Method for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder

Abstract

The application provides a method for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder, comprising the following steps: (1) mixing the waste ternary lithium ion battery electrode powder with concentrated sulfuric acid, and roasting under a mixed atmosphere of sulfur dioxide and air; (2) water immersion of the roasted material, and solid-liquid separation to obtain a lithium-containing cobalt-nickel-manganese sulfate solution and a graphite filter residue; (3) adding manganese sulfide to the lithium-containing cobalt-nickel-manganese sulfate solution to react, and solid-liquid separation to obtain a filtrate and a precipitate residue; (4) oxidizing and roasting the precipitate residue; (5) water immersion and acid immersion of the roasted product to obtain a nickel-cobalt sulfate solution, and impurity removal of the nickel-cobalt sulfate solution to obtain a battery-grade nickel-cobalt sulfate solution; and (6) sulfuration and manganese precipitation of the filtrate, solid-liquid separation after reaction, and obtaining of crude manganese sulfide and a lithium-rich solution. The method has low cost, high reduction rate of metals in the electrode powder, can realize recycling of sulfur, avoid pollution, and has high metal recovery rate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of recycling methods of waste lithium ion batteries, and particularly relates to a method for comprehensively utilizing valuable metals in electrode powder of waste ternary lithium ion batteries. BACKGROUND

[0002] Lithium ion batteries have unparalleled high energy density and excellent cycle stability, and have become the preferred energy storage device for portable electronic devices and power transmission systems. Waste lithium ion batteries contain a large amount of valuable metals, and the content is much higher than that of primary natural ores. Therefore, it is necessary to develop efficient and clean recycling processes to recover valuable metals from waste lithium ion batteries, so as to ensure the sustainable development of the lithium ion battery industry and alleviate the current resource shortage problem.

[0003] Waste lithium ion battery electrode powder includes waste lithium ion battery positive electrode powder and negative electrode powder, and contains organic matter, electrolyte salt, nickel, cobalt, manganese, copper, aluminum, carbonaceous material and the like. At present, the processes for recovering valuable metals from waste lithium ion battery electrode powder in China mainly include pyrometallurgy and hydrometallurgy.

[0004] The pyrometallurgical recovery process is represented by Umicore, which first reduces and smelts waste lithium ion batteries to obtain Co-Ni-Cu-Fe alloy, and then obtains high-purity single metals and compounds through hydrometallurgical methods. The pyrometallurgical process has the advantages of short process flow, low equipment requirement and strong operability, but also has the disadvantages of low process throughput, high energy consumption, serious environmental pollution and low product purity.

[0005] The hydrometallurgical recovery process is to leach all valuable metals in waste lithium ion battery electrode powder into solution, and then recover metal elements by stepwise purification methods such as precipitation or extraction. The hydrometallurgical recovery process is to leach all valuable metals in waste lithium ion battery electrode powder into solution, and then recover metal elements by stepwise purification methods such as precipitation or extraction. The hydrometallurgical recovery plant in China generally adopts the process route of extraction to recover valuable metals in waste lithium ion batteries. The extraction method has the advantage of high recovery purity, but also has the disadvantages of large reagent consumption, high operation and maintenance cost, low comprehensive recovery rate of lithium, complex process, easy to cause secondary pollution and the like.

[0006] The patent CN111333123A obtains a lithium cobalt nickel manganese sulfate solution and graphite residue by wet mixing sulfuric acid with the positive electrode material and then high-temperature roasting, and further hydrothermally reacting the solution to prepare a ternary precursor. The method has the advantages of short process and no need for further separation of cobalt nickel manganese lithium, but the method first wets the positive electrode material with water, then mixes it with 98% concentrated sulfuric acid and roasts it, which produces a large amount of water vapor in the roasting furnace, causing the insulating material in the furnace to absorb water and separate, and the furnace body to be corroded, making it difficult to realize large-scale industrial production. The patents CN114085997A, CN110760686A and CN111333123A are similar to the method of the patent CN111333123A, which roasts the waste battery positive electrode material with concentrated sulfuric acid, but obtains a lithium sulfate solution and a cobalt nickel manganese oxide-containing graphite residue phase after water immersion, only lithium enters the liquid phase, but the process of treating the metal residue phase has the problems of large sulfuric acid consumption, incomplete leaching of high-valence metals, and difficulty in impurity removal. The patent CN111254294A obtains a lithium sulfate solution and a cobalt nickel oxide-containing graphite residue phase by water immersion through the method of sulfuric acid curing roasting, so that lithium and manganese enter the liquid phase, and further ionizes manganese dioxide by electrolysis. This method has high energy consumption, and the acidity and impurity metal ion content of the electrolyte need to be strictly controlled, which is difficult to operate.

[0007] In the above-mentioned patent technologies, the method of sulfuric acid roasting is used to realize the selective leaching of lithium cobalt nickel manganese metal. In the roasting process, graphite acts as a reducing agent to reduce high-valence metals in the waste ternary positive electrode material to low-valence metals. However, graphite is easily oxidized by oxygen in the air, which affects the reduction effect of high-valence metals in the roasting process and the leaching efficiency. SUMMARY

[0008] To solve the above problems, the present application provides a method for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder.

[0009] To achieve the above-mentioned purpose, the following solutions are proposed:

[0010] A method for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder, comprising:

[0011] (1) Pre-mixing the waste ternary lithium ion battery electrode powder with concentrated sulfuric acid, and then transferring it into a furnace body to roast in a mixed atmosphere of sulfur dioxide and air to obtain a roasted material;

[0012] In this step, the following reactions mainly occur:

[0013] 4SO2+2Me2O3+O2→4MeSO4

[0014] SO2+Me2O3→2MeO+SO3

[0015] C + 2Me2O3→ CO2+ 4MeO

[0016] H2SO4+ 2Al2O3→ 2Al2(SO4)3+ H2O

[0017] H2SO4+ 2Me’O → 2Me’SO4+ H2O

[0018] Wherein Me represents Ni, Co, Mn, and Me’ represents Cu, Mg, Ca, Fe, Ni, Co, Mn.

[0019] (2) The calcined material is water immersed, solid-liquid separation is performed, and a lithium-containing cobalt-nickel-manganese sulfate solution and a graphite filter residue are obtained;

[0020] (3) Manganese sulfide is added to the lithium-containing cobalt-nickel-manganese sulfate solution to perform a double decomposition displacement reaction, and after the reaction is completed, solid-liquid separation is performed to obtain a filtrate and a nickel and cobalt sulfide precipitate residue, and the main double decomposition displacement reaction is as follows:

[0021] MnS + CoSO4→ CoS↓ + MnSO4

[0022] MnS + NiSO4→ NiS↓ + MnSO4

[0023] The following side reactions also occur:

[0024] MnS + CuSO4→ CuS↓ + MnSO4

[0025] MnS + FeSO4→ FeS↓ + MnSO4

[0026] (4) The nickel and cobalt sulfide precipitate residue is subjected to oxidation roasting to obtain a roasting product, and the roasting product is a nickel and cobalt sulfate and a nickel and cobalt oxide;

[0027] (5) The roasting product is subjected to water immersion and solid-liquid separation to obtain a nickel and cobalt sulfate solution and an oxide residue, and the oxide residue is subjected to acid immersion to obtain a nickel and cobalt sulfate solution, and the nickel and cobalt sulfate solutions obtained through water immersion and acid immersion are subjected to impurity removal to obtain a battery-grade nickel and cobalt sulfate solution, and the molar ratio of cobalt metal and nickel metal in the subsequent cobalt-nickel sulfate solution can be arbitrarily adjusted according to customer requirements;

[0028] (6) Manganese sulfide is added to the filtrate obtained in step (3) to perform sulfidation, and after the reaction, solid-liquid separation is performed to obtain crude manganese sulfide and a lithium-rich solution.

[0029] As preferred, in step (6), the crude manganese sulfide is partly returned to step (3) for reaction, and the rest is washed by anhydrous ethanol, vacuum dried, screened, and de-ironed by an electromagnetic de-ironer to obtain a high-purity manganese sulfide product. The washing by anhydrous ethanol is performed for multiple times, the vacuum drying temperature is 85-150℃, and the time is 2-12h. The purity of MnS in the obtained high-purity manganese sulfide product is not less than 99.5%.

[0030] In step (6), the lithium-rich solution is de-impure, carbonated, and centrifuged to obtain an industrial-grade lithium carbonate. The carbonation reaction temperature is 70-90℃, and the reaction time is 2-3h. The carbonation is performed by adding a saturated sodium carbonate solution to the de-impure lithium-rich solution for precipitation. The de-impurification includes adding a calcium carbonate solution to the lithium-rich solution first, and then adding a magnesium hydroxide solution. The pH of the solution after calcium removal is 8-9, and the pH of the solution after magnesium removal is 10-11. The impurity ion content in the solution after de-impurification can reach the industrial-grade level.

[0031] As preferred, in step (1), the concentration of sulfuric acid is determined according to the molar ratio n(H2SO4) : n(Co+Ni+Mn+2Li) of 0.7-0.9.

[0032] As preferred, in step (1), the roasting process controls the sulfur dioxide partial pressure to be 0.2-0.8atm. The mixed gas atmosphere of sulfur dioxide and air is provided by the flue gas of the oxidation roasting in step (4).

[0033] As preferred, in step (1), the roasting is two-stage roasting. The first-stage roasting temperature is 80-350℃, and is further preferred to be 100-200℃. The holding time of the first-stage roasting is 1-2h. The second-stage roasting temperature is 280-600℃, and is further preferred to be 300-450℃. The holding time of the second-stage roasting is 2-3h.

[0034] As preferred, in step (2), the water immersion is wet ball milling water immersion of the sintered material, and the liquid-solid ratio is 1-6L / kg. The wet ball milling water immersion time is 5-60min.

[0035] As preferred, in step (3), the manganese sulfide excess coefficient is 105-115%, and the manganese sulfide is product reuse from the manganese sulfidation process in step (6). The reaction temperature is 90-98℃, and the reaction time is 5-6h.

[0036] Preferably, in step (4), the oxidizing roasting is achieved by means of a roller kiln or a rotary kiln; the oxidizing roasting is two-stage roasting, the first stage is at 350-550 DEG C for 1-3 h, and the second stage is at 600-850 DEG C for 8-10 h; the oxidizing roasting is performed in an air atmosphere; and the flue gas generated in the oxidizing roasting is used as the roasting atmosphere in the roasting process in step (1).

[0037] Preferably, in step (5), the liquid-solid ratio of the water immersion is 1-6 mL / g, and the water immersion time is 20-120 min; the acid immersion time is 60-120 min, and the acid concentration of the acid immersion is 3-6 mol / L.

[0038] Preferably, in step (6), the sulfidizing manganese precipitation reaction temperature is 20-50 DEG C, the reaction time is 2-3 h, and the solution pH at the end of the sulfidizing manganese precipitation is 6.5-13; the sulfidizing manganese precipitation comprises adding one or two or more sulfides of sodium sulfide, sodium hydrosulfide and potassium sulfide into the cobalt-nickel-manganese-lithium-containing sulfate solution; and the excess coefficient of the sulfides is 100-120%.

[0039] Preferably, in step (5), the impurity removal is to remove iron, aluminum and copper ions in the solution; the method is to first add a small amount of hydrogen peroxide to oxidize the divalent iron ions into trivalent iron ions, then add a small amount of Co(OH)2 or Ni(OH)2 to adjust the pH of the nickel-cobalt sulfate solution to 4-5 and 5-6 in sequence, and the impurity metals (Fe, Al and Cu) are precipitated in the form of hydroxide precipitates, and then the precipitates are removed by filtering through a precision filter.

[0040] Compared with the prior art, the method has the following beneficial effects:

[0041] The method has low cost, high metal reduction rate in the electrode powder, and high metal recovery rate, and the cobalt, nickel, manganese and lithium in the electrode powder form stable sulfate MSO4 (M is Co, Ni and Mn), which can be efficiently leached into the solution by water immersion, and the use amount of concentrated sulfuric acid is low; the atmospheric sulfur dioxide is an intermediate product in the system, and is recycled and reused to efficiently utilize the sulfur element; in the method, the cobalt sulfide and the nickel sulfide are directly oxidized into cobalt sulfate and nickel sulfate at high temperature, the unconverted part is oxidized into cobalt oxide and nickel oxide, the cobalt sulfate and the nickel sulfate are leached by water immersion, the leaching residue, i.e., the cobalt oxide and the nickel oxide, is dissolved by adding a small amount of sulfuric acid solution, and finally, the battery-grade cobalt-nickel sulfate solution is obtained after impurity removal, which greatly reduces the use amount of sulfuric acid, and the gas overflowed in the sulfide oxidation process is collected and used in the sulfidizing roasting link, thereby avoiding pollution and improving the utilization rate of the sulfur element.

[0042] Under the premise of safety and environmental protection, in order to reduce the recovery cost of metal manganese, the high-purity manganese sulfide product is prepared by the precipitation method, the manganese sulfide crude material is used as raw material, the metathesis displacement reaction of MnS and Co 2+ , Ni 2+ is generated, CoS and NiS precipitate are generated, the impurity ions such as Fe, Al and Cu in the solution enter the slag phase, and the purpose of separating metal Mn and Co and Ni is achieved, in the method, metal Mn is recovered by the precipitation method, the cost is low, the process is simple, the manganese sulfide is used as a product and an intermediate product, and recycling is achieved in the system, without external purchase, the problems of low metal Mn precipitation rate and high recovery cost are solved.

[0043] The whole process of the method is that inorganic substances participate in reaction, there is no organic matter such as extractant, the recovery cost of electrode powder is reduced, and secondary pollution is reduced.

[0044] In summary, the application provides a new process route for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder, the process is combined by wet method and fire method, manganese sulfide is used as a system intermediate circulating product, under the premise of safety and environmental protection, the recovery cost of metal manganese is reduced, the comprehensive recovery rate of metal lithium is improved, the utilization rate of sulfur element is greatly improved, and the problems of low lithium ion recovery rate, high recovery cost and secondary pollution in the industrial production line are solved. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 It is a process flow chart of the method for comprehensive utilization of valuable metals in waste ternary lithium ion battery electrode powder. DETAILED DESCRIPTION

[0046] The application will be further described below in combination with specific embodiments and drawings, but the application is not limited to the following embodiments. Unless otherwise defined, all professional terms used in the following have the same meaning as understood by those skilled in the art. The professional terms used in the text are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the application.

[0047] In the following examples, the experimental methods are described, and unless otherwise specified, all reagents and materials can be obtained from commercial channels.

[0048] Example 1

[0049] (1) Acidification premixing: 1000 kg of waste ternary lithium ion battery electrode powder (W Co : 5.6%, W Ni : 13.6%, W Mn : 28.2%, W LiAdd 4.8% sulfuric acid to a horizontal ribbon mixer, then slowly and evenly add 925.8 kg of 98% concentrated sulfuric acid, and mix for 60 minutes.

[0050] (2) Calcination: The uniformly mixed premixed material is loaded into a pushboat-type steel high-temperature reduction furnace with 3 kg of material per boat. It is calcined in a mixed atmosphere of sulfur dioxide and air. In this step, the mixed atmosphere of sulfur dioxide and air is provided by the flue gas generated by the air calcination in step (8). The partial pressure of sulfur dioxide is 0.3 atm. The temperature of zone 1 of the high-temperature furnace is set at 120°C and the material stays for 1 hour. The temperature of zone 2 is set at 350°C and the material stays for 2.5 hours.

[0051] (3) Water leaching: After sintering, the material is transferred to an intermittent ball mill for wet ball milling and water leaching. The liquid-to-solid ratio is 3:1 L / kg. The material is fully ball-milled and stirred for 30 minutes to allow the metal sulfides coated with carbon or other impurities to dissolve better in the water. After water leaching, the slurry is separated into solid and liquid by a plate and frame filter press to obtain solution A and waste graphite slag. The leaching rates of the main metal elements are shown in Table 1.

[0052] (4) Metathesis displacement: 311.3 kg of manganese sulfide was added to solution A with an excess coefficient of 110%. The reaction temperature was 95℃ and the reaction time was 5.5 h. After solid-liquid separation by a filter press, solution B and cobalt-nickel sulfide slag were obtained.

[0053] (5) Manganese precipitation by sulfide: 873.6 kg of sodium sulfide with a purity of 50% was added to solution B, with an excess coefficient of 110%, a reaction temperature of 30℃, and a reaction time of 2 h. The crude MnS and lithium-rich filtrate were obtained by pressure filtration.

[0054] (6) MnS purification: 311.3 kg of crude MnS was returned to step (4), and the remaining 75.9 kg was added to anhydrous ethanol. After washing three times, it was transferred to a vacuum drying oven. The temperature was set at 105℃ and the time was 4h. After cooling to room temperature, it was sieved using an 80-mesh sieve. The material under the sieve was packaged after removing iron using an electromagnetic iron remover. The composition of the obtained MnS is shown in Table 1. The material over the sieve was returned to step (4) as raw material for the metathesis displacement process.

[0055] (7) Lithium carbide precipitation: Sodium carbonate is added to the lithium-containing filtrate obtained in step (6) for reaction. After calcium precipitation, the pH of the solution is 8.6. After 30 minutes, sodium hydroxide is added for precipitation reaction. After magnesium precipitation, the pH of the solution is 11. After filtration, 800 kg of saturated Na2CO3 solution (the molar amount of Na2CO3 is about 0.5 times the molar amount of lithium in the electrode powder) is added to the filtrate to precipitate Li2CO3. After filtration, solid Li2CO3 is obtained. The residual sodium ions are removed by hot water washing to obtain industrial grade Li2CO3.

[0056] (8) Oxidation roasting: the cobalt-nickel sulfide slag obtained in step (4) is transferred to a roller furnace and oxidized and roasted in an air atmosphere, the temperature of the first zone of the roller furnace is controlled at 400 DEG C for 2 h, the temperature of the second zone is 650 DEG C for 8 h, the main components of the sintered product are cobalt sulfate and nickel sulfate, and a small amount of cobalt oxide and nickel oxide, and the SO2 and SO3-containing flue gas generated by the oxidation roasting is transported to the steel reduction furnace of step (2) through a pipeline.

[0057] (9) Water immersion: the roasted product in step (8) is transferred to an interstitial ball mill for water immersion, the liquid-solid ratio is 3:1 mL / g, the water immersion time is 30 min, and after solid-liquid separation by a plate and frame filter, a cobalt sulfate and nickel sulfate solution and a cobalt-nickel oxide residue are obtained.

[0058] (10) Acid dissolution: the cobalt-nickel oxide residue in step (8) is added to 50 kg of 3 mol / L sulfuric acid solution, stirred and dissolved, the acid immersion time is 60-120 min, mixed with the cobalt sulfate and nickel sulfate solution of step (9), 1.5 kg of hydrogen peroxide is added to oxidize the divalent iron ions to trivalent iron ions, then a small amount of Co(OH)2 is added to adjust the pH of the solution to 4-5 and 5-6, respectively, and the impurity metals are precipitated in the form of hydroxide precipitates, then filtered through a precision filter to remove the precipitates, after impurity removal, battery-grade cobalt sulfate or battery-grade nickel sulfate is added to the solution according to customer requirements, and a battery-grade cobalt-nickel mixed sulfate solution is obtained.

[0059] Table 1 High-purity MnS component table

[0060]

[0061] As shown in Table 1, the purity of high-purity MnS is greater than 99.5%.

[0062] Table 2 Lithium carbonate component table

[0063]

[0064] As shown in Table 2, according to "Lithium Carbonate (GB / T11075-2013)", the purity of lithium carbonate is more than 98.5% as specified by Li2CO3-2, and close to 99.0% as specified by Li2CO3-1, the recovered lithium carbonate belongs to industrial-grade lithium carbonate, but the purity is also at a high level among industrial-grade, which reduces the difficulty of subsequent processing into battery-grade lithium carbonate.

[0065] Table 3 Main metal element leaching rate after water immersion

[0066]

[0067] The comprehensive recovery rates of Li and Mn in this embodiment are 91.58% and 98.06%, respectively; the comprehensive recovery rates of Ni and Co are 99.12% and 99.01%, respectively.

[0068] Example 2

[0069] Compared with Example 1, the difference lies in that the roasting temperature in step (2) is changed, specifically:

[0070] The mixed premix is transferred into a push boat type steel high temperature reduction furnace, 3 kg of material is loaded in each boat, the temperature of the high temperature furnace is set to 100°C in the first zone, the holding time is 1 h, and the temperature is set to 450°C in the second zone, the holding time is 2.5 h.

[0071] The leaching rates of main metal elements after water immersion in step (3) are shown in Table 2.

[0072] Table 4 Leaching rates of main metal elements after water immersion

[0073]

[0074] The comprehensive recovery rates of Li and Mn in this embodiment are 91.04% and 85.82%, respectively; the comprehensive recovery rates of Ni and Co are 98.75% and 98.54%, respectively.

[0075] Example 3

[0076] Compared with Example 1, the difference lies in that the roasting temperature in step (2) is changed, specifically:

[0077] The mixed premix is transferred into a push boat type steel high temperature reduction furnace, 3 kg of material is loaded in each boat, the temperature of the high temperature furnace is set to 100°C in the first zone, the holding time is 1 h, and the temperature is set to 550°C in the second zone, the holding time is 2.5 h.

[0078] The comprehensive recovery rates of Li and Mn in this embodiment are 90.13% and 85.82%, respectively; the comprehensive recovery rates of Ni and Co are 90.53% and 91.56%, respectively. The main reason is that part of Mn 2+ , Co 2+ and Ni 2+ are converted into oxide form in the roasting process, and the oxide is insoluble in water, resulting in a decrease in leaching rate and recovery rate.

[0079] Comparative Example 1

[0080] Compared with Example 1, the difference lies only in the roasting temperature of step (8), specifically:

[0081] (8) Oxidizing roasting: the obtained cobalt-nickel sulfide residue was transferred into a roller furnace, the temperature of the first zone of the roller furnace was controlled at 200°C, the holding time was 2h, the temperature of the second zone was 350°C, and the holding time was 8h.

[0082] It was calculated that the comprehensive recovery rates of Li and Mn in the embodiment were 91.44% and 98.54%, respectively; the comprehensive recovery rates of Ni and Co were 35.2% and 46.8%, respectively. The reason was that more cobalt-nickel sulfide was converted into cobalt-nickel oxide, and a large amount of sulfuric acid needed to be supplemented for acid dissolution.

[0083] Comparative Example 2

[0084] Compared with Example 1, the difference was that the amount of 98% concentrated sulfuric acid used in step (1) was larger, the roasting atmosphere in step (2) was only air atmosphere, and the oxygen generated in step (8) was not used in the roasting atmosphere of step (1). The addition amount of 98% concentrated sulfuric acid was n(H2SO4):n(Co+Ni+Mn+2Li) about 1.1, specifically:

[0085] (1) Acidification and premixing: 1000 kg of waste ternary lithium ion battery electrode powder (W Co : 5.6%, W Ni : 13.6%, W Mn : 28.2%, W Li : 4.8%) was added into a horizontal ribbon mixer, and then 1273 kg of 98% concentrated sulfuric acid was slowly and uniformly added, and the mixing time was 60 min.

[0086] (2) Roasting: the uniformly mixed premix was transferred into a push boat type steel high temperature reduction furnace, 3 kg of material was loaded in each boat, and roasting was carried out in air atmosphere, the temperature of the first zone of the high temperature furnace was set at 120°C, the material stayed for 1h, the temperature of the second zone was 350°C, and the material stayed for 2.5h.

[0087] The leaching rates of main metal elements after water immersion are shown in Table 5.

[0088] Table 5 Leaching rates of main metal elements after water immersion

[0089]

[0090] It was calculated that the comprehensive recovery rates of Li and Mn in the embodiment were 91.44% and 98.54%, respectively; the comprehensive recovery rates of Ni and Co were 35.2% and 46.8%, respectively. The reason was that more cobalt-nickel sulfide was converted into cobalt-nickel oxide, and a large amount of sulfuric acid needed to be supplemented for acid dissolution.

[0091] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.

Claims

1. A method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder, characterized in that, Comprise: (1) the waste and old ternary lithium ion battery electrode powder is premixed with concentrated sulfuric acid, then is transferred into a furnace body, and is roasted in a mixed atmosphere of sulfur dioxide and air to obtain a roasted material; In step (1), the roasting is two-stage roasting, the first-stage roasting temperature is 80-200 DEG C, the holding time of the first-stage roasting is 1-2 h, the second-stage roasting temperature is 300-600 DEG C, and the holding time of the second-stage roasting is 2-3 h; (2) the roasted material is water immersed, solid-liquid separation is carried out, and a lithium-containing cobalt-nickel-manganese sulfate solution and a graphite filter residue are obtained; (3) manganese sulfide is added into the lithium-containing cobalt-nickel-manganese sulfate solution to react, and after the reaction is completed, solid-liquid separation is carried out to obtain a filtrate and a nickel and cobalt sulfide precipitate residue; (4) the nickel and cobalt sulfide precipitate residue is oxidized and roasted to obtain a roasted product; (5) the roasted product is water immersed, solid-liquid separation is carried out, a nickel-cobalt sulfate solution and an oxide residue are obtained, the oxide residue is acid immersed to obtain a nickel-cobalt sulfate solution, and the nickel-cobalt sulfate solutions obtained through water immersion and acid immersion are impurity-removed to obtain a battery-grade nickel-cobalt sulfate solution; (6) the filtrate obtained in step (3) is subjected to manganese sulfidation, and after the reaction, solid-liquid separation is carried out to obtain crude manganese sulfide and a lithium-rich solution.

2. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to claim 1, characterized in that, In step (6), part of the crude manganese sulfide is returned to step (3) for reaction, and the other part of the crude manganese sulfide is washed with anhydrous ethanol, vacuum dried, sieved, and iron-removed to obtain a high-purity manganese sulfide product; The lithium-rich solution obtained in step (6) is impurity-removed, carbonized and lithium-precipitated, and centrifuged to obtain an industrial-grade lithium carbonate; the carbonization and lithium precipitation are carried out at a reaction temperature of 70-90 DEG C for 2-3 h; the carbonization and lithium precipitation is carried out by adding saturated sodium carbonate solution into the lithium-rich solution after impurity-removal to carry out a precipitation reaction; the impurity-removal includes adding calcium carbonate into the lithium-rich solution first, and then adding magnesium hydroxide.

3. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to claim 1, characterized in that, In step (1), the concentrated sulfuric acid is added in a molar ratio of n (H2SO4) : n (Co+Ni+Mn+2Li) of 0.7-0.

9.

4. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to claim 1, characterized in that, In step (1), the roasting process controls the sulfur dioxide partial pressure to be 0.2-0.8 atm; and the mixed atmosphere of sulfur dioxide and air is provided by the flue gas generated in the oxidation roasting in step (4).

5. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (2), the water immersion is wet ball milling water immersion of the sintered material, and the liquid-solid ratio is 1-6 L / kg, and the wet ball milling water immersion time is 5-60 min.

6. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (3), the amount of manganese sulfide is 105-115% of the theoretical amount; and the reaction temperature is 90-98 DEG C, and the reaction time is 5-6 h.

7. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (4), the oxidation roasting is realized by a roller kiln or a rotary kiln; the oxidation roasting is two-stage roasting, one-stage roasting is carried out at 350-550 DEG C for 1-3 h, and two-stage roasting is carried out at 600-850 DEG C for 8-10 h; the oxidation roasting is carried out in an air atmosphere; and the flue gas generated in the oxidation roasting is used as the roasting atmosphere in step (1).

8. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (5), the liquid-solid ratio of the water immersion is 1-6 mL / g, and the water immersion time is 20-120 min; the acid immersion time is 60-120 min, and the acid concentration of the acid immersion is 3-6 mol / L.

9. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (6), the sulfidation and manganese precipitation reaction temperature is 20-50 ℃, and the reaction time is 2-3 h; the sulfidation and manganese precipitation includes adding one or more than two sulfides of sodium sulfide, sodium hydrosulfide and potassium sulfide into the cobalt-nickel-manganese-lithium-containing sulfate filtrate; the addition amount of the sulfide is 100-120% of the theoretical amount.

10. The method for comprehensive utilization of valuable metals in waste ternary lithium-ion battery electrode powder according to any one of claims 1-4, characterized in that, In step (5), the impurity removal includes: first adding hydrogen peroxide to oxidize the divalent iron ions into trivalent iron ions, then adding a small amount of Co(OH)2 or Ni(OH)2 to adjust the pH to 4-5 and 5-6, respectively, to precipitate the impurity metals, and then filtering through a filter to remove the precipitate.

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