the secondary leaching solution to 11-12 to precipitate manganese.

[0040] Furthermore, in step 4), alkali salts such as potassium hydroxide, sodium carbonate, potassium carbonate, etc. can also be used instead of sodium hydroxide to precipitate manganese.

[0041] Furthermore, in step 5), the molar ratio of soda ash to lithium is 1:1.15-1.2.

[0042] Furthermore, the reaction conditions in step 5) are: reacting at 80-100° C. for 30-90 min.

[0043] Further, the solid-liquid ratio of the ternary lithium battery positive electrode material to the low eutectic solvent is 10-100 g / L. Exemplarily, the solid-liquid ratio of the ternary lithium battery positive electrode material to the low eutectic solvent can be 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L, etc., or an interval formed by any two point values.

[0044] Furthermore, after obtaining the nickel-rich precipitate, the cobalt-rich precipitate, and the manganese-rich precipitate, they need to be washed, dried, and calcined to finally obtain nickel oxide, cobalt oxide, and manganese oxide;

[0045] Among them, the selected washing reagent is anhydrous ethanol;

[0046] The selected drying condition is drying at a temperature of 50-80°C;

[0047] When calcining nickel-rich precipitate and cobalt-rich precipitate, the calcination temperature is controlled to be 400-800°C, and the calcination time is 1-3h; when calcining manganese-rich precipitate, the calcination temperature is controlled to be 600-1000°C, and the calcination time is 1-3h.

[0048] Furthermore, the positive electrode material of the ternary lithium battery is prepared by the following pretreatment process:

[0049] The purchased waste lithium-ion positive electrode sheet is heat-treated at 500-600°C for 0.5-1.5h, and the aluminum sheet is peeled off to obtain the positive electrode material of the ternary lithium battery.

[0050] The beneficial effects of the present invention are as follows:

[0051] The invention discloses application of a low eutectic solvent in recycling nickel in waste ternary lithium battery positive electrode materials. The new low eutectic solvent system containing choline chloride and tartaric acid can efficiently recover nickel in the positive electrode material of ternary lithium battery, with high nickel precipitation efficiency (more than 95%) and cobalt and manganese leaching efficiency (both close to 100%). However, due to the influence of the solubility of the low eutectic solvent system, lithium is not completely leached from the positive electrode material of the ternary lithium battery. According to the test of inductively coupled plasma emission spectrometer (ICP), the lithium content in the calcined nickel oxide is only about 4%, thereby achieving efficient separation of nickel and cobalt, manganese and lithium, reducing the loss of cobalt, manganese and lithium, and the leaching conditions are mild, the pollution is small and the cost is low. On this basis, a method for separating and recovering valuable metals in waste ternary lithium battery positive electrode materials is further developed. The method continues to use a step-by-step precipitation method for the leachate after nickel recovery, and can obtain cobalt-rich precipitates, manganese-rich precipitates and lithium-rich precipitates in turn, and finally achieves the selective separation of the four metals of nickel, cobalt, manganese and lithium, showing a high recovery efficiency, which is expected to be widely used in the separation and recovery of valuable metals in batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0053] Figure 1 A flow chart showing the separation and recovery of valuable metals in waste ternary lithium battery positive electrode materials according to the present invention.

[0054] Figure 2 is the XRD diagram of the nickel-rich precipitate and nickel oxide obtained in Example 1 of the present invention;

[0055] in, Figure 2 (a) is the XRD pattern of nickel-rich precipitate. Figure 2 (b) is the XRD pattern of nickel oxide after calcination of nickel-rich precipitate.

[0056] Figure 3 is a SEM image of the nickel-rich precipitate and nickel oxide obtained in Example 1 of the present invention;

[0057] in, Figure 3 (a) is the SEM image of nickel-rich precipitation. Figure 3 (b) is the SEM image of nickel oxide after calcination of nickel-rich precipitate. DETAILED DESCRIPTION

[0058] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0059] The present invention provides a method for selectively recovering valuable metals in waste ternary lithium battery positive electrode materials by using a new low eutectic solvent system. The low eutectic solvent system selected in the method has the effect of specifically precipitating nickel in the positive electrode material of the ternary lithium battery, so that the nickel element can be separated preferentially, with high nickel precipitation efficiency (more than 95%) and cobalt and manganese leaching efficiency (both close to 100%), and then various metals including cobalt, manganese and lithium are obtained by a step-by-step precipitation method. The selected low eutectic solvent system can achieve a high recovery efficiency of nickel elements at a lower leaching temperature and a shorter leaching time, and the method requires a short process, has a high step-by-step recovery efficiency for each metal of cobalt, manganese and lithium, has strong adjustability, is green and environmentally friendly, and has broad application value in separating and recovering valuable metals in batteries.

[0060] The following combination Figure 1 The present invention specifically describes a method for separating and recovering valuable metals in the positive electrode material of waste ternary lithium batteries, comprising the following steps:

[0061] (1) Pretreatment of waste ternary lithium-ion batteries

[0062] The waste lithium-ion positive electrode sheet is heat-treated at 500-600° C. for 0.5-1.5 h, and the aluminum sheet is peeled off to obtain the positive electrode material of the ternary lithium battery.

[0063] The positive electrode material of the ternary lithium battery is not limited to LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2、LiNi 0.5 Co 0.2 Mn 0.3 O2、LiNi 0.6 Co 0.2 Mn 0.2 O2 and LiNi 0.8 Co 0.1 Mn 0.1 Any one or more of O2.

[0064] (2) Preparation of low eutectic solvent

[0065] Choline chloride and tartaric acid are weighed in proportion, mixed, heated and stirred at 60-120° C. for 30-120 min to obtain a uniform and transparent extractant, and then a solvent is added to disperse the mixture to obtain a low eutectic solvent.

[0066] (3) Selective separation of nickel from cathode materials of ternary lithium batteries

[0067] The ternary lithium battery positive electrode material obtained in step (1) is added to the low eutectic solvent obtained in step (2) at a solid-liquid ratio of 10-100 g / L, and then stirred and leached at 60-120° C. for 10-240 min. After leaching, centrifugal separation is performed to obtain a primary leachate (containing cobalt, manganese and lithium) and a nickel-rich precipitate, wherein the centrifugal speed is 8000-12000 rpm and the centrifugal time is 5-20 min. The obtained nickel-rich precipitate is washed with anhydrous ethanol, dried at 50-80° C., and calcined to obtain nickel oxide, wherein the calcination temperature is 400-800° C. and the calcination time is 1-3 h.

[0068] (4) Selective separation of cobalt from primary leaching solution

[0069] Add ammonium oxalate solution to the primary leachate (pH 1-3) obtained in step (3), wherein the molar ratio of ammonium oxalate to cobalt is 1:1-1.5, react at 40-60°C for 30-120min, and centrifuge after leaching to obtain secondary leachate (containing manganese and lithium) and cobalt-rich precipitate, wherein the centrifugal speed is 8000-12000rpm and the centrifugal time is 5-20min. Wash the obtained cobalt-rich precipitate with anhydrous ethanol, dry it at 50-80°C, and calcine it to obtain cobalt oxide, wherein the calcination temperature is 400-800°C and the calcination time is 1-3h.

[0070] (5) Selective separation of manganese in secondary leaching solution

[0071] Sodium hydroxide is added to the secondary leaching solution obtained in step (4) to adjust the solution pH to 11-12, and the tertiary leaching solution (containing lithium) and manganese-rich precipitate are obtained by centrifugation, wherein the centrifugal speed is 8000-12000 rpm and the centrifugal time is 5-20 min. The obtained manganese-rich precipitate is washed with anhydrous ethanol, dried at 50-80° C., and calcined to obtain manganese oxide, wherein the calcination temperature is 600-1000° C. and the calcination time is 1-3 h.

[0072] (6) Lithium precipitation in the three leaching solutions

[0073] The tertiary leaching solution obtained in step (5) is evaporated and concentrated, and a soda solution is added to produce a precipitate, wherein the reaction equation is Li + +CO3 2- →Li2CO3↓. Then, lithium carbonate is obtained by washing with anhydrous ethanol and drying. The reaction conditions are: The reaction temperature is 80-100°C and the reaction time is 30-90 minutes.

[0074] The present invention will be further described in detail below by way of examples, which are not intended to further limit the content of the present invention. Those skilled in the art should understand that equivalent replacements made to the technical features of the present invention, or corresponding improvements, still fall within the protection scope of the present invention.

[0075] Example 1

[0076] Choline chloride and tartaric acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0077] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 20g / L, stirred and leached at 100℃ for 60min, and centrifuged to obtain nickel-rich precipitate and primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. After ICP testing, the lithium content in the calcined nickel oxide was only 4.15%, which shows that the low eutectic solvent system achieves efficient separation of nickel and cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60℃ overnight, and then calcined in a muffle furnace at 500℃ for 2h, and the heating rate was controlled to be 10℃ / min to obtain a nickel oxide product, and the product was characterized by XRD and SEM, as shown in Figure 2 and 3 shown by Figure 2 It is known that the product generated after calcination of the nickel-rich precipitate is compared with the nickel oxide standard card, confirming that nickel oxide is obtained, and the XRD of the product shows no impurity peaks, indicating that a high-purity nickel oxide product can be obtained under this low eutectic solvent system.

[0078] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.3. The mixture was reacted at 50°C for 2 hours, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 2 hours, with the heating rate controlled at 10°C / min, to obtain cobalt oxide.

[0079] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 10°C / min to obtain manganese oxide.

[0080] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 60 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 93.36%.

[0081] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0082] Example 2

[0083] Choline chloride and tartaric acid were prepared in a molar ratio of 2:3, and after mixing, they were heated and stirred at 90° C. for 60 minutes to obtain a leaching agent, and then deionized water with a mass of 10 wt % of the leaching agent was added to obtain a low eutectic solvent.

[0084] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 10 g / L, stirred and leached at 120°C for 20 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. According to ICP testing, the lithium content in the calcined nickel oxide was only 3.68%, indicating that the low eutectic solvent system achieved efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 1 h, and the heating rate was controlled to be 10°C / min to obtain a nickel oxide product;

[0085] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 55°C for 2 hours, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 2 hours, with the heating rate controlled at 10°C / min, to obtain cobalt oxide.

[0086] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 11, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 1h with a heating rate of 10°C / min to obtain manganese oxide.

[0087] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 90 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 93.52%.

[0088] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0089] Example 3

[0090] Choline chloride and tartaric acid were prepared in a molar ratio of 3:2, and after mixing, they were heated and stirred at 80° C. for 60 minutes to obtain a leaching agent, and then deionized water with a mass of 10 wt % of the leaching agent was added to obtain a low eutectic solvent.

[0091] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, stirred and leached at 120°C for 60 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The nickel precipitation efficiency and the cobalt-manganese leaching efficiency are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. According to ICP testing, the lithium content in the calcined nickel oxide was only 3.55%, indicating that the low eutectic solvent system achieved efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2 h, and the heating rate was controlled to be 5°C / min to obtain a nickel oxide product;

[0092] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 2 hours, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 2 hours, with the heating rate controlled at 5°C / min, to obtain cobalt oxide.

[0093] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 5°C / min to obtain manganese oxide.

[0094] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 95.43%.

[0095] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0096] Example 4

[0097] Choline chloride and tartaric acid were prepared in a molar ratio of 1:2, and after mixing, they were heated and stirred at 80° C. for 60 minutes to obtain a leaching agent, and then deionized water with a mass of 10 wt % of the leaching agent was added to obtain a low eutectic solvent.

[0098] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, stirred and leached at 100°C for 90 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. After ICP testing, the lithium content in the calcined nickel oxide was only 4.18%, which shows that the low eutectic solvent system achieves efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2 h, and the heating rate was controlled to be 5°C / min to obtain a nickel oxide product;

[0099] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 2 hours, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 2 hours, with the heating rate controlled at 5°C / min, to obtain cobalt oxide.

[0100] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 5°C / min to obtain manganese oxide.

[0101] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 92.82%.

[0102] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0103] Example 5

[0104] Choline chloride and tartaric acid were prepared in a molar ratio of 2:1, and after mixing, they were heated and stirred at 70° C. for 40 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0105] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 30 g / L, stirred and leached at 120°C for 90 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. According to ICP testing, the lithium content in the calcined nickel oxide was only 3.08%, indicating that the low eutectic solvent system achieved efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2 h, and the heating rate was controlled to be 5°C / min to obtain a nickel oxide product;

[0106] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 1 hour, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 1 hour, with the heating rate controlled at 5°C / min, to obtain cobalt oxide.

[0107] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 5°C / min to obtain manganese oxide.

[0108] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 96.24%.

[0109] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0110] Example 6

[0111] Choline chloride and tartaric acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 90° C. for 50 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0112] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 30 g / L, stirred and leached at 100°C for 120 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. After ICP testing, the lithium content in the calcined nickel oxide was only 3.99%, which shows that the low eutectic solvent system achieves efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2h, and the heating rate was controlled to be 5°C / min to obtain a nickel oxide product;

[0113] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 1 hour, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 1 hour, with the heating rate controlled at 5°C / min, to obtain cobalt oxide.

[0114] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 5°C / min to obtain manganese oxide.

[0115] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 95°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 94.66%.

[0116] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0117] Example 7

[0118] Choline chloride and tartaric acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 90° C. for 60 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0119] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 30 g / L, stirred and leached at 80°C for 150 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. According to ICP testing, the lithium content in the calcined nickel oxide was only 4.16%, which shows that the low eutectic solvent system achieves efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2 h, and the heating rate was controlled to be 10°C / min to obtain a nickel oxide product;

[0120] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 1 hour, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 1 hour, with the heating rate controlled at 10°C / min, to obtain cobalt oxide.

[0121] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 10°C / min to obtain manganese oxide.

[0122] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 93.02%.

[0123] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0124] Example 8

[0125] Choline chloride and tartaric acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 90° C. for 60 minutes to obtain a leaching agent, and then deionized water with a mass of 10 wt % of the leaching agent was added to obtain a low eutectic solvent.

[0126] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 O2 positive electrode material was fed at a solid-liquid ratio of 30 g / L, stirred and leached at 130°C for 10 min, and centrifuged to obtain a nickel-rich precipitate and a primary leaching solution. The precipitation efficiency of nickel and the leaching efficiency of cobalt and manganese are summarized in Table 1; lithium was not completely leached from the positive electrode material of the ternary lithium battery due to the solubility of the low eutectic solvent system. According to ICP testing, the lithium content in the calcined nickel oxide was only 3.99%, which shows that the low eutectic solvent system achieves efficient separation of nickel from cobalt, manganese and lithium; the nickel-rich precipitate was washed 3 times with anhydrous ethanol, dried at 60°C overnight, and then calcined in a muffle furnace at 500°C for 2 h, and the heating rate was controlled to be 5°C / min to obtain a nickel oxide product;

[0127] Ammonium oxalate solution was directly added to the primary leachate, with the molar ratio of ammonium oxalate to cobalt being 1:1.2. The mixture was reacted at 50°C for 2 hours, and centrifuged to obtain a secondary leachate and a cobalt-rich precipitate. The cobalt-rich precipitate was washed and dried, and then calcined in a muffle furnace at 500°C for 2 hours, with the heating rate controlled at 5°C / min, to obtain cobalt oxide.

[0128] Sodium hydroxide was added to the secondary leaching solution to adjust the solution pH to 12, and the tertiary leaching solution and manganese-rich precipitate were obtained by centrifugal separation. The manganese-rich precipitate was washed and dried, and then calcined in a muffle furnace at 800°C for 2h with a heating rate of 5°C / min to obtain manganese oxide.

[0129] The three leaching solutions are evaporated and concentrated, and a soda solution is added to produce lithium carbonate precipitation. The reaction conditions are: the molar ratio of soda ash to lithium is controlled to The reaction was carried out at 90°C for 120 minutes. The produced lithium carbonate precipitate was washed with anhydrous ethanol and dried to obtain a lithium carbonate with a purity of 93.28%.

[0130] The above is the process of step-by-step separation of the valuable metals nickel, cobalt, manganese and lithium in the positive electrode materials of ternary lithium batteries. The whole process is simple, the product has good crystallinity and high purity, and the obtained metals can not only be used for battery regeneration, but also can be used in their respective required fields.

[0131] Table 1 shows the metal recovery results corresponding to different leaching processes in Examples 1-8

[0132] sample Ni precipitation efficiency Co leaching efficiency Mn leaching efficiency Lithium carbonate purity Example 1 95.45％ 99.98％ 99.99％ 93.36％ Example 2 96.33％ 99.99％ 100.00％ 93.52％ Example 3 98.26％ 100.00％ 100.00％ 95.43％ Example 4 95.05％ 99.98％ 99.99％ 92.82％ Example 5 98.05％ 100.00％ 100.00％ 96.24％ Example 6 97.86％ 100.00％ 100.00％ 94.66％ Example 7 95.12％ 99.98％ 99.99％ 93.02％ Example 8 96.02％ 99.99％ 100.00％ 93.28％

[0133] Comparative Example 1

[0134] Choline chloride and urea were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0135] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 The O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, and leached with stirring at 100°C for 60 min. The leaching solution was obtained by centrifugation, and nickel was not selectively precipitated. The leaching efficiencies of nickel, cobalt, and manganese were 0.16%, 0.19%, and 0.13%, respectively.

[0136] Comparative Example 2

[0137] Choline chloride and propionic acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0138] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 The O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, and leached at 100°C for 60 min with stirring. The leaching solution was obtained by centrifugation, and nickel was not selectively precipitated. The leaching efficiencies of nickel, cobalt, and manganese were 16.32%, 16.18%, and 16.54%, respectively.

[0139] Comparative Example 3

[0140] Choline chloride and malonic acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0141] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2The O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, and leached with stirring at 100°C for 60 min. The leaching solution was obtained by centrifugation, and nickel was not selectively precipitated. The leaching efficiencies of nickel, cobalt, and manganese were 75.25%, 81.27%, and 84.62%, respectively.

[0142] Comparative Example 4

[0143] Choline chloride and malic acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0144] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 The O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, and leached with stirring at 100°C for 60 min. The leaching solution was obtained by centrifugation, and nickel was not selectively precipitated. The leaching efficiencies of nickel, cobalt, and manganese were 95.44%, 95.81%, and 94.90%, respectively.

[0145] Comparative Example 5

[0146] Choline chloride and p-toluenesulfonic acid were prepared in a molar ratio of 1:1, and after mixing, they were heated and stirred at 80° C. for 30 minutes to obtain a leaching agent, and then 5 wt % of deionized water of the leaching agent mass was added to obtain a low eutectic solvent.

[0147] The deep eutectic solvent and LiNi 0.6 Co 0.2 Mn 0.2 The O2 positive electrode material was fed at a solid-liquid ratio of 20 g / L, and leached with stirring at 100°C for 60 min. The leaching solution was obtained by centrifugation, and nickel was not selectively precipitated. The leaching efficiencies of nickel, cobalt, and manganese were 99.64%, 99.67%, and 98.85%, respectively.

[0148] None of the above comparative examples selectively precipitated nickel, and the effect of separating nickel from other elements in one step was only the simultaneous leaching of metal elements in the positive electrode material to varying degrees. Compared with the one-step method for separating nickel from other metal elements, the separation of metal elements in the comparative examples was more complicated, with more steps, and the leaching efficiency of cobalt and manganese was not complete enough compared with the embodiments, resulting in low product purity and mutual entrainment between solid samples.

[0149] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. Application of a deep eutectic solvent in the recovery of nickel from waste ternary lithium battery positive electrode materials, characterized in that: The low eutectic solvent is mixed with the positive electrode material of the ternary lithium battery, leached, and after solid-liquid separation, the nickel-rich precipitate and the leachate are collected; Wherein, the deep eutectic solvent consists of a leaching agent and a solvent; The leaching agents are choline chloride and tartaric acid.

2. The use according to claim 1, characterized in that: The molar ratio of the choline chloride to the tartaric acid is 1:10-10:

1.

3. The use according to claim 1, characterized in that: The molar ratio of the choline chloride to the tartaric acid is 1:2-2:

1.

4. The use according to claim 1, characterized in that: The solid-to-liquid ratio of the ternary lithium battery positive electrode material to the low eutectic solvent is 10-100 g / L.

5. The use according to claim 1, characterized in that: The leaching temperature is 50-150°C, and the leaching time is 5-360min.

6. The use according to claim 1, characterized in that: The leaching temperature is 80-120°C, and the leaching time is 40-90 minutes.

7. The use according to claim 1, characterized in that: The mass ratio of the additive to the leaching agent is 1:0.05-0.

1.

8. A method for separating and recovering valuable metals in waste ternary lithium battery positive electrode materials, characterized in that: The steps include: 1) mixing choline chloride and tartaric acid, adding a solvent, and preparing a deep eutectic solvent; 2) adding the positive electrode material of the ternary lithium battery into the low eutectic solvent, leaching, separating the solid and the liquid after the leaching, and collecting the primary leachate and the nickel-rich precipitate; 3) adding ammonium oxalate to the primary leachate, collecting the secondary leachate and the cobalt-rich precipitate after solid-liquid separation; 4) adding sodium hydroxide to the secondary leachate, collecting the tertiary leachate and manganese-rich precipitate after solid-liquid separation; 5) Add soda ash to the tertiary leaching solution and collect the lithium-rich precipitate.

9. The method according to claim 8, characterized in that The positive electrode material of the ternary lithium battery includes LiNi 1 / 3 Co 1 / 3Mn 1 / 3 O2、LiNi 0.5 Co 0.2 Mn 0.3 O2、LiNi 0.6 Co 0.2 Mn 0.2 O2 and LiNi 0.8 Co 0.1 Mn 0.1 One or more of O2.

10. The method according to claim 8, characterized in that The positive electrode material of the ternary lithium battery is prepared by the following pretreatment process: The waste lithium-ion positive electrode sheet is heat-treated at 500-600° C. for 0.5-1.5 h, and the aluminum sheet is peeled off to obtain the positive electrode material of the ternary lithium battery.

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