CN115215315A - Method for preparing manganese phosphate iron lithium electrode material by recycling iron and manganese from stainless steel slag - Google Patents

Method for preparing manganese phosphate iron lithium electrode material by recycling iron and manganese from stainless steel slag Download PDF

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CN115215315A
CN115215315A CN202210995853.8A CN202210995853A CN115215315A CN 115215315 A CN115215315 A CN 115215315A CN 202210995853 A CN202210995853 A CN 202210995853A CN 115215315 A CN115215315 A CN 115215315A
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manganese
iron
lithium
stainless steel
steel slag
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CN115215315B (en
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王梦晔
刘佳雯
王浩伟
何佳庆
高峰
黄丰
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines

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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to the field of industrial solid waste resource utilization, and particularly relates to a method for preparing a manganese iron phosphate lithium electrode material by recovering iron and manganese from stainless steel slag. The invention provides a method for preparing lithium manganese iron phosphate by recycling stainless steel slag, which comprises the following steps: mixing stainless steel slag with an acid solution and then roasting; (2) Soaking the roasted solid in water to obtain a ferro-manganese extracting solution; (3) Supplementing an iron source and ascorbic acid to the ferro-manganese extracting solution to prepare a ferro-manganese precursor solution; (4) And mixing the ferro-manganese precursor solution with a lithium source solution and a phosphorus source solution, carrying out hydrothermal treatment, and separating solids after reaction to obtain the lithium iron manganese phosphate material. The method is feasible and reliable, simple to operate and high in efficiency, can effectively recover the ferro-manganese resource from the stainless steel slag and regenerate the ferro-manganese-lithium iron phosphate material, replaces part of conventional raw materials with the steel slag waste as the raw material, reduces the production cost and realizes solid waste circulation.

Description

Method for preparing manganese phosphate iron lithium electrode material by recycling iron and manganese from stainless steel slag
Technical Field
The invention belongs to the field of industrial solid waste resource utilization, and particularly relates to a method for preparing a manganese iron phosphate lithium electrode material by recovering iron and manganese from stainless steel slag.
Background
The stainless steel slag is solid waste discharged in the stainless steel smelting process, and the discharge amount of the stainless steel slag is about 30 percent of the yield of stainless steel crude steel. The main chemical components of the stainless steel slag comprise common iron, silicon, magnesium, calcium and the like, and also comprise part of valuable metals such as nickel, manganese, chromium, molybdenum and the like. At present, most of the rust steel slag is mainly piled or buried in the open air, so that the resource waste is caused, a large amount of land is occupied, and partial oxides form various salts after being washed by rainwater in the piling process, so that the surrounding soil and water environment are influenced. The 3d transition metal (iron, manganese, nickel, cobalt and the like) contained in the stainless steel slag has important utilization value in the field of materials, particularly battery materials. Therefore, the stainless steel slag has the characteristics of secondary resources and environmental pollution, and the technical problem to be solved is how to fully utilize the steel slag, extract useful elements in the steel slag and apply the steel slag (such as preparing a lithium ion battery anode material).
In commercial lithium ion batteries, based on LiFePO 4 The battery system constructed has attracted much attention from the industry because of its low cost, high safety, high rate characteristics, and the like, but LiFePO 4 Has the disadvantages of low discharge plateau (about 3.4V) and low specific energy (580 Wh/kg). Lithium manganese iron phosphate (LiMn) x Fe 1-x PO 4 ) Is in lithium iron phosphate (LiFePO) 4 ) On the basis of the novel phosphate lithium ion battery anode material formed by doping manganese in a certain proportion, the co-doped manganese lithium iron phosphate not only can provide higher theoretical specific capacity (170 mAh/g), but also has higher discharge platform (3.8-4.1V discharge platform), the specific energy reaches 697Wh/kg, and the co-doped manganese lithium iron phosphate is widely regarded as the anode material. Therefore, the ferro-manganese resource recovered from the stainless steel slag is used as a raw material to replace the conventional raw material,and the material is regenerated into a lithium iron manganese phosphate material, so that the method has high environmental and economic benefits.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a method for preparing a manganese iron phosphate lithium electrode material by recovering iron and manganese from stainless steel slag, which comprises the following steps:
s1, adding stainless steel slag into an acid solution, and then roasting for 2-4h at 200-400 ℃;
s2, soaking and washing the roasted solid with water, and collecting washing liquor to obtain a ferro-manganese extracting solution;
s3, supplementing an iron source and a protective agent ascorbic acid to the ferro-manganese extracting solution to prepare a ferro-manganese precursor solution;
and S4, mixing the ferro-manganese precursor solution with a solution containing a lithium source and a phosphorus source, carrying out hydrothermal reaction on the obtained mixed solution, collecting solids after reaction, and washing and drying to obtain the lithium iron manganese phosphate electrode material.
Preferably, in step 1, the stainless steel slag can be replaced by waste slag containing metal iron and manganese, such as ferrochromium slag, ferronickel slag, silicomanganese slag and the like generated by stainless steel smelting.
Preferably, in step 1, the solid-to-liquid ratio of the stainless steel slag to the acid solution is 1 g/(1-5) ml.
Preferably, in the step 2, the amount of the water is 5 to 10 times of the total mass of the roasted product.
Preferably, in step 3, the iron source is supplemented in an amount such that the molar ratio of iron to manganese in the iron-manganese precursor solution is (95.
Preferably, in the step 3, the protective agent is ascorbic acid, and the dosage of the protective agent is 10-50% of the mass of iron in the ferro-manganese precursor solution.
Preferably, in step 4, the lithium source is lithium hydroxide or lithium carbonate, the phosphorus source is phosphoric acid, and the molar ratio of the lithium source to the iron-manganese source to the phosphorus source in the mixed solution is 1.2.
Preferably, in the step 4, the solvent used for the solution containing the lithium source and the phosphorus source is ethylene glycol and water, and the volume ratio of the ethylene glycol to the water is (1-1.5): 1.
Preferably, in the step 4, the hydrothermal reaction is carried out at 140-180 ℃ for 5-10 h.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing a manganese-iron-lithium phosphate electrode material by recovering iron and manganese from stainless steel slag. The method is feasible and reliable, simple to operate and high in efficiency, can effectively recover iron and manganese resources from the stainless steel slag and regenerate the iron and manganese phosphate lithium material, replaces part of conventional raw materials with the steel slag waste, reduces the production cost and realizes solid waste circulation, and the regenerated electrode material prepared by the method has good performance.
Drawings
Fig. 1 is an X-ray diffraction pattern of a lithium iron manganese phosphate electrode material.
Detailed Description
The following further describes embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of ferromanganese phosphate lithium electrode material
In this embodiment, the stainless steel slag is derived from residues discharged from a melting furnace in a stainless steel smelting process, the main metal elements and the contents thereof are 36% of calcium, 33% of manganese, 10% of chromium, 3.3% of iron, 1.5% of aluminum and 1.2% of magnesium, and the main phases thereof are metallic iron, calcium-magnesium-iron silicate, magnesium aluminate spinel and chrome manganese spinel, and the preparation method is as follows:
(1) Adding 5.0g of stainless steel slag into a porcelain boat, adding 5ml of hydrochloric acid solution (5 mol/L), uniformly mixing, placing the porcelain boat into a tube furnace, roasting at 300 ℃ for 2h, and cooling to room temperature after roasting;
(2) Washing the roasted solid by using 50ml of pure water for three times in total, and collecting washing liquor to obtain a ferro-manganese extracting solution;
(3) Adding 17g of ferric chloride hexahydrate solid to ensure that the molar ratio of iron to manganese is about 95 3+ Reduction to Fe 2+ And preventing the re-oxidation of the solution to obtain a ferro-manganese precursor solution;
(4) Uniformly mixing 35ml of pure water and 50ml of ethylene glycol, adding 0.9g of lithium carbonate and 2.9g of phosphoric acid, and uniformly stirring again to obtain an ethylene glycol aqueous solution of lithium phosphate;
(5) Adding 15ml of iron-manganese extracting solution into the ethylene glycol aqueous solution obtained in the step (4), and stirring for 2 hours at the rotating speed of 600rpm by using magnetic stirring; introducing the stirred mixture into a reaction kettle, reacting at 160 ℃ for 10 hours, and naturally cooling to room temperature;
(6) And (3) carrying out solid-liquid separation on the mixture obtained by the reaction, respectively washing the obtained solid for 2 times by using pure water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the manganese phosphate iron lithium electrode material.
Example 2 characterization of ferromanganese phosphate lithium electrode materials
(1) Characterization of the X-ray diffraction spectra of lithium manganese iron phosphate electrode materials
The lithium iron manganese phosphate electrode material prepared in example 1 was subjected to X-ray diffraction analysis using an X-ray diffractometer, and the analysis spectrum is shown in fig. 1, which shows that the main phase of the sample isLithium manganese iron phosphate (LiMn) x Fe 1-x PO 4 ) The invention proves that the lithium iron manganese phosphate electrode material is successfully prepared from the stainless steel slag.
(2) Electrochemical performance characterization of ferromanganese phosphate lithium electrode material
Pole piece manufacturing and battery assembling: the iron-manganese phosphate material prepared in example 1 was prepared according to the following formula: conductive agent (SP): adhesive (PVDF) =90:5:5, mixing slurry according to the proportion; coating, punching and drying the mixed slurry to prepare a positive electrode material; lithium metal sheet is used as a negative electrode material, a polypropylene microporous film is used as a diaphragm, and an electrolyte (LiPF) 6 /EC + DEC + DMC, in a volume ratio of 1.
And sealing the cell, standing for 2h, testing, and placing the button half cell on a blue test cabinet for testing, wherein the test voltage range is 2-4.4V, and the cycle multiplying power is 1C cycle.
Experimental tests show that the initial capacity of the material is 155mA/mg, and the initial coulombic efficiency is 68.3%, which indicates that the lithium iron manganese phosphate electrode material prepared from the stainless steel slag has large initial capacity and high initial coulombic efficiency.
In conclusion, the method successfully recovers the ferro-manganese material in the stainless steel slag and regenerates the ferro-manganese material into the lithium iron manganese phosphate material, reduces the production cost, realizes solid waste circulation, and is more energy-saving and environment-friendly.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (9)

1. A method for preparing a manganese iron phosphate lithium electrode material by recovering iron and manganese from stainless steel slag is characterized by comprising the following steps:
s1, adding stainless steel slag into an acid solution, and then roasting for 2-4h at 200-400 ℃;
s2, soaking and washing the roasted solid with water, and collecting washing liquor to obtain a ferro-manganese extracting solution;
s3, supplementing an iron source and a protective agent to the ferro-manganese extracting solution to prepare a ferro-manganese precursor solution;
and S4, mixing the ferro-manganese precursor solution with a solution containing a lithium source and a phosphorus source, carrying out hydrothermal reaction on the obtained mixed solution, collecting solids after reaction, and washing and drying to obtain the lithium iron manganese phosphate electrode material.
2. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 1, the stainless steel slag can be replaced by ferrochrome slag, ferronickel slag or silicomanganese slag containing iron and manganese.
3. The method for preparing the ferric manganese phosphate lithium electrode material by recovering the ferro-manganese from the stainless steel slag according to claim 1, wherein in the step 1, the concentration of the acid solution is 1.0 to 5.0mol/L, the acid solution is hydrochloric acid, nitric acid or sulfuric acid solution, and the solid-to-liquid ratio of the stainless steel slag to the acid solution is 1 g/(1 to 5) ml.
4. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 2, the amount of water is 5-10 times of the total mass of the roasted product.
5. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 3, the iron source is supplemented in an amount such that the molar ratio of iron to manganese in the iron-manganese precursor solution is (95.
6. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 3, the protective agent is ascorbic acid, and the amount of the protective agent is 10-50% of the mass of iron in the iron and manganese precursor solution.
7. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 4, the lithium source is lithium hydroxide or lithium carbonate, the phosphorus source is phosphoric acid, and the molar ratio of the lithium source to the iron and manganese to the phosphorus source in the mixed solution is 1.2.
8. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 4, the solvent used by the solution containing the lithium source and the phosphorus source is ethylene glycol and water, and the volume ratio of the ethylene glycol to the water is (1-1.5): 1.
9. The method for preparing the lithium iron manganese phosphate electrode material by recovering iron and manganese from the stainless steel slag according to claim 1, wherein in the step 4, the hydrothermal reaction is carried out at 140-180 ℃ for 5-10 h.
CN202210995853.8A 2022-08-18 2022-08-18 Method for preparing lithium iron manganese phosphate electrode material by recycling ferro-manganese from stainless steel slag Active CN115215315B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112125292A (en) * 2020-08-14 2020-12-25 中国科学院金属研究所 Hydrothermal synthesis method of lithium manganese iron phosphate
CN114023953A (en) * 2021-11-03 2022-02-08 惠州亿纬锂能股份有限公司 Modified lithium iron manganese phosphate cathode material and preparation method and application thereof
CN114583156A (en) * 2022-01-26 2022-06-03 合肥国轩高科动力能源有限公司 Method for preparing carbon-coated lithium manganese iron phosphate material by electrolyzing manganese slag

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112125292A (en) * 2020-08-14 2020-12-25 中国科学院金属研究所 Hydrothermal synthesis method of lithium manganese iron phosphate
CN114023953A (en) * 2021-11-03 2022-02-08 惠州亿纬锂能股份有限公司 Modified lithium iron manganese phosphate cathode material and preparation method and application thereof
CN114583156A (en) * 2022-01-26 2022-06-03 合肥国轩高科动力能源有限公司 Method for preparing carbon-coated lithium manganese iron phosphate material by electrolyzing manganese slag

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