Method for preparation of nickel-cobalt-manganese ternary material with aluminum oxide coating layer by taking retired lithium ion battery as raw material

A technology of lithium-ion batteries and ternary materials, applied to electrical components, secondary batteries, battery electrodes, etc., can solve problems such as waste, secondary pollution of aluminum resources, and problems not involving the treatment of aluminum-containing alkali immersion solutions, and achieve High structural stability, strong cycle performance, and the effect of avoiding waste of aluminum resources

Active Publication Date: 2019-07-12

SUNWODA ELECTRONICS

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AI-Extracted Technical Summary

Problems solved by technology

[0004] Although the above-mentioned existing methods can realize the recycling of nickel-cobalt-manganese elements in decommissioned lithium-ion batteries, they do not involve the treatment of the aluminum-containing alkali immersion solution produced in the step of aluminum removal treatment, if the aluminum-containing alkali immersion solution the...

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Method used

By mixing pure nickel-cobalt-manganese ternary material with aluminum-containing alkali immersion solution, and stirring after adding acid solution to obtain aluminum hydroxide and nickel-cobalt-manganese ternary material mixed suspension, aluminum hydroxide and nickel-cobalt-manganese The mixed suspension of the ternary material is placed in an aerobic environment and calcined to obtain the nickel-cobalt-manganese ternary material with an alumina coating layer, so that the aluminum-containing alkaline leaching solution obtained by mixing the positive electrode material with the alkali...

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Abstract

The invention discloses a method for preparation of a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer by taking a retired lithium ion battery as a raw material. The method comprises the steps of: disassembling a retired lithium ion battery to obtain a cathode material containing nickel, cobalt and manganese elements; mixing the cathode material and an alkali solutionfor alkaline leaching and filtering to obtain an aluminum-containing alkaline leaching solution and a dealuminized cathode material; taking the dealuminized cathode material as a raw material to prepare and obtain a nickel-cobalt-manganese ternary material; mixing the nickel-cobalt-manganese ternary material and the aluminum-containing alkaline leaching solution, and adding an acid solution into the mixed solution for stirring to obtain an aluminum hydroxide and nickel-cobalt-manganese ternary material mixed suspension; and putting the aluminum hydroxide and nickel-cobalt-manganese ternary material mixed suspension in an aerobic environment for calcination to obtain a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer. The method provided by the invention achieves cyclic utilization of the generated aluminum-containing alkaline leaching solution in the process of preparing the nickel-cobalt-manganese ternary material by taking the retired lithium ion batteryas a raw material and achieves the improvement of the structure stability and the cycle performance of the nickel-cobalt-manganese ternary material.

Application Domain

Cell electrodesWaste accumulators reclaiming +1

Technology Topic

Lithium electrodeAluminium oxide +13

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Examples

Experimental program(9)

Example Embodiment

[0039] Example 1

[0040] Refer to figure 1 The method of the present invention for preparing a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer using a decommissioned lithium-ion battery as a raw material includes:

[0041] S100. Disassemble the decommissioned lithium ion battery to obtain a positive electrode material containing nickel, cobalt and manganese;

[0042] S200, mixing the above-mentioned cathode material with an alkaline solution for alkaline leaching, and filtering to obtain an aluminum-containing alkaline leaching solution and a dealuminated cathode material;

[0043] S300, preparing a pure nickel-cobalt-manganese ternary material by using the above dealuminated cathode material as a raw material;

[0044] S400, mixing the above-mentioned pure nickel-cobalt-manganese ternary material and the above-mentioned aluminum-containing alkaline leaching solution, adding an acid solution and stirring to obtain a mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material;

[0045] S500: Place the above-mentioned mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material in an aerobic environment and calcinate to obtain a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer.

[0046] By mixing pure nickel cobalt manganese ternary material and aluminum-containing alkaline leaching solution, adding acid solution and stirring to obtain a mixed suspension of aluminum hydroxide and nickel cobalt manganese ternary material, the aluminum hydroxide and nickel cobalt manganese ternary material The mixed suspension is calcined in an aerobic environment to obtain a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer, so that the aluminum-containing alkaline leaching solution obtained by mixing the positive electrode material and the alkaline solution for alkaline leaching can be recycled, thereby In the process of preparing nickel-cobalt-manganese ternary materials with decommissioned ion batteries as raw materials, the purpose of no aluminum-containing alkaline leaching liquid discharge and avoiding the waste of aluminum resources is realized. Moreover, the nickel-cobalt-manganese ternary materials finally obtained in the present invention have The nickel-cobalt-manganese ternary material coated with aluminum oxide has the characteristics of high structural stability and strong cycle performance.

[0047] In this embodiment, preferably, the above step S300, preparing a pure nickel, cobalt and manganese ternary material using the above dealuminated cathode material as a raw material, includes:

[0048] S301, performing acid leaching and adjusting the metal molar concentration of the dealumed cathode material to obtain a leachate;

[0049] S302. Using the above-mentioned leaching solution as a raw material, obtaining a nickel-cobalt-manganese ternary precursor and a lithium-containing solution through a co-precipitation method and filtration;

[0050] S303. Concentrate the above lithium-containing solution, and obtain lithium carbonate through precipitation and filtration;

[0051] S304, mixing the above-mentioned nickel-cobalt-manganese ternary precursor and the above-mentioned lithium carbonate through ball milling, and obtaining the above-mentioned pure nickel-cobalt-manganese ternary material through high-temperature solid-phase reaction.

[0052] In addition, other methods can also be used to prepare pure nickel-cobalt-manganese ternary materials using the above dealuminated cathode materials as raw materials.

[0053] In this embodiment, preferably, the step S301 of performing acid leaching on the dealumination cathode material and adjusting the metal molar concentration to obtain the leachate includes:

[0054] S301a, mixing the dealumination positive electrode material with sulfuric acid for acid leaching to obtain an acid leaching solution;

[0055] S301b. Adding a mixture or one of nickel, cobalt, manganese and impurity element (M) sulfate to the acid leaching solution to obtain a leaching solution; wherein, the molar ratio of each element in the leaching solution conforms to the chemical formula Li(Ni x Co y Mn z ) 1-n M n O 2 , 0 <1, x+y+z=1. The impurity element may be a single doping element or a combination of multiple doping elements.

[0056] In this embodiment, preferably, the solute in the alkali solution is a mixture or one of sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, calcium hydroxide, and sodium bicarbonate. Since aluminum is an amphoteric metal element, the alkaline leaching process is used to selectively dissolve aluminum in the alkaline solution, and other metal elements still remain in the positive electrode material, which can achieve the purpose of leaching aluminum impurities in the positive electrode material.

[0057] In this embodiment, preferably, the concentration of the alkali solution is 0.1-1 mol/L;

[0058] In the above step of mixing the positive electrode material with an alkaline solution for alkaline leaching to obtain an aluminum-containing alkaline leaching solution and dealumination positive electrode material, the solid-to-liquid ratio of the positive electrode material and the alkaline solution is 100-500g/L, and the alkaline leaching temperature is 40-80℃, alkaline immersion time is 1-3h.

[0059] In this embodiment, preferably, the acid solution is a mixture or one of hydrochloric acid, sulfuric acid, and nitric acid.

[0060] In this embodiment, preferably, the concentration of the acid solution is 0.1-1 mol/L.

[0061] In this embodiment, preferably, the step of mixing the pure nickel-cobalt-manganese ternary material and the aluminum-containing alkaline leaching solution, adding an acid solution and stirring to obtain a mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material Wherein, the solid-liquid ratio of the pure nickel-cobalt-manganese ternary material and the aluminum-containing alkaline leaching solution is 20-100g/L, the reaction temperature is 20-60°C, the reaction time is 4-8h, and the stirring speed is 400-800rpm.

[0062] In this embodiment, preferably, in the step of calcining the above-mentioned mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material in an aerobic environment to obtain a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer, The calcination temperature is 400-900℃, and the calcination time is 10-20h.

[0063] A nickel-cobalt-manganese ternary material with an aluminum oxide coating layer of this embodiment has a clear layered structure, which has the characteristics of high structural stability and strong cycle performance; at the same time, a kind of aluminum oxide The nickel-cobalt-manganese ternary material of the coating layer has the characteristics of high crystallinity and high purity. In addition, a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer of this embodiment has the characteristics of large charge capacity and high first efficiency.

Example Embodiment

[0064] Example 2

[0065] The method for preparing a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer in the second embodiment of the present invention using a decommissioned lithium ion battery as a raw material is basically the same as the first embodiment.

[0066] specific:

[0067] In step S100, the specific operation is: fully discharge the decommissioned nickel-cobalt-manganese ternary lithium ion battery, and disassemble the positive electrode plate containing nickel, cobalt and manganese, and then ultrasonically clean and peel the positive electrode plate to obtain aluminum foil and The cathode material mixture is finally dried and sieved to obtain the cathode material.

[0068] In step S200, the solute in the alkali solution is sodium hydroxide; the concentration of the alkali solution is 0.1 mol/L; the solid-to-liquid ratio of the positive electrode material and the alkali solution is 100 g/L, the alkali leaching temperature is 40°C, The immersion time is 1h.

[0069] In step S301, it includes:

[0070] S301a. Mixing the dealumination positive electrode material with sulfuric acid to perform acid leaching to obtain an acid leaching solution; the purpose of this step is to leaching out valuable metal elements in the dealumination positive electrode material;

[0071] S301b. Adding a mixture or one of nickel, cobalt, manganese and impurity element (M) sulfate to the acid leaching solution to obtain a leaching solution; wherein, the molar ratio of each element in the leaching solution conforms to the chemical formula Li(Ni x Co y Mn z ) 1-n M n O 2 , 0 <1, x+y+z=1; in this embodiment, the metal elements in the acid leaching solution are measured by ICP emission spectrometer Then, nickel sulfate, cobalt sulfate, manganese sulfate, and titanium sulfate are added to the acid leaching solution to adjust the molar ratio of nickel, cobalt, and manganese to 5:2:3, and the molar ratio of total content of titanium to nickel, cobalt and manganese to 0.02 , Get the leachate.

[0072] In step S302, the co-precipitation method is specifically as follows: adding sodium hydroxide solution and/or aqueous ammonia solution to the leaching solution as a precipitating agent to uniformly precipitate the nickel, cobalt and manganese elements in the leaching solution as a ternary precursor of nickel, cobalt and manganese, and then After filtration, a nickel-cobalt-manganese ternary precursor and a lithium-containing solution are obtained.

[0073] In step S303, the precipitation method specifically includes: adding a saturated sodium carbonate solution as a precipitating agent to the concentrated lithium-containing solution, and filtering to obtain lithium carbonate after full reaction.

[0074] In step S304, the high-temperature solid-phase reaction specifically includes: calcination in the presence of oxygen at a high temperature of 850° C. for 12 hours.

[0075] In step S400, the acid solution is hydrochloric acid; the concentration of the acid solution is 0.1 mol/L. In addition, in this embodiment, the solid-to-liquid ratio of the pure nickel-cobalt-manganese ternary material and the aluminum-containing alkaline leaching solution is 20 g/L, and the reaction temperature is 60°C. When the three are mixed to a pH value of 6, aluminum hydroxide is precipitated on the surface of the pure nickel-cobalt-manganese ternary material, and then stirred at a speed of 400 rpm for 4 hours to obtain a mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material.

[0076] In step S500, the above-mentioned mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material is filtered and washed before being calcined in an aerobic environment. ,dry. In the step of calcining the mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material in an aerobic environment to obtain a nickel-cobalt-manganese ternary material with an alumina coating layer, the calcination temperature is 500°C and the calcination time For 10h.

[0077] The mass fraction of aluminum oxide in the nickel-cobalt-manganese ternary material with aluminum oxide coating layer prepared in this embodiment is 1 wt.%.

[0078] figure 2 , image 3 These are the XRD images (X-ray diffraction images; X-ray diffraction images) and SEM images (Scanning Electron Microscope images) of the nickel-cobalt-manganese ternary material with aluminum oxide coating prepared by the decommissioned lithium ion battery in this example. . See figure 2 , The nickel-cobalt-manganese ternary material with aluminum oxide coating is a typical a-NaFeO 2 The layered structure belongs to the hexagonal crystal system, R3m space group; the two pairs of diffraction peaks 006/102 and 108/110 have a very high degree of splitting, indicating that the material has a good layered structure; the diffraction peaks are sharp and the background is smooth, indicating that the The material has good crystallinity and purity. See image 3 The nickel-cobalt-manganese ternary material with an aluminum oxide coating layer is composed of secondary particles formed by agglomeration of a large number of primary particles, with a primary particle size of 200-400nm and a secondary particle size of 3-4μm.

[0079] See Figure 4 , The nickel-cobalt-manganese ternary material with aluminum oxide coating of this embodiment is at room temperature and in the first charge and discharge within the voltage range of 4.3-2.8V, the 0.1C gram capacity can reach 167.2mAh/g, the first effect It is 87.6%. See Figure 5 The nickel-cobalt-manganese ternary material with aluminum oxide coating layer of this embodiment is at room temperature, and in the voltage range of 4.3-2.8V, and the current density is 1C. After 200 cycles, the capacity retention rate is 97.3%. . In addition, the nickel-cobalt-manganese ternary material with an aluminum oxide coating layer of this embodiment is at 45°C, and in the voltage range of 4.3-2.8V, and the current density is 1C. After 200 cycles, the capacity retention rate is 96.2%; after 200 cycles at 60°C, the capacity retention rate is 94.5%.

Example Embodiment

[0080] Example 3

[0081] The method for preparing a nickel-cobalt-manganese ternary material with an aluminum oxide coating layer by using a decommissioned lithium-ion battery as a raw material in Embodiment 3 of the present invention is basically the same as Embodiment 1.

[0082] specific:

[0083] In step S100, the specific operation is: fully discharge the decommissioned nickel-cobalt-manganese ternary lithium ion battery, and disassemble the positive electrode plate containing nickel, cobalt and manganese, and then ultrasonically clean and peel the positive electrode plate to obtain aluminum foil and The cathode material mixture is finally dried and sieved to obtain the cathode material.

[0084] In step S200, the solute in the alkali solution is sodium hydroxide; the concentration of the alkali solution is 0.5 mol/L; the solid-to-liquid ratio of the positive electrode material and the alkali solution is 200 g/L, the alkali leaching temperature is 50°C, The immersion time is 1h.

[0085] In step S301, it includes:

[0086] S301a. Mixing the dealumination positive electrode material with sulfuric acid to perform acid leaching to obtain an acid leaching solution; the purpose of this step is to leaching out valuable metal elements in the dealumination positive electrode material;

[0087] S301b. Adding a mixture or one of nickel, cobalt, manganese and impurity element (M) sulfate to the acid leaching solution to obtain a leaching solution; wherein, the molar ratio of each element in the leaching solution conforms to the chemical formula Li(Ni x Co y Mn z ) 1-n M n O 2 , 0 <1, x+y+z=1; in this embodiment, the metal elements in the acid leaching solution are measured by ICP emission spectrometer Then add nickel sulfate, cobalt sulfate, manganese sulfate, and zirconium sulfate to the acid leaching solution to adjust the molar ratio of nickel, cobalt, and manganese to 6:2:2, and the molar ratio of zirconium to the total content of nickel, cobalt and manganese to 0.01 , Get the leachate.

[0088] In step S302, the co-precipitation method is specifically as follows: adding sodium hydroxide solution and/or aqueous ammonia solution to the leaching solution as a precipitating agent to uniformly precipitate the nickel, cobalt and manganese elements in the leaching solution as a ternary precursor of nickel, cobalt and manganese, and then After filtering, a nickel-cobalt-manganese ternary precursor and a lithium-containing solution are obtained.

[0089] In step S303, the precipitation method specifically includes: adding a saturated sodium carbonate solution as a precipitating agent to the concentrated lithium-containing solution, and filtering to obtain lithium carbonate after full reaction.

[0090] In step S304, the high-temperature solid-phase reaction specifically includes: calcination in the presence of oxygen at a high temperature of 800° C. for 15 hours.

[0091] In step S400, the acid solution is sulfuric acid; the concentration of the acid solution is 0.5 mol/L. In addition, in this embodiment, the solid-to-liquid ratio of the pure nickel-cobalt-manganese ternary material and the aluminum-containing alkaline leaching solution is 50 g/L, and the reaction temperature is 60°C. When the three are mixed to a pH of 7, aluminum hydroxide is precipitated on the surface of the pure nickel-cobalt-manganese ternary material, and then stirred at a speed of 400 rpm for 6 hours to obtain a mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material.

[0092] In step S500, the above-mentioned mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material is filtered and washed before being calcined in an aerobic environment. ,dry. In the step of calcining the mixed suspension of aluminum hydroxide and nickel-cobalt-manganese ternary material in an aerobic environment to obtain a nickel-cobalt-manganese ternary material with an alumina coating layer, the calcination temperature is 600°C, and the calcination time For 15h.

[0093] The mass fraction of aluminum oxide in the nickel-cobalt-manganese ternary material with aluminum oxide coating layer prepared in this embodiment is 2 wt.%.

[0094] Image 6 , Figure 7 These are the XRD and SEM images of the nickel-cobalt-manganese ternary material with an aluminum oxide coating layer prepared by using a decommissioned lithium ion battery in this embodiment. See Image 6 , The nickel-cobalt-manganese ternary material with aluminum oxide coating is a typical a-NaFeO 2 The layered structure belongs to the hexagonal crystal system, R3m space group; the two pairs of diffraction peaks 006/102 and 108/110 have a very high degree of splitting, indicating that the material has a good layered structure; the diffraction peaks are sharp and the background is smooth, indicating that the The material has good crystallinity and purity. See Figure 7 The nickel-cobalt-manganese ternary material with an aluminum oxide coating layer is composed of secondary particles formed by agglomeration of a large number of primary particles, with a primary particle size of 100-200nm and a secondary particle size of 5-6μm.

[0095] The nickel-cobalt-manganese ternary material with aluminum oxide coating layer of this embodiment is at room temperature and in the first charge and discharge in the voltage range of 4.3-2.8V, the 0.1C gram capacity can reach 174mAh/g, and the first effect is 86.5 %. The nickel-cobalt-manganese ternary material with an aluminum oxide coating layer of the present embodiment is at room temperature, in the voltage range of 4.3-2.8V, and the current density is 1C. After 200 cycles, the capacity retention rate is 98.6%. In addition, the nickel-cobalt-manganese ternary material with an aluminum oxide coating layer of this embodiment is at 45°C, in the voltage range of 4.3-2.8V, and the current density is 1C. After 200 cycles, the capacity retention rate is 97.3%; after 200 cycles at 60°C, the capacity retention rate is 96.6%.

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PUM

Property	Measurement	Unit
Particle size	200.0 ~ 600.0	nm
Particle size	10.0 ~ 11.0	µm
Particle size	2.0 ~ 4.0	µm
tensile		MPa
Particle size		Pa
strength	10

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Classification and recommendation of technical efficacy words

Improve structural stability

Method for preparation of nickel-cobalt-manganese ternary material with aluminum oxide coating layer by taking retired lithium ion battery as raw material

AI-Extracted Technical Summary

Problems solved by technology

Method used

Abstract

Image

Examples

Example Embodiment

Example Embodiment

Example Embodiment

PUM

Description & Claims & Application Information

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