CN115259127A - Preparation method and application of lithium iron manganese phosphate material - Google Patents
Preparation method and application of lithium iron manganese phosphate material Download PDFInfo
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- CN115259127A CN115259127A CN202210932824.7A CN202210932824A CN115259127A CN 115259127 A CN115259127 A CN 115259127A CN 202210932824 A CN202210932824 A CN 202210932824A CN 115259127 A CN115259127 A CN 115259127A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 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 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 28
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 27
- 239000010935 stainless steel Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 24
- 239000008247 solid mixture Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- -1 ferrous manganese salt Chemical class 0.000 claims abstract description 10
- 239000004615 ingredient Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 22
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 229960004793 sucrose Drugs 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000011819 refractory material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009963 fulling Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution 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
-
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a lithium manganese iron phosphate material, which comprises the steps of preparing ingredients of iron phosphate, lithium carbonate, deionized water, a ferrous salt and a ferrous manganese salt, then preparing a first mixed solution and a second mixed solution respectively, adding the second mixed solution into the first mixed solution, continuously mixing and stirring, reacting for 15-18H in a magnetic stirring type hydrothermal kettle to obtain a third mixed solution, filling the third mixed solution into a stainless steel sagger, placing the stainless steel sagger in a drying room, drying for 6-7H to obtain a solid mixture, taking the solid mixture out of the stainless steel sagger, transferring the solid mixture into a rotary furnace for sintering to obtain a solid, grinding the solid by using a grinding machine, screening and filtering the ground powder to obtain fine particles which are the lithium manganese iron phosphate material, wherein the electrode ion conductivity of the lithium manganese iron phosphate material prepared by the method is improved to a certain extent, and the lithium iron phosphate material is suitable for large current and convenient for popularization and application.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium manganese iron phosphate materials, and particularly relates to a preparation method and application of a lithium manganese iron phosphate material.
Background
The lithium manganese iron phosphate is used as a high-voltage phosphate material and is an upgraded product of the lithium iron phosphate material, and the energy density of the lithium manganese iron phosphate battery can be improved by about 20% compared with that of the lithium iron phosphate battery under the same capacity exertion. In the preparation of lithium manganese iron phosphate, an iron source, a manganese source, a phosphorus source and a lithium source are mixed and then crushed to a nanometer size by a sand mill, but the energy consumption of the used high-energy ball milling solid phase method is high, the production efficiency is low, and the uniformity of the obtained particles is poor.
Through retrieval, chinese patent document, application number 202111489423.0, the invention discloses a preparation method of a lithium iron manganese phosphate anode material, and the invention forms uniform nano-particles by tucking reactant adding speed, high-speed stirring and temperature control, and adjusting nucleation and growth speed; then, mixing the doped meta-cord, a carbon source, ammonium dihydrogen phosphate, lithium carbonate and a deposition precursor of a ferro-manganese compound, and sintering at a high temperature to obtain a meta-cord doped lithium manganese iron phosphate anode material; the particles formed by the coprecipitation method have uniform shape and granularity, and compared with the existing high-energy ball-milling solid-phase method, the method has the advantages of lower energy consumption and high production efficiency. The following drawbacks still exist:
the electrode of the lithium iron manganese phosphate material prepared by the method has poor ionic conductivity, is not suitable for large-current charge and discharge, and is blocked in application, so that the preparation method of the lithium iron manganese phosphate material and the application thereof are needed to solve the existing problems.
Disclosure of Invention
The invention aims to provide a preparation method and application of a lithium manganese iron phosphate material, the electrode ionic conductivity of the lithium manganese iron phosphate material prepared by the method is improved to a certain extent, and the lithium manganese iron phosphate material is suitable for large-current charge and discharge so as to solve the problems in the background art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium iron manganese phosphate material comprises the following steps:
s1, preparing ingredients, wherein the ingredients comprise: iron phosphate, lithium carbonate, deionized water, a divalent iron salt and a divalent manganese salt;
s2, weighing iron phosphate and lithium carbonate, adding the weighed iron phosphate and lithium carbonate into a magnetic stirring type hydrothermal kettle, and adding deionized water into a mixing tank to be fully stirred and mixed to obtain a first mixed solution;
s3, adding a ferrous salt and a ferrous manganese salt into a mixing tank, adding deionized water into the mixing tank, and fully stirring and mixing to obtain a second mixed solution;
s4, adding the second mixed solution into the first mixed solution, continuously mixing and stirring, heating the magnetic stirring type hydrothermal kettle to 180-240 ℃, and reacting for 15-18H to obtain a third mixed solution;
s5, filling the third mixed solution into a stainless steel sagger, and placing the stainless steel sagger in a drying room to be dried for 6-7H at the temperature of 65-75 ℃ to obtain a solid mixture;
s6, taking the solid mixture out of the stainless steel sagger, transferring the solid mixture into a rotary furnace, and sintering the solid mixture for 6H-10H at the temperature of 750 +/-20 ℃ to obtain a solid;
and S7, grinding the solid by using a grinder, and screening and filtering the ground powder to obtain fine particles which are the lithium iron manganese phosphate material.
Preferably, in the step S1, the iron phosphate needs to be dried and ground when in use, the iron phosphate is placed in a stainless steel container during drying, the stainless steel container is then placed in a drying chamber to be dried at 220 ℃ ± 10 ℃ for 6-7H, the dried iron phosphate is cooled and then ground by a grinding machine, during specific grinding, lithium carbonate, sucrose and pure water are selected to be mixed and ground to obtain mixed slurry, and the ratio of the lithium carbonate to the sucrose to the pure water is 1:1: and 2, dispersing the mixed slurry by using a dispersion machine, and drying by using spray drying equipment to obtain particles.
Preferably, the lithium carbonate is colorless monoclinic crystal or white powder and has a density of 2.11g/cm 3 The melting point is 723 ℃, and the solvent is soluble in dilute acid, slightly soluble in water and insoluble in alcohol and acetone.
Preferably, in step S2, the usage ratio of the iron phosphate to the lithium carbonate to the deionized water is 1:1: and 6, when the iron phosphate, the lithium carbonate and the deionized water are mixed and stirred in the magnetic stirring type hydrothermal kettle, stirring and mixing are carried out at normal temperature, and the magnetic stirring type hydrothermal kettle does not need to be heated.
Preferably, the ratio of the ferrous salt to the ferrous manganese salt to the deionized water in step S3 is 1:1:2, the blending tank is stainless steel jar or glass jar, and the blending tank uses the glass puddler to carry out manual stirring when the stirring, makes ferrous salt and bivalent manganese salt all fuse with deionized water.
Preferably, the magnetic stirring type hydrothermal kettle in the step S4 comprises a kettle body, a stirrer, a magnetic coupling driver, a heating mechanism and a driving motor, wherein the stirrer is rotatably installed at the inner bottom of the kettle body and is connected with the driving motor through the magnetic coupling driver, and the magnetic coupling driver is a driving device for coupling driving by using a permanent magnet material and is used for driving the stirrer to perform stirring operation; the heating mechanism is arranged on the side wall of the kettle body.
Preferably, the heating mechanism includes heating coil and temperature controller, heating coil fixes inside the cauldron body lateral wall, the temperature controller is installed at the outer wall of the cauldron body, just the temperature controller passes through the wire with heating coil and is connected.
Preferably, in the step S6, the rotary furnace includes a steel cylindrical furnace body, a refractory material is lined in the side wall of the furnace body, the furnace body is driven by a motor through a gear to rotate slowly, a plug is plugged at one end of the furnace body, nitrogen gas needs to be introduced into the furnace body during sintering, and the solid is mixed and sintered under the protection of the nitrogen gas.
Preferably, the powder ground by the grinder in the step S7 is filtered and screened by a screen, the mesh size of the screen is smaller than 50um, and the particles filtered by the screen and larger than 50um need to be secondarily ground and screened by the grinder.
The application of the lithium iron manganese phosphate material prepared by the preparation method of the lithium iron manganese phosphate material in the lithium ion battery is provided.
Compared with the prior art, the preparation method and the application of the lithium iron manganese phosphate material provided by the invention have the following advantages:
the method comprises the steps of firstly preparing ingredients of iron phosphate, lithium carbonate, deionized water, a ferrous salt and a ferrous manganese salt, then respectively preparing a first mixed solution and a second mixed solution, adding the second mixed solution into the first mixed solution, continuously mixing and stirring, heating a magnetic stirring type hydrothermal kettle to 180-240 ℃ for reacting for 15-18H to obtain a third mixed solution, filling the third mixed solution into a stainless steel sagger, placing the stainless steel sagger in a drying room for drying for 6-7H at 65-75 ℃ to obtain a solid mixture, taking the solid mixture out of the stainless steel sagger, transferring the solid mixture into a rotary furnace for sintering for 6H-10H at 750 +/-20 ℃ to obtain a solid, grinding the solid by using a grinder, screening and filtering the ground powder to obtain fine particles of a lithium manganese iron phosphate material.
Drawings
FIG. 1 is a block flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a lithium iron manganese phosphate material as shown in figure 1, which comprises the following steps:
s1, preparing ingredients, wherein the ingredients comprise: iron phosphate, lithium carbonate, deionized water, a ferrous salt and a ferrous manganese salt;
the ferric phosphate need be dried and ground when using, arrange the ferric phosphate in the stainless steel container when drying, put into the drying chamber with the stainless steel container again and carry out 220 ℃ 10 ℃ drying 6-7H, use the machine of grinding after the ferric phosphate cooling after will drying to grind, select lithium carbonate and cane sugar and pure water to mix grinding and obtain mixed slurry during concrete grinding, the proportion of lithium carbonate, cane sugar and pure water is 1:1: and 2, dispersing the mixed slurry by using a dispersing machine, and drying by using spray drying equipment to obtain the particles.
The lithium carbonate is colorless monoclinic crystal or white powder, and the density is 2.11g/cm 3 The melting point is 723 ℃, and the solvent is soluble in dilute acid, slightly soluble in water and insoluble in alcohol and acetone.
S2, weighing iron phosphate and lithium carbonate, adding the weighed iron phosphate and lithium carbonate into a magnetic stirring type hydrothermal kettle, and adding deionized water into a mixing tank to be fully stirred and mixed to obtain a first mixed solution;
the use ratio of the iron phosphate to the lithium carbonate to the deionized water is 1:1: and 6, when the iron phosphate, the lithium carbonate and the deionized water are mixed and stirred in the magnetic stirring type hydrothermal kettle, stirring and mixing are carried out at normal temperature, and the magnetic stirring type hydrothermal kettle does not need to be heated.
S3, adding a ferrous salt and a ferrous manganese salt into a mixing tank, adding deionized water into the mixing tank, and fully stirring and mixing to obtain a second mixed solution;
the use ratio of the ferrous salt to the ferrous manganese salt to the deionized water is 1:1:2, the blending tank is stainless steel jar or glass jar, and the blending tank uses the glass puddler to carry out manual stirring when the stirring, makes ferrous salt and manganous salt all fuse with deionized water.
S4, adding the second mixed solution into the first mixed solution, continuously mixing and stirring, heating the magnetic stirring type hydrothermal kettle to 180-240 ℃, and reacting for 15-18H to obtain a third mixed solution;
the magnetic stirring type hydrothermal kettle comprises a kettle body, a stirrer, a magnetic coupling driver, a heating mechanism and a driving motor, wherein the stirrer is rotatably arranged at the inner bottom of the kettle body and is connected with the driving motor through the magnetic coupling driver, and the magnetic coupling driver is a driving device for coupling transmission by using a permanent magnet material and is used for driving the stirrer to stir; the heating mechanism is arranged on the side wall of the kettle body.
Heating mechanism includes heating coil and temperature controller, heating coil fixes inside the cauldron body lateral wall, the temperature controller is installed at the outer wall of the cauldron body, just the temperature controller passes through the wire with heating coil and is connected.
S5, filling the third mixed solution into a stainless steel sagger, and placing the stainless steel sagger in a drying room to be dried for 6-7H at the temperature of 65-75 ℃ to obtain a solid mixture;
s6, taking the solid mixture out of the stainless steel sagger, transferring the solid mixture into a rotary furnace, and sintering the solid mixture for 6H-10H at the temperature of 750 +/-20 ℃ to obtain a solid;
the rotary furnace comprises a steel cylindrical furnace body, a refractory material is lined in the side wall of the furnace body, the furnace body is driven by a motor to rotate slowly through a gear, a plug cover is plugged at one end of the furnace body, nitrogen needs to be introduced into the furnace body during sintering, and solid is mixed and sintered under the protection of nitrogen.
S7, grinding the solid by using a grinder, and screening and filtering the ground powder to obtain fine particles which are lithium iron manganese phosphate materials;
grind powder after the machine grinds and use the screen cloth to filter the screening, the mesh size of screen cloth is less than 50um, the screen cloth filters out particulate matter that is greater than 50um and need use the machine of grinding to need carry out secondary grinding and screening.
The lithium iron manganese phosphate material prepared by the method and the lithium iron manganese phosphate material prepared by the existing method respectively select five samples and use a conductivity meter to carry out conductivity detection, and the detection results are as follows:
(the prior method is a preparation method of a lithium iron manganese phosphate anode material disclosed by the patent number 202111489423.0)
| Categories | This application (s/cm) | Existing methods (s/cm) |
| 1 st time | 1.08*10 -1 | 0.88*10 -1 |
| 2 nd time | 1.3*10 -1 | 0.73*10 -1 |
| 3 rd time | 1.15*10 -1 | 0.81*10 -1 |
| 4 th time | 1.23*10 -1 | 0.79*10 -1 |
| 5 th time | 1.16*10 -1 | 0.83*10 -1 |
The test results of the tables show that the conductivity of the lithium iron manganese phosphate material prepared by the method is obviously improved compared with the conductivity of the lithium iron manganese phosphate material prepared by the existing method, so that the lithium iron manganese phosphate material is convenient for large-current charge and discharge.
The application of the lithium iron manganese phosphate material prepared by the preparation method of the lithium iron manganese phosphate material in the lithium ion battery is provided.
In summary, ingredients of iron phosphate, lithium carbonate, deionized water, a ferrous iron salt and a ferrous manganese salt are prepared firstly, then a first mixed solution and a second mixed solution are prepared respectively, the second mixed solution is added into the first mixed solution to be mixed and stirred continuously, a magnetic stirring type hydrothermal kettle is heated to 180-240 ℃ to react for 15-18H to obtain a third mixed solution, the third mixed solution is filled into a stainless steel sagger, the stainless steel sagger is placed in a drying room to be dried for 6-7H at 65-75 ℃ to obtain a solid mixture, the solid mixture is taken out of the stainless steel sagger and is transferred into a rotary furnace to be sintered for 6H-10H at 750 +/-20 ℃ to obtain a solid, the solid is ground by a grinding machine, the ground powder is screened and filtered, the fine particles are a lithium manganese iron phosphate material, the conductivity of the lithium manganese iron phosphate material prepared by the method is improved to a certain extent, and the lithium iron phosphate material is suitable for large-current charging and discharging and is convenient for popularization and application.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a lithium iron manganese phosphate material is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing ingredients, wherein the ingredients comprise: iron phosphate, lithium carbonate, deionized water, a divalent iron salt and a divalent manganese salt;
s2, weighing iron phosphate and lithium carbonate, adding the weighed iron phosphate and lithium carbonate into a magnetic stirring type hydrothermal kettle, and adding deionized water into a mixing tank to be fully stirred and mixed to obtain a first mixed solution;
s3, adding a ferrous salt and a ferrous manganese salt into a mixing tank, adding deionized water into the mixing tank, and fully stirring and mixing to obtain a second mixed solution;
s4, adding the second mixed solution into the first mixed solution, continuously mixing and stirring, heating the magnetic stirring type hydrothermal kettle to 180-240 ℃, and reacting for 15-18H to obtain a third mixed solution;
s5, filling the third mixed solution into a stainless steel sagger, and placing the stainless steel sagger in a drying room to be dried for 6-7H at the temperature of 65-75 ℃ to obtain a solid mixture;
s6, taking the solid mixture out of the stainless steel sagger, transferring the solid mixture into a rotary furnace, and sintering the solid mixture for 6H-10H at the temperature of 750 +/-20 ℃ to obtain a solid;
and S7, grinding the solid by using a grinder, and screening and filtering the ground powder to obtain fine particles which are the lithium iron manganese phosphate material.
2. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps that in the step S1, the iron phosphate is required to be dried and ground when in use, the iron phosphate is placed in a stainless steel container when being dried, then the stainless steel container is placed in a drying chamber to be dried for 6-7H at the temperature of 220 +/-10 ℃, the dried iron phosphate is cooled and then ground by using a grinding machine, during specific grinding, lithium carbonate, cane sugar and pure water are selected to be mixed and ground to obtain mixed slurry, and the proportion of the lithium carbonate, the cane sugar and the pure water is 1:1: and 2, dispersing the mixed slurry by using a dispersion machine, and drying by using spray drying equipment to obtain particles.
3. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: the lithium carbonate is colorless monoclinic crystal or white powder, and the density is 2.11g/cm 3 The melting point is 723 ℃, and the solvent is soluble in dilute acid, slightly soluble in water and insoluble in alcohol and acetone.
4. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: in the step S2, the use ratio of the iron phosphate to the lithium carbonate to the deionized water is 1:1: and 6, when the iron phosphate, the lithium carbonate and the deionized water are mixed and stirred in the magnetic stirring type hydrothermal kettle, stirring and mixing are carried out at normal temperature, and the magnetic stirring type hydrothermal kettle does not need to be heated.
5. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: in the step S3, the use ratio of the ferrous salt to the ferrous manganese salt to the deionized water is 1:1:2, the blending tank is stainless steel jar or glass jar, and the blending tank uses the glass puddler to carry out manual stirring when the stirring, makes ferrous salt and bivalent manganese salt all fuse with deionized water.
6. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: the magnetic stirring type hydrothermal kettle in the step S4 comprises a kettle body, a stirrer, a magnetic coupling driver, a heating mechanism and a driving motor, wherein the stirrer is rotatably installed at the inner bottom of the kettle body and is connected with the driving motor through the magnetic coupling driver, and the magnetic coupling driver is a driving device which is used for carrying out coupling driving by using a permanent magnet material and is used for driving the stirrer to carry out stirring operation; the heating mechanism is arranged on the side wall of the kettle body.
7. The method for preparing the lithium iron manganese phosphate material according to claim 6, wherein the method comprises the following steps: heating mechanism includes heating coil and temperature controller, heating coil fixes inside the cauldron lateral wall, the outer wall at the cauldron body is installed to the temperature controller, just the temperature controller passes through the wire with heating coil and is connected.
8. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: and S6, the rotary furnace comprises a steel cylindrical furnace body, a refractory material is lined in the side wall of the furnace body, the furnace body is driven by a motor to rotate slowly through a gear, a plug cover is sealed at one end of the furnace body, nitrogen is required to be introduced into the furnace body during sintering, and the solid is mixed and sintered under the protection of the nitrogen.
9. The method for preparing the lithium iron manganese phosphate material according to claim 1, wherein the method comprises the following steps: and S7, filtering and screening the powder ground by the grinder by using a screen, wherein the mesh size of the screen is less than 50um, and the particles filtered out by the screen and larger than 50um need to be secondarily ground and screened by using the grinder.
10. An application of the lithium iron manganese phosphate material prepared by the preparation method of the lithium iron manganese phosphate material in the lithium ion battery, according to any one of claims 1 to 9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014034775A1 (en) * | 2012-08-31 | 2014-03-06 | 戸田工業株式会社 | Method for producing carbon composite lithium manganese iron phosphate particle powder, carbon composite lithium manganese iron phosphate particle powder, and nonaqueous electrolyte secondary battery using carbon composite lithium manganese iron phosphate particle powder |
| CN104934601A (en) * | 2015-06-15 | 2015-09-23 | 北京石油化工学院 | Preparation method of lithium manganese ferric phosphate anode material |
| CN107697895A (en) * | 2017-09-13 | 2018-02-16 | 苏州安锰新能源科技有限公司 | A kind of nanoporous manganese pyrophosphate and preparation method thereof |
| CN110600708A (en) * | 2019-09-25 | 2019-12-20 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of step-by-step metal ion-doped and carbon-coated lithium iron phosphate positive electrode material |
| CN114014292A (en) * | 2021-11-04 | 2022-02-08 | 湖南安尔信新材料有限责任公司 | Preparation method of lithium iron manganese phosphate |
| WO2022111186A1 (en) * | 2020-11-24 | 2022-06-02 | 上海华谊新材料有限公司 | Lithium iron manganese phosphate composite, preparation method therefor, and lithium-ion battery positive electrode |
| CN114583313A (en) * | 2022-03-11 | 2022-06-03 | 江苏协鑫锂电科技有限公司 | Method for recycling waste phosphate positive electrode material |
-
2022
- 2022-08-04 CN CN202210932824.7A patent/CN115259127A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014034775A1 (en) * | 2012-08-31 | 2014-03-06 | 戸田工業株式会社 | Method for producing carbon composite lithium manganese iron phosphate particle powder, carbon composite lithium manganese iron phosphate particle powder, and nonaqueous electrolyte secondary battery using carbon composite lithium manganese iron phosphate particle powder |
| CN104934601A (en) * | 2015-06-15 | 2015-09-23 | 北京石油化工学院 | Preparation method of lithium manganese ferric phosphate anode material |
| CN107697895A (en) * | 2017-09-13 | 2018-02-16 | 苏州安锰新能源科技有限公司 | A kind of nanoporous manganese pyrophosphate and preparation method thereof |
| CN110600708A (en) * | 2019-09-25 | 2019-12-20 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of step-by-step metal ion-doped and carbon-coated lithium iron phosphate positive electrode material |
| WO2022111186A1 (en) * | 2020-11-24 | 2022-06-02 | 上海华谊新材料有限公司 | Lithium iron manganese phosphate composite, preparation method therefor, and lithium-ion battery positive electrode |
| CN114014292A (en) * | 2021-11-04 | 2022-02-08 | 湖南安尔信新材料有限责任公司 | Preparation method of lithium iron manganese phosphate |
| CN114583313A (en) * | 2022-03-11 | 2022-06-03 | 江苏协鑫锂电科技有限公司 | Method for recycling waste phosphate positive electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 饶媛媛;王康平;曾晖;: "磷酸锰铁锂材料在锂电池中的研究进展", 电源技术, no. 02 * |
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