CN-121972495-A - Regeneration method of hard carbon negative plate waste and regenerated hard carbon material

CN121972495ACN 121972495 ACN121972495 ACN 121972495ACN-121972495-A

Abstract

The application discloses a regeneration method of hard carbon negative plate waste and regenerated hard carbon materials, and relates to the technical field of electrode material regeneration; the regeneration method comprises the steps of standing hard carbon negative electrode sheet waste in an environment of-50 ℃ to-30 ℃, crushing and sorting to obtain hard carbon waste, adding the hard carbon waste into a degumming liquid, heating and stirring the hard carbon waste, and simultaneously carrying out ultrasonic treatment to degumm the hard carbon waste, wherein the degumming liquid comprises a volatile organic solvent, weak alkaline inorganic salt and a nonionic surfactant which is mutually soluble with the volatile organic solvent. According to the application, the hard carbon negative electrode slice waste is firstly kept stand in a low-temperature environment, so that the binder on the hard carbon negative electrode slice waste is embrittled, the strength of the subsequent degumming condition is reduced, the hard carbon waste is obtained through crushing and sorting, and the hard carbon waste is degummed by using the degumming liquid under the conditions of heating, stirring and ultrasonic, so that the mild and efficient degumming is realized, and the damage to the hard carbon structure is avoided.

Inventors

MA ZHIYUAN
LIANG ZHIYUN
YANG HAIMIN
SHI DINGREN
Teng Huaiping

Assignees

山东威尔能新能源材料科技有限公司

Dates

Publication Date: 20260505
Application Date: 20260227

Claims (10)

1. The regeneration method of the hard carbon negative plate waste material is characterized by comprising the following steps of: Standing the hard carbon negative electrode slice waste in an environment of-50 ℃ to-30 ℃ and then crushing and sorting to obtain hard carbon waste; adding the hard carbon waste into a degumming liquid, heating and stirring, and simultaneously carrying out ultrasonic treatment to degumm the hard carbon waste, wherein the degumming liquid comprises a volatile organic solvent, a weak alkaline inorganic salt and a nonionic surfactant which is mutually soluble with the volatile organic solvent.
2. The method for regenerating a hard carbon negative electrode sheet waste according to claim 1, wherein the volatile organic solvent comprises anhydrous ethanol and/or isopropanol; the weakly basic inorganic salt comprises sodium bicarbonate and/or potassium bicarbonate; the nonionic surfactant comprises at least one of polyethylene glycol, polypropylene glycol and tween-80.
3. The regeneration method of the hard carbon negative plate waste material according to claim 1 or 2, wherein the amount of the weakly basic inorganic salt is 3-5 wt% of the mass of the volatile organic solvent; The dosage of the nonionic surfactant is 1-2 wt% of the mass of the volatile organic solvent.
4. The method for regenerating a hard carbon negative electrode sheet waste according to claim 3, further comprising preparing a degluing solution, the preparing a degluing solution comprising: Dissolving the nonionic surfactant in the volatile organic solvent; And adding the weakly alkaline inorganic salt into the volatile organic solvent in batches, and performing ultrasonic dispersion to obtain the degumming liquid, wherein the particle size range of the weakly alkaline inorganic salt is 1-10 mu m.
5. The method for regenerating a hard carbon negative electrode sheet waste according to claim 1 or 2, wherein the adding the hard carbon waste to the degumming liquid, heating and stirring while performing ultrasonic treatment comprises: And adding the hard carbon waste into the degumming liquid according to a liquid-solid ratio (15-20) of 1mL/g, stirring the degumming liquid at a constant temperature of 60-85 ℃ for 90-120 min, and simultaneously carrying out auxiliary degumming by adopting ultrasonic waves with a frequency of 20 kHz-30 kHz.
6. The method for regenerating a hard carbon negative electrode sheet waste according to claim 1, further comprising, after said degumming of said hard carbon waste: Separating degummed hard carbon materials from the degummed liquid, washing, drying and sorting the degummed hard carbon materials in sequence to obtain first hard carbon materials, wherein the particle size of the first hard carbon materials is 2-20 mu m, And mixing the first hard carbon material with fumed silica, and performing ball milling treatment and heat treatment to obtain a second hard carbon material, wherein the difference between D90 and D10 in the particle size distribution of the second hard carbon material is 8-9 mu m.
7. The method for regenerating a hard carbon negative plate waste material according to claim 6, wherein the amount of the fumed silica is 0.3wt% to 0.5wt% of the mass of the first hard carbon material; The particle size of the fumed silica is 5 nm-20 nm.
8. The method of recycling hard carbon negative electrode sheet waste according to claim 6, wherein mixing the first hard carbon material with fumed silica and performing ball milling treatment and heat treatment comprises: Mixing the first hard carbon material with fumed silica to obtain a mixture, and ball-milling the mixture at a rotating speed of 200-300 r/min for 30-60 min; And (3) preserving the temperature of the mixture at 600-800 ℃ in an inert gas atmosphere for 30-120 min.
9. The method of recycling waste hard carbon negative plates of claim 6, wherein the tap density of the second hard carbon material is 1.2g/cm 3 ~1.4g/cm 3 .
10. A regenerated hard carbon material prepared by the method for regenerating a hard carbon negative electrode sheet waste material according to any one of claims 1 to 9.

Description

Regeneration method of hard carbon negative plate waste and regenerated hard carbon material Technical Field The application relates to the technical field of regeneration of electrode materials, in particular to a regeneration method of hard carbon negative plate waste and a regenerated hard carbon material. Background The hard carbon negative electrode plate can generate waste electrode plates and leftover materials in the coating and cutting processes. The hard carbon negative electrode plate waste material has complete structure of a hard carbon material body without charge and discharge circulation, but the hard carbon negative electrode plate waste material cannot be directly recycled in battery production due to the adhesion of an adhesive on the surface. At present, most of the hard carbon negative electrode plate waste is directly discarded or subjected to extensive incineration treatment, so that not only is the waste of high-value hard carbon resources caused, but also environmental pressure is caused because the binder is difficult to degrade. Disclosure of Invention In a first aspect of the present application, there is provided a method for regenerating a hard carbon negative electrode sheet waste material, the regeneration method comprising the steps of: Standing the hard carbon negative electrode slice waste in an environment of-50 ℃ to-30 ℃ and then crushing and sorting to obtain hard carbon waste; adding the hard carbon waste into a degumming liquid, heating and stirring, and simultaneously carrying out ultrasonic treatment to degumm the hard carbon waste, wherein the degumming liquid comprises a volatile organic solvent, a weak alkaline inorganic salt and a nonionic surfactant which is mutually soluble with the volatile organic solvent. In some optional embodiments of the first aspect of the application, the volatile organic solvent comprises anhydrous ethanol and/or isopropanol. In some alternative embodiments of the first aspect of the application, the weakly basic inorganic salt comprises sodium bicarbonate and/or potassium bicarbonate. In some alternative embodiments of the first aspect of the application, the nonionic surfactant comprises at least one of polyethylene glycol, polypropylene glycol, and tween-80. In some optional embodiments of the first aspect of the present application, the amount of the weakly basic inorganic salt is 3wt% to 5wt% of the mass of the volatile organic solvent; The dosage of the nonionic surfactant is 1-2 wt% of the mass of the volatile organic solvent. In some optional embodiments of the first aspect of the application, the regeneration method further comprises preparing a degummed liquor, the preparing a degummed liquor comprising: dissolving a nonionic surfactant in a volatile organic solvent; adding weak alkaline inorganic salt into the volatile organic solvent in batches, and performing ultrasonic dispersion to obtain a degumming solution, wherein the particle size range of the weak alkaline inorganic salt is 1-10 mu m. In some optional embodiments of the first aspect of the application, adding hard carbon waste to the de-glue solution, heating and stirring while simultaneously sonicating comprises: Adding the hard carbon waste into the degumming liquid according to the liquid-solid ratio (15-20) of 1mL/g, stirring the degumming liquid at the constant temperature of 60-85 ℃ for 90-120 min, and simultaneously carrying out auxiliary degumming by adopting ultrasonic waves with the frequency of 20 kHz-30 kHz. In some optional embodiments of the first aspect of the present application, after degumming the hard carbon waste, the method further comprises: Separating degummed hard carbon materials from degummed liquid, washing, drying and sorting the degummed hard carbon materials in sequence to obtain first hard carbon materials, wherein the particle size of the first hard carbon materials is 2-20 mu m, And mixing the first hard carbon material with fumed silica, and performing ball milling treatment and heat treatment to obtain a second hard carbon material, wherein in the particle size distribution of the second hard carbon material, the difference between D90 and D10 is 8-9 mu m. In some alternative embodiments of the first aspect of the application, the fumed silica is present in an amount of from 0.3wt% to 0.5wt% based on the mass of the first hard carbon material. In some optional embodiments of the first aspect of the present application, the fumed silica has a particle size of 5nm to 20nm. In some alternative embodiments of the first aspect of the present application, mixing and ball milling and heat treating the first hard carbon material with fumed silica comprises: mixing the first hard carbon material with fumed silica to obtain a mixture, and ball-milling the mixture at a rotating speed of 200-300 r/min for 30-60 min; And (3) insulating the mixture in an inert gas atmosphere at 600-800 ℃ for 30-120 min. In some alternative embodiments of the f