A method for recovering cobalt metal glass prepared from waste lithium ion batteries

Abstract

The present application belongs to the technical field of solid waste resource recycling, and particularly relates to a method for recovering and preparing cobalt metal glass from waste lithium ion batteries. In the method, the internal electrode material of the waste lithium ion battery is heated and then subjected to a redox reaction in a vacuum environment, and when Co element is generated, the internal atoms are rapidly subjected to random motion; the heating source is turned off to restore to room temperature and then ground to obtain granular material, and the cobalt metal glass is obtained through magnetic separation based on the magnetism of the cobalt metal glass. The obtained cobalt metal glass has the characteristics of good toughness, high breaking strength and high magnetic permeability, and has high utilization value. Moreover, the method of the present application completely uses the electrode material of the waste lithium ion battery as raw material, does not need to add additional reagents, greatly saves the cost, avoids the secondary pollution caused by the wet metallurgy to the environment, is environmentally friendly and clean, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention belongs to the field of solid waste resource recycling technology. More specifically, it relates to a method for preparing cobalt metal glass from waste lithium-ion batteries. Background Technology

[0002] From smartphones to laptops and other portable electronic devices, lithium-ion batteries have been widely used in every aspect of life worldwide since their invention. According to statistics from the Ministry of Industry and Information Technology, my country's total lithium-ion battery production reached 324 GWh in 2021, with the total output value of the entire lithium battery industry exceeding 600 billion yuan. However, at the same time, safety accidents caused by lithium-ion batteries occur every year. In particular, discarded lithium-ion batteries are prone to short circuits, bulging, and thermal runaway, often leading to fires and causing significant crises. Furthermore, lithium-ion batteries contain various heavy metals, fluorides, and volatile organic compounds. Improper disposal of discarded lithium-ion batteries not only results in the loss of large amounts of valuable metal resources but also negatively impacts the environment and ecological cycle. Therefore, the safe and harmless treatment and recycling of discarded lithium-ion batteries is of paramount importance.

[0003] Currently, the recycling of waste lithium-ion batteries is mainly divided into hydrometallurgy and pyrometallurgy. Hydrometallurgy mainly recovers metal materials from waste lithium-ion batteries through multiple steps such as acid leaching or alkaline leaching. However, hydrometallurgy consumes a large amount of acidic and oxidizing substances, resulting in high costs, and the leaching wastewater can easily cause secondary pollution. Pyrometallurgy mainly reduces metal ions in lithium-ion batteries through heating. For example, a Chinese patent application discloses a method for recovering valuable metals from waste lithium-ion batteries. This method mixes waste lithium-ion batteries with added carbon powder and performs low-temperature roasting and reduction treatment to obtain valuable metal alloys and oxide slag. However, the purity of this valuable metal alloy product is not high, and further separation and purification are required before it can be used. Similarly, a Chinese patent application discloses a novel and efficient method for the comprehensive utilization of waste lithium-ion batteries, which uses acetylene black to reduce lithium cobalt oxide to obtain metallic cobalt through vacuum heat treatment. However, the physical properties of this product are poor, limiting its application range.

[0004] Therefore, there is an urgent need for a method that conforms to my country's green and sustainable development, is low-cost, requires no additional reducing agents, and can fully and rationally utilize waste lithium-ion batteries to recycle and prepare high-value products with good physical properties from waste lithium-ion batteries. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the defects and shortcomings of existing methods for recycling metals from waste lithium-ion batteries, which require the addition of additional reducing agents and result in products with low purity or poor physical properties. This invention provides a low-cost method that does not require the addition of additional reducing agents and can fully and rationally utilize waste lithium-ion batteries to recover and prepare high-value cobalt metal glass with good physical properties from waste lithium-ion batteries.

[0006] The above-mentioned objective of this invention is achieved through the following technical solution:

[0007] A method for preparing cobalt metal glass from waste lithium-ion batteries specifically includes the following steps:

[0008] S1. Disassemble the waste lithium-ion battery and heat the resulting electrode material to 1400~1500℃ under vacuum conditions to fully react; under this temperature condition, the atoms inside the Co element undergo random motion.

[0009] S2. Cool to room temperature (to rapidly reduce the internal temperature so that the internal atoms cannot quickly return to their regular arrangement), grind, and perform magnetic separation (cobalt metal glass is magnetic) to obtain cobalt metal glass.

[0010] This invention involves heating the internal electrode material of spent lithium-ion batteries in a vacuum environment to induce a redox reaction, generating elemental Co. During this process, the atoms within the material undergo rapid, random motion. After the heating source is turned off and the mixture is allowed to return to room temperature, it is ground to obtain granular material. This granular material is then magnetically separated using the magnetism of cobalt metal glass to obtain cobalt metal glass. The resulting cobalt metal glass exhibits good toughness, high fracture strength, and high magnetic permeability, demonstrating significant utilization value. Furthermore, this method utilizes only spent lithium-ion battery electrode material as raw material, requiring no additional reagents, thus greatly reducing costs and avoiding secondary pollution caused by hydrometallurgy. It is environmentally friendly and suitable for large-scale industrial production.

[0011] Furthermore, the lithium-ion battery includes lithium nickel cobalt manganese oxide batteries, lithium cobalt oxide batteries, and lithium nickel cobalt aluminum oxide batteries.

[0012] Preferably, in step S1, the reaction temperature is 1400~1450℃. More preferably, in step S1, the reaction temperature is 1400℃.

[0013] Furthermore, in step S1, the vacuum condition is 0.1~1 Pa. In practice, it has been found that the reaction under these conditions can significantly improve the stability of the reduction product. Preferably, in step S1, the vacuum condition is 0.1~0.5 Pa; more preferably, in step S1, the vacuum condition is 0.1 Pa.

[0014] Further, in step S1, the reaction time is 80-100 min. In practice, it has been found that within this reaction time range, the internal atomic structure achieves better quality. Preferably, in step S1, the reaction time is 85-95 min; more preferably, in step S1, the reaction time is 90 min.

[0015] Furthermore, in step S1, the heating rate is 10~12 °C / min. Preferably, in step S1, the heating rate is 10~11 °C / min; more preferably, in step S1, the heating rate is 10 °C / min.

[0016] Further, in step S2, the particle size after grinding is less than 5 mm. Preferably, in step S2, the particle size after grinding is 0.1 mm < particle size < 5 mm.

[0017] Preferably, before disassembly, the waste lithium-ion battery is fully discharged, and then the metal casing and separator material of the waste lithium-ion battery are disassembled to obtain the internal electrode material.

[0018] In addition, the present invention also provides a cobalt metal glass prepared by the method.

[0019] Furthermore, the cobalt metal glass includes the metal elements Co, Cu, Mn, Ni, and Al.

[0020] Additionally, the present invention also claims the use of the cobalt metal glass in magnetic amplifiers, pulse compressors, diode spike suppressors, and magnetic head materials.

[0021] The present invention has the following beneficial effects:

[0022] This invention provides a method for preparing cobalt metallic glass from spent lithium-ion batteries. The method involves heating the internal electrode material of the spent lithium-ion batteries under vacuum to induce a redox reaction, generating elemental Co. During this process, the atoms within the battery undergo rapid, random motion. After the heating source is turned off and the mixture is allowed to return to room temperature, it is ground to obtain granular material with a particle size of less than 5 mm. The cobalt metallic glass is then obtained through magnetic separation using the magnetic properties of the cobalt metallic glass. The resulting cobalt metallic glass exhibits good toughness, high fracture strength, and high magnetic permeability, demonstrating significant utilization value. Furthermore, this method utilizes only the electrode material from spent lithium-ion batteries as raw material, eliminating the need for additional reagents, thus greatly reducing costs and avoiding secondary pollution caused by hydrometallurgy. It is environmentally friendly and suitable for large-scale industrial production. Attached Figure Description

[0023] Figure 1This is a physical image of the cobalt metal glass obtained by a method for preparing cobalt metal glass from waste lithium-ion batteries according to Embodiment 1 of the present invention.

[0024] Figure 2 This is an SEM image of cobalt metal glass obtained by a method for preparing cobalt metal glass from waste lithium-ion batteries according to Embodiment 1 of the present invention.

[0025] Figure 3 This is an EDS image of cobalt metal glass obtained by a method for preparing cobalt metal glass from waste lithium-ion batteries according to Embodiment 1 of the present invention.

[0026] Figure 4 This is the Xrd plot of cobalt metal glass obtained by a method for preparing cobalt metal glass from waste lithium-ion batteries according to Embodiment 1 of the present invention.

[0027] Figure 5 This is a CP-MS metal element content diagram of cobalt metal glass obtained by a method for preparing cobalt metal glass from waste lithium-ion batteries according to Embodiment 1 of the present invention. Detailed Implementation

[0028] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0029] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0030] Example 1: A method for preparing cobalt metallic glass from waste lithium-ion batteries.

[0031] The method for preparing cobalt metal glass from waste lithium-ion batteries specifically includes the following steps:

[0032] Waste lithium nickel cobalt manganese oxide (LiNi) x Co y Mn z After the O2 battery is fully discharged, the metal casing and separator material of the waste lithium-ion battery are manually disassembled. The internal electrode material is placed in a corundum crucible and heated to 1400 ℃ at a rate of 10 ℃ / min in the heating zone of a vacuum tube furnace with the internal pressure controlled at 0.1 Pa. The temperature is maintained at 1400 ℃ for 90 min to carry out the redox reaction, allowing the atoms inside the Co element to undergo sufficient random motion. After the reaction is complete, the heating source is turned off and the mixture is allowed to return to room temperature. The resulting product is then ground in an agate crucible to obtain granular material with a particle size of less than 5 mm. Magnetic separation is performed to obtain cobalt metal glass (see image). Figure 1 ).

[0033] Using an electronic universal testing machine and Young's modulus formula: E = σ / ε, the fracture strength of the cobalt metal glass was measured and calculated to be 4987 MPa and the strength to be 5.72 Gpa, which is significantly higher than that of ordinary cobalt-based metal materials. The magnetic permeability of the obtained cobalt metal glass was measured to be 74829 H / m using an impact galvanometer.

[0034] SEM images of the obtained cobalt metallic glass are shown in the attached image. Figure 2 As shown in the figure, the cobalt metal glass particles produced have a diameter of about 0.12 cm, and in addition to the internal spheres, the surface is covered with a layer of particles.

[0035] The EDS diagram of the obtained cobalt metallic glass is shown in the figure below. Figure 3 As can be seen from the figure, the approximate content of elements inside the cobalt metal glass mainly includes metals such as cobalt, manganese, and nickel. Among them, cobalt metal accounts for the highest proportion, while the other main metals are nickel and manganese.

[0036] The Xrd plot of the obtained cobalt metallic glass is shown in the figure below. Figure 4 As can be seen from the figure, no obvious cobalt element peaks were observed in the XRD spectrum, which proves that the cobalt metal glass material prepared in the embodiments of the present invention has an amorphous structure.

[0037] The metal element content of the obtained cobalt glass was determined by ICP-MS, and the results are shown in [reference needed]. Figure 5 As can be seen from the figure, the main metal element in the cobalt metal glass prepared in Example 1 of the present invention is Co, and the other metals with relatively large contents are nickel, manganese and copper, which is consistent with the data obtained from the EDS experiment.

[0038] As can be seen from the above, the cobalt metal glass prepared in Example 1 of the present invention has good toughness, fracture strength, wear resistance and magnetic permeability, and can be widely used in magnetic amplifiers, pulse compressors, diode spike suppressors, magnetic head materials and other fields.

[0039] Example 2: A method for preparing cobalt metal glass from waste lithium-ion batteries.

[0040] The method for preparing cobalt metal glass from waste lithium-ion batteries specifically includes the following steps:

[0041] Waste lithium nickel cobalt manganese oxide (LiNi) x Co y Mn zAfter the O2 battery is fully discharged, the metal casing and separator material of the waste lithium-ion battery are manually disassembled. The internal electrode material is placed in a corundum crucible and heated to 1500 ℃ at a heating rate of 12 ℃ / min in the heating zone of a vacuum tube furnace with the internal gas pressure controlled at 1 Pa. The temperature is maintained at 1500 ℃ for 100 min to carry out the redox reaction, in which the atoms inside the Co element undergo sufficient random motion. After the reaction is complete, the heating source is turned off and the mixture is allowed to return to room temperature. The resulting product is then ground through an agate crucible to obtain granular material with a particle size of less than 5 mm. Magnetic separation is then performed to obtain cobalt metal glass.

[0042] Using an electronic universal testing machine and Young's modulus formula: E = σ / ε, the fracture strength of the cobalt metal glass was measured and calculated to be 3298 MPa and the strength to be 3.48 Gpa, which is significantly higher than that of ordinary cobalt-based metal materials. The magnetic permeability of the obtained cobalt metal glass was measured to be 60156 H / m using an impact galvanometer.

[0043] As can be seen from the above, the cobalt metal glass prepared in Example 2 of the present invention has good toughness, fracture strength, wear resistance and magnetic permeability, and can be widely used in magnetic amplifiers, pulse compressors, diode spike suppressors, magnetic head materials and other fields.

[0044] Example 3: A method for preparing cobalt metallic glass from waste lithium-ion batteries.

[0045] The method for preparing cobalt metal glass from waste lithium-ion batteries specifically includes the following steps:

[0046] Waste lithium nickel cobalt manganese oxide (LiNi) x Co y Mn z After the O2 battery is fully discharged, the metal casing and separator material of the waste lithium-ion battery are manually disassembled. The internal electrode material is placed in a corundum crucible and heated to 1450 ℃ at a heating rate of 11 ℃ / min in the heating zone of a vacuum tube furnace with the internal gas pressure controlled at 0.5 Pa. The temperature is maintained at 1450 ℃ for 80 min to carry out the redox reaction, in which the atoms inside the Co element undergo sufficient random motion. After the reaction is complete, the heating source is turned off and the mixture is allowed to return to room temperature. The resulting product is then ground through an agate crucible to obtain granular material with a particle size of less than 5 mm. Magnetic separation is then performed to obtain cobalt metal glass.

[0047] Using an electronic universal testing machine and Young's modulus formula: E = σ / ε, the fracture strength of the cobalt metal glass was measured and calculated to be 3924 MPa and the strength to be 3.82 Gpa, which is significantly higher than that of ordinary cobalt-based metal materials. The magnetic permeability of the obtained cobalt metal glass was measured to be 67347 H / m using an impact galvanometer.

[0048] As can be seen from the above, the cobalt metal glass prepared in Example 3 of the present invention has good toughness, fracture strength, wear resistance and magnetic permeability, and can be widely used in magnetic amplifiers, pulse compressors, diode spike suppressors, magnetic head materials and other fields.

[0049] Example 4: A method for preparing cobalt metal glass from waste lithium-ion batteries

[0050] The method for preparing cobalt metal glass from waste lithium-ion batteries specifically includes the following steps:

[0051] Waste lithium nickel cobalt manganese oxide (LiNi) x Co y Mn z After the O2 battery is fully discharged, the metal casing and separator material of the waste lithium-ion battery are manually disassembled. The internal electrode material is placed in a corundum crucible and heated to 1500 ℃ at a heating rate of 10 ℃ / min in the heating zone of a vacuum tube furnace with the internal pressure controlled at 0.5 Pa. The temperature is maintained at 1500 ℃ for 100 min to carry out the redox reaction, in which the atoms inside the Co element undergo sufficient random motion. After the reaction is complete, the heating source is turned off and the mixture is allowed to return to room temperature. The resulting product is then ground through an agate crucible to obtain granular material with a particle size of less than 5 mm. Magnetic separation is then performed to obtain cobalt metal glass.

[0052] Using an electronic universal testing machine and Young's modulus formula: E = σ / ε, the fracture strength of the cobalt metal glass was measured and calculated to be 4384 MPa and the strength to be 4.92 Gpa, which is significantly higher than that of ordinary cobalt-based metal materials. The magnetic permeability of the obtained cobalt metal glass was measured to be 70716 H / m using an impact galvanometer.

[0053] As can be seen from the above, the cobalt metal glass prepared in Example 4 of the present invention has good toughness, fracture strength, wear resistance and magnetic permeability, and can be widely used in magnetic amplifiers, pulse compressors, diode spike suppressors, magnetic head materials and other fields.

[0054] Comparative Example 1: A method for preparing crystalline cobalt from spent lithium-ion batteries.

[0055] The method for preparing crystalline cobalt from waste lithium-ion batteries specifically includes the following steps:

[0056] Waste lithium nickel cobalt manganese oxide (LiNi) x Co y Mn z After the O2 battery is fully discharged, the metal casing and separator material of the waste lithium-ion battery are manually disassembled. The internal electrode material is placed in a corundum crucible and heated to 1200 ℃ at a heating rate of 10 ℃ / min in the heating zone of a vacuum tube furnace with the internal gas pressure controlled at 0.1 Pa. The temperature is maintained at 1200 ℃ for 100 min to carry out the redox reaction, in which the atoms inside the Co element undergo sufficient random motion. After the reaction is complete, the heating source is turned off and the mixture is allowed to return to room temperature. The resulting product is then ground through an agate crucible to obtain granular material with a particle size of less than 5 mm. Magnetic separation is then performed to obtain crystalline cobalt.

[0057] Using an electronic universal testing machine and Young's modulus formula: E = σ / ε, the fracture strength of the cobalt crystal was measured and calculated to be 1384 MPa and the strength to be 0.92 Gpa. The magnetic permeability of the obtained cobalt metallic glass was measured to be 7646 H / m using an impact galvanometer.

[0058] Table 1 is obtained by comparing and summarizing the performance measurements of the embodiments and comparative examples of the present invention.

[0059] Table 1 Performance comparison of the embodiments and comparative examples

[0060]

[0061] As shown in Table 1, the cobalt metallic glasses prepared in Examples 1-4 of this invention exhibit fracture strength exceeding 3000 MPa and strength exceeding 3 GPa, demonstrating good toughness and fracture strength; their magnetic permeability exceeds 60000 H / m, also exhibiting good magnetic permeability, and their performance is better than existing cobalt-based materials. Compared with Comparative Example 1, the fracture strength, strength, and magnetic permeability are all significantly higher than those of Comparative Example 1.

[0062] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention and are preferred embodiments, not limitations on the embodiments of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A cobalt metal glass prepared from recycled waste lithium-ion batteries, characterized in that, Specifically, it is prepared by the following steps: S1. After fully discharging the waste lithium-ion battery, disassemble the metal shell and separator material of the waste lithium-ion battery, and heat the internal electrode material to 1400~1500℃ under vacuum conditions to fully react. S2. Cool to room temperature, grind, and magnetically separate to obtain cobalt metal glass; The vacuum condition is 0.1~1 Pa; the reaction time is 80~100 min; the particle size after grinding is less than 5 mm; The cobalt metal glass has a fracture strength of over 3000 MPa, a strength of over 3 GPa, and a magnetic permeability of over 60000 H / m.

2. The cobalt metal glass according to claim 1, characterized in that, The lithium-ion batteries include lithium nickel cobalt manganese oxide batteries, lithium cobalt oxide batteries, and lithium nickel cobalt aluminum oxide batteries.

3. The cobalt metal glass according to claim 1, characterized in that, In step S1, the reaction temperature is 1400~1450℃.

4. The cobalt metal glass according to claim 1, characterized in that, In step S1, the heating rate is 10~12℃ / min.

5. The cobalt metal glass according to any one of claims 1 to 4, characterized in that, The cobalt metal glass contains the metal elements Co, Ni, Mn, and Cu.

6. The application of the cobalt metal glass according to any one of claims 1 to 5 in magnetic amplifiers, pulse compressors, diode spike suppressors, and magnetic head materials.

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