阅读说明：本技术 一种从含锰元素的锂离子电池正极废料中回收锰的方法 (Method for recovering manganese from manganese-containing lithium ion battery anode waste ) 是由 王大辉 陈怀敬 于 2019-11-13 设计创作，主要内容包括：本发明公开了一种从含锰元素的锂离子电池正极废料中回收锰的方法；其包括以下步骤：(1)获得粉末状含锰正极废料；(2)含锰废料与添加剂混合后在有氧条件下通过焙烧获得产物；(3)将焙烧产物进行水浸、过滤获得含锰产品,产品为二氧化锰和含高锰酸钾溶液,或二氧化锰和含高锰酸钠的溶液；本发明工艺回收锰的流程短、成本低、易操作、对设备防腐要求低、回收获得的锰产品附加值高、处理过程中不产生二次污染。(The invention discloses a method for recovering manganese from manganese-containing lithium ion battery anode waste; which comprises the following steps: (1) obtaining powdery manganese-containing anode waste; (2) mixing the manganese-containing waste with an additive, and roasting under an aerobic condition to obtain a product; (3) soaking and filtering the roasted product to obtain a manganese-containing product, wherein the product is a manganese dioxide and potassium permanganate-containing solution or a manganese dioxide and sodium permanganate-containing solution; the process has the advantages of short flow of manganese recovery, low cost, easy operation, low requirement on equipment corrosion resistance, high added value of the recovered manganese product and no secondary pollution in the treatment process.)

1. A method for recovering manganese from lithium ion battery anode waste containing manganese elements is characterized by comprising the following steps:

(1) obtaining powdery manganese-containing anode waste;

(2) the product is obtained by roasting: fully mixing the manganese-containing anode waste material obtained in the step (1) with an additive according to the mass ratio of 1:0.01-4.0 to obtain a mixture, and roasting the obtained mixture for 0.5-10 hours at the temperature of 800 ℃ under the aerobic condition to obtain a roasted product;

(3) soaking in water, and filtering to obtain a manganese-containing product: and (3) leaching the roasted product obtained in the step (2) by using a sodium hydroxide or potassium hydroxide solution with the pH value of 10-14 at the temperature of 20-40 ℃, wherein the leaching time is 5-30 minutes, filtering is carried out after the leaching treatment is finished, filter residue can be used as a raw material for recovering other valuable metals after being washed, the pH value of the filtrate is adjusted to 6-8, filtering is carried out, the filter residue is a manganese dioxide product, and the filtrate is a product containing potassium permanganate or a solution containing sodium permanganate.

2. The method for recovering manganese from the manganese-containing lithium ion battery positive electrode waste material in claim 1, wherein in the step (2), oxygen-enriched air with the volume content of more than or equal to 22% is introduced into the mixture, and the flow rate of the introduced oxygen-enriched air is controlled, so that the volume content of oxygen in the outlet furnace gas is controlled to be more than or equal to 10%.

3. The method for recovering manganese from manganese-containing lithium ion battery positive electrode scrap according to claim 1, wherein in the step (2), the mixture is calcined in an air atmosphere.

4. The method for recovering manganese from the manganese-containing lithium ion battery positive electrode waste material according to claim 1, wherein the additive in the step (2) is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide.

5. The method for recovering manganese from the manganese-containing lithium ion battery cathode waste material according to claim 1, wherein the additive in the step (2) is a mixture formed by fully mixing one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide with one or more of potassium nitrate, sodium nitrate, ammonium nitrate, calcium nitrate, hydrogen peroxide, potassium chlorate and sodium chlorate according to a mass ratio of 1: 0.01-2.5.

6. The method for recovering manganese from manganese-containing lithium ion battery positive electrode waste materials according to claim 1, wherein the manganese-containing positive electrode waste material in the step (1) comprises: the collected positive electrode waste obtained after disassembly, crushing, sorting, screening and flotation separation of the discarded lithium ion battery, or the positive electrode waste obtained after crushing, sorting, screening and flotation separation of the positive electrode leftover materials generated in the production process of the lithium ion battery, or the positive electrode waste generated in the development and production process of the positive electrode material of the lithium ion battery, or the waste formed by manganese-containing filter residues generated in the process of recovering other valuable metals except manganese from the discarded lithium ion battery, or the mixture formed by any combination of the four waste materials.

Technical Field

The invention relates to a method for recovering manganese from manganese-containing lithium ion battery anode waste.

Background

Lithium ion batteries have been widely used in the fields of mobile phones, notebook computers, mobile power sources, electric bicycles, electric automobiles, unmanned aerial vehicles, energy storage and the like. Under the influence of continuous and rapid expansion of new energy automobile market, the demand of power lithium ion batteries is greatly increased in recent two years. Because the service life of the lithium ion battery is 2-3 years generally, the problems of environmental pollution and resource waste caused by scrapping the lithium ion battery are increasingly prominent, and the problem of how to reasonably dispose the discarded lithium ion battery is not negligible.

Manganese is the positive electrode of lithium ion batteryImportant components in materials, the method for extracting manganese from the waste lithium ion battery is disclosed and reported as follows: zhang Weixin et al reported LiMn as the anode material of waste lithium ion batteries in Vol.60 No.5, 2009, 1181-supplement 1185 of the chemical industry journal₂O₄Selectively leaching lithium ions in sulfuric acid solution as raw material, and preparing lambda-MnO by in-situ conversion₂. Patent [ CN201410246379.4]A process for recovering Mn and Cu from the used Li-ion battery includes such steps as recovering Co, Ni, Li and Al from the used Mn-series Li-ion battery, and separating to obtain Cu-contained material²⁺、Mn²⁺Electrolysis of ionic solution to obtain metallic copper and MnO₂. Ludongliang et al, in "Battery" Vol.48 No.6, 2018, 428-plus 432, reported the use of malic acid-hydrogen peroxide system for LiNi as anode material of waste lithium ion battery_0.5Co_0.2Mn_0.3Leaching, and oxidizing and precipitating manganese by using potassium permanganate solution to obtain manganese dioxide. Patent [ CN201910226757.5]The method for comprehensively recycling valuable metals from waste lithium ion batteries comprises the steps of crushing waste battery pole pieces, roasting the battery pole pieces, soaking in water, and filtering to obtain a lithium bicarbonate solution and water-soaking slag containing nickel, cobalt and manganese; and performing acid leaching and precipitation on the nickel-cobalt-manganese water leaching residue to obtain a precipitate containing nickel, cobalt and manganese. Patent [ CN201910019519.7]The method for recycling the waste lithium manganate positive electrode is reported, and the lithium manganate positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid are mixed, dried and calcined to obtain the lithium manganese iron phosphate positive electrode material. Patent [ CN201811093693.8]A method and system for recovering lithium and manganese from waste lithium manganate batteries are disclosed. Disassembling a positive plate from the waste lithium manganate battery; valuable metal elements in the positive plate are leached by acid, lithium ions in the acidified leaching solution are separated from other cations different from the lithium ions, and alkaline substances are adopted to precipitate and separate out manganese ions in the solution, so that the recovery of manganese is realized. [ CN201811066427.6]Discloses a method for treating nickel cobalt lithium manganate ternary waste. And adding alkali to the ternary waste for dissolving, reducing and dissolving in hot water to obtain the lithium hydroxide, thereby realizing the separation between lithium and nickel, cobalt and manganese. Patent [ CN201910166801.8]Reports about the recovery of valuable lithium ion batteries from waste lithium ion batteriesElemental methods. And carrying out reduction reaction on the anode material powder in one or more mixed gas of nitrogen, helium, neon and argon or in a vacuum atmosphere to obtain a thermal reaction product, and then carrying out alkali leaching and acid dissolution on the leaching residue to dissolve nickel, cobalt, manganese and the like to obtain the nickel, cobalt and manganese and the like for recovery. Patent [ CN201910327216.1]A method for recovering valuable metals from waste lithium ion battery materials is reported. Reducing and roasting the waste battery material under the condition that one of H2, natural gas, liquefied petroleum gas and coal gas is used as a reducing agent and protective gas, and performing water leaching, ammonia leaching and selective manganese extraction on a roasted product to obtain a manganese sulfate solution. Patent [ CN201810816435.1]A method for preparing a ternary cathode material by recycling a waste lithium ion battery cathode material is reported, the waste cathode material is subjected to alkaline leaching, reduction roasting and lithium extraction, then is leached by inorganic acid, a nickel-cobalt-manganese salt solution is prepared according to the requirement of a product after the leachate is subjected to impurity removal, and then a precursor is prepared by coprecipitation.

The method for recovering manganese from the anode waste of the lithium ion battery reported at present generally comprises the steps of dissolving an anode material obtained from a scrapped lithium ion battery in an acid solution, enabling metals such as lithium, nickel, cobalt, manganese and the like to enter the solution in the form of ions, then extracting manganese ions by using P204, and performing back extraction to obtain manganese sulfate. The method of reducing or sulfating roasting and water leaching the waste anode material and hydrogen, carbon, aluminum, natural gas, liquefied petroleum gas, coal gas, sodium bisulfate and the like is adopted, lithium is separated from nickel, cobalt, manganese and the like, and then ammonia leaching and acid leaching are adopted to recover manganese, and the recovery of manganese also has the problems of long recovery process and high cost.

Disclosure of Invention

The invention provides a method for recovering manganese from lithium ion battery anode waste containing manganese elements, and aims to solve the problems of long recovery process, high recovery cost, low added value of products obtained by recovering manganese, high-concentration salt-containing wastewater generated in the recovery process and the like in the existing technology for recovering manganese from lithium ion battery anode waste.

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

a method for recovering manganese from lithium ion battery anode waste containing manganese elements comprises the following steps:

(1) obtaining powdery manganese-containing anode waste;

(2) the product is obtained by roasting: fully mixing the manganese-containing anode waste material obtained in the step (1) with an additive according to the mass ratio of 1:0.01-4.0 to obtain a mixture, and roasting the obtained mixture for 0.5-10 hours at the temperature of 800 ℃ under the aerobic condition to obtain a roasted product;

(3) soaking in water, and filtering to obtain a manganese-containing product: and (3) leaching the roasted product obtained in the step (2) by using a sodium hydroxide or potassium hydroxide solution with the pH value of 10-14 at the temperature of 20-40 ℃, wherein the leaching time is 5-30 minutes, filtering is carried out after the leaching treatment is finished, filter residue can be used as a raw material for recovering other valuable metals after being washed, the pH value of the filtrate is adjusted to 6-8, filtering is carried out, the filter residue is a manganese dioxide product, and the filtrate is a product containing potassium permanganate or a solution containing sodium permanganate.

Further, in the step (2), oxygen-enriched air with volume content not less than 22% is introduced into the mixture, and the flow of the introduced oxygen-enriched air is controlled, so that the volume content of oxygen in the outlet furnace gas is controlled to be not less than 10%.

Further, in the step (2), the mixture is calcined in an air atmosphere.

Further, the additive in the step (2) is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide.

Further, the additive in the step (2) is a mixture formed by fully mixing one or more substances of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide with one or more substances of potassium nitrate, sodium nitrate, ammonium nitrate, calcium nitrate, hydrogen peroxide, potassium chlorate and sodium chlorate according to a mass ratio of 1: 0.01-2.5.

Further, the manganese-containing cathode waste in the step (1) comprises: the collected positive electrode waste obtained after disassembly, crushing, sorting, screening and flotation separation of the discarded lithium ion battery, or the positive electrode waste obtained after crushing, sorting, screening and flotation separation of the positive electrode leftover materials generated in the production process of the lithium ion battery, or the positive electrode waste generated in the development and production process of the positive electrode material of the lithium ion battery, or the waste formed by manganese-containing filter residues generated in the process of recovering other valuable metals except manganese from the discarded lithium ion battery, or the mixture formed by any combination of the four waste materials.

The manganese-containing positive electrode waste material is a mixture formed by mixing one or more of lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide and a lithium-rich manganese-based material, or a mixture containing manganese elements formed by mixing one or more of lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide and a lithium-rich manganese-based material with one or more of lithium cobaltate, lithium nickel oxide and lithium nickel cobalt aluminate.

The invention has the beneficial effects that:

compared with the prior art, the method has the advantages of short flow of manganese recovery, low cost, easy operation, low requirement on equipment corrosion resistance, high added value of the recovered manganese product and no secondary pollutant generated in the treatment process.

Detailed Description

A method for recovering manganese from lithium ion battery anode waste containing manganese elements comprises the following three steps:

(1) obtaining powdery manganese-containing anode waste; the manganese-containing positive electrode scrap includes: the collected positive electrode waste obtained after disassembly, crushing, sorting, screening and flotation separation of the discarded lithium ion battery, or the positive electrode waste obtained after crushing, sorting, screening and flotation separation of the positive electrode leftover materials generated in the production process of the lithium ion battery, or the positive electrode waste generated in the development and production process of the positive electrode material of the lithium ion battery, or the waste formed by manganese-containing filter residues generated in the process of recovering other valuable metals except manganese from the discarded lithium ion battery, or the mixture formed by any combination of the four wastes; no matter which kind of manganese-containing anode waste is adopted, the manganese-containing anode waste is required to be formed into powder, and then the manganese-containing anode waste is mixed with an additive to be roasted, if the anode waste is not powdery, the manganese-containing anode waste can be crushed and ground by a conventional means to form powder; the manganese-containing positive electrode waste material can be a mixture formed by mixing one or more of lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide and a lithium-rich manganese-based material, or a mixture containing manganese elements formed by mixing one or more of lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide and a lithium-rich manganese-based material with one or more of lithium cobaltate, lithium nickel oxide and lithium nickel cobalt aluminate;

(2) the product is obtained by roasting: fully mixing the manganese-containing anode waste material obtained in the step (1) with an additive according to the mass ratio of 1:0.01-4.0 to obtain a mixture, and roasting the obtained mixture for 0.5-10 hours at the temperature of 800 ℃ under the aerobic condition to obtain a roasted product; the aerobic conditions here are: introducing oxygen-enriched air with the volume content of more than or equal to 22% into the obtained mixture, and controlling the flow of the introduced oxygen-enriched air to control the volume content of oxygen in the outlet furnace gas to be more than or equal to 10%, or roasting the obtained mixture in an air atmosphere; the additive used here can be one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide, or a mixture formed by fully mixing one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium oxide, sodium peroxide and potassium peroxide with one or more of potassium nitrate, sodium nitrate, ammonium nitrate, calcium nitrate, hydrogen peroxide, potassium chlorate and sodium chlorate according to a mass ratio of 1: 0.01-2.5;

(3) soaking in water, and filtering to obtain a manganese-containing product: and (3) leaching the roasted product obtained in the step (2) by using a sodium hydroxide or potassium hydroxide solution with the pH value of 10-14 at the temperature of 20-40 ℃, wherein the leaching time is 5-30 minutes, filtering is carried out after the leaching treatment is finished, filter residue can be used as a raw material for recovering other valuable metals after being washed, the pH value of the filtrate is adjusted to 6-8, filtering is carried out, the filter residue is a manganese dioxide product, and the filtrate is a product containing potassium permanganate or a solution containing sodium permanganate.