CN114497538A - Gradient-coated high-performance lithium iron phosphate composite material and preparation method thereof - Google Patents
Gradient-coated high-performance lithium iron phosphate composite material and preparation method thereof Download PDFInfo
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- CN114497538A CN114497538A CN202111678935.1A CN202111678935A CN114497538A CN 114497538 A CN114497538 A CN 114497538A CN 202111678935 A CN202111678935 A CN 202111678935A CN 114497538 A CN114497538 A CN 114497538A
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- iron phosphate
- lithium iron
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- 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 179
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 147
- 239000000463 material Substances 0.000 claims abstract description 122
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims description 69
- 238000002156 mixing Methods 0.000 claims description 59
- 239000013078 crystal Substances 0.000 claims description 55
- 239000002002 slurry Substances 0.000 claims description 49
- 238000004321 preservation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 6
- 238000010902 jet-milling Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 3
- 238000007599 discharging Methods 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 238000005056 compaction Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 229910000398 iron phosphate Inorganic materials 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 239000004576 sand Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 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 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- H01M4/36—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention discloses a preparation method of a gradient-coated high-performance lithium iron phosphate composite material. According to the method, different coating modifications are respectively carried out on primary particles of the material according to different sizes, so that the large, medium and small particles of the material have gradient, uniform and complete coating layers, and particularly, the small particles with small sizes and larger than the surface in the material are better coated and modified, and the structural stability of the whole particles of the material is greatly improved. The capacity retention rate of a battery 1C prepared from the lithium iron phosphate composite material prepared by the method is more than 98.0% in 200 cycles of charging and discharging, and the compaction density of the lithium iron phosphate composite material is 2.61g/cm3The above.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a gradient-coated high-performance lithium iron phosphate composite material and a preparation method thereof.
Background
In recent years, the application field of the lithium ion battery is continuously expanded due to the characteristics of portability, high efficiency, long cycle life, good safety performance and the like, and the lithium ion battery is gradually applied to the field of electric automobiles. The lithium iron phosphate is widely researched and applied due to the fact that the lithium iron phosphate is high in charging and discharging efficiency, good in cycling stability, more durable in battery, high in safety, low in price and rich in resources, but due to the fact that the electronic conductivity and the ionic conductivity of the lithium iron phosphate are low, the lithium iron phosphate material in the lithium iron phosphate cannot be fully utilized under the condition of high-current charging and discharging, the theoretical capacity of the lithium iron phosphate cannot be exerted in the actual application process, the electrochemical performance of the lithium iron phosphate is poor, and therefore some modification means are generally adopted to improve the performance of the lithium iron phosphate in the actual application.
Patent CN 104821399B discloses a method for preparing a lithium iron phosphate positive electrode material by adding a conductive polymer into a lithium iron phosphate material, which effectively improves the rate capability of a battery, and the method is not enough in that the coated lithium ions in small particles are more likely to participate in the reaction of SEI film formation, and the lost lithium is more than large particles, so that the small particles are more likely to cause lithium loss, and the rate capability of the material is often poor when the layer is thicker.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a gradient-coated high-performance lithium iron phosphate composite material, and the compaction density of the lithium iron phosphate composite material is 2.61g/cm3As described above, the lithium iron phosphate composite material is used for preparing a battery with 1C discharge capacity of more than 150.8mAh/g and 1C charge-discharge capacity retention rate of more than 98.0% in 200 cycles.
The invention also aims to provide a preparation method of the gradient coated lithium iron phosphate composite material.
A preparation method of a gradient-coated high-performance lithium iron phosphate composite material comprises the following steps:
s1, preparing a small-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.05: 1-1.06: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.15-0.25 mu m, spray drying, and performing primary sintering and crushing to obtain a small-particle lithium iron phosphate single crystal material;
mixing the small-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.3-0.4% of the mass of the small-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain the small-particle lithium iron phosphate material;
s2, preparing a medium-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.03: 1-1.04: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.35-0.45 mu m, spray drying, and sintering and crushing for one time to obtain a medium-particle lithium iron phosphate single crystal material;
mixing the medium-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.2-0.3% of the mass of the medium-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain a medium-particle lithium iron phosphate material;
s3, preparing a large-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.01: 1-1.02: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.55-0.65 mu m, spray drying, and sintering and crushing for one time to obtain a large-particle lithium iron phosphate single crystal material;
mixing a large-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.1-0.2% of the mass of the large-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain a large-particle lithium iron phosphate material;
s4, preparing a lithium iron phosphate composite material:
and mixing the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material in proportion, adding a carbon source, sintering for three times, screening and demagnetizing to obtain the lithium iron phosphate composite material.
In the scheme, the lithium iron phosphate composite material is prepared by adopting a gradient coating method, lithium iron phosphate is ground until the granularity D50 is 0.15-0.25 mu m, the granularity D50 is 0.35-0.45 mu m, and the granularity D50 is 0.55-0.65 mu m, lithium iron phosphate single crystal materials with different particle sizes are prepared, then the lithium iron phosphate single crystal materials are respectively coated and modified, secondary sintering is carried out at the temperature of 750-850 ℃, and the lithium iron phosphate composite material obtained by mixing and sintering for three times has gradient, uniform and complete coating, so that the whole particle structure stability of the material is better, the lithium content in small, medium and large lithium iron phosphate materials in the lithium iron phosphate composite material is gradually increased, the defect that the loss of small particles in the first charging and discharging process is more than that of large particles is overcome, and the whole particle structure stability of the material is greatly improved, so that the compaction density, energy density and rate capability of the lithium iron phosphate composite material are improved.
In the steps S1 to S2, the grinded particles produce sphere-like secondary particles composed of primary particles in the sintering process, and the air flow pulverization in the steps S1 to S2 opens the agglomerated secondary particles to exist independently in a separated primary particle state. The jet milling mode is adopted, and primary particles with smaller volume cannot be damaged.
Preferably, in the steps S1 to S3, the deionized water is added according to the proportion that the solid content of the mixed slurry is 40-60%.
Preferably, in the step S1, the primary sintering temperature for preparing the small-particle lithium iron phosphate single crystal material is 550-600 ℃.
Preferably, in the step S1, the primary sintering heat preservation time for preparing the small-particle lithium iron phosphate single crystal material is 4-5 h.
Preferably, in the step S2, the primary sintering temperature for preparing the medium-particle lithium iron phosphate single crystal material is 600-650 ℃.
Preferably, in the step S2, the primary sintering heat preservation time for preparing the medium-particle lithium iron phosphate single crystal material is 5-6 h.
Preferably, in the step S2, the primary sintering temperature for preparing the medium-particle lithium iron phosphate single crystal material is 650-700 ℃.
Preferably, in the step S2, the primary sintering heat preservation time for preparing the medium-particle lithium iron phosphate single crystal material is 6-7 h.
Preferably, in the steps S1-S3, the secondary sintering heat preservation time is 10-12 h.
Preferably, in the steps s1 to s3, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium oxalate and lithium dihydrogen phosphate.
Preferably, in the steps s1 to s3, the metal ion coating is an oxide and/or a compound of one or more of aluminum, titanium, zinc, strontium, vanadium, zirconium, magnesium, yttrium and tin.
Preferably, in the step s4, the mixing ratio of the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material is 1:1: 4-2: 1: 2.
The carbon source can enable the material to form an amorphous conductive network in the sintering process, and the amorphous conductive network wraps the lithium iron phosphate material particles and the metal ion coating layer, so that the electronic conductivity of the material can be further improved, the metal ion coating layer can be more firmly coated, and the rate capability and the cycle performance of the material can be improved. The carbon source may be selected from carbon sources for conventionally preparing lithium iron phosphate materials, and preferably, in step s4, the carbon source is one or more of glucose, starch, phenolic resin, polyvinyl alcohol, polyethylene glycol, sucrose, fructose, maltose, cyclodextrin, citric acid, and polyglycerol.
The high-performance lithium iron phosphate composite material with gradient coating is prepared by adopting the method.
Compared with the prior art, the invention realizes the following beneficial effects:
the invention discloses a gradient-coated high-performance lithium iron phosphate composite material which is prepared by preparing three lithium iron phosphate single crystal materials with particle sizes, and mixing and sintering after gradient coating. The battery prepared from the lithium iron phosphate composite material has good cycle performance, the capacity retention rate of 200 cycles of 1C charging and discharging is not lower than 98.0%, and the compaction density of the lithium iron phosphate composite material is 2.61g/cm3Thus, the discharge capacity of the battery 1C is more than 150.8 mAh/g.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
S1, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.06: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the particle size D50 of particles in the slurry is 0.15 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a small-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 550 ℃, and the heat preservation time is 5 hours;
mixing the small-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.4% of the mass of the small-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the small-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.04: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the granularity D50 of particles in the slurry is 0.35 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a medium-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 600 ℃, and the heat preservation time is 6 hours;
mixing the medium-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.3% of the mass of the medium-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the medium-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s3, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.02: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the granularity D50 of particles in the slurry is 0.55 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a large-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 650 ℃, and the heat preservation time is 7 hours;
mixing the large-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.2% of the mass of the large-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the large-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s4, mixing the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material according to the proportion of 1:1: 2, mixing, adding polyethylene glycol accounting for 1.4 percent of the total mass of the three materials, uniformly mixing, placing the mixture in a box furnace in an inert gas atmosphere for three times of sintering, and screening to remove magnetism to obtain a high-performance lithium iron phosphate composite material 1 with gradient coating; the temperature of the third sintering is 550 ℃, and the heat preservation time is 5 hours.
Example 2
The steps are the same as those of embodiment 1, except that in step s4, the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material are mixed in a ratio of 1:1: 3, and mixing to obtain the lithium iron phosphate composite material 2.
Example 3
The steps are the same as those of embodiment 1, except that in step s4, the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material are mixed in a ratio of 1:1:4, and mixing to obtain the lithium iron phosphate composite material 3.
Example 4
The steps are the same as those of the embodiment 1, except that in the step S4, the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material are prepared according to the following steps of: 1:4, and mixing to obtain the lithium iron phosphate composite material 4.
Example 5
S1, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.06: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the particle size D50 of particles in the slurry is 0.25 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a small-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 550 ℃, and the heat preservation time is 5 hours;
mixing the small-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.3% of the mass of the small-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the small-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.04: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the granularity D50 of particles in the slurry is 0.45 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a medium-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 600 ℃, and the heat preservation time is 6 hours;
mixing the medium-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.2% of the mass of the medium-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the medium-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s3, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.02: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the granularity D50 of particles in the slurry is 0.65 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a large-particle lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 650 ℃, and the heat preservation time is 7 hours;
mixing the large-particle lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.1% of the mass of the large-particle lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain the large-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s4, mixing the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material according to the proportion of 1:1:4, mixing, adding polyethylene glycol accounting for 1.4 percent of the total mass of the three materials, uniformly mixing, placing the mixture in a box furnace in an inert gas atmosphere for three-time sintering, and screening and demagnetizing to obtain a high-performance lithium iron phosphate composite material 5 with gradient coating; the temperature of the third sintering is 550 ℃, and the heat preservation time is 5 hours.
Example 6
The procedure was the same as in example 5, except that in step s1, the molar ratio of lithium carbonate to iron phosphate was 1.05: 1, mixing; in the step S2, the mol ratio of the lithium carbonate to the iron phosphate is 1.03: 1, mixing; in the step S3, the mol ratio of the lithium carbonate to the iron phosphate is 1.01: 1 to obtain the lithium iron phosphate composite material 6.
Example 7
The steps are the same as those in example 5, except that in the step s1 to step s3, the temperature of secondary sintering is 750 ℃, and the lithium iron phosphate composite material 7 is obtained.
Example 8
The steps are the same as those of the embodiment 5, except that in the steps S1-S3, the temperature of secondary sintering is 850 ℃, and the lithium iron phosphate composite material 8 is obtained.
Comparative example 1 (without gradient coating)
S1, mixing lithium carbonate and iron phosphate according to a molar ratio of 1.03: 1, mixing, adding deionized water, mixing to prepare slurry, placing the slurry in a sand mill, grinding until the particle size D50 of particles in the slurry is 0.45 mu m, then performing spray drying to obtain dried powder, placing the dried powder in a box furnace in an inert atmosphere for primary sintering, and then crushing by using a jet mill to obtain a lithium iron phosphate single crystal material; wherein the weight of the added water is 50 percent of the solid content of the slurry, the temperature of the primary sintering is 600 ℃, and the heat preservation time is 5 hours;
mixing a lithium iron phosphate single crystal material and a tetrabutyl titanate coating accounting for 0.2% of the mass of the lithium iron phosphate single crystal material at a high speed in a high-speed mixer, and then placing the mixture in a box furnace in an inert gas atmosphere for secondary sintering to obtain a small-particle lithium iron phosphate material; the temperature of the secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, adding polyethylene glycol with the mass of 1.4% of the lithium iron phosphate material, uniformly mixing, placing the mixture in a box furnace in an inert gas atmosphere for three-time sintering, and sieving to remove magnetism to obtain a high-performance lithium iron phosphate composite material 9 with gradient coating; the temperature of the third sintering is 550 ℃, and the heat preservation time is 5 hours.
Comparative example 2
The procedure was the same as in example 5, except that in step s1, the molar ratio of lithium carbonate to iron phosphate was 1.07: 1, mixing; in the step S3, the mol ratio of lithium carbonate to iron phosphate is 1.01: 1 to obtain the lithium iron phosphate composite material 10.
Comparative example 3
The steps are the same as those of the embodiment 5, except that in the step S1, the small-particle lithium iron phosphate single crystal material and the tetrabutyl titanate coating accounting for 0.5% of the mass of the small-particle lithium iron phosphate single crystal material are mixed at a high speed in a high-speed mixer to obtain the lithium iron phosphate composite material 11.
Comparative example 4
The steps are the same as those of the embodiment 5, except that in the steps S1-S3, the temperature of the secondary sintering is 860 ℃, and the lithium iron phosphate composite material 12 is obtained.
Comparative example 5
The steps are the same as those of the embodiment 5, except that in the steps S1-S3, the temperature of the secondary sintering is 740 ℃, and the lithium iron phosphate composite material 13 is obtained.
Comparative example 6
The steps are the same as example 5, except that in step s1, the particles in the slurry are ground to a particle size D50 of 0.35 μm, in step s2, the particles in the slurry are ground to a particle size D50 of 0.55 μm, and in step s3, the particles in the slurry are ground to a particle size D50 of 0.75 μm, so as to obtain the lithium iron phosphate composite material 14.
Comparative example 7
The procedure is the same as in example 5, except that in step s1, grinding is performed until the particle size D50 of the particles in the slurry is 0.35 μm, so as to obtain the lithium iron phosphate composite material 15.
Comparative example 8
The procedure is the same as in example 5, except that in step s2, the slurry is ground until the particle size D50 of the particles in the slurry is 0.55 μm, so as to obtain the lithium iron phosphate composite material 16.
Comparative example 9
The procedure is the same as in example 5, except that in step s3, the slurry is ground until the particle size D50 of the particles in the slurry is 0.75 μm, so as to obtain the lithium iron phosphate composite material 17.
Performance testing
The lithium iron phosphate composite materials prepared in the above examples and comparative examples were subjected to a compaction density test, and the lithium iron phosphate composite materials were mixed with carbon black as a conductive agent and polytetrafluoroethylene as a binder to prepare electrode sheets, and metal lithium was used as a negative electrode to assemble a simulated button cell, which was subjected to an electrical performance test, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the capacity retention rate of the battery 1C prepared from the lithium iron phosphate composite material prepared by the method is more than 98.0 percent in 200 cycles of charging and discharging, the 0.1C discharge capacity is not less than 164.9mAh/g, the 1C discharge capacity is not less than 150.8mAh/g, and the compaction density of the lithium iron phosphate composite material is 2.61g/cm3The above.
As can be seen by comparing comparative example 1 and example 5, when no gradient particles are involved in the preparation process, the performance of the prepared lithium iron phosphate composite material is obviously reduced, the capacity retention rate of the prepared battery 1C in charging and discharging for 200 weeks is only 95.3%, the discharge capacity at 0.1C is only 156.9mAh/g, the discharge capacity at 1C is only 139.0mAh/g, and the compaction density of the lithium iron phosphate composite material is only 2.42g/cm3。
Comparing comparative example 2 and example 5, it can be seen that, when the small-particle lithium iron phosphate single crystal material is prepared, the molar ratio of lithium carbonate to iron phosphate is higher than 1.06: 1, the performance of the prepared lithium iron phosphate composite material is obviously reduced, and the capacity retention rate of a battery 1C prepared from the lithium iron phosphate composite material in 200 charge-discharge cycles is lower than 98.0%.
Comparing comparative example 3 with example 5, it can be seen that when the addition amount of the tetrabutyl titanate coating exceeds 0.4% of the mass of the small-particle lithium iron phosphate single crystal material in the preparation of the small-particle lithium iron phosphate material, the performance of the prepared lithium iron phosphate composite material is obviously reduced, and the capacity retention rate of 200 cycles of charging and discharging of a battery 1C prepared by adopting the lithium iron phosphate composite material is 97.2%.
Comparing comparative examples 4 to 5 with example 5, it can be seen that, when the temperature of the secondary sintering is not in the range of 750 ℃ to 850 ℃ in the steps s1 to s3, the performance of the prepared lithium iron phosphate composite material is obviously reduced, the capacity retention rate of the battery 1C prepared by using the composite material for charging and discharging at 200 cycles is 97.3% and 97.0%, and the discharge capacity of the battery at 0.1C is also lower than 164.0 mAh/g.
Comparing comparative examples 6 to 9 with example 5, it can be seen that, when the particle size D50 of the particles in the slurry is not within the range of the claims in steps s1 to s3, the performance of the prepared lithium iron phosphate composite material is significantly reduced, the capacity retention rate of the battery 1C prepared by using the composite material is less than 97.0% at 200 cycles of charging and discharging, and the 0.1C discharge capacity is not more than 163.1 mAh/g.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a gradient-coated high-performance lithium iron phosphate composite material is characterized by comprising the following steps of:
s1, preparing a small-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.05: 1-1.06: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.15-0.25 mu m, drying, sintering once, and carrying out jet milling to obtain a small-particle lithium iron phosphate single crystal material;
mixing the small-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.3-0.4% of the mass of the small-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain the small-particle lithium iron phosphate material;
s2, preparing a medium-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.03: 1-1.04: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.35-0.45 mu m, drying, sintering once, and carrying out jet milling to obtain a medium-particle lithium iron phosphate single crystal material;
mixing the medium-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.2-0.3% of the mass of the medium-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain a medium-particle lithium iron phosphate material;
s3, preparing a large-particle lithium iron phosphate material:
according to the molar ratio of a lithium source to ferric phosphate of 1.01: 1-1.02: 1, mixing, adding deionized water to prepare slurry, grinding until the particle size D50 of particles in the slurry is 0.55-0.65 mu m, drying, sintering once, and carrying out jet milling to obtain a large-particle lithium iron phosphate single crystal material;
mixing a large-particle lithium iron phosphate single crystal material and a metal ion coating accounting for 0.1-0.2% of the mass of the large-particle lithium iron phosphate single crystal material, and performing secondary sintering at 750-850 ℃ to obtain a large-particle lithium iron phosphate material;
s4, preparing a lithium iron phosphate composite material:
and mixing the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material in proportion, adding a carbon source, sintering for three times, screening and demagnetizing to obtain the lithium iron phosphate composite material.
2. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the steps S1 to S3, the deionized water is added according to a proportion that the solid content of the mixed slurry is 40-60%.
3. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the step S1, the primary sintering temperature for preparing the small-particle lithium iron phosphate single crystal material is 550-600 ℃.
4. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the step S2, the primary sintering temperature for preparing the medium-particle lithium iron phosphate single crystal material is 600-650 ℃.
5. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the step S3, the primary sintering temperature for preparing the large-particle lithium iron phosphate single crystal material is 650-700 ℃.
6. The preparation method of the lithium iron phosphate composite material according to claim 1, wherein in the steps S1-S3, the secondary sintering heat preservation time is 10-12 h.
7. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the steps S1 to S3, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium oxalate and lithium dihydrogen phosphate.
8. The method for preparing the lithium iron phosphate composite material according to claim 1, wherein in the steps S1 to S3, the metal ion coating is an oxide and/or a compound of one or more of aluminum, titanium, zinc, strontium, vanadium, zirconium, magnesium, yttrium and tin.
9. The preparation method of the lithium iron phosphate composite material according to claim 1, wherein in step S4, the mixing mass ratio of the small-particle lithium iron phosphate material, the medium-particle lithium iron phosphate material and the large-particle lithium iron phosphate material is 1:1: 4-2: 1: 2.
10. A gradient-coated high-performance lithium iron phosphate composite material prepared by the preparation method of any one of claims 1 to 9.
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