CN115652077A - Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery - Google Patents
Method for selectively separating and recovering lithium and manganese from waste lithium manganate battery Download PDFInfo
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- CN115652077A CN115652077A CN202211074571.0A CN202211074571A CN115652077A CN 115652077 A CN115652077 A CN 115652077A CN 202211074571 A CN202211074571 A CN 202211074571A CN 115652077 A CN115652077 A CN 115652077A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries, which comprises the following steps: (1) Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive; (2) Roasting the lithium manganate anode powder obtained by pretreatment and sulfates such as ferrous sulfate, ferric sulfate, ammonium bisulfate and the like at a certain temperature for two sections to convert lithium elements of the lithium manganate into corresponding sulfates; (3) Leaching the roasted product obtained in the second step by using water to obtain a lithium sulfate leaching solution and leaching residues rich in iron and manganese oxides. The invention skillfully utilizes the difference of high-temperature decomposition of the roasted product lithium sulfate and manganese sulfate, simply and efficiently realizes the selective separation and recovery of lithium and manganese from the waste lithium manganate battery, has simple process, and does not need to add the traditional acid-base leaching agent. The method can realize selective recovery and separation of lithium and manganese in the waste lithium manganate batteries, and is a novel method for efficiently recovering valuable elements of lithium and manganese from the waste lithium manganate batteries.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of solid waste resources, and mainly relates to a method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries.
Background
In recent years, the continuous development and market expansion in the fields of electric automobiles, electronic devices, and energy storage have promoted the widespread use of lithium ion batteries. Among them, lithium manganate batteries are favored by the market due to their relatively high energy density. The number of lithium batteries has seen explosive growth due to their relatively high energy density, low cost and good safety performance. The charge-discharge cycle of the lithium ion battery is about 500-1000 times in actual use, and the service life of the lithium ion battery is 3-5 years. The scrapping peak of the waste lithium battery is expected to be met in China before and after 2022 years. LiMn 2 O 4 The main component of the battery is the positive electrode (LiMn) 2 O 4 Powder, binder and aluminum foil), negative electrodes (graphite, binder and copper foil), separators, electrolyte, and a housing. Lithium manganate batteries have a tendency to recycle waste lithium batteries because the content of valuable metals is higher than that of raw ores and the price of raw materials of lithium batteries is rapidly increased. The recycling of waste lithium ion batteries has become a worldwide focus from the point of view of economic efficiency and strategic resources. However, if the waste lithium battery is not recycled, not only precious metal resources are wasted, but also serious harm is caused. Such as heavy metal, fluorine and organic contamination. Therefore, the key point of recycling the waste lithium ion batteries of the electric vehicles is to find an efficient and environment-friendly green cleaning process.
The researchers have conducted extensive research aiming at the resource utilization of valuable elements in the waste lithium manganate batteries. In patent CN114715923A, a lithium manganate battery positive electrode material is subjected to oxidation leaching by a potassium hydroxide solution to obtain a mixed slurry, and then the mixed slurry is subjected to cooling and solid-liquid separation to obtain a potassium permanganate crystal and a separation liquid, and then carbon dioxide or the mixed separation liquid and potassium carbonate are introduced into the separation liquid to perform solid-liquid separation to obtain lithium carbonate. In patent CN109207725a, a lithium manganate battery positive electrode material is immersed in an acidic substance, and meanwhile, hydrogen peroxide is added to leach valuable metal elements in the positive electrode material, so as to obtain an acidified leachate, and then the acidified leachate is respectively input into an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane, so as to finally obtain a concentrated lithium-containing solution and a solution containing other cations; finally, adding a lithium precipitator into the lithium-containing solution, and reacting to obtain a lithium precipitate. CN108123185A is a method for preparing manganese oxide, which comprises mixing a lithium manganate battery positive electrode material with an appropriate amount of carbon powder, calcining and reducing, adding water into the calcined material, slurrying, pumping into a stirring device, adding dilute acid dropwise to adjust and maintain the pH of the slurried calcined material mixed solution at 3.0-6.5, soaking, filtering to obtain a filtrate, removing impurities with sodium hydroxide, adding soluble carbonate, precipitating lithium carbonate, and drying the filter cake to obtain manganese oxide capable of preparing lithium manganate circularly. However, the above method has problems of expensive raw materials and complicated process, and limits the recycling of the waste lithium manganate batteries to some extent. Therefore, it is necessary to find cheaper raw materials or simpler operation process to meet the resource utilization of the waste lithium manganate battery.
The invention uses sulfate as an auxiliary agent, mixes the sulfate with the anode powder of the waste lithium manganate battery for two-stage roasting, extracts and separates lithium elements of the lithium manganate battery into a solution, and leaching residues are ferromanganese oxides and can be used for steel smelting. The process adopts the mixed roasting and leaching process of the lithium manganate and the sulfate, has simple operation, low production cost and easy separation, realizes the recycling of the lithium manganate battery and the sulfate, simultaneously has little leached iron in the solution, and greatly simplifies the purification process. The process combines the characteristics of lithium manganate and sulfate, recycles solid wastes, and has the characteristics of remarkable economic benefit and environmental friendliness.
Disclosure of Invention
The invention provides a method for selectively separating and recycling lithium and manganese from waste lithium manganate batteries, aiming at the problem of resource utilization of the waste lithium manganate batteries.
The invention discloses a method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries, which takes waste lithium manganate batteries and sulfates such as ferrous sulfate, ferric sulfate, ammonium bisulfate and the like as raw materials, and comprises the following process steps in sequence:
1. pretreatment of waste lithium manganate battery
Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
2. sulfate decomposition lithium manganate battery cathode material
Uniformly mixing the lithium manganate battery anode powder which is finely ground to be less than 150 mu m with sulfates such as ferrous sulfate, ferric sulfate, ammonium bisulfate and the like, and controlling the mass ratio of the lithium manganate battery anode material to the sulfates to be 1:1-8; roasting the mixture at the first stage temperature of 300-700 ℃ for 30-240 min, and then heating to the second stage temperature of 800-1000 ℃ for 30-240 min to obtain a solid product;
3. leaching of roasted product
Leaching the solid product obtained in the step 2 with water at 25-100 ℃, and performing solid-liquid separation on the leaching slurry to obtain filter residue (the main component is Fe) 2 O 3 、Mn 2 O 3 、FeMnO 3 ) And a leachate comprising lithium sulfate;
according to the method, the sulfate and lithium manganate battery are subjected to a displacement reaction at a low temperature to generate lithium sulfate and manganese sulfate. Lithium sulfate is very stable at high temperature, while manganese sulfate can be thermally decomposed to release SO 2 Production of Mn 2 O 3 ，Mn 2 O 3 With Fe continuously 2 O 3 Reaction to form FeMnO 3 . Through the roasting at the two ends, the reaction of the lithium manganate battery is accurately controlled to realize the effective recovery of lithium and manganese.
2MnSO 4 ＝Mn 2 O 3 +2SO 2 (g)+1.5O 2 (g) (1)
Mn 2 O 3 +Fe 2 O 3 ＝2FeMnO 3 (2)
Compared with the prior art, the invention has the following advantages: (1) The process adopts sulfate as an auxiliary agent, thereby avoiding the circulation problem and greatly reducing the overall energy consumption; (2) the reaction conditions of the process are mild; (3) The process adopts cheap sulfate as an auxiliary agent, has wide sources, reduces the environmental pollution and saves the production cost; (4) The method has the advantages of simple process, convenient operation, no waste residue discharge, no secondary pollution, low production cost and industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
The main chemical composition (mass%) of the lithium manganate positive electrode powder used in each of the following examples was 59.52% by weight of Mn, 3.6% by weight of Li, 0.1% by weight of Al, and the XRD analysis result showed that the main phase in the blast furnace slag was lithium manganate.
Example one
(1) Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
(2) Uniformly mixing the lithium manganate battery anode powder which is finely ground to be less than 150 mu m with ferric sulfate, controlling the mass ratio of the lithium manganate battery anode powder to the ferric sulfate to be 1:4, roasting the mixture at 600 ℃ for 180min, then continuously heating to 800 ℃ and continuously roasting for 180min to obtain a solid product;
(3) Leaching the solid product obtained in the step 2 with water at 100 ℃, and performing solid-liquid separation on the leaching slurry to obtain filter residue (the main component is Fe) 2 O 3 、Mn 2 O 3 Or FeMnO 3 ) And a leachate comprising lithium sulfate.
Example two
(1) Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
(2) Uniformly mixing the fine-ground lithium manganate battery anode powder below 150 mu m with ammonium bisulfate, controlling the mass ratio of the lithium manganate battery anode material to the ammonium bisulfate to be 1:6, roasting the mixture at 300 ℃ for 120min, then continuously heating to 900 ℃ and continuously roasting for 120min to obtain a solid product;
(3) Leaching the solid product obtained in the step 2 with water at 80 ℃, and carrying out solid-liquid separation on the leaching slurrySeparating to obtain filter residue (containing Mn as main component) 2 O 3 ) And a leachate comprising lithium sulfate.
EXAMPLE III
(1) Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
(2) Uniformly mixing the lithium manganate battery anode powder which is finely ground to be less than 150 mu m with ammonium sulfate, controlling the mass ratio of the lithium manganate battery anode powder to the ammonium sulfate to be 1:4, roasting the mixture at 400 ℃ for 120min, then continuously heating to 1000 ℃ and continuously roasting for 180min to obtain a solid product;
(3) Leaching the solid product obtained in the step 2 with water at 60 ℃, and performing solid-liquid separation on the leaching slurry to obtain filter residue (the main component is Mn) 2 O 3 ) And a leachate containing lithium sulfate.
Example four
(1) Discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
(2) Uniformly mixing the lithium manganate battery anode powder which is finely ground to be less than 150 mu m with ferrous sulfate, controlling the mass ratio of the lithium manganate battery anode powder to the ferrous sulfate to be 1:7, roasting the mixture at 700 ℃ for 240min, then continuously heating to 900 ℃ and continuously roasting for 240min to obtain a solid product;
(3) Leaching the solid product obtained in the step 2 with water at 50 ℃, and performing solid-liquid separation on the leaching slurry to obtain filter residue (the main component is Fe) 2 O 3 、Mn 2 O 3 Or FeMnO 3 ) And a leachate comprising lithium sulfate.
Claims (4)
1. A method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries is characterized by comprising the following steps:
step 1: discharging, disassembling and classifying the waste lithium manganate battery to obtain a positive electrode material, and then carrying out high-temperature treatment to remove the adhesive;
step 2: uniformly mixing lithium manganate positive electrode powder which is finely ground to be less than 150 mu m with one or more of ferrous sulfate, ferric sulfate, ammonium bisulfate and other sulfates according to a certain mass ratio, and roasting at a certain temperature for two sections to obtain a solid product;
and step 3: leaching the solid product obtained in the step 1 with water at a certain temperature, and performing solid-liquid separation on the leaching slurry to obtain a solid product with a main component of Fe 2 O 3 、Mn 2 O 3 Or FeMnO 3 The filter residue and the leaching solution containing lithium sulfate.
2. The method for selectively separating and recovering lithium and manganese from the waste lithium manganate batteries according to claim 1, wherein the mass ratio of the anode material of the lithium manganate battery to the sulfate in the step 2 is 1:1-8.
3. The method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries as claimed in claim 1, wherein the roasting temperature for the first stage roasting of the mixing of the materials in step 2 is 300-700 ℃ and the roasting time is 30-240 min, and the roasting temperature for the second stage roasting is 800-1000 ℃ and the roasting time is 30-240 min.
4. The method for selectively separating and recovering lithium and manganese from waste lithium manganate batteries as claimed in claim 1, characterized in that the solid product in step 3 has a water immersion temperature of 25-100 ℃, a leaching time of 10-180 min, and a liquid-solid mass ratio of 1-20.
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| CN117401917A (en) * | 2023-09-15 | 2024-01-16 | 青岛理工大学 | Preparation method of lithium salt modified sulphoaluminate cement and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117401917A (en) * | 2023-09-15 | 2024-01-16 | 青岛理工大学 | Preparation method of lithium salt modified sulphoaluminate cement and product thereof |
| CN117401917B (en) * | 2023-09-15 | 2024-04-05 | 青岛理工大学 | Preparation method of lithium salt modified sulphoaluminate cement and product thereof |
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