阅读说明：本技术 一种废弃锂亚氯酰电池资源回收方法 (Method for recycling waste lithium thionyl chloride battery resources ) 是由 赖辛宇 张永祥 张万琦 于 2021-08-24 设计创作，主要内容包括：本发明公开了一种废弃锂亚氯酰电池资源回收方法,包括如下步骤：步骤一,将废弃锂亚氯酰电池进行拆解,分别收集正极金属片、负极金属片、电解液、以及正极的硫/碳黑混合物；步骤二,硫/碳黑混合物用乙醇清洗,过滤后得到滤渣；将滤渣加入到酸溶液中,加热、搅拌、过滤,用水清洗至中性,干燥；步骤三,于含有静电稳定剂的醇溶液中将磁性材料均匀分散,并加入表面修饰剂；然后加入氯化锂、氯化铝和氢氧化钠,反应得到磁性微孔锂吸附剂；将磁性微孔锂吸附剂浸入含有锂的电解液,使其中至少部分的锂离子被磁性微孔锂吸附剂吸附。解决了针对锂电池资源回收没有合理方法,对锂电池随便丢弃,不仅污染环境,还造成资源浪费的问题。(The invention discloses a method for recovering waste lithium chloroidene battery resources, which comprises the following steps: disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture; step two, cleaning the sulfur/carbon black mixture by using ethanol, and filtering to obtain filter residue; adding the filter residue into acid solution, heating, stirring, filtering, washing with water to neutrality, and drying; step three, uniformly dispersing the magnetic material in an alcoholic solution containing the electrostatic stabilizer, and adding a surface modifier; then adding lithium chloride, aluminum chloride and sodium hydroxide, and reacting to obtain a magnetic microporous lithium adsorbent; and immersing the magnetic microporous lithium adsorbent into an electrolyte containing lithium, so that at least part of lithium ions in the electrolyte are adsorbed by the magnetic microporous lithium adsorbent. The problems that no reasonable method exists for recycling lithium battery resources, the lithium battery is discarded at will, the environment is polluted, and resource waste is caused are solved.)

1. A method for recycling waste lithium chlorite battery resources is characterized by comprising the following steps:

disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture;

step two, cleaning the sulfur/carbon black mixture collected in the step one with ethanol, and filtering to obtain filter residue; adding the filter residue into an acid solution, heating, stirring, filtering, washing with water to be neutral, and drying to obtain a sulfur/carbon black product;

step three, uniformly dispersing the magnetic material in an alcoholic solution containing an electrostatic stabilizer, adding a surface modifier, and reacting at 35-40 ℃ to obtain the surface-modified magnetic material; then adding lithium chloride, aluminum chloride and sodium hydroxide with the molar ratio of 0.8:1:2, reacting to obtain a magnetic microporous lithium adsorbent, wherein the pH value at the end of the reaction is 5-7;

immersing the magnetic microporous lithium adsorbent in the electrolyte solution containing lithium to allow at least a portion of the lithium ions therein to be adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water.

2. The method for recycling waste lithium chlorite ion battery resources as claimed in claim 1, wherein in the second step, the concentration of the acid solution is 0.5 to 2 mol/L.

3. The method for recycling waste lithium chlorite battery resources as claimed in claim 1, wherein in the second step, the acid solution is a mixture of a hydrochloric acid solution and a nitric acid solution.

4. The method for recycling waste lithium chloroidene battery resources as claimed in claim 1, wherein the heating temperature in the second step is 70-90 ℃ and the stirring time is 5-10 h.

5. The method for recycling waste lithium chloroidene battery resources as claimed in claim 1, wherein the magnetic microporous lithium adsorbent is powder, has an average particle diameter of 80-250nm, contains pores having an average pore diameter of 1.55-1.7nm, and has a static adsorption capacity of 8.5-13.4mg/g for lithium ions.

6. The method for recycling the waste lithium chloroidene battery resource as claimed in claim 1, wherein in the third step, the magnetic microporous lithium adsorbent is separated from the mixed system by an external magnetic field.

7. The method for recycling waste lithium chloroidene battery as claimed in claim 1, wherein the alcohol solution is selected from the group consisting of methanol, ethanol and hexane diol.

8. The method for recycling waste lithium chloroidene batteries according to claim 1, wherein in the third step, the surface modifier comprises any one or a combination of two or more of 3-aminopropyltriethoxysilane, mercaptopropyltriethoxysilane, tetrabutyl silicate, polyethyleneimine, diethylenetriamine, polyvinylpyrrolidone, octadecyltrichlorosilane and tween.

9. The method for recycling waste lithium vinylidene chloride battery resources as claimed in claim 1, wherein in the third step, the static stabilizer is sodium acetate, and the mass percentage of the sodium acetate in the alcoholic solution is 0.8%.

Technical Field

The invention relates to the technical field of lithium chlorite battery recovery, in particular to a method for recovering waste lithium chlorite battery resources.

Background

The lithium thionyl chloride battery takes metal lithium as a negative electrode, liquid thionyl chloride as a positive active substance and porous materialsCarbon is an electrochemical system power supply of the anode current collector. Wherein, SOCl₂Is not only a reaction substance but also a non-aqueous inorganic solvent, dissolves LiAlCl₄The solution after the additives is inorganic electrolyte, and the system battery is a novel high-energy chemical power source developed in recent years. The overall reaction mechanism is: 4Li +2SOCl₂→4LiCl+S+SO₂When the battery discharges, the generated elemental sulfur is attached to the surface of the positive carbon black in situ, meanwhile, the electrolyte is changed into LiCl until the reaction is terminated, if the battery is abandoned, the environment is easily polluted due to improper treatment, the current recycling threshold of the battery is high, and the current domestic recycling technology of the abandoned lithium thionyl chloride battery is recently reported.

Disclosure of Invention

The invention aims to provide a method for recycling waste lithium chloroidene battery resources, aiming at the defects in the prior art.

In order to achieve the purpose, the invention adopts the technical scheme that:

the method for recycling the waste lithium chlorite battery resource comprises the following steps:

disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture;

step two, cleaning the sulfur/carbon black mixture collected in the step one with ethanol, and filtering to obtain filter residue; adding the filter residue into an acid solution, heating, stirring, filtering, washing with water to be neutral, and drying to obtain a sulfur/carbon black product;

step three, uniformly dispersing the magnetic material in an alcoholic solution containing an electrostatic stabilizer, adding a surface modifier, and reacting at 35-40 ℃ to obtain the surface-modified magnetic material; then adding lithium chloride, aluminum chloride and sodium hydroxide with the molar ratio of 0.8:1:2, reacting to obtain a magnetic microporous lithium adsorbent, wherein the pH value at the end of the reaction is 5-7;

immersing the magnetic microporous lithium adsorbent in the electrolyte solution containing lithium to allow at least a portion of the lithium ions therein to be adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water.

Further, in the second step, the concentration of the acid solution is 0.5-2 mol/L.

Further, in the second step, the acid solution is a mixture of a hydrochloric acid solution and a nitric acid solution.

Further, in the second step, the heating temperature is 70-90 ℃, and the stirring time is 5-10 h.

Furthermore, the magnetic microporous lithium adsorbent is powder, the average particle size is 80-250nm, the average pore diameter of pores is 1.55-1.7nm, and the static adsorption capacity for lithium ions is 8.5-13.4 mg/g.

Further, in the third step, an external magnetic field is adopted to separate the magnetic microporous lithium adsorbent from the mixed system.

Further, in the third step, the alcohol solution is selected from any one or a combination of several of methanol, ethanol and hexanediol.

Further, in the third step, the surface modifier comprises any one or a combination of more than two of 3-aminopropyltriethoxysilane, mercaptopropyltriethoxysilane, tetrabutyl silicate, polyethyleneimine, diethylenetriamine, polyvinylpyrrolidone, octadecyltrichlorosilane and tween.

Further, in the third step, the static stabilizer is sodium acetate, and the mass percentage of the sodium acetate in the alcoholic solution is 0.8%.

By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:

the lithium chloroidene battery is disassembled, metal sheets of the positive and negative electrodes at the top end and the bottom end of the lithium chloroidene battery are disassembled, the metal sheets of the positive and negative electrodes are collected and processed in a centralized manner, and a product obtained by processing a sulfur/carbon black mixture of the positive electrode can be directly used as a positive electrode material of the lithium-sulfur battery; collecting an electrolyte containing LiCl in the battery, and enriching and recovering lithium by using a magnetic microporous lithium adsorbent; the problems that no reasonable method exists for recycling lithium battery resources, the lithium battery is discarded at will, the environment is polluted, and resource waste is caused are solved.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1

The embodiment provides a method for recycling waste lithium chloroidene battery resources, which comprises the following steps:

disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture;

step two, cleaning the sulfur/carbon black mixture collected in the step one with ethanol, and filtering to obtain filter residue; adding the filter residue into a mixed solution of a hydrochloric acid solution (the concentration is 1mol/L) and a nitric acid solution (the concentration is 1mol/L), heating to 70 ℃, stirring for 10 hours, filtering, washing with water to be neutral, and drying to obtain a sulfur/carbon black product;

step three, uniformly dispersing the magnetic material in a methanol solution containing sodium acetate (the mass percentage is 0.8%), adding mercaptopropyl triethoxysilane, and reacting at 35 ℃ to obtain the magnetic material with the modified surface; then adding lithium chloride, aluminum chloride and sodium hydroxide with the molar ratio of 0.8:1:2, reacting to obtain a magnetic microporous lithium adsorbent, wherein the pH value at the end of the reaction is 5-7;

immersing the magnetic microporous lithium adsorbent into an electrolyte containing lithium, so that at least part of lithium ions in the electrolyte are adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water.

The magnetic microporous lithium adsorbent is powder, the average particle size is 80-250nm, the average pore diameter of pores is 1.55-1.7nm, and the static adsorption capacity for lithium ions is 8.5-13.4 mg/g.

In the third step, an external magnetic field is adopted to separate the magnetic microporous lithium adsorbent from the mixed system.

Example 2

The embodiment provides a method for recycling waste lithium chloroidene battery resources, which comprises the following steps:

disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture;

step two, cleaning the sulfur/carbon black mixture collected in the step one with ethanol, and filtering to obtain filter residue; adding the filter residue into a mixed solution of a hydrochloric acid solution (the concentration is 0.8mol/L) and a nitric acid solution (the concentration is 0.8mol/L), heating to 90 ℃, stirring for 5 hours, filtering, washing with water to be neutral, and drying to obtain a sulfur/carbon black product;

step three, uniformly dispersing the magnetic material in an ethanol solution containing sodium acetate (the mass percentage is 0.8%), adding diethylenetriamine and polyvinyl pyrrolidone, and reacting at 40 ℃ to obtain the surface-modified magnetic material; then adding lithium chloride, aluminum chloride and sodium hydroxide with the molar ratio of 0.8:1:2, reacting to obtain a magnetic microporous lithium adsorbent, wherein the pH value at the end of the reaction is 5-7;

immersing the magnetic microporous lithium adsorbent into an electrolyte containing lithium, so that at least part of lithium ions in the electrolyte are adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water.

The magnetic microporous lithium adsorbent is powder, the average particle size is 80-250nm, the average pore diameter of pores is 1.55-1.7nm, and the static adsorption capacity for lithium ions is 8.5-13.4 mg/g.

In the third step, an external magnetic field is adopted to separate the magnetic microporous lithium adsorbent from the mixed system.

Example 3

The embodiment provides a method for recycling waste lithium chloroidene battery resources, which comprises the following steps:

disassembling the waste lithium chloroidene battery, and respectively collecting a positive metal sheet, a negative metal sheet, electrolyte and a positive sulfur/carbon black mixture;

step two, cleaning the sulfur/carbon black mixture collected in the step one with ethanol, and filtering to obtain filter residue; adding the filter residue into a mixed solution of a hydrochloric acid solution (the concentration is 0.5mol/L) and a nitric acid solution (the concentration is 0.5mol/L), heating to 80 ℃, stirring for 8 hours, filtering, washing with water to be neutral, and drying to obtain a sulfur/carbon black product;

step three, uniformly dispersing the magnetic material in a hexanediol solution containing sodium acetate (the mass percentage is 0.8%), adding a surface modifier diethylenetriamine, and reacting at 38 ℃ to obtain the surface-modified magnetic material; then adding lithium chloride, aluminum chloride and sodium hydroxide with the molar ratio of 0.8:1:2, reacting to obtain a magnetic microporous lithium adsorbent, wherein the pH value at the end of the reaction is 5-7;

immersing the magnetic microporous lithium adsorbent into an electrolyte containing lithium, so that at least part of lithium ions in the electrolyte are adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water.

The magnetic microporous lithium adsorbent is powder, the average particle size is 80-250nm, the average pore diameter of pores is 1.55-1.7nm, and the static adsorption capacity for lithium ions is 8.5-13.4 mg/g.

In the third step, an external magnetic field is adopted to separate the magnetic microporous lithium adsorbent from the mixed system.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.