CN115092902A - Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag - Google Patents
Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 48
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 48
- 239000011572 manganese Substances 0.000 title claims abstract description 48
- 239000002893 slag Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 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 19
- 239000010406 cathode material Substances 0.000 title claims description 13
- 238000002386 leaching Methods 0.000 claims abstract description 80
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 18
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 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
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 239000011707 mineral Substances 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims 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 description 5
- 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
- 239000002253 acid Substances 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
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 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
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 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 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VRHPRPVJMYLUBR-UHFFFAOYSA-K manganese(3+);phosphate;hydrate Chemical compound O.[Mn+3].[O-]P([O-])([O-])=O VRHPRPVJMYLUBR-UHFFFAOYSA-K 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 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
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 uniformly mixing Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
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- 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
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- 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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The method for preparing the lithium manganese iron phosphate anode material by utilizing the iron-rich manganese slag comprises the following steps of: (1) recovering iron-rich manganese 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 two leaching solutions to obtain a 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 (4) sintering and dehydrating the ferric manganese phosphate coprecipitation product obtained in the step (3), and calcining the product matched with lithium to obtain the lithium ferric manganese phosphate anode material. The method adopts sectional leaching to recover the iron and manganese elements in the manganese slag, the leaching effect of the iron and manganese elements is good, and then phosphoric acid and hydrogen peroxide are adopted to synthesize an iron and manganese phosphate coprecipitation product, so that the obtained product can be directly utilized and recovered, and the method is low in energy consumption, economic and efficient; the lithium ferric manganese phosphate anode material provided 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, and particularly relates to a method for preparing a lithium iron manganese phosphate positive electrode material by utilizing iron-rich manganese slag.
Background
At present, the battery industry is mainly directly synthesized by mineral resources, and industrially produced batteries 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 substantial increase in the demand for mineral resources, raising concerns 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.
The wet leaching recovery of iron and manganese from iron and manganese-rich slag and the preparation of lithium manganese iron phosphate are a technology which is completely different from the traditional production technology. Because the metallurgical waste slag usually contains elements such as lithium, cobalt, nickel, rare earth and the like, and the content of the elements is usually higher than that of primary ore, the metallurgical waste slag is also an important secondary resource of a battery material, and the leached ferro-manganese element can be directly used for synthesizing a lithium iron manganese phosphate material, so that the large-scale production is easy. However, since the iron-manganese-rich slag contains complicated elements, the operation of extracting the iron and manganese elements is complicated, and the yield is not high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing a lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag, which is simple and convenient to operate, good in recovery effect of iron and manganese elements and excellent in electrochemical performance of the obtained lithium manganese iron phosphate cathode material.
The technical scheme adopted by the invention for solving the technical problems is that the method for preparing the lithium manganese iron phosphate anode material by utilizing the iron-rich manganese slag comprises the following steps:
(1) recovering iron-rich manganese 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 two leaching solutions to obtain a 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 (4) sintering and dehydrating the iron-manganese phosphate coprecipitation product obtained in the step (3) at a low temperature, and calcining the product matched with lithium to obtain the lithium manganese phosphate anode material.
Further, in the step (1), the iron content of the iron-rich manganese slag is 20-40wt%, and the average manganese content is 3-5 wt%.
Further, in the step (1), drying treatment is carried out when the iron-rich manganese slag is recovered, wherein the drying temperature is 100-150 ℃, preferably 120 ℃, and the drying time is 5-30 hours, preferably 10-20 hours.
Further, in the step (2), the ore powder is continuously leached twice by using sulfuric acid in the two-stage leaching, the solid-to-liquid ratio of the ore powder and a leaching agent in the first leaching is controlled to be 1: 5-15, preferably 1:10, the concentration of the 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 hours, preferably 3 hours, the stirring strength is 100-500 r/min, preferably 200r/min, and the ore powder is washed by deionized water after leaching.
Further, in the step (2), after the mineral powder is leached for the first time, performing solid-liquid separation to obtain filter residue, performing secondary leaching on the filter residue, controlling the solid-liquid ratio of the filter residue to a leaching agent in the secondary leaching to be 1: 5-15, preferably 1:10, controlling the concentration of sulfuric acid in the leaching agent to be 5-10 mol/L, preferably 6mol/L, the leaching temperature to be 70-90 ℃, preferably 85 ℃, the leaching time to be 10-30 hours, preferably 20 hours, the stirring strength to be 100-500 r/min, preferably 85 ℃, and pickling the filter residue with sulfuric acid after leaching.
Further, in the step (3), the phosphoric acid accounts for 0.05-0.15 mol/L, preferably 0.1. mol/L.
Further, in the step (3), the step of purifying and removing impurities is to adjust the pH value of the leachate to 1.8-2.3, control the concentration of phosphoric acid to 0.1-0.3mol/L and the concentration of hydrogen peroxide to 0.1-0.2mol/L, enable the P/M value (the ratio of phosphoric acid to metal element) to be 1.00-1.05: 1, preferably 1.03:1, and cooperatively remove aluminum, barium and magnesium elements in the mixed leachate.
Further, in the step (3), the iron manganese phosphate coprecipitation product is white.
Further, in the step (4), the sintering dehydration temperature is 200-400 ℃, preferably 300 ℃.
Further, in the step (4), the calcining temperature of the lithium is 600-900 ℃, preferably 800 ℃, and the amount of the lithium is Li: m is 1.00-1.05: 1, preferably 1.03: 1.
Research shows that the leaching rate of the iron and the manganese elements can hardly reach the highest leaching rate by only leaching the iron-containing manganese slag once, because the leaching rate of the iron element increases and the leaching rate of the manganese tends to decrease. According to the invention, excessive sulfuric acid is added as a leaching agent, two-stage leaching is carried out, firstly, the best manganese leaching rate is obtained under mild conditions, then, the second-step enhanced leaching is carried out on filter residues to ensure that the leaching rate of iron is the highest, wet-process leaching is carried out, iron and manganese elements in iron-rich manganese residues are separated and recovered into the leaching solution, the leaching solution obtained in two times is collected and directionally precipitated, and a synthesized iron-manganese phosphate coprecipitation product is used as a precursor polymer of a positive electrode material to synthesize the lithium manganese iron phosphate positive electrode material.
The method has low energy consumption, does not need high temperature and pure oxygen sintering, directly adopts a wet method to recover manganese slag resources, has low cost, and is suitable for large-scale production. The lithium ferric manganese phosphate material synthesized by the invention forms a special electrode material doped with various rare and precious elements such as lithium, cobalt, nickel and the like, enhances the electronic conductivity and rich active sites, provides high reversible capacity, and keeps excellent long-term cycle performance under the high current density of 0.5C.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts sectional leaching to recover the iron and manganese elements in the manganese slag, the leaching effect of the iron and manganese elements is good, then phosphoric acid and hydrogen peroxide are adopted to synthesize the iron-manganese phosphate coprecipitation product, and the recovered product is directly utilized, so that the method is low in energy consumption, economic and efficient.
(2) The lithium ferric manganese phosphate anode material provided by the invention has excellent electrochemical performance and excellent long cycle performance.
(3) The method is simple and convenient to operate, short in process flow and beneficial to large-scale production.
Drawings
Fig. 1 is an XRD spectrum of the lithium ferric manganese phosphate cathode material obtained in example 1.
Fig. 2 is a graph showing electrochemical performance test of the lithium ferric manganese phosphate positive electrode material obtained in example 1.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
In the following examples, the leaching rate of iron and manganese elements was measured by ICP, and electrochemical data was measured by an electrochemical workstation.
All materials used are, unless otherwise specified, those commonly available on the market.
Example 1
The method for preparing the lithium ferric manganese phosphate anode material by utilizing the iron-rich manganese slag comprises the following steps of:
(1) drying the iron-rich manganese slag in a 120 ℃ oven for 20 hours, crushing and grinding the iron-rich manganese slag, and sieving the crushed iron-rich manganese slag with a 200-mesh sieve to prepare mineral powder;
(2) performing two-stage leaching on 10g of the mineral powder obtained in the step (1), adding 100ml of 1mol/L sulfuric acid solution into the first stage of leaching, filtering the leached solution, washing with deionized water to obtain leachate and leaching residues, wherein the leaching temperature is 85 ℃, the leaching time is 3 hours, and the stirring strength is 200 r/min; transferring the leaching residue into 100ml of 6mol/L sulfuric acid for second-stage leaching at 85 ℃ for 20h, washing with 6mol/L sulfuric acid solution to obtain a leaching solution, and combining the leaching solution and the first-stage leaching solution to obtain an iron-manganese mixed leaching solution;
(3) preparing 0.1 mol/L leachate and 0.1 mol/L phosphoric acid solution to ensure that the P/M is 1.03:1, adding 0.13mol/L hydrogen peroxide, adjusting the pH value of the mixed solution to 1.8, reacting for 15min, filtering and drying to obtain an amorphous iron-manganese phosphate hydrate coprecipitation product;
(4) and (4) sintering and dehydrating the amorphous ferric manganese phosphate hydrate coprecipitation product obtained in the step (3) at 300 ℃, and then calcining lithium in a ratio of 1.4:1 at 800 ℃ for 8h to obtain the lithium ferric manganese phosphate cathode material.
Through detection, the leaching rate of iron in the iron-rich manganese slag is 95%, and the leaching rate of manganese element is 98%.
Assembling the battery: weighing 0.08 g of lithium manganese iron phosphate positive electrode material obtained in the embodiment 1 of the invention, adding 0.01 g of acetylene black serving as a conductive agent, 0.01 g of polyvinylidene fluoride serving as a binder, N-methylpyrrolidone serving as a dispersing agent, uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, and assembling the positive electrode plate into a CR2032 button cell by taking a metal lithium plate as a negative electrode, a composite film of PE and PP as a diaphragm and 1mol/L of LiPF6/DMC: EC (volume ratio 1: 1) as electrolyte in a vacuum glove box.
The assembled battery is detected to have the capacity of 157.8mAh/g at 0.5C (1C =158.7 mAh/g) multiplying power within the voltage range of 2-4.2V; the discharge at 0.1C, 0.2C, 0.5C, 2C and 5C is respectively 175.6 mAh/g, 170.5 mAh/g, 163.4 mAh/g, 147.8 mAh/g and 133.9 mAh/g; the capacity retention rate after 200 cycles at 0.5C magnification was 95.1%.
Comparative example
The method for preparing the lithium ferric manganese phosphate anode material by utilizing the iron-rich manganese slag comprises the following steps of:
(1) drying the iron-rich manganese slag in a 120 ℃ oven for 20 hours, crushing and grinding the iron-rich manganese slag, and sieving the crushed iron-rich manganese slag with a 200-mesh sieve to prepare mineral powder;
(2) and (2) performing primary leaching on 10g of the mineral powder obtained in the step (1), adding 100ml of 3mol/L sulfuric acid solution into the leaching, filtering the leached solution, washing the leached solution by deionized water to obtain leachate and leaching residues, wherein the leaching temperature is 85 ℃, the leaching time is 23h, and the stirring intensity is 200 r/min.
(3) Preparing 0.1 mol/L leachate and 0.1 mol/L phosphoric acid solution to ensure that the P/M is 1.03:1, adding 0.13mol/L hydrogen peroxide, adjusting the pH value of the mixed solution to 1.8, reacting for 15min, filtering and drying to obtain an amorphous iron-manganese phosphate hydrate coprecipitation product;
(4) and (4) sintering and dehydrating the amorphous ferric manganese phosphate hydrate coprecipitation product obtained in the step (3) at 300 ℃, and then calcining lithium in a ratio of 1.4:1 at 800 ℃ for 8h to obtain the lithium ferric manganese phosphate cathode material.
Through detection, the leaching rate of iron in the iron-rich manganese slag of the comparative example is only 40%, and the leaching rate of manganese element is 90%.
Assembling the battery: 0.08 g of lithium manganese iron phosphate anode material obtained in the comparative example of the invention is weighed, 0.01 g of acetylene black serving as a conductive agent and 0.01 g of polyvinylidene fluoride serving as a binder are added, N-methyl pyrrolidone serving as a dispersing agent are uniformly mixed and coated on aluminum foil to prepare an anode plate, and a CR2032 button cell is assembled in a vacuum glove box by taking a metal lithium plate as a negative electrode, a composite film of PE and PP as a diaphragm and 1mol/L of LiPF6/DMC: EC (volume ratio 1: 1) as electrolyte.
Through detection, the discharge gram capacity of the assembled battery is 115.7mAh/g within the voltage range of 2-4.2V and under the multiplying power of 0.5C; the discharge at 0.1C, 0.2C, 0.5C, 2C and 5C is 121.6, 118.5, 113.4, 112.9 and 111.4mAh/g respectively; the capacity retention rate after 200 cycles under 0.5C multiplying power is 27.4%, and the overall performance of the battery is poor.
Claims (7)
1. The method for preparing the lithium ferric manganese phosphate anode material by utilizing the iron-rich manganese slag is characterized by comprising the following steps of:
(1) recovering iron-rich manganese 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 two leaching solutions to obtain a 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 (4) sintering and dehydrating the iron manganese phosphate coprecipitation product obtained in the step (3), and calcining the product matched with lithium to obtain the lithium iron manganese phosphate anode material.
2. The method for preparing the lithium ferric manganese phosphate cathode material by using the iron-rich manganese slag according to claim 1, wherein in the step (1), the content of iron in the iron-rich manganese slag is 20-40wt%, and the average content of manganese is 3-5 wt%.
3. The method for preparing the lithium manganese iron phosphate cathode material by using the iron-rich manganese slag according to claim 1 or 2, wherein in the step (2), the ore powder is leached twice continuously by using sulfuric acid in the two-stage leaching, the solid-to-liquid ratio of the ore powder and the leaching agent in the first leaching is controlled to be 1: 5-15, the concentration of the sulfuric acid in 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 strength is 100-500 r/min, and the ore powder is washed by using deionized water after leaching.
4. The method for preparing the lithium manganese iron phosphate cathode material by using the iron-rich manganese slag according to any one of claims 1 to 3, wherein in the step (2), after the mineral powder is subjected to primary leaching, solid-liquid separation is performed to obtain filter residue, the filter residue is subjected to secondary leaching, the solid-liquid ratio of the filter residue to a leaching agent in the secondary 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 residue is subjected to acid pickling by using sulfuric acid after the leaching.
5. The method for preparing lithium manganese iron phosphate cathode material from iron-rich manganese slag according to any one of claims 1 to 4, wherein in the step (3), the purification and impurity removal are performed to adjust the pH value of the leachate to 1.8-2.3, the concentration of phosphoric acid is controlled to 0.1-0.3mol/L, the concentration of hydrogen peroxide is controlled to 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 leachate are synergistically removed.
6. The method for preparing the lithium manganese iron phosphate cathode material by using the iron-rich manganese slag according to any one of claims 1 to 5, wherein the sintering dehydration temperature in the step (4) is 200 to 400 ℃.
7. The method for preparing the lithium manganese iron phosphate cathode material by using the iron-rich manganese slag according to any one of claims 1 to 6, wherein in the step (4), the temperature for calcining the lithium is 600 to 900 ℃, and the amount of the lithium is Li: m is 1.00-1.05: 1.
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