CN115304045A - Application of lithium iron manganese phosphate as electrode material in brine electrochemical lithium extraction - Google Patents
Application of lithium iron manganese phosphate as electrode material in brine electrochemical lithium extraction Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 239000012267 brine Substances 0.000 title claims abstract description 54
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 238000000605 extraction Methods 0.000 title claims abstract description 52
- 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 35
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 49
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 229940062993 ferrous oxalate Drugs 0.000 claims description 6
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 6
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940006116 lithium hydroxide Drugs 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001728 nano-filtration Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 230000005684 electric field Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HVTQDSGGHBWVTR-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-phenylmethoxypyrazol-1-yl]-1-morpholin-4-ylethanone Chemical compound C(C1=CC=CC=C1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CCOCC1 HVTQDSGGHBWVTR-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014822 LiMn2O4LiFePO4 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
Abstract
The invention relates to application of lithium manganese iron phosphate as an electrode material in brine electrochemical lithium extraction, wherein the chemical formula of the lithium manganese iron phosphate is LiFe x Mn 1‑x PO 4 The value of x ranges from 0 to 0.99, and x is not 0. Uniformly mixing a lithium source, an iron source and a manganese source, fully grinding to obtain a precursor, and sintering to prepare lithium manganese iron phosphate (LiFe) with adjustable manganese iron proportion x Mn 1‑x PO 4 )。LiFe x Mn 1‑x PO 4 The lithium ion selective membrane has good selectivity on lithium ions, and realizes high-efficiency separation of lithium resources; and can be adapted to salt lake brine systems composed of different ions by regulating and controlling the iron-manganese ratio.
Description
Technical Field
The invention belongs to the technical field of lithium extraction from brine, and particularly relates to application of lithium iron manganese phosphate as an electrode material in lithium extraction from brine in an electrochemical manner.
Background
Lithium is the lightest metal element in nature and is a vital element in a new energy system. In recent two years, with the rapid development of power batteries and the field of energy storage, the consumption of lithium resources is increased sharply. The lithium output steadily increases year by year, but the supply and demand are insufficient, and the market supply and demand are seriously unbalanced. Lithium is obtained mainly by two ways: solid lithium ore, and salt lake brine, underground brine, seawater and other lithium resources. Due to the problems of high energy consumption, high cost and pollution caused by ore resource development, the extraction of lithium from salt lake brine is expected to become a key way for solving the imbalance of lithium supply and demand.
Various methods have been developed to extract lithium from solution, the most widely used being the lime soda evaporation process. This method is low cost and profitable, but since the process is based on solar evaporation, its efficiency and rate are greatly affected by the environment. In recent years, new methods for extracting lithium have emerged, such as ion sieve adsorption, nanofiltration, extraction, and electrochemical extraction based on lithium ion batteries. Although ion sieves have high lithium adsorption capacity and selectivity, the materials are generally in powder form, and their flowability and solution permeability are slow and inefficient. The nanofiltration membrane has a dielectric repulsion effect, a Taonan effect, a steric hindrance effect and the like, so that the nanofiltration membrane has a barrier effect on multivalent and high-molecular-weight compounds, and monovalent or small-molecular substances can permeate the nanofiltration membrane, but the cost is high and the operation is complex. The extraction method has obvious advantages in the process of extracting lithium from salt lake brine with high magnesium-lithium ratio, high extraction rate and low production cost. However, the extraction process has high requirements on equipment materials, equipment pipelines are easy to corrode, and the working environment has great harm to human bodies. Electrochemical techniques have proven to be effective methods for extracting lithium ions from brine, because they can significantly improve the productivity of lithium ions, and are low in energy consumption and environmentally friendly. The development of electrode materials in electrochemical lithium extraction systems has a great influence on the extraction efficiency and capacity of lithium.
LiFePO 4 Although inexpensive, liFePO is used as an electrode material 4 The using voltage of the lithium extraction anode is lower than that of other common anode materials, and the lithium extraction anode has the defects of low conductivity, insufficient rate performance and the like, the defects limit the lithium extraction capacity and the lithium extraction efficiency of the lithium extraction anode, and further limit the lithium extraction anode in saline lake brine bodies with different magnesium-lithium ratiosThe application in the system.
Disclosure of Invention
The invention applies lithium manganese iron phosphate as an electrode material to the electrochemical lithium extraction of salt lake brine, and solves the problem of LiFePO of the existing electrode material 4 Long lithium extraction time and poor conductivity, and can not be applied to salt lake brine systems with different magnesium-lithium ratios.
The iron and manganese ions in the lithium iron manganese phosphate material have similar radiuses and are easy to form solid solutions, so that the lithium iron manganese phosphate material can realize the atomic-level mixing. And the iron ions and the manganese ions are positioned in the same position in the crystal structure of the material, so that the proportion of the iron ions and the manganese ions can be regulated and controlled at will, and the lithium iron manganese phosphate material with any proportion can be obtained.
In addition, the doping of Mn element can increase the charge and discharge platform of the battery material, shorten the lithium extraction time and improve the lithium extraction efficiency. The method can reduce the charge transfer impedance, reduce the polarization degree of the material, improve the conductivity of the material, and improve the utilization rate and the capacity of lithium extraction sites.
Furthermore, the invention provides lithium iron manganese phosphate (LiFe) with a customizable proportion of manganese and iron suitable for salt lake brine systems with different ion compositions x Mn 1-x PO 4 ) The preparation method of the electrode material comprises the following specific steps of, wherein the value range of x is 0-0.99, and x is not 0:
And 2, drying the ball-milled mixture in a forced air drying oven, grinding, calcining for 3-5 h at 300-400 ℃ in an argon or nitrogen atmosphere, raising the temperature to 700-800 ℃ and calcining for 10-12 h, wherein the heating rate is 3-5 ℃/min. And finally, naturally cooling to room temperature, grinding and collecting for later use.
The use proportion of the manganese acetate and the ferrous oxalate raw materials in the step 1 can be changed to control the lithium iron manganese phosphate (LiFe) x Mn 1-x PO 4 ) The ferromanganese ratio in the steel is the value of x.
Lithium manganese iron phosphate (LiFe) with different manganese-iron ratios x Mn 1-x PO 4 ) In salt lake brine with different magnesium-lithium ratios, the electrochemical properties of the salt lake brine are respectively advantageous. For example, as the manganese content increases, the adsorption capacity of the material increases, but the cycle retention decreases; the cycle retention of the material increases with increasing iron content, but the adsorption capacity decreases somewhat. Therefore, the lithium iron manganese phosphate material suitable for different manganese-iron ratios of the salt lake brine can be customized according to the electrochemical performance requirements such as required adsorption capacity, cycle retention rate and the like.
The invention has the advantages and beneficial effects that:
(1) Through the regulation and control of the ferromanganese proportion, aiming at the ion composition of different brine, the electrode material can be customized, and the universal applicability of the electrochemical lithium extraction technology facing the complex and variable ion composition of different brine is increased.
(2) The doping of Mn element can enlarge LiFePO 4 The cell volume of (a), which provides a more unobstructed path for the transport of lithium ions between the electrolyte and the electrode, can accelerate the electrolyte into the micropores and thereby increase ionic and electronic conductivity.
(3) The doping of Mn element can increase the charge and discharge platform of the battery material, shorten the lithium extraction time and improve the lithium extraction efficiency; the method can reduce the charge transfer impedance, reduce the polarization degree of the material, improve the conductivity of the material, and improve the utilization rate and the capacity of lithium extraction active sites.
Drawings
Fig. 1 is an XRD spectrum of lithium manganese iron phosphate with different ferromanganese ratios: (a) LiFe 0.19 Mn 0.81 PO 4 ；(b)LiFe 0.49 Mn 0.51 PO 4 ；(c)LiFe 0.73 Mn 0.27 PO 4 。
Fig. 2 is an SEM image of lithium manganese iron phosphate with different ferromanganese ratios: (a) LiFe 0.19 Mn 0.81 PO 4 ；(b)LiFe 0.49 Mn 0.51 PO 4 ；(c)LiFe 0.73 Mn 0.27 PO 4 。
FIG. 3 shows the lithium iron manganese phosphate (LiFe) obtained in example 4 0.49 Mn 0.51 PO 4 ) Mapping of (2).
Fig. 4 shows EDS analysis results of lithium iron manganese phosphates with different ferromanganese ratios: (a) LiFe 0.19 Mn 0.81 PO 4 ；(b)LiFe 0.49 Mn 0.51 PO 4 ；(c)LiFe 0.73 Mn 0.27 PO 4 。
FIG. 5 shows lithium iron manganese phosphate (LiFe) obtained in example 4 0.49 Mn 0.51 PO 4 ) Cyclic voltammetry test results in simulated brine containing lithium and no lithium Atacama.
Fig. 6 shows the cyclic voltammetry test results of lithium manganese iron phosphate with different ferromanganese ratios in 1M LiCl: (a) LiFe 0.19 Mn 0.81 PO 4 ；(b)LiFe 0.49 Mn 0.51 PO 4 ；(c)LiFe 0.73 Mn 0.27 PO 4 。
Detailed Description
The present invention is further described in the following examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
The invention applies lithium manganese iron phosphate as an electrode material to the electrochemical lithium extraction of salt lake brine, compared with lithium iron phosphate (LiFePO) 4 ) The characteristic of high voltage of manganese enables the lithium extraction battery to have a higher voltage platform, which is beneficial to shortening the lithium extraction time and improving the overall lithium extraction efficiency. Secondly, the incorporation of Mn expands the LiFePO 4 The cell volume of (a), which provides a more unobstructed path for the transport of lithium ions between the electrolyte and the electrode, can accelerate the electrolyte into the micropores and thereby increase ionic and electronic conductivity. Therefore, the doping of the Mn element can firstly increase the reversibility of the material, reduce the charge transfer resistance and reduce the polarization degree of the material.
Example 1
Weighing (0.01 mol) lithium hydroxide, (0.0025 mol) ferrous oxalate, (0.0075 mol) manganese acetate, (0.01 mol) ammonium dihydrogen phosphate, and (0.0055 mol) citric acid as a carbon source, and 40mL of absolute ethyl alcohol as a medium, adding into a ball milling tank, ball milling for 8h at the rotating speed of 190rpm, and carrying out suction filtration.
And drying the ball-milled mixture in a 40 ℃ forced air drying oven for 24h, grinding, calcining at 350 ℃ for 3h under argon atmosphere, raising the temperature to 700 ℃ and calcining for 10h, wherein the temperature rise rate is 5 ℃/min. Finally, naturally cooling to room temperature, grinding, and collecting to obtain lithium iron manganese phosphate (LiFe) 0.19 Mn 0.81 PO 4 ) An electrode material.
(1) Preparation of the electrodes
Lithium iron manganese phosphate (LiFe) obtained in example 1 was dissolved in N-methylpyrrolidone as a solvent 0.19 Mn 0.81 PO 4 ) The acetylene black and the PVDF are 8:1:1 mixing, beating, and uniformly coating the slurry on a carbon sheet (the area of the coated active material is 1 cm) 2 And drying at 40 ℃ for 12h, and recording the quality change of the electrode plate before and after coating.
(2) Asymmetric capacitance lithium extraction process
Simulated brine of Dongtai Ginella (Qinghai, china) was used as the source liquid, and the composition thereof is shown in Table 1. Lithium iron manganese phosphate (LiFe) obtained in example 1 was used 0.19 Mn 0.81 PO 4 ) For the positive electrode and AC for the negative electrode, a lithium extraction experiment was performed for 30 consecutive cycles.
The circulating lithium extraction process comprises the following specific steps: adopting an asymmetric capacitance lithium extraction device to remove the lithium-state Fe 0.19 Mn 0.81 PO 4 As a battery pole, an AC electrode is used as a capacitor pole, and an asymmetric capacitor system is combined. Firstly, pumping brine, applying a constant current external electric field to enable lithium ions and chloride ions in the electrolyte to respectively move to the positive electrode and the negative electrode, and thus, the lithium ions are embedded into Fe 0.19 Mn 0.81 PO 4 Electrode formation of LiFe 0.19 Mn 0.81 PO 4 Chloride ions adsorb to the AC. After a period of lithium intercalation process, stopping feeding the brine, switching the feeding liquid to be 0.1mM lithium chloride solution as a lithium recovery liquid, releasing lithium ions and chloride ions at the positive electrode and the negative electrode respectively into the lithium recovery liquid by applying opposite electric field directions,LiFe 0.19 Mn 0.81 PO 4 reconversion to delithiated Fe 0.19 Mn 0.81 PO 4 And the concentration of the lithium ions in the recovery liquid is enriched, namely, the process is repeated and circularly repeated to complete a complete electrochemical lithium extraction experiment, the concentration of the lithium ions in the brine is continuously reduced, and the concentration of the lithium ions in the recovery liquid is continuously enriched.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 31.4mg/g in the brine system and a cycle retention rate of 93.8% after 30 cycles, as shown in table 2, as determined by ICP testing.
Example 2
The procedure was as in example 1 except that the east platform gilel (chinese Qinghai) simulated brine in step (2) was replaced with Atacama (chile) simulated brine.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 35.3mg/g in the brine system and a cycle retention rate of 95.1% after 30 cycles, as shown in table 2, as determined by ICP testing.
Example 3
The procedure was as in example 1 except that the Totynday Ginella (China Qinghai) simulated brine in step (2) was replaced with Zabuye (China Tibet) simulated brine.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 37.6mg/g in the brine system and a cycle retention rate of 95.2% after 30 cycles, as shown in table 2, according to an ICP test.
Example 4
Lithium hydroxide (0.01 mol), ferrous oxalate (0.005 mol), manganese acetate (0.005 mol), ammonium dihydrogen phosphate (0.01 mol) and citric acid (0.0055 mol) were weighed as carbon sources, and the preparation procedure was the same as in example 1. Obtaining LiFe 0.49 Mn 0.51 PO 4 An electrode material. The method of preparing it into an electrode and applying it to the cyclic lithium extraction process was the same as in example 1.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 29.1mg/g in the brine system and a cycle retention rate of 95.4% after 30 cycles, as shown in table 2, as determined by ICP testing.
Example 5
The procedure was as in example 4 except that the east platform gilel (chinese Qinghai) simulated brine in step (2) was replaced with Atacama (chile) simulated brine.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 33.8mg/g in the brine system and a cycle retention rate of 96.3% after 30 cycles, as shown in table 2, as determined by ICP test.
Example 6
The same procedure as in example 4 was repeated, except that the simulated brine of east tai gilel (qinghai, china) in step (2) was replaced with a simulated brine of zabuer (tibet, china).
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 35.2mg/g in the brine system and a cycle retention rate of 96.5% after 30 cycles, as shown in table 2, as determined by ICP testing.
Example 7
Lithium hydroxide (0.01 mol), ferrous oxalate (0.0075 mol), manganese acetate (0.0025 mol), ammonium dihydrogen phosphate (0.01 mol), and citric acid (0.0055 mol) were weighed as carbon sources, and the preparation procedure was the same as in example 1. Obtaining LiFe 0.73 Mn 0.27 PO 4 An electrode material. The method of preparing it into an electrode and applying it to the cyclic lithium extraction process was the same as in example 1.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 28.7mg/g in the brine system and a cycle retention rate of 96.5% after 30 cycles, as shown in table 2, as determined by ICP test.
Example 8
The procedure was as in example 7 except that the east platform gilel (chinese Qinghai) simulated brine in step (2) was replaced with Atacama (chile) simulated brine.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 33.5mg/g in the brine system and a cycle retention rate of 97.8% after 30 cycles, as shown in table 2, as determined by ICP test.
Example 9
The same procedure as in example 7 was repeated, except that the simulated brine of east tai gilel (qinghai, china) in step (2) was replaced with a simulated brine of zabuer (tibet, china).
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 34.4mg/g in the brine system and a cycle retention rate of 98.6% after 30 cycles, as shown in table 2, as determined by ICP testing.
The XRD patterns of lithium manganese iron phosphate with different manganese iron ratios are shown in figure 1, and the crystal structure is an olivine structure with an oblique power pmnb, which is similar to that of a standard card (PDF # 13-0336). No other impurity peak is found in the diffraction diagram, the diffraction peak has a narrow and sharp shape, and the prepared samples are pure phases and have good crystallinity.
Fig. 2 is a scanning electron microscope image of lithium iron manganese phosphate materials with different manganese-iron ratios. The particles are different in size and consist of finely-divided small particles and blocky secondary agglomerated particles, and the particles are found to be changed from small to large along with the increase of the manganese content in a high-power SEM image, and the agglomeration condition is aggravated. It is reported in the literature that changes in morphology will have a significant impact on electronic and ionic conductivity and permeability. On one hand, the smaller particle size can shorten the transmission distance of lithium ions among the crystal grains and improve the electrochemical performance, and on the other hand, the reduction of the size and the ordering of the appearance can provide more reaction specific surface area.
FIG. 3 shows the lithium iron manganese phosphate (LiFe) obtained in example 4 0.49 Mn 0.51 PO 4 ) The Mapping graph of (1) shows that the elements Fe, mn, P and O in the material are uniformly distributed in FIG. 4. Fig. 4 shows EDS analysis results of lithium manganese iron phosphate with different ferromanganese ratios.
Lithium iron manganese phosphate (LiFe) obtained in example 4 in a three-electrode system 0.49 Mn 0.51 PO 4 ) For the working electrode, a platinum gauze was used as counter electrode and Ag/AgCl as reference electrode, and cyclic voltammetry tests (sweep rate 0.5 mV/s) were carried out in a mixed electrolyte with or without LiCl, respectively. As shown in FIG. 5, contains Li + Has two distinct redox peaks, and the other one does not contain Li + No significant redox peak was observed in the mixed solution CV curve of (1). The results show that lithium ions selectively react with the electrode, while other cationsThe ions hardly participate in any reaction. The adopted mixed electrolyte is Atacama simulated salt lake brine.
FIG. 6 is a CV curve diagram of the prepared three lithium iron manganese phosphate materials with different iron-manganese ratios at a sweep rate of 0.5 mV/s. It can be seen from the CV curve that all materials have two pairs of redox peaks, corresponding to Fe in the vicinity of 0.3V 2+ /Fe 3+ And Mn in the vicinity of 0.9V 2+ /Mn 3+ And as the proportion of iron and manganese increases, fe 2+ /Fe 3 The intensity of the corresponding redox peak is significantly enhanced.
Under the voltage of 0-1.2V, the lithium manganese iron phosphate with different iron-manganese ratios obtained by the method is respectively circulated for 30 times under the multiplying power of 1C in simulation brine of east-Tai Ginella, atacama and Zabuya (China Tibet) with different magnesium-lithium ratios, and the lithium recovery condition is shown in table 2.
TABLE 1 compositions of different simulated brines used in the examples
TABLE 2 summary of lithium recovery for the specific examples
Comparative example 1
Adopting Atacama (Chilean) simulated brine as source liquid, and adding LiFePO 4 The method of preparing an electrode and applying to the cyclic lithium extraction process was the same as in example 1.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 25.6mg/g in the brine system and a cycle retention rate of 93.65% after 30 cycles, as shown in table 3, as determined by ICP testing.
Comparative example 2
Except that LiFePO in comparative example 10 4 Replacement by LiMn 2 O 4 The rest is the same as in comparative example 1.
After 30 cycles of lithium extraction, the electrode material has a lithium adsorption capacity of 27.2mg/g in the brine system and a cycle retention rate of 87.04% after 30 cycles, as shown in table 3, as determined by ICP test.
TABLE 3 summary of lithium recovery for comparative examples
| LiMn 2 O 4 | LiFePO 4 | LiFe 0.19 Mn 0.81 PO 4 | LiFe 0.49 Mn 0.51 PO 4 | LiFe 0.73 Mn 0.27 PO 4 | |
| Time/h | 3 | 5 | 4 | 4 | 4 |
| Capacity mg/g | 27.20 | 25.6 | 35.3 | 33.8 | 33.5 |
| 30 cycles of circulation retention rate% | 87.04 | 93.65 | 95.1 | 96.3 | 97.8 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (3)
1. Application of lithium manganese iron phosphate as electrode material in electrochemical extraction of lithium from brine, wherein the chemical formula of the lithium manganese iron phosphate is LiFe x Mn 1-x PO 4 The value of x ranges from 0 to 0.99, and x is not 0.
2. The use of claim 1, wherein the ferromanganese ratio is adjusted to suit different magnesium-lithium ratios of the salt lake brine.
3. The use according to claim 1 or 2, characterized in that the preparation process of lithium iron manganese phosphate comprises the following steps:
step 1, adopting a solid-phase reaction method, and performing reaction according to the following steps of 0.95-1.05: 0.01 to 0.99:0.01 to 0.99: 0.95-1.05: weighing lithium hydroxide, ferrous oxalate, manganese acetate, ammonium dihydrogen phosphate and citric acid according to a molar ratio of 0.5-0.6, taking absolute ethyl alcohol as a medium, wherein the addition amount of the absolute ethyl alcohol accounts for 90-95% of the total amount of the materials, performing ball milling for 8-10 h at a rotating speed of 180-200 rpm, and performing suction filtration;
and 2, drying and grinding the ball-milled mixture, calcining for 3-5 h at 300-400 ℃ in an argon or nitrogen atmosphere, then raising the temperature to 700-800 ℃ for calcining for 10-12 h, and finally naturally cooling to room temperature to obtain the lithium iron manganese phosphate electrode material.
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