阅读说明：本技术 一种废旧锰酸锂电池中锰锂短程分离及功能吸附材料制备的方法 (Method for short-distance separation of manganese and lithium in waste lithium manganate battery and preparation of functional adsorption material ) 是由 陈湘萍 何路凤 何志强 李静 于 2020-05-11 设计创作，主要内容包括：一种废旧锰酸锂电池中锰锂短程分离及功能吸附材料制备的方法,包括以下步骤；在室温下,将废旧锂电池置于放电溶液中浸泡,使其充分放电后,取出置于干燥箱中干燥,待用；将正极材料置于浸泡溶液中,用超声清洗仪超声,取出在干燥箱中烘干,剥离后得到黑色粉末,将得到的黑色粉末以双氧水和硫酸亚铁为还原剂,无机酸为浸出剂；调控固液比、温度、酸浓度及反应时间条件,进行浸出；将得到的固体及液体调控比例,置于反应釜中,在烘箱中进行水热处理,过滤得到固体；对水热处理后的固体进行过滤,烘干；对固体继续置于马弗炉中处理固体,将固体进行研磨,得到吸附材料；本发明具有浸出率高,吸附效果好得特点。(A method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of a functional adsorption material comprises the following steps; at room temperature, placing the waste lithium battery in a discharging solution for soaking, taking out the waste lithium battery after the waste lithium battery is fully discharged, and placing the waste lithium battery in a drying oven for drying for later use; placing the anode material in a soaking solution, performing ultrasonic treatment by using an ultrasonic cleaning instrument, taking out the anode material and drying the anode material in a drying oven, and stripping the anode material to obtain black powder, wherein hydrogen peroxide and ferrous sulfate are used as reducing agents, and inorganic acid is used as a leaching agent; regulating and controlling solid-liquid ratio, temperature, acid concentration and reaction time condition to leach; regulating the proportion of the obtained solid and liquid, placing the solid and liquid in a reaction kettle, carrying out hydrothermal treatment in an oven, and filtering to obtain a solid; filtering and drying the solid after the hydrothermal treatment; continuously placing the solid in a muffle furnace to treat the solid, and grinding the solid to obtain an adsorption material; the invention has the characteristics of high leaching rate and good adsorption effect.)

1. A method for short-range separation of manganese and lithium in waste lithium manganate batteries and preparation of a functional adsorption material is characterized by comprising the following steps;

(1) at room temperature, placing the waste lithium battery in a discharging solution for soaking, taking out the waste lithium battery after the waste lithium battery is fully discharged, and placing the waste lithium battery in a drying oven for drying for later use;

(2) placing the anode material in a soaking solution, performing ultrasonic treatment by using an ultrasonic cleaning instrument, taking out the anode material, drying the anode material in a drying box, and stripping to obtain black powder;

(3) taking hydrogen peroxide and ferrous sulfate as reducing agents and inorganic acid as a leaching agent for the black powder obtained in the step (2); regulating and controlling solid-liquid ratio, temperature, acid concentration and reaction time condition to leach;

(4) regulating and controlling the proportion of the solid and the liquid obtained in the step (3), placing the solid and the liquid in a reaction kettle, carrying out hydrothermal treatment in an oven, and filtering to obtain a solid;

(5) filtering and drying the solid subjected to the hydro-thermal treatment in the step (4); continuously placing the solid in a muffle furnace to treat the solid, and grinding the solid to obtain an adsorption material;

(6) and (4) statically adsorbing the solid obtained in the step (5) in a lithium solution system, and measuring the adsorption rate of the adsorbent.

2. The method for preparing the short-distance separation and functional adsorption material for manganese and lithium in the waste lithium manganate batteries according to claim 1, wherein the discharge solution in the step (1) is 3mol/L of Na₂SO₄Soaking the solution for 24 h.

3. The method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of functional adsorbing material according to claim 1, characterized in that in step (2), the power of the ultrasonic cleaning instrument is 100W, the ultrasonic time is 5min, and the soaking solution is oxalic acid solution with concentration of 0.10 mol/L.

4. The method for preparing the short-distance separation and functional adsorption material for manganese and lithium in the waste lithium manganate batteries according to claim 1, wherein in the step (3), the solid-to-liquid ratio is 10mL/g to 50mL/g, the acid concentration is 0.2mol/L to 1.0mol/L, the temperature is 50 ℃ to 90 ℃, the reaction time is 30min to 80min, and the concentration of the reducing agent is 1% to 5%.

5. The method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of functional adsorbing material according to claim 1, characterized in that, in the step (3), the inorganic acid is one of citric acid, tartaric acid, phosphoric acid, nitric acid and sulfuric acid.

6. The method for preparing the short-distance separation and functional adsorption material for manganese and lithium in the waste lithium manganate batteries according to claim 1, wherein the hydrothermal treatment temperature in the step (4) is 120-160 ℃, and the reaction time is 6-24 hours.

7. The method for preparing the short-distance separation and functional adsorption material for manganese and lithium in the waste lithium manganate batteries according to claim 1, wherein the muffle furnace calcination temperature in the step (5) is 650-750 ℃, and the reaction time is 6-24 hours.

8. The method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of functional adsorbing material according to claim 1, characterized in that in step (6), the lithium solution system mainly comprises lithium sulfate, lithium hydroxide and lithium phosphate solution.

Technical Field

The invention relates to the technical field of lithium battery electrode materials, in particular to a method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of a functional adsorption material.

Background

At present, the lithium ion battery has advantages of wide use temperature range, high working voltage, large energy density, low self-discharge rate, no memory effect, long shelf life and the like, and the ratio of the lithium ion battery to the lithium ion battery is gradually increased in the battery market. Correspondingly, the waste amount of the lithium ion battery is increased day by day, and the lithium ion battery contains high-economic-value metals such as lithium, cobalt, copper and the like, so that the lithium ion battery has important significance for relieving social resource pressure and reducing potential environmental risks in terms of recovery.

Although a great deal of research is conducted on recycling of lithium ion batteries all over the world, the recycling technology is still at a laboratory level due to the complex structure of waste lithium ion batteries, and at present, the methods for recycling valuable metals in waste lithium ion batteries mainly comprise pyrometallurgy, biological metallurgy, wet metallurgy and the like. The pyrometallurgical effect is good, the output is high, but the high temperature technology can increase investment equipment and cause secondary pollution aggravation in the metal recovery engineering. The efficiency of the biological metallurgy is low, and the development of the biological metallurgy is limited. In hydrometallurgy, typical leaching agents are organic acid and inorganic acid, and the current research situation is that the leaching effect of valuable metals in waste lithium ion batteries is better no matter the leaching agents are organic acid or inorganic acid. The organic acid has high price and is difficult to separate valuable metals, and the development of the organic acid is limited. Inorganic acid (H)₂SO₄、HNO₃HCL) is strong acid, has strong corrosion to equipment and generates SO in the leaching process₂、NO_XAnd the like, causing secondary pollution. Aiming at the problems, the valuable metals are leached by using (citric acid, tartaric acid, phosphoric acid, nitric acid and sulfuric acid) as a leaching agent in the valuable metal leaching process, and a functional adsorption material is prepared in the short-range separation process.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of a functional adsorption material.

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

a method for short-distance separation of manganese and lithium in waste lithium manganate batteries and preparation of a functional adsorption material comprises the following steps;

(1) at room temperature, placing the waste lithium battery in a discharging solution for soaking, taking out the waste lithium battery after the waste lithium battery is fully discharged, and placing the waste lithium battery in a drying oven for drying for later use;

(2) and (3) placing the anode material in the soaking solution, performing ultrasonic treatment by using an ultrasonic cleaning instrument, taking out the anode material, drying the anode material in a drying box, and stripping to obtain black powder.

Stripping by adopting an ultrasonic-assisted stripping method and a dilute acid soaking-ultrasonic oscillation coupling method, washing and drying the aluminum foil obtained after stripping, and taking black powder obtained after suction filtration and drying as lithium ion battery powder;

(3) taking hydrogen peroxide and ferrous sulfate as reducing agents and inorganic acid as a leaching agent for the black powder (anode material powder) obtained in the step (2); regulating and controlling solid-liquid ratio, temperature, acid concentration and reaction time condition to leach;

(4) regulating and controlling the proportion of the solid and the liquid obtained in the step (3), placing the solid and the liquid in a reaction kettle, carrying out hydrothermal treatment in an oven, and filtering to obtain a solid;

(5) filtering and drying the solid subjected to the hydro-thermal treatment in the step (4); continuously placing the solid in a muffle furnace to treat the solid, and grinding the solid to obtain an adsorption material;

(6) and (4) statically adsorbing the solid obtained in the step (5) in a lithium solution system, and measuring the adsorption rate of the adsorbent.

The discharging solution in the step (1) is 3mol/L of Na₂SO₄Solutions ofThe soaking time is 24 h.

In the step (2), the power of the ultrasonic cleaning instrument is 100W, the ultrasonic time is 5min, and the soaking solution is oxalic acid solution with the concentration of 0.10 mol/L.

In the step (3), the solid-liquid ratio is 10 mL/g-50 mL/g, the acid concentration is 0.2 mol/L-1.0 mol/L, the temperature is 50 ℃ to 90 ℃, the reaction time is 30 min-80 min, and the concentration of the reducing agent is 1% to 5%.

And (3) the inorganic acid is one of citric acid, tartaric acid, phosphoric acid, nitric acid and sulfuric acid.

The hydrothermal treatment temperature of the step (4) is 120-160 ℃, and the reaction time is 6-24 h.

And (5) calcining in a muffle furnace at 650-750 ℃ for 6-24 h.

And (4) the lithium solution system in the step (6) is mainly a lithium sulfate solution, a lithium hydroxide solution and a lithium phosphate solution.

The invention has the beneficial effects that:

the invention prepares the performance of leaching reaction and leaching material under the system of (tartaric acid, phosphoric acid, nitric acid and sulfuric acid) of the waste lithium ion battery again, carries out high-efficiency green resource recovery on the metal of the waste lithium ion battery, develops the reutilization of the material performance after recovery, optimizes the leaching reaction experiment condition, ensures that the leaching rate of lithium ions reaches over 90 percent and can reach 98 percent at most, and the prepared functional adsorption material has good adsorption capacity on the lithium ions and can maximally reach 0.45g of lithium adsorbed by 1g of the adsorption material. The problems of low recovery efficiency of valuable metals in the waste lithium ion batteries, secondary pollution, difficult separation of the valuable metals in leachate and the like are solved.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Figure 2 SEM characterization of the adsorbent material.

Detailed Description

The present invention will be described in further detail with reference to examples.