CN115092902B - Method for preparing lithium iron manganese phosphate positive electrode material by using iron-manganese-rich slag - Google Patents
Method for preparing lithium iron manganese phosphate positive electrode material by using iron-manganese-rich slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 32
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title description 7
- 238000002386 leaching Methods 0.000 claims abstract description 84
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 21
- 239000011707 mineral Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 6
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- AMOBFARMENYMCJ-UHFFFAOYSA-K iron(2+) manganese(2+) phosphate hydrate Chemical compound O.P(=O)([O-])([O-])[O-].[Fe+2].[Mn+2] AMOBFARMENYMCJ-UHFFFAOYSA-K 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The method for preparing the lithium iron manganese phosphate anode material by utilizing the iron manganese rich slag comprises the following steps: (1) recycling the iron-manganese-rich slag to prepare mineral powder; (2) Adding sulfuric acid into the mineral powder obtained in the step (1), carrying out two-stage leaching, and combining the leaching solutions to obtain mixed leaching solution; (3) Purifying and removing impurities from the mixed leaching solution obtained in the step (2) to obtain a ferric manganese phosphate coprecipitation product; (4) And (3) sintering and dehydrating the iron-manganese phosphate coprecipitation product obtained in the step (3), and calcining the product with lithium to obtain the iron-manganese-lithium phosphate anode material. The method adopts sectional leaching to recycle the ferro-manganese element in the manganese slag, has good leaching effect, and then adopts phosphoric acid and hydrogen peroxide to synthesize the ferro-manganese phosphate coprecipitation product, so that the recycled product can be directly utilized, and the energy consumption is low, and the method is economical and efficient; the lithium iron manganese phosphate anode material prepared by the invention has excellent electrochemical performance and excellent long-cycle performance.
Description
Technical Field
The invention relates to a preparation method of a lithium iron manganese phosphate positive electrode material, in particular to a method for preparing a lithium iron manganese phosphate positive electrode material by utilizing iron-rich manganese slag.
Background
Currently, the battery industry mainly synthesizes the lithium ion battery directly from mineral resources, and the batteries produced in industry comprise alkaline batteries, zinc batteries, lead-acid batteries, lithium ion batteries and the like, wherein the lithium ion batteries are widely applied by virtue of the advantages of high energy density, chemical stability, good cycle performance and the like. However, the rapid development of lithium ion batteries has led to a great increase in the demand for mineral resources, causing concern about the supply of battery materials. In addition, the shortage of mineral resources and the rising of raw material prices have hindered the rapid development of the battery industry.
Wet leaching recovery of iron and manganese from iron and manganese rich slag and making lithium iron manganese phosphate is a technology that is quite different from traditional production processes. Because the metallurgical waste slag generally contains elements such as lithium, cobalt, nickel, rare earth and the like, the content is generally higher than that of primary ore, the metallurgical waste slag is also an important secondary resource of battery materials, and the leached iron-manganese element can be directly used for synthesizing lithium iron manganese phosphate materials, so that the method is easy for large-scale production. However, at the same time, the extraction operation of the ferro-manganese element is complex and the yield is not high because the elements contained in the ferro-manganese-rich slag are complex.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the method for preparing the lithium iron manganese phosphate anode material by utilizing the slag rich in iron and manganese, which is simple and convenient to operate, good in iron and manganese element recovery effect and excellent in electrochemical performance.
The technical scheme adopted for solving the technical problems is that the method for preparing the lithium iron manganese phosphate anode material by utilizing the iron-manganese-rich slag comprises the following steps:
(1) Recovering the iron-manganese-rich slag to prepare mineral powder;
(2) Adding sulfuric acid into the mineral powder obtained in the step (1), carrying out two-stage leaching, and combining the leaching solutions to obtain mixed leaching solution;
(3) Purifying and removing impurities from the mixed leaching solution obtained in the step (2) to obtain a ferric manganese phosphate coprecipitation product;
(4) And (3) sintering and dehydrating the coprecipitation product of the ferric manganese phosphate obtained in the step (3) at a low temperature, and calcining the coprecipitation product of the ferric manganese phosphate with lithium to obtain the lithium manganese phosphate anode material.
Further, in the step (1), the content of iron in the iron-manganese-rich slag is 20-40wt%, and the average content of manganese is 3-5wt%.
In the step (1), the iron-manganese-rich slag is dried at 100-150 ℃, preferably 120 ℃ for 5-30 hours, preferably 10-20 hours.
In the step (2), the two-stage leaching is to continuously leach the mineral powder twice by using sulfuric acid, the solid-liquid ratio of the mineral powder to the leaching agent in the first leaching is controlled to be 1:5-15, preferably 1:10, the concentration of sulfuric acid in the leaching agent is 0.5-1.5 mol/L, preferably 1.0mol/L, the leaching temperature is 70-90 ℃, preferably 85 ℃, the leaching time is 2-5 h, preferably 3h, the stirring intensity is 100-500 r/min, preferably 200r/min, and the mineral powder is washed by deionized water after leaching.
In the step (2), after the mineral powder is leached for the first time, solid-liquid separation is carried out to obtain filter residues, the filter residues are leached for the second time, the solid-liquid ratio of the filter residues to the leaching agent in the second leaching is controlled to be 1:5-15, preferably 1:10, the concentration of sulfuric acid in the leaching agent is 5-10 mol/L, preferably 6mol/L, the leaching temperature is 70-90 ℃, preferably 85 ℃, the leaching time is 10-30 h, preferably 20h, the stirring intensity is 100-500 r/min, preferably 85 ℃, and the filter residues are pickled by sulfuric acid after leaching.
Further, in the step (3), the phosphoric acid is 0.05-0.15 mol/L, preferably 0.1.mol/L.
In the step (3), the pH value of the leaching solution is regulated to be 1.8-2.3, the concentration of phosphoric acid is controlled to be 0.1-0.3mol/L, the concentration of hydrogen peroxide is controlled to be 0.1-0.2mol/L, the P/M value (the ratio of phosphoric acid to metal element amount) is 1.00-1.05:1, preferably 1.03:1, and the aluminum, the barium and the magnesium elements in the mixed leaching solution are cooperatively removed.
Further, in the step (3), the iron-manganese phosphate coprecipitation product is white.
Further, in the step (4), the sintering and dehydrating temperature is 200-400 ℃, preferably 300 ℃.
Further, in the step (4), the calcination temperature of the lithium is 600-900 ℃, preferably 800 ℃, and the amount of lithium is: m is 1.00-1.05:1, preferably 1.03:1.
It is found that the result that the highest leaching rate of iron and manganese is achieved by only one leaching of the iron-manganese-containing slag is difficult to achieve, because the leaching rate of iron element is increased and the leaching rate of manganese is decreased at the same time. According to the invention, excessive sulfuric acid is added as a leaching agent, two-stage leaching is carried out, firstly, the optimal manganese leaching rate is obtained under mild conditions, then, the second-step intensified leaching is carried out on filter residues to enable the leaching rate of iron to reach the highest, wet leaching is carried out, iron and manganese elements in iron-manganese-rich slag are separated and recovered into leaching liquid, the leaching liquid is collected twice, directional precipitation is carried out, and a co-precipitation product of iron and manganese phosphate is synthesized to be used as a precursor polymer of a positive electrode material, so that the positive electrode material of iron and manganese lithium phosphate is synthesized.
The method has low energy consumption, does not need high temperature and pure oxygen sintering, directly adopts a wet method to recycle manganese slag resources, has low cost and is suitable for large-scale production. The lithium iron manganese phosphate material synthesized by the invention forms a special electrode material doped with various rare and noble elements such as lithium, cobalt, nickel and the like, enhances electron conductivity and abundant active sites, provides high reversible capacity, and maintains excellent long-term cycle performance at a high current density of 0.5 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method adopts sectional leaching to recycle the iron and manganese elements in the manganese slag, has good leaching effect of the iron and manganese elements, and then adopts phosphoric acid and hydrogen peroxide to synthesize the iron-manganese phosphate coprecipitation product, directly utilizes the recycled product, and has low energy consumption, economy and high efficiency.
(2) The lithium iron manganese phosphate anode material prepared by the invention has excellent electrochemical performance and excellent long-cycle performance.
(3) The invention has simple and convenient operation and short process flow, and is beneficial to mass production.
Drawings
Fig. 1 is an XRD pattern of the lithium iron manganese phosphate positive electrode material obtained in example 1.
Fig. 2 is an electrochemical performance test chart of the lithium iron manganese phosphate cathode material obtained in example 1.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
In the following examples, the leaching rate of the ferro-manganese element was measured by ICP and the electrochemical data was measured by an electrochemical workstation.
Unless otherwise specified, all materials were used as common commercial products.
Example 1
The method for preparing the lithium iron manganese phosphate anode material by utilizing the iron manganese rich slag comprises the following steps:
(1) Drying the iron-manganese-rich slag in an oven at 120 ℃ for 20 hours, crushing, grinding, and sieving with a 200-mesh sieve to prepare mineral powder;
(2) Performing two-stage leaching on 10g of mineral powder obtained in the step (1), adding 100ml of 1mol/L sulfuric acid solution into the first-stage leaching, wherein the leaching temperature is 85 ℃, the time is 3 hours, the stirring intensity is 200r/min, filtering the leached solution, and washing with deionized water to obtain leaching liquid and leaching slag; transferring the leaching slag into 100ml of 6mol/L sulfuric acid for second stage leaching, wherein the leaching temperature is 85 ℃ and the leaching time is 20h, washing with 6mol/L sulfuric acid solution to obtain leaching liquid, and combining the leaching liquid with the first stage leaching liquid to obtain ferro-manganese mixed leaching liquid;
(3) Preparing a leaching solution with the concentration of 0.1 mol/L and a phosphoric acid solution with the concentration of 0.1 mol/L, enabling the P/M to be 1.03:1, adding hydrogen peroxide with the concentration of 0.13mol/L, adjusting the pH value of the mixed solution to be 1.8, reacting for 15min, filtering and drying to obtain an amorphous iron-manganese phosphate hydrate coprecipitation product;
(4) And (3) sintering and dehydrating the amorphous iron-manganese phosphate hydrate coprecipitation product obtained in the step (3) at 300 ℃, and then carrying out lithium matching calcination at the temperature of 800 ℃ in a ratio of 1.4:1, wherein the calcination time is 8 hours, so as to obtain the iron-manganese lithium phosphate anode material.
Through detection, the leaching rate of iron in the iron-manganese-rich slag of the embodiment is 95%, and the leaching rate of manganese element is 98%.
Assembling a battery: weighing 0.08 g of the lithium iron manganese phosphate anode material obtained in the embodiment 1 of the invention, adding 0.01 g of acetylene black as a conductive agent and 0.01 g of polyvinylidene fluoride as a binder, uniformly mixing N-methylpyrrolidone as a dispersing agent, coating the mixture on an aluminum foil to prepare an anode plate, taking a metal lithium plate as a negative electrode, taking a PE and PP composite film as a diaphragm in a vacuum glove box, and taking 1mol/L LiPF6/DMC (volume ratio of 1:1) as electrolyte to assemble the CR2032 button cell.
The assembled battery has a discharge gram capacity of 157.8mAh/g under the multiplying power of 0.5C (1C=158.7 mAh/g) in the voltage range of 2-4.2V; discharge at 0.1C,0.2C, 0.5C, 2C, 5C was 175.6, 170.5, 163.4, 147.8, 133.9mAh/g, respectively; 0.5 The capacity retention after 200 cycles at C-rate was 95.1%.
Comparative example
The method for preparing the lithium iron manganese phosphate anode material by utilizing the iron manganese rich slag comprises the following steps:
(1) Drying the iron-manganese-rich slag in an oven at 120 ℃ for 20 hours, crushing, grinding, and sieving with a 200-mesh sieve to prepare mineral powder;
(2) And (3) carrying out one-stage leaching on 10g of mineral powder obtained in the step (1), adding 100ml of 3mol/L sulfuric acid solution into the leaching solution, wherein the leaching temperature is 85 ℃, the time is 23h, the stirring intensity is 200r/min, filtering the leached solution, and washing the leached solution with deionized water to obtain leaching solution and leaching slag.
(3) Preparing a leaching solution with the concentration of 0.1 mol/L and a phosphoric acid solution with the concentration of 0.1 mol/L, enabling the P/M to be 1.03:1, adding hydrogen peroxide with the concentration of 0.13mol/L, adjusting the pH value of the mixed solution to be 1.8, reacting for 15min, filtering and drying to obtain an amorphous iron-manganese phosphate hydrate coprecipitation product;
(4) And (3) sintering and dehydrating the amorphous iron-manganese phosphate hydrate coprecipitation product obtained in the step (3) at 300 ℃, and then carrying out lithium matching calcination at the temperature of 800 ℃ in a ratio of 1.4:1, wherein the calcination time is 8 hours, so as to obtain the iron-manganese lithium phosphate anode material.
Through detection, the leaching rate of iron in the iron-manganese-rich slag of the comparative example is only 40%, and the leaching rate of manganese element is 90%.
Assembling a battery: weighing 0.08 g of the lithium iron manganese phosphate anode material obtained in the comparative example, adding 0.01 g of acetylene black as a conductive agent and 0.01 g of polyvinylidene fluoride as a binder, uniformly mixing N-methylpyrrolidone as a dispersing agent, coating the mixture on an aluminum foil to prepare an anode plate, taking a lithium metal plate as a negative electrode, taking a PE and PP composite film as a diaphragm in a vacuum glove box, and taking 1mol/L LiPF6/DMC:EC (volume ratio 1:1) as electrolyte to assemble the CR2032 button cell.
The assembled battery is detected, and the discharge gram capacity of the assembled battery is 115.7mAh/g under the voltage range of 2-4.2V and the multiplying power of 0.5C; discharge at 0.1C,0.2C, 0.5C, 2C, 5C was 121.6, 118.5, 113.4, 112.9, 111.4mAh/g, respectively; 0.5 The capacity retention rate after 200 circles of circulation under the C multiplying power is 27.4%, and the overall performance of the battery is poor.
Claims (2)
1. The method for preparing the lithium iron manganese phosphate anode material by utilizing the iron manganese rich slag is characterized by comprising the following steps of:
(1) Recovering the iron-manganese-rich slag to prepare mineral powder;
(2) Adding sulfuric acid into the mineral powder obtained in the step (1), carrying out two-stage leaching, and combining the leaching solutions to obtain mixed leaching solution;
(3) Purifying and removing impurities from the mixed leaching solution obtained in the step (2) to obtain a ferric manganese phosphate coprecipitation product;
(4) Sintering and dehydrating the iron-manganese phosphate coprecipitation product obtained in the step (3), and calcining with lithium to obtain an iron-manganese-lithium phosphate anode material;
in the step (2), the two-stage leaching is to continuously leach mineral powder twice by using sulfuric acid, the solid-to-liquid ratio of mineral powder to a leaching agent in the first leaching is controlled to be 1:5-15, the sulfuric acid concentration of the leaching agent is 0.5-1.5 mol/L, the leaching temperature is 70-90 ℃, the leaching time is 2-5 h, the stirring intensity is 100-500 r/min, and the mineral powder is washed by deionized water after leaching;
in the step (2), after the mineral powder is leached for the first time, solid-liquid separation is carried out to obtain filter residues, the filter residues are leached for the second time, the solid-liquid ratio of the filter residues to the leaching agent in the second leaching is controlled to be 1:5-15, the concentration of sulfuric acid in the leaching agent is 5-10 mol/L, the leaching temperature is 70-90 ℃, the leaching time is 10-30 h, the stirring intensity is 100-500 r/min, and the filter residues are pickled by sulfuric acid after leaching;
in the step (3), the pH value of the leaching solution is saved to 1.8-2.3, the concentration of phosphoric acid is controlled to be 0.1-0.3mol/L, the concentration of hydrogen peroxide is controlled to be 0.1-0.2mol/L, the P/M value is 1.00-1.05:1, and the aluminum, barium and magnesium elements in the mixed leaching solution are cooperatively removed;
in the step (4), the sintering and dehydration temperature is 200-400 ℃;
in the step (4), the calcination temperature of the lithium is 600-900 ℃, and the amount of the lithium is as follows: m is 1.00-1.05:1.
2. The method for preparing a lithium iron manganese phosphate cathode material by using the iron-manganese-rich slag according to claim 1, wherein in the step (1), the iron content in the iron-manganese-rich slag is 20-40wt% and the average manganese content is 3-5wt%.
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