Short-process high-performance single-crystallization regeneration method for waste ternary material
By combining dry ball milling pre-activation and wet autogenous grinding, the problems of uneven particle contact and poor diffusion during the regeneration of waste ternary materials have been solved, realizing the regeneration of high-performance single crystal materials suitable for large-scale production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-22
- Publication Date
- 2026-04-14
AI Technical Summary
Existing technologies cannot achieve homogeneous regeneration of waste ternary materials through simple heat of dissolution and electrochemical lithium replenishment methods, resulting in poor performance of regenerated ternary single crystal materials, uneven contact between particles, small contact area, and poor solid-solid uniform diffusion.
A process combining dry ball milling pre-activation and wet autogenous grinding was adopted. Waste ternary materials were treated by zirconium ball media milling and zirconium-free media autogenous grinding to promote uniform contact and solid-solid diffusion with supplementary elements. Subsequently, calcination was carried out in an oxygen atmosphere to form high-performance single crystal materials.
The single-crystal normalization of waste ternary materials was achieved, and the resulting recycled ternary single-crystal materials have excellent performance, comparable to commercial ternary cathode materials. The operation is simple and efficient, and suitable for large-scale production.
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Figure CN121862933A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for regenerating waste ternary materials, and particularly to a short-process, high-performance single-crystal regeneration method for waste ternary materials, belonging to the field of waste battery recycling technology. Background Technology
[0002] Lithium-ion battery ternary materials exhibit high energy density and theoretical capacity, and have been widely used in daily life. However, limited by their effective cycle life (8-10 years), a large number of ternary materials have been retired in recent years. Direct recycling, as an emerging key method for processing waste ternary materials, has the advantages of short process and low energy consumption. However, waste ternary materials are diverse, classified into 111 series, 523 series, 622 series, 713 series, 811 series, etc., based on the Ni-Co-Mn elemental ratio. They can also be classified into single-crystal and polycrystalline materials based on crystal phase. Therefore, the composition and crystal phase characteristics of waste ternary materials are quite complex. While simple methods such as heat of solution and electrochemical lithium replenishment can induce the performance recovery of individual failed electrode materials, they are insufficient to solve the problem of the non-uniform physical properties of waste ternary materials. Therefore, if a single-crystal normalization method could be used to transform different complex waste ternary materials into ternary materials with a specific crystal phase structure, it would help achieve homogeneous recycling of waste ternary materials. However, uneven contact and small contact area between particles during the single crystal regeneration process, as well as poor uniform diffusion of the added elements, result in poor performance of the regenerated ternary single crystal material. Summary of the Invention
[0003] To address the technical deficiencies of existing technologies, the present invention aims to provide a short-process, high-performance single-crystal regeneration method for waste ternary materials. This method involves a process of "dry ball milling pre-activation + wet autogenous grinding + calcination" to achieve single-crystal normalization of waste ternary materials. The resulting regenerated ternary single-crystal materials exhibit excellent performance, comparable to commercial ternary cathode materials. Furthermore, this method is simple to operate, efficient, and has a short process, meeting the requirements for large-scale production.
[0004] To achieve the above technical objectives, this invention provides a short-process high-performance single-crystal regeneration method for waste ternary materials. The method involves dry ball milling of waste ternary materials with grinding media to obtain pre-activated material; wet auto-milling of the pre-activated material and supplementary element raw materials without grinding media to obtain a mixed slurry; and calcining the mixed slurry in an oxygen atmosphere to obtain regenerated single-crystal ternary materials.
[0005] The key to this invention lies in promoting the activation of waste ternary materials and ensuring uniform contact between the waste ternary material particles and the supplementary elements through two-stage grinding, thereby increasing the solid-solid diffusion rate and achieving the normalization of single crystals in the recycled waste ternary materials. This invention first subjects the waste ternary materials to dry ball milling with grinding media. This process utilizes the grinding media to physically depolymerize the waste ternary materials, obtaining smaller, more uniform primary particles. Simultaneously, the physical impact of the grinding media on the waste ternary materials increases the surface defects of the primary particles, enhancing their reactivity. Then, the depolymerized and pre-activated waste ternary materials are subjected to wet self-grinding without grinding media with the supplementary element raw material. This primarily utilizes the self-grinding between the raw material particles, which not only strengthens the dispersion between the waste ternary materials and the supplementary element raw material but also allows the supplementary element raw material to slurry up and fully contact the primary particles of the waste ternary materials in an ionic state, increasing the solid-solid diffusion rate during subsequent calcination. This achieves homogenization and crystal transformation of the waste ternary materials, resulting in high-quality recycled ternary single crystal materials.
[0006] As a preferred option, the ternary material is 523, 622, 7-series or 8-series.
[0007] As a preferred embodiment, the dry ball milling conditions are as follows: using zirconium balls as the milling medium, a ball-to-material mass ratio of 2-5:1, a ball mill speed of 300-800 rpm, and a time of 1-30 minutes. If the ball mill speed is too low or the milling time is too short, the secondary particle deagglomeration of the waste ternary material will be incomplete, leaving large-sized particles and affecting the uniformity of the recycled material particles. If the ball mill speed is too high or the milling time is too long, it will cause physical damage to the primary particles of the waste ternary material and may introduce impurities, affecting the final regeneration performance. A further preferred ball mill speed is 400-600 rpm. A further preferred time is 1-5 minutes. If the ball-to-material mass ratio is too low, the secondary particle deagglomeration effect will be poor; if the ball-to-material mass ratio is too high, it will cause excessive damage to the primary particles.
[0008] As a preferred embodiment, the conditions for the wet autogenous grinding treatment are as follows: no zirconium balls are added as the milling medium, water is used as the solvent medium, the liquid-to-solid ratio is 1 mL: 8~15 g, the mill speed is 1000~3000 rpm, and the time is 10 min~3 h. If the mill speed is too low or the time is too short, the autogenous grinding effect between particles is insufficient, making it difficult to form a uniform slurry; if the mill speed is too high or the time is too long, the required energy consumption is too high, increasing the cost of material processing, without further significant improvement in the autogenous grinding effect. If the amount of water added is too low, the supplementary element raw materials are difficult to fully slurry, which is not conducive to obtaining uniform single-crystal ternary materials. If the amount of water added is too high, the solid content of the supplementary element raw material slurry is low, which is not conducive to the subsequent calcination process.
[0009] As a preferred option, the supplementary element raw materials are determined based on the missing elements in the waste ternary materials, including one or more of lithium, nickel, cobalt and manganese sources.
[0010] As a preferred embodiment, the lithium source includes at least one of lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate, and lithium citrate.
[0011] As a preferred embodiment, the nickel source includes at least one of nickel carbonate, nickel nitrate, nickel acetate, nickel citrate, nickel acetate, and basic nickel carbonate.
[0012] As a preferred embodiment, the cobalt source includes at least one of cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt citrate, cobalt oxalate, and basic cobalt carbonate.
[0013] As a preferred embodiment, the manganese source includes at least one of manganese carbonate, manganese nitrate, manganese acetate, manganese citrate, manganese oxalate, and basic manganese carbonate.
[0014] As a preferred embodiment, the calcination includes a two-stage sintering process. The first-stage sintering conditions are: temperature of 450℃~600℃ and time of 1h~6h; the second-stage sintering conditions are: temperature of 750℃~950℃ and time of 6h~12h.
[0015] The calcination process of this invention includes a low-temperature first-stage sintering process and a high-temperature second-stage sintering process. The calcination process is carried out in an oxidizing atmosphere. The purpose of the low-temperature first-stage sintering is, on the one hand, to remove impurities, such as organic binders and carbon materials, through oxidation, and on the other hand, to form a uniform metastable intermediate phase at a low temperature. If the sintering time is too short or the temperature is too low, it is difficult for particles to complete effective diffusion within the solid phase, and the metastable layered structure is difficult to form completely. If the sintering temperature is too high or the time is too long, it will not only increase energy consumption, but also cause the crystallinity of the waste ternary material to increase and crystal phase fusion to occur between particles, resulting in a longer diffusion distance of the added element ions, which leads to impurities in the crystal phase of the recycled material and the generation of impurity crystal phases. High-temperature two-stage sintering primarily forms highly crystalline single-crystal particles with a single crystal phase. If the sintering temperature is too low or the sintering time is too short, single-crystal particles are difficult to form, and the layered phase crystallization is incomplete with low crystallinity. If the sintering temperature is too high or the sintering time is too long, internal degradation will occur within the formed single-crystal particles, leading to partial collapse of the layered structure and release of lattice oxygen. Therefore, this invention strictly controls the conditions during the calcination process, which is beneficial for obtaining highly crystalline regenerated ternary cathode materials with a single crystal phase.
[0016] The waste ternary material of this invention is obtained from decommissioned ternary or ternary electrode materials provided by enterprises. The waste ternary cathode material powder is obtained by separation using existing conventional techniques.
[0017] Compared with the prior art, the technical solution of the present invention brings the following beneficial technical effects:
[0018] This invention uses a process of "dry ball milling pre-activation + wet auto-grinding + calcination" to normalize the single crystals of waste ternary materials. The resulting recycled ternary single crystal materials have excellent performance, comparable to commercial ternary cathode materials.
[0019] This invention employs a "dry ball milling pre-activation + wet autogenous grinding" process on waste ternary cathode materials. This process enables the deagglomeration, activation, and thorough dispersion of the waste ternary cathode materials with supplementary element raw materials. It improves the contact between the waste ternary material particles and the supplementary element raw materials, promotes solid-solid phase ion migration, and ultimately yields high-performance directly regenerated ternary single-crystal materials. This invention solves the technical problems in existing technologies, such as uneven particle contact and small contact area during single-crystal regeneration, and poor solid-solid uniform diffusion of the supplementary elements, which lead to poor performance of the regenerated ternary single-crystal materials.
[0020] The present invention provides a simple, efficient, and short process for regenerating waste ternary cathode materials, which is suitable for large-scale production. Attached Figure Description
[0021] Figure 1 The image shows the XRD pattern of the regenerated single-crystal ternary material in Example 1; from Figure 1 As can be seen, the regenerated single-crystal ternary material has good crystallinity, and its XRD pattern is a typical layered structure phase diagram. There are no impurity peaks in the XRD pattern, which proves that the material is relatively well fused.
[0022] Figure 2 This is a scanned image of the mixture of waste ternary cathode materials from Example 1 after ball milling without grinding media; from Figure 2 Scanning electron microscopy reveals that the surface of the primary particles of the waste ternary cathode material is coated with a gel-like substance. This indicates that the secondary particles are relatively completely deagglomerated, and that after ball milling without grinding media, the other raw material components have evolved into a uniform medium and are uniformly adhered to the surface of the primary particles of the waste ternary cathode material.
[0023] Figure 3 SEM image of the regenerated single-crystal ternary material prepared in Example 1; Figure 3 The scanning electron microscope images show that the regenerated ternary cathode material particles exhibit a single-crystal morphology and a relatively smooth surface, indicating the disappearance of defects during the regeneration process. In addition, the particle size of the regenerated single-crystal ternary material is less than 5 μm.
[0024] Figure 4 TEM image of the regenerated single-crystal ternary material prepared in Example 1; Figure 4 The transmission electron microscope (TEM) images show that the lattice fringes in the regenerated single-crystal ternary material are more obvious and the crystal phase is more complete, indicating that the crystal phase in the waste ternary cathode material has been effectively regenerated.
[0025] Figure 5 This serves as the charge-discharge platform for the regenerated single-crystal ternary material prepared in Example 1; Figure 5 It can be seen that within the voltage range of 2.8V to 4.3V, at a current density of 0.1C, the discharge capacity of the regenerated ternary single crystal material can reach 173 mAh / g. Moreover, the charge-discharge plateau diagram shown is a typical ternary charge-discharge plateau, similar to that of commercial ternary single crystals, indicating the effective phase transition during the energy storage process of the regenerated material.
[0026] Figure 6 The recycled single-crystal ternary material prepared in Example 1 is recycled; Figure 6 The charge-discharge cycle curves for regenerated ternary single-crystal materials. Figure 6 As can be seen, within a voltage range of 2.8V to 4.3V and a current density of 0.1C, after 100 charge-discharge cycles, the material's capacity can be maintained at 150 mAh / g, with a capacity retention rate of 92%, indicating that the recycled ternary material exhibits a stable crystal phase structure and high reversibility. Detailed Implementation
[0027] The following examples are used to illustrate the content of this invention, but are not intended to limit the scope of protection of the claims of this invention.
[0028] Although this specification describes specific embodiments, it does not imply that each embodiment contains only one independent technical solution. This descriptive method is for clarity only, and those skilled in the art should consider the specification as a whole. The technical solutions in the various embodiments can also be appropriately combined to form other embodiments that can be understood by those skilled in the art, and such other embodiments are also within the scope of protection of the claims of this invention.
[0029] Comparative Example 1
[0030] S1: Targeting 622 single crystal material, 1 mol of waste ternary 811 material was added to a ball mill jar. According to ICP results, the chemical formula of this batch of waste ternary material was Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar and ball-milled without adding zirconium balls as the milling medium. The milling speed was 1500 rpm, and the milling time was 20 min. 10 mL of deionized water was added to obtain mixed material B.
[0031] S2: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550℃ for 3 hours and 800℃ for 8 hours to finally obtain 622 series recycled ternary single crystal materials.
[0032] The comparative example is mainly to illustrate that without pre-activation treatment, the secondary particles in the material are not completely deagglomerated, resulting in incomplete contact between the waste material and the lithium salt. During the crystal phase transformation process, the material grows unevenly, leading to poor material performance.
[0033] Comparative Example 2
[0034] S1: Targeting 622 single crystal material, 1 mol of waste ternary 811 material was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, with zirconium balls added as the milling medium. The milling speed was 500 rpm, the milling time was 5 min, and the ball-to-material mass ratio was 3:1, resulting in a recycled ternary mixture of waste materials.
[0035] S2: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550℃ for 3 hours and 800℃ for 8 hours to finally obtain 622 series recycled ternary single crystal materials.
[0036] The comparative example is mainly to illustrate that without the addition of wet autogenous grinding, the uneven distribution of particles and supplementary elements leads to poor performance of recycled materials.
[0037] Comparative Example 3
[0038] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, and zirconium balls were added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0039] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0040] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination at 1000℃ for 9 hours in an oxygen atmosphere to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0041] The comparative example is mainly to illustrate that if only one high-temperature calcination is used, the crystallinity of the waste ternary material will increase and the crystal phases will merge between particles, which will prolong the diffusion distance of the added elements' ions, resulting in impure crystal phases in the recycled material and the generation of impurity crystal phases.
[0042] Example 1
[0043] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, and zirconium balls were added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0044] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0045] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0046] Example 2
[0047] S1: The waste 712 series was placed in a ternary ball mill jar for ball milling, and zirconium balls were added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0048] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.68 Co 0.095 Mn 0.198 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.165 mol Co(NO3)2·6H2O, and 0.062 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, and the ball milling speed was 1500 rpm for 20 min to obtain mixed slurry B.
[0049] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0050] Example 3
[0051] S1: The waste 523 series was placed in a ternary ball mill jar for ball milling, and zirconium balls were added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0052] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.47 Co 0.19 Mn 0.28 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0.47 mol Ni(NO3)2·6H2O, 0.09 mol Co(NO3)2·6H2O, and 0 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0053] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0054] Example 4
[0055] S1: The waste 811+523 series was placed in a ternary ball mill jar for ball milling. Zirconium balls were added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0056] S2: Targeting 622 single crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the overall stoichiometry of each element in this batch of waste ternary material was Li. 0.9 Ni 0.63 Co 0.146 Mn 0.197Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.075 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.064 mol Co(NO3)2·6H2O, and 0.013 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0057] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0058] Example 5
[0059] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, and zircon balls were added as the ball milling medium. The ball milling speed was 300 rpm, the ball milling time was 1 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0060] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0061] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0062] Example 6
[0063] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 800 rpm, the ball milling time was 3 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0064] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0065] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0066] Example 7
[0067] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0068] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.4 mol LiOH, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0069] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0070] Example 8
[0071] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0072] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol basic nickel carbonate, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0073] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0074] Example 9
[0075] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0076] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.0513 mol cobalt citrate, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0077] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0078] Example 10
[0079] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0080] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol manganese acetate. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0081] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0082] Example 11
[0083] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0084] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1000 rpm, and the ball milling time was 10 min to obtain mixed slurry B.
[0085] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0086] Example 12
[0087] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0088] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 3000 rpm, and the ball milling time was 3 h to obtain mixed slurry B.
[0089] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0090] Example 13
[0091] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0092] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0093] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 450°C for 1 hour and 850°C for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0094] Example 14
[0095] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0096] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0097] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 600℃ for 6 hours and 850℃ for 9 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0098] Example 15
[0099] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0100] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the ball milling time was 20 min to obtain mixed slurry B.
[0101] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 750°C for 6 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0102] Example 16
[0103] S1: The waste 811 series was placed in a ternary ball mill jar for ball milling, with zirconium balls added as the ball milling medium. The ball milling speed was 500 rpm, the ball milling time was 5 min, and the ball-to-material mass ratio was 3:1. The waste ternary pre-activated A material was obtained, and its elemental content was determined by ICP.
[0104] S2: Targeting 622 single-crystal material, 1 mol of waste ternary pre-activated material A was added. According to ICP results, the chemical formula of this batch of waste ternary material is Li. 0.9 Ni 0.78 Co 0.095 Mn 0.099 Based on the elemental ratio of Li-Ni-Co-Mn in the 622 series, the elemental supplementation amounts were calculated to be 0.2 mol Li2CO3, 0 mol Ni(NO3)2·6H2O, 0.155 mol Co(NO3)2·6H2O, and 0.151 mol Mn(NO3)2·4H2O. The mixture was placed in a ball mill jar for ball milling, without adding zirconium balls as the milling medium. 10 mL of deionized water was added, the ball milling speed was 1500 rpm, and the milling time was 20 min, yielding mixed slurry B.
[0105] S3: The mixed slurry B is placed in a tube furnace for high-temperature calcination in an oxygen atmosphere. The calcination conditions are 550°C for 3 hours and 950°C for 12 hours to finally obtain 622 series recycled ternary single crystal materials. The recycled materials do not require washing.
[0106] The electrochemical performance of the recycled ternary materials in Comparative Examples 1-3 and Examples 1-16 was tested and compared with the performance of commercial materials. The test results are shown in Table 1.
[0107] 1) Sample preparation
[0108] Regenerated ternary single-crystal material and acetylene black were mixed and added to a pre-prepared PVDF gel (dissolved in NMP). The mass ratio of regenerated material, acetylene black, and PVDF was 8 / 1 / 1. The resulting slurry was coated onto aluminum foil and then dried in a vacuum oven at 100°C for 12 hours. The resulting electrode was cut into small round pieces using a slicing machine to become the obtained positive electrode material. The aluminum foil was loaded with 2 mg of C14. -2 Active substances.
[0109] The obtained positive electrode sheet, electrolyte, lithium metal, battery casing, separator, etc., are placed in an argon-filled glove box for battery assembly. After sealing, the resulting battery is an assembled coin cell.
[0110] Note: All embodiments use the above-described electrode material preparation method.
[0111] 2) Testing Methods
[0112] After the obtained button cells were left to stand for 8 hours, they were placed on the blue electrode test channel for electrochemical performance testing, with the voltage range set to 2.8~4.3 V. The obtained data are directly displayed on the blue electrode tester and can be directly used.
[0113]
[0114]
Claims
1. A short-process, high-performance single-crystal regeneration method for waste ternary materials, characterized in that: Waste ternary materials are subjected to dry ball milling with grinding media to obtain pre-activated material; the pre-activated material and supplementary element raw materials are subjected to wet auto-milling without grinding media to obtain mixed slurry; the mixed slurry is placed in an oxygen atmosphere for calcination to obtain recycled single crystal ternary materials.
2. The method for short-process high-performance single-crystal regeneration of waste ternary materials according to claim 1, characterized in that: The ternary material is 523, 622, 7-series or 8-series.
3. The method for short-process high-performance single-crystal regeneration of waste ternary materials according to claim 1, characterized in that: The conditions for the dry ball milling process are as follows: zirconium balls are used as the milling medium, the ball-to-material mass ratio is 2~5:1, the ball mill speed is 300 rpm~800 rpm, and the time is 1 min~30 min.
4. The method for short-process high-performance single-crystal regeneration of waste ternary materials according to claim 1, characterized in that: The conditions for the wet auto-grinding process are as follows: no zirconium balls are added as the milling medium, water is used as the solvent medium, the liquid-to-solid ratio is 1mL: 8~15g, the milling speed is 1000~3000rpm, and the time is 10min~3h.
5. The short-process high-performance single-crystal regeneration method for waste ternary materials according to claim 1, characterized in that: The supplementary element raw materials are determined based on the corresponding missing elements in the waste ternary materials, including one or more of lithium, nickel, cobalt and manganese sources; The lithium source includes at least one of lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate, and lithium citrate. The nickel source includes at least one of nickel carbonate, nickel nitrate, nickel acetate, nickel citrate, nickel acetate, and basic nickel carbonate; The cobalt source includes at least one of cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt citrate, cobalt oxalate, and basic cobalt carbonate. The manganese source includes at least one of manganese carbonate, manganese nitrate, manganese acetate, manganese citrate, manganese oxalate, and basic manganese carbonate.
6. A short-process high-performance single-crystal regeneration method for waste ternary materials according to any one of claims 1 to 5, characterized in that: The calcination process includes two sintering stages. The first sintering stage has the following conditions: temperature of 450℃~600℃ and time of 1h~6h. The second sintering stage has the following conditions: temperature of 750℃~950℃ and time of 6h~12h.