CN110970618A - Preparation method of low-cost lithium iron phosphate composite material - Google Patents
Preparation method of low-cost lithium iron phosphate composite material Download PDFInfo
- Publication number
- CN110970618A CN110970618A CN201911330250.0A CN201911330250A CN110970618A CN 110970618 A CN110970618 A CN 110970618A CN 201911330250 A CN201911330250 A CN 201911330250A CN 110970618 A CN110970618 A CN 110970618A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium
- lithium iron
- low
- phosphate composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000006258 conductive agent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 239000004576 sand Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010790 dilution Methods 0.000 claims abstract description 7
- 239000012895 dilution Substances 0.000 claims abstract description 7
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 7
- 238000010902 jet-milling Methods 0.000 claims abstract description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a low-cost lithium iron phosphate composite material, which comprises the following steps of mixing lithium carbonate, an iron source and a doping element source, wherein the molar ratio of a lithium element to the iron element to the doping element is 0.95-1.05: 0.95-1.05: 0-0.05, adding an organic carbon source to obtain a mixed material A, wherein the iron source is a mixture of ferric oxide and ferric phosphate; adding phosphoric acid into pure water for dilution, adding the mixed material A for ball milling, adding the nano graphite conductive agent for uniform dispersion, then transferring into a sand mill for grinding, and performing spray drying to obtain a material B; wherein the molar ratio of the phosphorus element to the lithium element is 0.95-1.05: 0.95 to 1.05; placing the material B in an atmosphere furnace, heating up to 550-750 ℃ in an inert atmosphere, sintering at a constant temperature for 5-12 hours, and cooling to obtain a lithium iron phosphate sintered material C; and carrying out jet milling on the sintered material C to obtain the lithium iron phosphate anode material. The invention reduces the cost of raw materials, optimizes the synthesis process and greatly improves the material performance.
Description
Technical Field
The invention belongs to the technical field of lithium iron phosphate positive electrode material production processes, and particularly relates to a preparation method of a low-cost lithium iron phosphate composite material.
Background
The lithium iron phosphate material has the advantages of stable phosphorus-oxygen co-bonded structure, good cycle performance, excellent safety, rich and cheap raw materials and the like, and becomes one of the first choices of the anode material of the lithium ion power battery. However, the space structure of the lithium iron phosphate determines that the lithium iron phosphate has slow ionic conductivity and low electronic conductivity, and the battery has serious influence on large-current discharge and poor rate capability.
At present, the mainstream process of the domestic lithium iron phosphate anode material manufacturer is an iron phosphate line, and the lithium iron phosphate material prepared by the process has the characteristics of high capacity, excellent performance and higher cost, while the iron oxide line adopted has lower cost and poorer material performance.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a low-cost lithium iron phosphate composite material, which adopts cheap iron oxide and phosphoric acid as raw materials, reduces the cost of the raw materials, optimizes the raw materials in the synthesis process, and greatly improves the material performance by using a modifier, a mixed iron source and the like.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a low-cost lithium iron phosphate composite material comprises the following steps,
(1) mixing lithium carbonate, an iron source and a doping element source, wherein the molar ratio of lithium element to iron element to the doping element is 0.95-1.05: 0.95-1.05: 0-0.05, adding an organic carbon source to obtain a mixed material A, wherein the iron source is a mixture of ferric oxide and ferric phosphate;
(2) adding phosphoric acid into pure water for dilution, adding the mixed material A for ball milling, adding the nano graphite conductive agent for uniform dispersion, then transferring into a sand mill for grinding, and performing spray drying to obtain a material B; wherein the molar ratio of the phosphorus element to the lithium element is 0.95-1.05: 0.95 to 1.05;
(3) placing the material B in an atmosphere furnace, heating up to 550-750 ℃ in an inert atmosphere, sintering at a constant temperature for 5-12 hours, and cooling to obtain a lithium iron phosphate sintered material C;
(4) and carrying out jet milling on the sintered material C to obtain the lithium iron phosphate anode material.
Preferably, in the step 1), the weight ratio of ferric phosphate in the mixture of iron sources is 5-15%.
Preferably, in step 1), the doping element includes one or more of Ti, Zn, Mn, Zr, Mg, Al, V, Cr, and Nb.
Preferably, in step 1), the organic carbon source comprises one or more than two of glucose, sucrose and polyethylene glycol; the mass of the organic carbon source is 5-10% of the total mass.
Preferably, in the step 2), the amount of the added nano graphite conductive agent is 0.5-2% of the total mass; the sand grinding is performed to control the granularity D50 to be 0.3-0.45 μm.
Preferably, in the step 3), the temperature is increased at a heating rate of 5-20 ℃/min under an inert atmosphere.
Preferably, in step 3), the inert gas is one or two of nitrogen, argon and neon.
The invention also provides a positive electrode, which comprises the lithium iron phosphate composite material prepared by the preparation method.
The invention also provides a lithium ion battery, which is characterized in that: comprising the lithium iron phosphate composite material obtained by the preparation method or the positive electrode.
Compared with the prior art, the preparation method of the low-cost lithium iron phosphate composite material has the following advantages:
the invention adopts cheap ferric oxide and phosphoric acid as iron source and phosphorus source, thus effectively reducing the cost of raw materials; meanwhile, the nano graphite conductive agent is used, so that the electronic conductivity of the material is greatly improved, and a small amount of iron phosphate is doped in the iron oxide, so that the material performance is promoted, the particles are nano, and the lithium ion migration rate is increased. The lithium iron phosphate material prepared by the invention has high capacity, good multiplying power, easy processing and other excellent performances.
Drawings
Fig. 1 is an SEM image of a lithium iron phosphate composite prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the lithium iron phosphate composite prepared in comparative example 1 according to the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
Lithium carbonate, an iron source and titanium dioxide are mixed according to the mol ratio of Li: fe: ti is 0.95: 1: 0.01, mixing, wherein the iron source is a mixture of ferric oxide and iron phosphate, the mass percent of the iron phosphate is 5%, and adding a carbon source (sucrose) according to 5% of the total mass of the materials to obtain a mixed material A;
slowly pouring phosphoric acid into a ball milling tank with pure water for dilution, adding the mixed material A for ball milling (the molar ratio of phosphorus element to lithium element is 1:1 in the whole solution), simultaneously adding a nano graphite conductive agent according to 0.5 percent of the total mass of the materials, then transferring into a sand mill for grinding, controlling the particle size D50 to be 0.45 mu m, then drying by spraying to obtain a material B, placing the material B into an atmosphere furnace, and putting the material B into an N atmosphere furnace2Heating to 750 ℃ at the speed of 8 ℃/min under the atmosphere, sintering for 6h at the constant temperature, naturally cooling to obtain a material C, and carrying out jet milling on the material C to obtain the lithium iron phosphate anode material.
Example 2:
lithium carbonate, an iron source and niobium pentoxide are mixed according to the mol ratio of Li: fe: nb is 1.05: 1: 0.02, mixing, wherein the iron source is a mixture of ferric oxide and ferric phosphate, the mass percent of the ferric phosphate is 10%, and adding a carbon source (the carbon source comprises sucrose and polyethylene glycol in a mass ratio of 7:3) according to 8% of the total mass of the materials to obtain a mixed material A;
slowly pouring phosphoric acid into a ball milling tank with pure water for dilution, adding the mixed material A for ball milling (the molar ratio of phosphorus element to lithium element is 1:1 in the whole solution), simultaneously adding a nano graphite conductive agent according to 1.2% of the total mass of the materials, then transferring into a sand mill for grinding, controlling the particle size D50 to be 0.38 mu m, then drying by spraying to obtain a material B, placing the material B into an atmosphere furnace, and putting the material B into an N atmosphere furnace2Heating to 680 ℃ at a speed of 14 ℃/min under the atmosphere, sintering for 9h at a constant temperature, naturally cooling to obtain a material C, and carrying out jet milling on the material C to obtain the lithium iron phosphate anode material.
Example 3:
lithium carbonate, an iron source, phosphoric acid and vanadium pentoxide are mixed according to the mol ratio of Li: fe: v is 1: 1.05: 0.04, wherein the iron source is a mixture of ferric oxide and iron phosphate, the mass percent of the iron phosphate is 15%, and a carbon source (the carbon source is glucose) is added according to 10% of the total mass of the materials to obtain a mixed material A;
slowly pouring phosphoric acid into a ball milling tank with pure water for dilution, adding the mixed material A for ball milling (the molar ratio of phosphorus element to lithium element is 1:1 in the whole solution), simultaneously adding a nano graphite conductive agent according to 2% of the total mass of the materials, then transferring into a sand mill for grinding, controlling the particle size D50 to be 0.3 mu m, then performing spray drying to obtain a material B, placing the material B into an atmosphere furnace, and putting the material B into an N atmosphere furnace2Heating to 600 ℃ at a speed of 20 ℃/min under the atmosphere, sintering at the constant temperature for 12h, naturally cooling to obtain a material C, and carrying out jet milling on the material C to obtain the lithium iron phosphate anode material.
Comparative example 1:
lithium carbonate, ferric oxide and niobium pentoxide are mixed according to the mol ratio of Li: fe: nb is 1.05: 1: 0.02, mixing, and adding a carbon source (glucose is used as the carbon source) according to 10% of the total mass of the materials to obtain a mixed material A;
slowly pouring phosphoric acid into a ball milling tank with pure water added in advance for dilution, and then addingBall milling the mixed material A (the molar ratio of phosphorus element to lithium element in the whole solution is 0.95: 1.05), then drying by spraying to obtain a material B, placing the material B in an atmosphere furnace, and performing N reaction on the material B2Heating to 700 ℃ at a speed of 15 ℃/min under the atmosphere, sintering at the constant temperature for 10h, naturally cooling to obtain a material C, and carrying out jet milling on the material C to obtain the lithium iron phosphate anode material.
And (3) performance testing:
(1) preparation of the Battery
Preparation of the Positive electrode
93 g of positive electrode active materials LiFePO obtained in examples 1 to 3 and comparative example 1 were added to the reaction solution45 g of polyvinylidene fluoride (PVDF) as a binder and 3 g of acetylene black as a conductive agent were added to 85 g of N-methylpyrrolidone, and then stirred in a vacuum stirrer to form a uniform positive electrode slurry. The positive electrode slurry was uniformly coated on both sides of an aluminum foil having a thickness of 16 μm, and then dried at 118 ℃, rolled, and cut to obtain a positive electrode having a size of 540 × 43.5 mm, which contained about 6.5 g of an active ingredient LiFePO4。
Preparation of the negative electrode
93 g of natural graphite as a negative active ingredient, 1.4 g of CMC and 2g of carbon black as a conductive agent are added into 120 g of deionized water, then the mixture is stirred uniformly in a vacuum stirrer, and finally 1.6 g of SBR is added to be stirred slowly for 40 minutes to form uniform negative electrode slurry. The negative electrode slurry was uniformly coated on both sides of a copper foil having a thickness of 8 μm, and then dried at 90 c, rolled, and cut to obtain a negative electrode having a size of 500 × 44 mm, which contained about 3.7 g of natural graphite as an active ingredient.
Assembly of a battery
Respectively winding the positive electrode, the negative electrode and the polyethylene film into a pole core of a square lithium ion battery, and then winding LiPF6The electrolyte was dissolved in a mixed solvent of EC/EMC/DEC ═ 1:1:1 at a concentration of 1 mol/liter to prepare a nonaqueous electrolyte, and the electrolyte was poured into a battery aluminum case at an amount of 3.2g/Ah and sealed to prepare lithium ion secondary batteries a1-A3 and B1, respectively.
(2) Battery performance testing
Respectively placing the prepared lithium ion batteries A, B, C, D on a test cabinet, and carrying out constant-current and constant-voltage charging at 1C in a constant temperature box of 25 ℃, wherein the upper limit of charging is 3.65V; after standing for 20 minutes, discharging from 3.65 volts to 2.0 volts by using 1C current, recording the first discharge capacity of the battery, and then performing constant-current constant-voltage charging by using 1C current, wherein the upper limit of the charging is 3.65 volts, and the specific data are shown in the following table:
TABLE 1 comparison of full cell capacity and rate performance data
From the data in the table above, it can be seen that the battery prepared by the positive electrode material prepared by the method of the present invention has much higher 0.1C capacity and rate capability than the reference battery prepared by the comparative example, and also has excellent cycle and processing properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a low-cost lithium iron phosphate composite material is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(1) mixing lithium carbonate, an iron source and a doping element source, wherein the molar ratio of lithium element to iron element to the doping element is 0.95-1.05: 0.95-1.05: 0-0.05, adding an organic carbon source to obtain a mixed material A, wherein the iron source is a mixture of ferric oxide and ferric phosphate;
(2) adding phosphoric acid into pure water for dilution, adding the mixed material A for ball milling, adding the nano graphite conductive agent for uniform dispersion, then transferring into a sand mill for grinding, and performing spray drying to obtain a material B; wherein the molar ratio of the phosphorus element to the lithium element is 0.95-1.05: 0.95 to 1.05;
(3) placing the material B in an atmosphere furnace, heating up to 550-750 ℃ in an inert atmosphere, sintering at a constant temperature for 5-12 hours, and cooling to obtain a lithium iron phosphate sintered material C;
(4) and carrying out jet milling on the sintered material C to obtain the lithium iron phosphate anode material.
2. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 1), the weight ratio of ferric phosphate in the mixture of the iron sources is 5-15%.
3. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 1), the doping elements comprise one or more than two of Ti, Zn, Mn, Zr, Mg, Al, V, Cr and Nb.
4. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 1), the organic carbon source comprises one or more than two of glucose, sucrose and polyethylene glycol; the mass of the organic carbon source is 5-10% of the total mass.
5. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 2), the amount of the added nano graphite conductive agent is 0.5-2% of the total mass; the sand grinding is performed to control the granularity D50 to be 0.3-0.45 μm.
6. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 3), heating at a heating rate of 5-20 ℃/min in an inert atmosphere.
7. The method of preparing a low-cost lithium iron phosphate composite according to claim 1, wherein: in the step 3), the inert gas is one or more than two of nitrogen, argon and neon.
8. A positive electrode characterized in that: the lithium iron phosphate composite material obtained by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery, characterized by: the lithium iron phosphate composite material obtained by the preparation method according to any one of claims 1 to 7 or the positive electrode according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911330250.0A CN110970618A (en) | 2019-12-20 | 2019-12-20 | Preparation method of low-cost lithium iron phosphate composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911330250.0A CN110970618A (en) | 2019-12-20 | 2019-12-20 | Preparation method of low-cost lithium iron phosphate composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110970618A true CN110970618A (en) | 2020-04-07 |
Family
ID=70035613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911330250.0A Pending CN110970618A (en) | 2019-12-20 | 2019-12-20 | Preparation method of low-cost lithium iron phosphate composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110970618A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113321197A (en) * | 2021-05-27 | 2021-08-31 | 合肥国轩电池材料有限公司 | Lithium iron phosphate material and preparation method thereof |
| WO2023174130A1 (en) * | 2022-03-14 | 2023-09-21 | 湖北万润新能源科技股份有限公司 | Iron-based composite phosphate positive electrode material and preparation method therefor, positive plate and sodium ion battery |
| WO2024011621A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Lithium manganese iron phosphate positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electric device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101973539A (en) * | 2010-10-28 | 2011-02-16 | 浙江瑞邦科技有限公司 | Method for synthesizing lithium iron phosphate anode material at low cost |
| CN102013490A (en) * | 2010-11-02 | 2011-04-13 | 三峡大学 | High rate lithium iron phosphate anode material and preparation method thereof |
| CN104409732A (en) * | 2014-12-11 | 2015-03-11 | 上海宝钢磁业有限公司 | Preparation method for lithium iron phosphate material by adopting mixed iron source |
| CN110247036A (en) * | 2019-06-10 | 2019-09-17 | 张雪花 | A kind of LiFePO based on lithium ion battery4Base composite positive pole and preparation method |
-
2019
- 2019-12-20 CN CN201911330250.0A patent/CN110970618A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101973539A (en) * | 2010-10-28 | 2011-02-16 | 浙江瑞邦科技有限公司 | Method for synthesizing lithium iron phosphate anode material at low cost |
| CN102013490A (en) * | 2010-11-02 | 2011-04-13 | 三峡大学 | High rate lithium iron phosphate anode material and preparation method thereof |
| CN104409732A (en) * | 2014-12-11 | 2015-03-11 | 上海宝钢磁业有限公司 | Preparation method for lithium iron phosphate material by adopting mixed iron source |
| CN110247036A (en) * | 2019-06-10 | 2019-09-17 | 张雪花 | A kind of LiFePO based on lithium ion battery4Base composite positive pole and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113086959B (en) * | 2021-02-26 | 2022-03-01 | 云南航开科技有限公司 | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113321197A (en) * | 2021-05-27 | 2021-08-31 | 合肥国轩电池材料有限公司 | Lithium iron phosphate material and preparation method thereof |
| CN113321197B (en) * | 2021-05-27 | 2023-11-07 | 合肥国轩电池材料有限公司 | Lithium iron phosphate material and preparation method thereof |
| WO2023174130A1 (en) * | 2022-03-14 | 2023-09-21 | 湖北万润新能源科技股份有限公司 | Iron-based composite phosphate positive electrode material and preparation method therefor, positive plate and sodium ion battery |
| WO2024011621A1 (en) * | 2022-07-15 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Lithium manganese iron phosphate positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery and electric device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9634315B2 (en) | Carbon containing binderless electrode formation | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| JP5278994B2 (en) | Lithium secondary battery | |
| CN112768687A (en) | Lithium-site-doped modified high-nickel low-cobalt ternary cathode material for lithium ion battery and preparation method thereof | |
| CN110970618A (en) | Preparation method of low-cost lithium iron phosphate composite material | |
| CN114759179A (en) | Method for synthesizing anode material sodium iron phosphate for sodium ion battery | |
| CN114665058A (en) | Preparation method of lithium ion battery anode material lithium iron manganese phosphate | |
| CN112490518A (en) | Positive electrode lithium supplement additive, preparation method thereof, positive electrode and lithium ion battery | |
| CN111082038A (en) | Low-boron-content lithium-boron alloy electrode material for lithium battery and application | |
| CN102339999B (en) | Polyanion composite material, its preparation method and application | |
| CN115810744A (en) | Double-coated positive electrode material and preparation method and application thereof | |
| CN114094089A (en) | Positive electrode lithium supplement additive, preparation thereof and application thereof in lithium supplement of positive electrode of lithium ion battery | |
| CN107645016A (en) | A kind of lithium sulphur electrolyte of negative pole lithium protection and preparation method thereof | |
| CN104393291A (en) | LiFePO4 positive electrode material modified jointly by doping and coating and preparation method thereof | |
| CN115642257A (en) | Lithium supplement agent, preparation method thereof, positive electrode material and lithium ion battery | |
| CN109980221B (en) | High-voltage lithium ion battery positive electrode material and preparation method and application thereof | |
| CN101651198A (en) | Doped lithium iron phosphate material and preparation method and application thereof | |
| CN114937809A (en) | Organic electrolyte with low freezing point and sodium ion battery using same | |
| CN109309207B (en) | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery | |
| CN111864189B (en) | Lithium battery positive electrode material and preparation method thereof | |
| CN118198354A (en) | Battery positive electrode material and preparation method thereof | |
| CN109273670A (en) | A kind of lithium anode and preparation method thereof with high-specific-surface mesoporous protective film | |
| CN117790795A (en) | Doped multi-layer coated iron phosphate-based sodium ion battery positive electrode material and preparation method thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN117525391A (en) | Polyanion positive electrode material of sodium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200407 |
|
| RJ01 | Rejection of invention patent application after publication |