CN114497538B - 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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- CN114497538B CN114497538B CN202111678935.1A CN202111678935A CN114497538B CN 114497538 B CN114497538 B CN 114497538B CN 202111678935 A CN202111678935 A CN 202111678935A CN 114497538 B CN114497538 B CN 114497538B
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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 173
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 136
- 239000000463 material Substances 0.000 claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 62
- 239000002002 slurry Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 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
- 239000005955 Ferric phosphate Substances 0.000 claims description 16
- 229940032958 ferric phosphate Drugs 0.000 claims description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 16
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 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
- 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
- 238000010902 jet-milling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 230000005389 magnetism Effects 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
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 238000005056 compaction Methods 0.000 abstract description 6
- 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
- 239000000203 mixture Substances 0.000 description 11
- 239000011261 inert gas 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
- 238000004537 pulping Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011163 secondary particle Substances 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
- 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
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 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
- 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
- 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a gradient coated high-performance lithium iron phosphate composite material. According to the method, primary particles of the material are respectively coated and modified differently according to the difference of large, medium and small, so that the large, medium and small particles of the material have gradient, uniform and complete coating layers, and particularly, some small particles in the material are better coated and modified than the large small particles in the material, and the structural stability of the whole particles of the material is greatly improved. The battery prepared from the lithium iron phosphate composite material prepared by the method has the capacity retention rate of more than 98.0% at the period of 1C charge and discharge and the compaction density of 2.61g/cm 3 The 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 lithium ion battery has the characteristics of portability, high efficiency, long cycle life, good safety performance and the like, so that the application field of the lithium ion battery is continuously expanded, and the lithium ion battery is gradually applied to the field of electric automobiles. The lithium iron phosphate has high charge and discharge efficiency, good cycle stability, more durable battery, high safety, low price and rich resources, and is widely studied and applied, but the internal lithium iron phosphate material is not fully utilized under the condition of high-current charge and discharge due to low electronic and ionic conductivity, so that the theoretical capacity of the lithium iron phosphate is not exerted in the practical application process, and the electrochemical performance of the lithium iron phosphate is poor, and the practical application generally adopts some modification means to improve the performance of the lithium iron phosphate.
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 has the defects that coated lithium ions in small particles are more likely to participate in a reaction for forming an SEI film, and lost lithium is more relatively large particles, so that the small particles are more likely to cause lithium loss, and the rate capability of the material is often degraded when the layer is thicker.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a gradient coated high-performance lithium iron phosphate composite material, the compaction density of the lithium iron phosphate composite material is 2.61g/cm 3 The discharge capacity of the battery 1C prepared from the lithium iron phosphate composite material is above 150.8mAh/g, and the capacity retention rate of the battery 1C after 200 weeks of charge and discharge is above 98.0%.
The invention further aims at providing 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 mole ratio of the lithium source to the ferric phosphate of 1.05:1 to 1.06:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.15-0.25 mu m, spray drying, and sintering and crushing once to obtain a small-particle lithium iron phosphate monocrystal material;
mixing the small-particle lithium iron phosphate monocrystal material with a metal ion coating accounting for 0.3-0.4% of the mass of the 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 mole ratio of the lithium source to the ferric phosphate of 1.03:1 to 1.04:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.35-0.45 mu m, spray drying, and sintering and crushing once to obtain a granular lithium iron phosphate monocrystal material;
mixing the medium-particle lithium iron phosphate monocrystal material and a metal ion coating accounting for 0.2-0.3% of the mass of the medium-particle lithium iron phosphate monocrystal 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 mole ratio of the lithium source to the ferric phosphate of 1.01:1 to 1.02:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.55-0.65 mu m, spray drying, and sintering and crushing once to obtain a large-particle lithium iron phosphate monocrystal material;
mixing the large-particle lithium iron phosphate monocrystal material with a metal ion coating accounting for 0.1-0.2% of the mass of the material, and performing secondary sintering at 750-850 ℃ to obtain the large-particle lithium iron phosphate material;
s4, preparing a lithium iron phosphate composite material:
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 a proportion, adding a carbon source, sintering for three times, sieving and removing magnetism 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 to have the granularity D50 of 0.15-0.25 mu m, the granularity D50 of 0.35-0.45 mu m and the granularity D50 of 0.55-0.65 mu m to prepare lithium iron phosphate single crystal materials with different particle sizes, the lithium iron phosphate single crystal materials are respectively coated and modified, are subjected to secondary sintering at 750-850 ℃, and are mixed for three times to obtain the lithium iron phosphate composite material, so that the lithium iron phosphate composite material has gradient, uniform and complete coating, the overall particle structure stability of the material is better, the lithium content in the small-medium-large lithium iron phosphate material in the lithium iron phosphate composite material is gradually increased, the defect that the lithium is relatively large in the primary charging and discharging process of small particles can be overcome, the overall particle structure stability of the material is greatly improved, and the compaction density, the energy density and the rate performance of the lithium iron phosphate composite material are improved.
In steps s1 to s2, the milled particles produce, during sintering, spheroidized secondary particles composed of primary particles, and the jet milling described in steps s1 to s2 opens the agglomerated secondary particles and exists independently in the form of separate primary particles. The primary particles with smaller volumes are not destroyed by adopting the jet milling mode.
Preferably, in the steps S1 to S3, the deionized water is added according to the proportion of 40-60% of the solid content of the slurry after mixing.
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 monocrystal material is 4-5 h.
Preferably, in the step S2, the primary sintering temperature for preparing the medium-particle lithium iron phosphate monocrystal material is 600-650 ℃.
Preferably, in the step S2, the primary sintering heat preservation time for preparing the medium-particle lithium iron phosphate monocrystal material is 5-6 h.
Preferably, in the step S2, the primary sintering temperature for preparing the medium-particle lithium iron phosphate monocrystal material is 650-700 ℃.
Preferably, in the step S2, the primary sintering heat preservation time for preparing the medium-particle lithium iron phosphate monocrystal material is 6-7 h.
Preferably, in the steps S1 to S3, the secondary sintering heat preservation time is 10 to 12 hours.
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 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 lead 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, and meanwhile, the metal ion coating layer is coated more firmly, thereby being beneficial to improving the multiplying power performance and the cycle performance of the material. The carbon source may be selected from carbon sources conventionally used for preparing lithium iron phosphate materials, 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 has the following beneficial effects:
the invention discloses a gradient coated high-performance lithium iron phosphate composite material, which is prepared by preparing three particle size lithium iron phosphate single crystal materials, 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 1C charge and discharge for 200 weeks is not lower than 98.0%, and meanwhile, the compaction density of the lithium iron phosphate composite material is 2.61g/cm 3 The discharge capacity of the prepared battery 1C is more than 150.8 mAh/g.
Detailed Description
The invention is further illustrated in detail below in connection with specific examples which are provided solely for the purpose of illustration and are not intended to limit the scope of the invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
S1, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.06:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.15 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain a small-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 550 ℃, and the heat preservation time is 5 hours;
mixing the small-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.4% of the mass of the small-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain the small-particle lithium iron phosphate material; the temperature of secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.04:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.35 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain the medium-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 600 ℃, and the heat preservation time is 6 hours;
mixing the medium-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.3% of the mass of the medium-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain a medium-particle lithium iron phosphate material; the temperature of secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s3, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.02:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.55 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain a large-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 650 ℃, and the heat preservation time is 7 hours;
mixing the large-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.2% of the mass of the large-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain the large-particle lithium iron phosphate material; the temperature of 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 a ratio of 1:1:2 mixing and 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 inert gas atmosphere for three times of sintering, and sieving and demagnetizing to obtain the 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 procedure is the same as in example 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 according to a ratio of 1:1:3, mixing to obtain the lithium iron phosphate composite material 2.
Example 3
The procedure is the same as in example 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 according to a ratio of 1:1:4, mixing to obtain the lithium iron phosphate composite material 3.
Example 4
The procedure is the same as in example 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 according to a ratio of 2:1:4, mixing to obtain the lithium iron phosphate composite material 4.
Example 5
S1, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.06:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.25 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain a small-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 550 ℃, and the heat preservation time is 5 hours;
mixing the small-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.3% of the mass of the small-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain the small-particle lithium iron phosphate material; the temperature of secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.04:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.45 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain the medium-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 600 ℃, and the heat preservation time is 6 hours;
mixing the medium-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.2% of the mass of the medium-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain a medium-particle lithium iron phosphate material; the temperature of secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s3, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.02:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.65 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain a large-particle lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 650 ℃, and the heat preservation time is 7 hours;
mixing the large-particle lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.1% of the mass of the large-particle lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain the large-particle lithium iron phosphate material; the temperature of 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 a ratio of 1:1:4, mixing and adding polyethylene glycol accounting for 1.4% of the total mass of the three materials, uniformly mixing, placing the mixture in a box furnace in inert gas atmosphere for three times of sintering, and sieving and demagnetizing to obtain the 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 is the same as in example 5, except that in step s1, the molar ratio of lithium carbonate to iron phosphate is 1.05:1, mixing; in the step S2, the molar ratio of the lithium carbonate to the ferric phosphate is 1.03:1, mixing; in the step S3, the molar ratio of the lithium carbonate to the ferric phosphate is 1.01: and 1, mixing to obtain the lithium iron phosphate composite material 6.
Example 7
The steps are the same as those of example 5 except that in the steps s1 to s3, the secondary sintering temperature is 750 ℃, and the lithium iron phosphate composite material 7 is obtained.
Example 8
The steps are the same as those of example 5 except that in the steps s1 to s3, the secondary sintering temperature is 850 ℃, and the lithium iron phosphate composite material 8 is obtained.
Comparative example 1 (without gradient coating)
S1, mixing lithium carbonate and ferric phosphate according to a molar ratio of 1.03:1, mixing, adding deionized water, mixing, pulping, grinding the slurry in a sand mill until the particle size D50 of particles in the slurry is 0.45 mu m, then performing spray drying to obtain dry powder, placing the dry powder in a box-type furnace with inert atmosphere, performing primary sintering, and crushing by using a jet mill to obtain the lithium iron phosphate monocrystal material; wherein the weight of the added water is 50 percent according to the solid content of the slurry, the temperature of primary sintering is 600 ℃, and the heat preservation time is 5 hours;
mixing the lithium iron phosphate monocrystal material and tetrabutyl titanate coating accounting for 0.2% of the mass of the lithium iron phosphate monocrystal material at high speed in a high-speed mixer, and then placing the mixture in a box-type furnace in inert gas atmosphere for secondary sintering to obtain a small-particle lithium iron phosphate material; the temperature of secondary sintering is 780 ℃, and the heat preservation time is 10 hours;
s2, adding polyethylene glycol accounting for 1.4% of the mass of the lithium iron phosphate material into the lithium iron phosphate material, uniformly mixing, placing the mixture in a box furnace in inert gas atmosphere, performing three-time sintering, and sieving and demagnetizing the mixture 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 is the same as in example 5, except that in step s1, the molar ratio of lithium carbonate to iron phosphate is 1.07:1, mixing; in the step S3, the molar ratio of the lithium carbonate to the ferric phosphate is 1.01:1, and mixing to obtain the lithium iron phosphate composite material 10.
Comparative example 3
The steps are the same as those of example 5, except that in step s1, small-particle lithium iron phosphate single crystal material and tetrabutyl titanate coating accounting for 0.5% of the mass of the small-particle lithium iron phosphate single crystal material are mixed at high speed in a high-speed mixer, and then the lithium iron phosphate composite material 11 is obtained.
Comparative example 4
The steps are the same as those of example 5 except that in the steps s1 to s3, the secondary sintering temperature is 860 ℃, and the lithium iron phosphate composite material 12 is obtained.
Comparative example 5
The steps are the same as those of example 5 except that in the steps s1 to s3, the secondary sintering temperature is 740 ℃, and the lithium iron phosphate composite material 13 is obtained.
Comparative example 6
The procedure was the same as in example 5, except that in step S1, the particles were milled to a particle size D50 of 0.35 μm in the slurry, in step S2, the particles were milled to a particle size D50 of 0.55 μm in the slurry, and in step S3, the particles were milled to a particle size D50 of 0.75 μm in the slurry, to obtain the lithium iron phosphate composite material 14.
Comparative example 7
The procedure was the same as in example 5, except that in step s1, the particles were milled to a particle size D50 of 0.35 μm in the slurry, to obtain a lithium iron phosphate composite 15.
Comparative example 8
The procedure was the same as in example 5, except that in step s2, the slurry was milled to a particle size D50 of 0.55 μm to obtain a lithium iron phosphate composite 16.
Comparative example 9
The procedure was the same as in example 5, except that in step s3, the slurry was milled to a particle size D50 of 0.75 μm to obtain a lithium iron phosphate composite 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 an electrode sheet was prepared using the lithium iron phosphate composite material and carbon black as a conductive agent, polytetrafluoroethylene as a binder, and a metal lithium as a negative electrode, and assembled into a simulated button cell, and subjected to an electrical property test, the test results of which are shown in table 1:
TABLE 1
As can be seen from Table 1, the battery prepared from the lithium iron phosphate composite material prepared by the method has a capacity retention rate of more than 98.0% at 200 weeks of charge and discharge, a 0.1C discharge capacity of not less than 164.9mAh/g, a 1C discharge capacity of not less than 150.8mAh/g, and a compaction density of 2.61g/cm 3 The above.
As can be seen from comparing comparative example 1 with 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 1C charge-discharge 200-week capacity retention rate of the prepared battery is only 95.3%, the 0.1C discharge capacity is only 156.9mAh/g, the 1C discharge capacity is only 139.0mAh/g, and the compacted density of the lithium iron phosphate composite material is also only 2.42g/cm 3 。
As can be seen by comparing comparative example 2 with example 5, when 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 the battery 1C prepared by the lithium iron phosphate composite material is lower than 98.0% after 200 weeks of charge and discharge.
As can be seen from comparing comparative example 3 with example 5, when the added 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 the battery 1C prepared by adopting the lithium iron phosphate composite material for charging and discharging for 200 weeks is 97.2%.
As can be seen by comparing comparative examples 4 to 5 with example 5, when the secondary sintering temperature is not within 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 prepared battery 1C after charging and discharging is 97.3% and 97.0% and the 0.1C discharge capacity is also lower than 164.0mAh/g.
As can be seen by comparing comparative examples 6 to 9 with example 5, when any of the particle sizes D50 of the particles in the slurry is not within the scope of claims in the steps S1 to S3, the performance of the lithium iron phosphate composite material is significantly reduced, the capacity retention rate of the battery 1C prepared by using the lithium iron phosphate composite material is less than 97.0% at 200 weeks of charge and discharge, and the discharge capacity of the battery 0.1C is not more than 163.1mAh/g.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the 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 mole ratio of the lithium source to the ferric phosphate of 1.05:1 to 1.06:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.15-0.25 mu m, drying, sintering at one time, and jet milling to obtain small-particle lithium iron phosphate monocrystal materials;
mixing the small-particle lithium iron phosphate monocrystal material with a metal ion coating accounting for 0.3-0.4% of the mass of the 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 mole ratio of the lithium source to the ferric phosphate of 1.03:1 to 1.04:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.35-0.45 mu m, drying, sintering at one time, and jet milling to obtain a granular lithium iron phosphate monocrystal material;
mixing the medium-particle lithium iron phosphate monocrystal material and a metal ion coating accounting for 0.2-0.3% of the mass of the medium-particle lithium iron phosphate monocrystal 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 mole ratio of the lithium source to the ferric phosphate of 1.01:1 to 1.02:1 mixing and adding deionized water to prepare slurry, grinding until the granularity D50 of particles in the slurry is 0.55-0.65 mu m, drying, sintering at one time, and jet milling to obtain a large-particle lithium iron phosphate monocrystal material;
mixing the large-particle lithium iron phosphate monocrystal material with a metal ion coating accounting for 0.1-0.2% of the mass of the material, and performing secondary sintering at 750-850 ℃ to obtain the large-particle lithium iron phosphate material;
s4, preparing a lithium iron phosphate composite material:
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 a proportion, adding a carbon source, sintering for three times, sieving and removing magnetism to obtain the lithium iron phosphate composite material.
2. The method for preparing a lithium iron phosphate composite material according to claim 1, wherein in the steps s1 to s3, the deionized water is added in a proportion that the solid content of the slurry after mixing is 40% -60%.
3. The method for preparing a lithium iron phosphate composite material according to claim 1, wherein in step s1, the primary sintering temperature of the preparation of the small-particle lithium iron phosphate single crystal material is 550-600 ℃.
4. The method for preparing a lithium iron phosphate composite material according to claim 1, wherein in step s2, the primary sintering temperature for preparing the medium-sized lithium iron phosphate single crystal material is 600-650 ℃.
5. The method for preparing a lithium iron phosphate composite material according to claim 1, wherein in step s3, the primary sintering temperature of the preparation of the large-particle lithium iron phosphate single crystal material is 650-700 ℃.
6. The method for preparing a lithium iron phosphate composite material according to claim 1, wherein in the steps s1 to s3, the secondary sintering heat preservation time is 10 to 12 hours.
7. The method for preparing a 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 a 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 method for preparing a 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 method of any one of claims 1 to 9.
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