CN116573627A - Vanadium-containing ore Na + Method for preparing lithium vanadium phosphate lithium battery anode material by in-situ doping - Google Patents
Vanadium-containing ore Na + Method for preparing lithium vanadium phosphate lithium battery anode material by in-situ doping Download PDFInfo
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- CN116573627A CN116573627A CN202211575488.1A CN202211575488A CN116573627A CN 116573627 A CN116573627 A CN 116573627A CN 202211575488 A CN202211575488 A CN 202211575488A CN 116573627 A CN116573627 A CN 116573627A
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- Prior art keywords
- vanadium
- lithium
- sodium
- phosphate
- situ doping
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 72
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 title abstract description 12
- UGYGKUZIOVCMED-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[V+5].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[V+5].[Li+] UGYGKUZIOVCMED-UHFFFAOYSA-K 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000011734 sodium Substances 0.000 claims abstract description 35
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims description 29
- 238000002386 leaching Methods 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 15
- 229910052708 sodium Inorganic materials 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 159000000000 sodium salts Chemical class 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- QRVIVVYHHBRVQU-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QRVIVVYHHBRVQU-UHFFFAOYSA-H 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KGHAYBAGTGGGBA-UHFFFAOYSA-N [O--].[O--].[O--].[Na+].[V+5] Chemical compound [O--].[O--].[O--].[Na+].[V+5] KGHAYBAGTGGGBA-UHFFFAOYSA-N 0.000 description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000012002 vanadium phosphate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate cathode material by in-situ doping takes vanadium-containing ore as an initial raw material, prepares a vanadium-sodium-containing compound through a metallurgical wet process, then directly calcines the vanadium-sodium-containing compound after mixing with lithium carbonate and ammonium dihydrogen phosphate, and directly dopes sodium element into the lithium vanadium phosphate material through a liquid-phase in-situ doping method to produce the lithium vanadium phosphate material with good electrochemical performance. The sodium salt of the patent is original in vanadium-containing ores, and no additional addition is needed; the sodium element is mixed and added in the liquid phase, so that the sodium element is easy to uniformly distribute, and the electrochemical uniformity of the lithium vanadium phosphate electrode is facilitated; lithium carbonate is used as a lithium source, compared to fluorineAnd lithium is converted, so that the cost is lower. The invention organically combines the traditional metallurgical production process with the production process of the new energy lithium ion battery anode material, and has the advantages of simplifying the preparation process of the material, reducing the production cost of the material, being suitable for industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and in particular relates to vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate cathode material by in-situ doping.
Background
Lithium ion secondary batteries have higher operating voltages, higher energy densities and power densities and thus are dominant in the field of batteries for consumer electronics. However, electric vehicle batteries and energy storage batteries, which are highly valued for solving energy and environmental problems, place higher demands on current lithium ion batteries, which also place higher demands on positive and negative electrode materials that limit the performance and cost of lithium ion batteries. The lithium vanadium phosphate has high theoretical specific capacity (3.0-4.3V, 133mAh/g theoretical capacity; 3.0-4.8V theoretical capacity up to 197 mAh/g), good cycle performance, high working voltage and outstanding low-temperature performance, and is a new generation of lithium ion battery anode material with great potential. Li (Li) 3 V 2 (PO 4 ) 3 Is a typical polyanion type positive electrode material, in the polyanion structure, larger phosphate ions replace oxygen ions in the traditional metal oxide type positive electrode material, on one hand, the structural stability of the material is improved, on the other hand, the distance between metal vanadium ions is increased, and Li is reduced 3 V 2 (PO 4 ) 3 Electron conductivity of (c) is defined. Currently, for Li 3 V 2 (PO 4 ) 3 The problem of low conductivity is mainly solved by researchers through two methods of surface modification and ion doping. The patent document with publication number of CN111072004A, namely a sodium doped lithium vanadium fluorophosphate material, a preparation method and application thereof, has the general formula: li (Li) (1-x) /Na x VPO 4 F, wherein x is more than 0 and less than or equal to 0.3; the preparation method of the sodium-doped lithium vanadium fluorophosphate material comprises the following steps: mixing a vanadium source, a phosphorus source and a carbon source at 60-100 ℃ and drying; calcining the product in inert atmosphere to obtain carbon-doped vanadium phosphate; mixing carbon-doped vanadium phosphate, liF and a sodium source, and performing dry ball milling to obtain uniformly mixed powder; calcining the powder to obtain the sodium-doped lithium vanadium fluorophosphate material, wherein the calcining temperature is 650-800 ℃ and the calcining time is 1-6h, and the sodium-doped lithium vanadium fluorophosphate material is prepared. The Na ion doping used in the above patent method belongs to an external doping mode, and sodium salt needs to be added additionally, such as sodium carbonate, sodium fluoride, sodium chloride and the like, so that the complexity of the production process and the increase of the production cost can be caused; secondly, the doping process adopts dry ball milling, so that the phenomenon of uneven distribution of sodium elements exists, and the uniformity of the produced lithium vanadium fluorophosphate material is poor; again, the use of lithium fluoride as a lithium salt can corrode production equipment, thereby reducing the controllability of the production process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims at the problems of low electron conductivity and the like of the lithium vanadium phosphate anode material in the prior art, prepares the vanadium-sodium-containing compound by taking vanadium-containing ore as an initial raw material, directly dopes sodium element into the lithium vanadium phosphate material by a liquid-phase in-situ doping method, effectively improves the electrochemical performance of the lithium vanadium phosphate, and the prepared lithium vanadium phosphate anode material has obviously higher multiplying power performance and cycle performance.
To achieve the above object, the present invention provides a vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate lithium battery anode material by in-situ doping comprises the following steps:
(1) the method comprises the steps of using vanadium slag extracted from a converter as a basic raw material, putting the vanadium slag into a ball mill for ball milling, obtaining refined vanadium slag after magnetic separation, and taking the refined vanadium slag and sodium carbonate according to Na 2 CO 3 /V 2 O 5 The mass ratio is 1.6-1.8, and the materials are evenly mixed. The mixing process of the raw materials is to uniformly mix the vanadium slag extracted from the converter with the roasting auxiliary agent sodium carbonate so as to facilitate the reaction.
(2) And (3) placing the mixture obtained in the step (1) into a muffle furnace for roasting at 770-790 ℃ in an air atmosphere for 30-60min to obtain clinker. And oxidizing and roasting to jointly generate soluble vanadium sodium oxide with sodium carbonate.
(3) Ball milling the clinker obtained in the step (2) to about 120 meshes of particle size, adding a proper amount of water, heating to 80-90 ℃, reacting for 15-30min, stirring at a speed of 100-300r/min in the leaching process, and filtering after the leaching is finished to obtain vanadium-containing leaching solution. Soluble vanadium and sodium elements in the vanadium-sodium oxide are led into the solution through leaching of the aqueous solution.
(4) Taking the vanadium-containing leaching solution obtained in the step (3), and carrying out treatment according to (NH) 4 ) 2 SO 4 : adding ammonium sulfate with the mass ratio of V of 1.2-2.0, adjusting the pH value of the solution from 9-10 to 1.8-2.0 by using dilute sulfuric acid with the volume ratio of 1:1, heating to 90-100 ℃, and precipitating for 30-60min to obtain the vanadium-containing compound. The step is a precipitation process of the oxide containing vanadium and sodium, and the soluble vanadium generated in the step (3) is subjected to precipitation reaction to generate the compound containing vanadium and sodium.
(5) Mixing the vanadium-containing compound obtained in the step (4) with lithium carbonate, ammonium dihydrogen phosphate and sucrose; placing the uniformly mixed substances into a vacuum tube furnace, and roasting for 3-5 hours at the temperature of 300-400 ℃ under the argon atmosphere; then the temperature is increased to 800-850 ℃ and roasting is carried out for 8-12h, thus obtaining the in-situ Na + Doped lithium vanadium phosphate material.
In the technical scheme, further, the ball milling granularity of the vanadium slag in the step (1) is-120 meshes and is more than 80%.
In the above technical solution, further, in the step (3), the liquid-solid ratio (volume/mass) is 1.5-2.0:1.
in the above technical solution, further, in step (5), the vanadium-containing compound: lithium carbonate: ammonium dihydrogen phosphate: the mass ratio of sucrose is 1:0.592:1.755:0.326.
the lithium battery anode material prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, vanadium-containing ore is used as an initial raw material, a vanadium-sodium compound is prepared through a metallurgical wet process, then the vanadium-sodium compound is directly roasted after being mixed with lithium carbonate and monoammonium phosphate, and sodium element is directly doped into a vanadium-lithium phosphate material through a liquid-phase in-situ doping method, so that the vanadium-lithium phosphate material with good electrochemical performance is produced. The sodium salt of the patent is original in vanadium-containing ores, does not need to be additionally added, and can simplify the production process and reduce the production cost; in addition, the sodium element is added in a liquid phase in a mixing way, so that the uniform distribution of the sodium element is facilitated, and the electrochemical uniformity of the lithium vanadium phosphate electrode is facilitated; and thirdly, the lithium carbonate is used as a lithium salt, so that the cost is lower compared with that of lithium fluoride, and the long-term operation of production equipment is facilitated. The invention organically combines the traditional metallurgical production process with the production process of the new energy lithium ion battery anode material, and has the advantages of simplifying the preparation process of the material, reducing the production cost of the material, being suitable for industrial production and the like.
Drawings
FIG. 1 is a photograph of the microscopic morphology of the sodium vanadium compound of example 3;
FIG. 2 is a photograph of the micro morphology of the sodium doped lithium vanadium phosphate material prepared in example 3;
FIG. 3 is a phase structure of the lithium vanadium phosphate material prepared in example 3;
FIG. 4 is a graph showing CV curve test of the lithium vanadium phosphate material prepared in example 3;
fig. 5 is an electrochemical performance graph of the lithium vanadium phosphate material prepared in example 3.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way. For the sake of avoiding redundancy, the raw materials in the following examples are all commercially available unless specifically stated, and the quality grades are all industrial grades; the methods used are conventional methods unless otherwise specified. The vanadium slag component and the leaching liquid component all use the chemical titration national standard method. The electrochemical performance test adopts the current test standard of the lithium ion battery industry.
Button cell test standard for lithium ion battery industry: the prepared LVP positive electrode material is prepared according to the following proportion of 8:1:1, mixing the conductive agent Super P and the binder PVDF, adding an appropriate amount of NMP to adjust the viscosity of the slurry, and stirring the slurry at a constant temperature by a constant-temperature magnetic stirrer for 10 hours to uniformly disperse the slurry. Uniformly coating the aluminum foil with a coating device with a thickness of 90 mu m, transferring the aluminum foil to a vacuum oven, drying the aluminum foil at 120 ℃ for 12 hours under vacuum condition to remove solvent NMP, and manufacturing a wafer with a size of 14mm by using a wafer punching machine after drying the pole piece. In the inert gas atmosphere of a glove box, metal lithium is used as a negative electrode, LVP is used as a positive electrode to prepare a CR2025 button cell for testing electrochemical performance. The electrolyte was 1M LiPF6 in EC:DEC:EMC =1:1:1 (v), and the activation process was completed at room temperature with a current of 0.1C.
Example 1
Vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate lithium battery anode material by in-situ doping comprises the following steps:
the vanadium slag extracted by the converter is used as a basic raw material, a proper amount of vanadium slag is put into a ball mill for ball milling until the ball milling granularity of the vanadium slag is-120 meshes more than 80%, and the refined vanadium slag is obtained after magnetic separation, wherein the components are shown in the table 1. Taking the refined vanadium slag and a proper amount of sodium carbonate according to Na 2 CO 3 /V 2 O 5 Mixing evenly with the mass ratio of 1.6; placing the mixture into a muffle furnace for roasting at 770 ℃ in an air atmosphere for 30min to obtain clinker; ball milling the clinker until the granularity of the clinker is about 120 meshes, and then adding a proper amount of water to ensure that the liquid-solid ratio is 1.5:1 (volume ml/mass g), heating to 80 ℃, reacting for 15min, stirring at a speed of 100r/min in the leaching process, and filtering after the leaching to obtain vanadium-containing leaching solution, wherein the components are shown in table 2; collecting vanadium-containing leaching solution, and processing according to (NH) 4 ) 2 SO 4 Adding ammonium sulfate into the ratio of V=1.2, adjusting the pH value of the solution from 9-13 to 1.8 by using dilute sulfuric acid with the volume ratio of 1:1, heating to 90 ℃, and precipitating for 30min to obtain a vanadium-containing compound; 0.49g of the vanadium-containing compound was mixed with 0.29g of lithium carbonate, 0.86g of monoammonium phosphate and 0.16g of sucrose. After being uniformly mixed, the materials are put into a vacuum tube furnace, baked for 3 hours at 300 ℃ under the argon atmosphere, then the temperature is increased to 800 ℃ and baked for 8 hours, thus obtaining the in-situ Na + Doped lithium vanadium phosphate material.
TABLE 1 vanadium slag composition
| TV | TFe | CaO | MgO | SiO 2 | Cr | |
| Vanadium slag/% | 9.12 | 28.7 | 1.85 | 3.94 | 15.95 | 0.21 |
TABLE 2 composition of leachate
| V | P | Na | Cr | |
| Lixivium/(g/l) | 33.7 | <0.01 | 26.9 | 1.12 |
The lithium vanadium phosphate material obtained in example 1 was assembled into a coin cell battery, and its electrochemical performance was tested, the test voltage range was 3.0 to 4.3V, and the test results are shown in table 3.
Example 2
Vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate lithium battery anode material by in-situ doping comprises the following steps:
the method comprises the steps of using converter vanadium extraction vanadium slag as a basic raw material, putting a proper amount of vanadium slag into a ball mill for ball milling until the ball milling granularity of the vanadium slag is-120 meshes more than 80%, obtaining refined vanadium slag after magnetic separation, and taking the refined vanadium slag and a proper amount of sodium carbonate according to Na 2 CO 3 /V 2 O 5 Mixing evenly with the mass ratio of 1.7; placing the mixture into a muffle furnace for roasting at 780 ℃ in an air atmosphere for 40min to obtain clinker; ball milling the clinker until the granularity of the clinker is about 120 meshes, and then adding a proper amount of water to ensure that the liquid-solid ratio is 1.8:1 (volume ml/mass g), heating to 85 ℃, reacting for 30min, stirring at a speed of 200r/min in the leaching process, and filtering after the leaching is finished to obtain vanadium-containing leaching solution; collecting vanadium-containing leaching solution, and processing according to (NH) 4 ) 2 SO 4 Adding ammonium sulfate into the ratio of V=1.6, adjusting the pH value of the solution from 9-13 to 2.0 by using dilute sulfuric acid with the volume ratio of 1:1, heating to 100 ℃, and precipitating for 60min to obtain a vanadium-containing compound; taking the vanadium-containing compound0.98g of the compound was mixed with 0.58g of lithium carbonate, 1.72g of monoammonium phosphate and 0.32g of sucrose. After being uniformly mixed, the materials are put into a vacuum tube furnace, baked for 5 hours at 400 ℃ under the argon atmosphere, then the temperature is increased to 850 ℃ and baked for 12 hours, thus obtaining the in-situ Na + Doped lithium vanadium phosphate material.
The lithium vanadium phosphate material obtained in example 2 was assembled into a coin cell battery, and the electrochemical performance thereof was tested, the test voltage range was 3.0 to 4.3V, and the test results are shown in table 1.
Example 3
Vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate lithium battery anode material by in-situ doping comprises the following steps:
the method comprises the steps of using vanadium slag extracted from a revolving furnace as a basic raw material, putting the vanadium slag into a ball mill for ball milling until the ball milling granularity of the vanadium slag is-120 meshes more than 80%, obtaining refined vanadium slag after magnetic separation, and taking the refined vanadium slag and a proper amount of sodium carbonate according to Na 2 CO 3 /V 2 O 5 Mixing evenly with the mass ratio of 1.8; placing the mixture into a muffle furnace for roasting at 790 ℃ in air atmosphere for 60min to obtain clinker; ball milling the clinker until the granularity of the clinker is about 120 meshes, and then adding a proper amount of water, wherein the liquid-solid ratio is 2.0:1 (volume ml/mass g), heating to 90 ℃, reacting for 30min, stirring at a speed of 300r/min in the leaching process, and filtering after the leaching is finished to obtain vanadium-containing leaching solution; collecting vanadium-containing leaching solution, and processing according to (NH) 4 ) 2 SO 4 Adding ammonium sulfate into the ratio of V=2.0, adjusting the pH value of the solution from 9-13 to 2.0 by using dilute sulfuric acid with the volume ratio of 1:1, heating to 100 ℃, and precipitating for 60min to obtain a vanadium-containing compound; 1.47g of the vanadium-containing compound was mixed with 0.87g of lithium carbonate, 2.58g of monoammonium phosphate and 0.48g of sucrose. Mixing, placing into a vacuum tube furnace, roasting at 400 deg.C for 5 hr under argon atmosphere, raising temperature to 850 deg.C, roasting for 12 hr to obtain in-situ Na + Doped lithium vanadium phosphate material.
In example 3, the resulting microscopic morphology photograph of the sodium vanadium compound obtained during precipitation, as shown in fig. 1, consisted of flaky or needle-like particles, disordered microstructure.
In example 3, as shown in fig. 2, according to the scanning electron microscope picture of the prepared sodium doped lithium vanadium phosphate material, the microscopic morphology of the sodium vanadium compound is changed into small irregular spherical particles from the acicular disordered structure of the flaky particles after being mixed with lithium carbonate, ammonium dihydrogen phosphate and sucrose for roasting.
In example 3, as shown in fig. 3, each diffraction peak in the LVP sample graph and JCPDS card: 01-072-7074, indicating that the material is a lithium vanadium phosphate material.
The lithium vanadium phosphate material obtained in example 3 was assembled into a coin cell battery, and its electrochemical performance was tested, the test voltage range was 3.0 to 4.3V, and the test results are shown in table 3.
Table 3 electrochemical performance test results of lithium vanadium phosphate materials of various examples assembled button cells
CV curve test of the lithium vanadium phosphate material prepared in example 3, as shown in FIG. 4; the electrochemical properties of the lithium vanadium phosphate material prepared in example 3 are shown in fig. 5.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (5)
1. Vanadium-containing ore Na + The method for preparing the lithium vanadium phosphate cathode material by in-situ doping is characterized by comprising the following steps:
(1) using convertersThe vanadium slag is used as a basic raw material, ball milling is carried out on the vanadium slag, and refined vanadium slag is obtained after magnetic separation; taking the refined vanadium slag and sodium carbonate according to Na 2 CO 3 /V 2 O 5 Mixing evenly with the mass ratio of 1.6-1.8;
(2) roasting the mixture obtained in the step (1) at 770-790 ℃ in air atmosphere for 30-60min to obtain clinker;
(3) ball milling the clinker obtained in the step (2) to about 120 meshes of particle size, then adding a proper amount of water, heating to 80-90 ℃, reacting for 15-30min, stirring at a speed of 100-300r/min in the leaching process, and filtering after the leaching is finished to obtain vanadium-containing leaching solution;
(4) taking the vanadium-containing leaching solution obtained in the step (3), and carrying out treatment according to (NH) 4 ) 2 SO 4 : adding ammonium sulfate with the mass ratio of V of 1.2-2.0, adjusting the pH value of the solution from 9-10 to 1.8-2.0 by using dilute sulfuric acid with the volume ratio of 1:1, heating to 90-100 ℃, and precipitating for 30-60min to obtain a vanadium-containing compound;
(5) mixing the vanadium-containing compound obtained in the step (4) with lithium carbonate, ammonium dihydrogen phosphate and sucrose; placing the uniformly mixed substances into a vacuum tube furnace, and roasting for 3-5 hours at the temperature of 300-400 ℃ under the argon atmosphere; then the temperature is increased to 800-850 ℃ and roasting is carried out for 8-12h, thus obtaining the in-situ Na + Doped lithium vanadium phosphate material.
2. Vanadium-containing ore Na according to claim 1 + The method for preparing the lithium vanadium phosphate cathode material by in-situ doping is characterized by comprising the following steps of: the ball milling granularity of the vanadium slag in the step (1) is-120 meshes and is more than 80 percent.
3. The method according to claim 1, wherein: the liquid-solid ratio in the step (3) is 1.5-2.0:1.
4. the method according to claim 1, wherein: the vanadium-containing compound in step (5): lithium carbonate: ammonium dihydrogen phosphate: the mass ratio of sucrose is 1:0.592:1.755:0.326.
5. a lithium battery positive electrode material prepared according to the method of any one of claims 1-4.
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