CN115924873A - Preparation method of spherical nano lithium iron phosphate - Google Patents
Preparation method of spherical nano lithium iron phosphate Download PDFInfo
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- CN115924873A CN115924873A CN202211649263.6A CN202211649263A CN115924873A CN 115924873 A CN115924873 A CN 115924873A CN 202211649263 A CN202211649263 A CN 202211649263A CN 115924873 A CN115924873 A CN 115924873A
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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 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000001694 spray drying Methods 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000005469 granulation Methods 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000002612 dispersion medium Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000010979 pH adjustment Methods 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 150000007524 organic acids Chemical group 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 239000005955 Ferric phosphate Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 229940032958 ferric phosphate Drugs 0.000 claims description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- ROUPZXDBSPQFLE-UHFFFAOYSA-N triazanium;phosphate;hydrate Chemical compound [NH4+].[NH4+].[NH4+].O.[O-]P([O-])([O-])=O ROUPZXDBSPQFLE-UHFFFAOYSA-N 0.000 claims description 5
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydrogen ions Chemical class 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 9
- 238000004537 pulping Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229960001031 glucose Drugs 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LNXSCYVUIWDODU-UHFFFAOYSA-L azanium iron(2+) phosphate hydrate Chemical compound [NH4+].O.[Fe+2].[O-]P([O-])([O-])=O LNXSCYVUIWDODU-UHFFFAOYSA-L 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000009817 primary granulation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application provides a preparation method of spherical nano lithium iron phosphate, which comprises the following steps: step S1: adding an iron source, a phosphorus source, a lithium source, a carbon source and a doping substance into a dispersion medium, and grinding the slurry by using a superfine grinding machine; step S2: in the process of grinding the slurry by using an ultrafine grinding machine, when the granularity D50 of the slurry reaches below 1 mu m, adding a slurry pH value regulator into the slurry to regulate the pH value of the slurry, controlling the pH value range of the slurry to be 9.5-10.5, wherein the slurry pH value regulator is organic acid with carboxyl groups; and step S3: carrying out spray drying granulation on the slurry after the pH adjustment is finished to obtain a spherical precursor mixed by large balls and small balls; and step S4: and calcining the spherical precursor in an inert gas atmosphere protective furnace to obtain the spherical lithium iron phosphate anode material mixed by large balls and small balls. The preparation method of the spherical nano lithium iron phosphate is simple in process and has lower requirements on production environment and production equipment.
Description
Technical Field
The application relates to the field of new energy materials, in particular to a preparation method of spherical nano lithium iron phosphate.
Background
The lithium iron phosphate is used as one of the anode materials of the lithium ion battery, has relatively high theoretical capacity and stable charge-discharge voltage platform, and makes the organic electrolyte safer in battery application. The lithium ion battery using the lithium iron phosphate has the advantages of high safety, good electrode reaction reversibility, high thermal stability, environmental friendliness and the like, so the lithium iron phosphate becomes one of the preferred anode materials of the anode material of the lithium ion battery. However, compared with ternary lithium cathode materials, the lithium iron phosphate has a low lithium ion migration rate, which results in poor high-rate charge and discharge performance. A large number of researches show that the rate capability and the low-temperature capability of the lithium iron phosphate material can be obviously improved by reducing the grain size of the lithium iron phosphate.
Chinese patent CN109607505A discloses a preparation method for improving the low temperature performance of lithium iron phosphate, which improves the low temperature performance of a lithium iron phosphate material by a composite carbon source and doping and nanocrystallization; however, the particle size of the lithium iron phosphate prepared by the patent is between 100 and 120nm, and the nano-scale lithium iron phosphate has good electrochemical performance, but the tap density is low, and the problems of low density, difficult processing and the like in the practical application process exist. In contrast, chinese patents CN101162776A and CN106229505A disclose that spherical or spheroidal lithium iron phosphate is prepared by a process method for preparing a spherical lithium iron phosphate material to achieve both processability and electrochemical performance. However, the lithium iron phosphate electrode material disclosed in CN101162776A uses lithium iron phosphate as a matrix, forms particles by coating nano carbon material particles, nano metal or nano metal oxide conductive layer outside the matrix, and processes the lithium iron phosphate into composite spherical or spheroidal particles by using the steps of spray drying, pulverization treatment, spheroidization treatment, mechanical fusion and the like; although the patent can prepare the high-performance lithium iron phosphate material, the process is adoptedThe process is long, the interference factors are many, and the problems of large energy consumption, difficult control of sphericity and the like exist in the actual production. The high-density spherical lithium iron phosphate material disclosed in the Chinese patent CN106229505A is prepared by mixing a lithium source, an iron-phosphorus compound, a dopant and a carbon source in a dry method, presintering the mixture in a protective gas, grinding the mixture, performing sphericization treatment on a precursor by using a two-fluid or four-fluid spray drying device, and reacting the precursor by using an organic compound to achieve the effect of vapor deposition coating, thereby preparing the high-density spherical nano lithium iron phosphate material with the primary particle size of 50-100 nm and the secondary particle size of 3-10 mu m; the material powder disclosed in this patent has a conductivity of up to 10 -1 S/cm, the capacity, low temperature and rate performance of the LFP material and the performances of processing, circulation and the like can be well considered; however, the use of organic gas phase coating in the patent has high requirements on kiln equipment, and the use of two-fluid or four-fluid spray drying equipment has limited requirements on the solid content of slurry feeding, which is not favorable for the low-cost control requirement of the lithium iron phosphate production process.
How to provide a method for preparing spherical nano lithium iron phosphate, which has relatively simple process, relatively low requirements on preparation environment and preparation equipment and relatively low preparation cost, needs to be considered by the technical personnel in the field.
Disclosure of Invention
The embodiment of the application provides a preparation method of spherical nano lithium iron phosphate, which has the advantages of relatively simple process, relatively low requirements on preparation environment and preparation equipment and relatively low preparation cost.
The embodiment of the application provides a preparation method of spherical nano lithium iron phosphate, which comprises the following steps:
step S1: adding an iron source, a phosphorus source, a lithium source, a carbon source and a doping substance into a dispersion medium, and grinding the slurry by using a superfine grinding machine;
step S2: adding a slurry pH value regulator into the slurry when the granularity D50 of the slurry reaches below 1 mu m in the process of grinding the slurry by using an ultrafine grinding machine, and controlling the pH value of the slurry to be 9.5-10.5, wherein the slurry pH value regulator is an organic acid with a carboxyl group;
and step S3: carrying out spray drying granulation on the slurry after the pH adjustment is finished to obtain a spherical precursor mixed by large balls and small balls;
and step S4: and calcining the spherical precursor in an inert gas atmosphere protection furnace to obtain the spherical lithium iron phosphate anode material mixed by large balls and small balls.
In one possible embodiment, the iron source comprises one or both of iron phosphate dihydrate, iron ammonium phosphate monohydrate; the phosphorus source comprises one or two of ammonium dihydrogen phosphate, ferric phosphate dihydrate, ferric ammonium phosphate monohydrate and lithium dihydrogen phosphate; the lithium source comprises one or two of lithium carbonate, lithium hydroxide, lithium phosphate and lithium acetate; the carbon source comprises one or more of glucose, sucrose and fructose; the doping substance comprises one or more of zirconium (Zr), titanium (Ti), manganese (Mn), magnesium (Mg), vanadium (V) and compounds thereof; the dispersion medium is pure water with the conductivity less than 10 us/cm.
In one possible embodiment, the ratio of iron to phosphorus in the iron source and the phosphorus source ranges from 0.96 to 1.05, the ratio of lithium iron in the lithium source and the iron source ranges from 1.00 to 1.03, the total ratio of the carbon source after pyrolysis ranges from 1.0% to 2.0%, and the total ratio of the doping material ranges from 0.01% to 1%.
In one possible embodiment, the particle size in the slurry after the slurry is ground using an ultra-fine grinder is in the range of 30 to 150nm.
In one possible embodiment, the slurry pH adjusting agent comprises one or two of citric acid, malic acid, salicylic acid.
In one possible embodiment, the slurry pH adjuster is added in an amount of from 0.01 to 0.03 in terms of hydrogen ion to lithium ion molar ratio.
In a possible embodiment, in step 3, the slurry is subjected to spray drying granulation by using a centrifugal spray drying device, and an atomizing disc of the centrifugal spray drying device adopts a structure of combining a large circular hole and a small circular hole.
In a possible embodiment, in the atomizing disc of the centrifugal spray drying apparatus, the ratio of the cross-sectional area of the large circular hole to the cross-sectional area of the small circular hole is 10% to 50%:50 to 90 percent, and the diameter of the large round hole is 2 to 5 times of that of the small round hole.
In a possible embodiment, in step 4, the inert gas atmosphere protection furnace comprises at least one of a tube furnace, a box furnace, a tunnel furnace and a rotary furnace capable of circulating nitrogen or argon, the calcination temperature is 700 to 750 ℃, the calcination holding time is 4 to 10 hours, the calcination process adopts a segmented temperature rise rate, the temperature rise rate of 200 to 550 ℃ is 0 to 2 ℃/min, and the temperature rise rate of other temperature intervals is 3 to 10 ℃/min.
In one possible embodiment, in the spherical precursor mixed by the large and small spheres, the large spheres have a diameter ranging from 10 to 20 μm, and the small spheres have a diameter ranging from 1 to 10 μm; the particle size distribution range of the large and small ball mixed spherical lithium iron phosphate anode material is 1-30 mu m, and the apparent density is more than 0.85g/cm 3 。
Compared with the prior art, the preparation method of the spherical nano lithium iron phosphate can realize the preparation of the high-density spherical nano lithium iron phosphate by the process methods of raw material mixing, wet pulping, slurry pretreatment, spray drying granulation and sintering. According to the preparation method of the spherical nano lithium iron phosphate, slurry pH value regulator is adopted to carry out slurry pretreatment in the wet pulping stage so as to regulate the characteristics of the nano slurry, so that the phenomenon of uneven slurry caused by agglomeration of primary nano particles can be effectively reduced or even avoided. Meanwhile, according to the preparation method of the spherical nano lithium iron phosphate, the size distribution of the spheres is regulated and controlled through the structure of the large and small hole combination of the centrifugal atomizing disk, so that the prepared lithium iron phosphate precursor is in a mode of close packing of large and small spheres, and the close packing of the precursor is not only beneficial to the thermal uniformity in the material reaction process, but also beneficial to improving the kiln load and reducing the production cost.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing spherical nano lithium iron phosphate provided in an embodiment of the present application.
Fig. 2 is a schematic view of a scanning electron microscope of lithium iron phosphate prepared in example 1 of the present application.
Fig. 3 is a schematic view of a 0.2C charge-discharge curve of lithium iron phosphate prepared in example 1 of the present application.
Fig. 4 is a schematic view of a 1C charge-discharge curve of lithium iron phosphate prepared in example 1 of the present application.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
The following description will refer to the accompanying drawings to more fully describe the present disclosure. Exemplary embodiments of the present application are illustrated in the accompanying drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. These exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Like reference numerals designate identical or similar components.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Further, as used herein, "comprises" and/or "comprising" and/or "having," integers, steps, operations, components, and/or components, but does not preclude the presence or addition of one or more other features, regions, integers, steps, operations, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Furthermore, unless otherwise explicitly defined herein, terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and this application and will not be interpreted in an idealized or overly formal sense.
Embodiments of the present application will now be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, an embodiment of the present application provides a method for preparing spherical nano lithium iron phosphate, including the following steps:
step S1: adding an iron source, a phosphorus source, a lithium source, a carbon source and a doping substance into a dispersion medium, and grinding the slurry by using an ultrafine grinding machine.
In one embodiment, the iron source comprises one or both of ferric phosphate dihydrate and ferric ammonium phosphate monohydrate; the phosphorus source comprises one or two of ammonium dihydrogen phosphate, ferric phosphate dihydrate, ferric ammonium phosphate monohydrate and lithium dihydrogen phosphate.
In one embodiment, the lithium source includes one or two of lithium carbonate, lithium hydroxide, lithium phosphate, and lithium acetate.
In one embodiment, the carbon source comprises one or more of glucose, sucrose, fructose.
In one embodiment, the dopant species includes one or more of zirconium (Zr), titanium (Ti), manganese (Mn), magnesium (Mg), vanadium (V), and compounds thereof.
In one embodiment, the dispersion medium is pure water with conductivity less than 10 us/cm.
In one embodiment, the ratio (molar ratio) of iron to phosphorus in the iron source and the phosphorus source ranges from 0.96 to 1.05. Further, the ratio of iron to phosphorus in the iron source and the phosphorus source may be specifically 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, and 1.04.
In one embodiment, the ratio (molar ratio) of lithium iron in the lithium source to iron in the iron source ranges from 1.00 to 1.03. Further, the ratio of lithium iron in the lithium source to the iron source may be 1.02.
In one embodiment, the carbon source is cracked to a proportion of 1.0% to 2.0% of the total (total product). Further, the percentage of the carbon source after cracking may be 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%.
In one embodiment, the doping material accounts for 0.01% to 1% of the total (total product) ratio. Further, the doping substance may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% in the entire proportion.
Step S2: in the process of grinding the slurry by using the ultra-fine grinding machine, when the granularity D50 of the slurry reaches below 1 mu m, adding a slurry pH value regulator into the slurry to regulate the pH value of the slurry, and controlling the pH value of the slurry to be 9.5-10.5, wherein the slurry pH value regulator is an organic acid with a carboxyl group.
Further, the pH of the slurry may be specifically 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, and 10.4. The pH value of the slurry is adjusted, so that the agglomeration phenomenon caused by agglomeration of nano particles can be effectively reduced or even eliminated, and the slurry is more uniform.
In one embodiment, the particle size of the slurry is in the range of 30 to 150nm after the slurry is ground by an ultra-fine grinder. Further, the particle size in the slurry may be 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, and 140nm.
In one embodiment, the slurry pH adjuster includes one or two of citric acid, malic acid, salicylic acid.
In one embodiment, the addition amount of the slurry pH adjuster is from 0.01 to 0.03 in terms of a molar ratio of hydrogen ions to lithium ions. Further, the addition amount of the slurry pH adjuster may be specifically a molar ratio of hydrogen ions to lithium ions of 0.02.
And step S3: and carrying out spray drying granulation on the slurry after the pH adjustment is finished to obtain a spherical precursor mixed by large balls and small balls.
In one embodiment, the slurry is spray-dried and granulated by using a centrifugal spray drying device, and an atomizing disc of the centrifugal spray drying device adopts a structure of combining a large circular hole and a small circular hole.
In one embodiment, in the atomizing disk of the centrifugal spray drying apparatus, the ratio of the cross-sectional area of the large circular hole to the cross-sectional area of the small circular hole is (10% to 50%): (50% to 90%) of the diameter of the large circular hole is 2 to 5 times the diameter of the small circular hole.
And step S4: and calcining the spherical precursor in an inert gas atmosphere protection furnace to obtain the spherical lithium iron phosphate anode material mixed by large balls and small balls.
In one embodiment, the inert gas atmosphere protection furnace comprises at least one of a tube furnace, a box furnace, a tunnel furnace and a rotary furnace capable of circulating nitrogen or argon, the calcination temperature is 700 to 750 ℃, the calcination heat preservation time is 4 to 10 hours, the calcination process adopts a segmented temperature rise rate, the temperature rise rate of 200 to 550 ℃ is 0 to 2 ℃/min, and the temperature rise rate of other temperature intervals is 3 to 10 ℃/min.
Understandably, the slurry with high uniformity obtained by the steps can be dried and granulated to obtain a spherical precursor with good mixed large and small spheres, and the spherical lithium iron phosphate anode material with mixed large and small spheres is further obtained by sintering. The powder composed of the spherical particles can disperse small spherical particles in gaps generated after the large spherical particles are stacked, namely, the small spherical particles are filled in the gaps of the large spherical particles, so that the lithium iron phosphate anode material is integrally stacked more tightly, and the stacking density (loose packing density) of the lithium iron phosphate anode material is effectively improved.
Further, the centrifugal atomizing disk of this application direct adoption aperture combination carries out the granulation of spherical material, directly obtains the spherical precursor that big ball and small ball mixes, and then obtains the spherical lithium iron phosphate cathode material that big ball and small ball mix. The method avoids re-granulation by other methods such as secondary grinding, crushing and the like after primary granulation, avoids damage to materials and simplifies and rationalizes the working procedures.
In one embodiment, in the spherical precursor mixed by the large spheres and the small spheres, the diameter of the large spheres ranges from 10 to 20 μm, and the diameter of the small spheres ranges from 1 to 10 μm; the particle size distribution range of the large and small ball mixed spherical lithium iron phosphate anode material is 1-30 mu m, and the apparent density is more than 0.85g/cm 3 。
Compared with the prior art, the preparation method of the spherical nano lithium iron phosphate can realize the preparation of the high-density spherical nano lithium iron phosphate by the process methods of raw material mixing, wet pulping, slurry pretreatment, spray drying granulation and sintering. According to the preparation method of the spherical nano lithium iron phosphate, slurry pH value regulator is adopted to carry out slurry pretreatment in the wet pulping stage so as to regulate the characteristics of the nano slurry, and the phenomenon of uneven slurry caused by agglomeration of primary nano particles is effectively reduced or even avoided. Meanwhile, according to the preparation method of the spherical nano lithium iron phosphate, the size distribution of the balls is regulated and controlled through the structure of the large and small hole combination of the centrifugal atomizing disk, so that the prepared lithium iron phosphate precursor is in a mode of large and small ball tight packing, the tight packing of the precursor is not only beneficial to the thermal uniformity in the material reaction process, but also beneficial to improving the kiln loading capacity and reducing the production cost. Furthermore, this application directly adopts the centrifugal atomizing disk of big aperture combination to carry out the granulation of spherical material and obtains the spherical lithium iron phosphate cathode material that big-small ball mixes, avoids secondary grinding, crushing, has avoided just making the process simplify more rationally to the destruction of material.
Example 1
1000g of iron phosphate dihydrate (with an iron-phosphorus ratio of 0.99), 200g of lithium carbonate (with a purity of 99.6%), 9g of lithium dihydrogen phosphate and 2.1g of nano-magnesium oxide are accurately weighed and then sequentially added into 1000g of pure water, 75g of anhydrous glucose is added in the stirring process, full grinding is carried out in a single-machine double-barrel mode in an ultrafine sand mill, the granularity and the pH value of the slurry are measured by sampling once every grinding, when the granularity D50 of the slurry reaches 0.98 mu m, 10g of citric acid is weighed and slowly added into the slurry, the slurry is continuously ground until the granularity D50 of the slurry is 80nm, and at the moment, the pH value of the slurry is 10.15.
The slurry is dried and granulated by using LPG-5 type centrifugal spray drying equipment, and is subjected to spray drying and granulation by using an atomizing disc in a hole combination form with a large hole diameter of 4.8mm and a small hole diameter of 2mm to obtain a ball stacking precursor with a spherical particle size of 1-30 mu m. The apparent density of the precursor is 0.75g/cm as shown by a loose density test 3 。
Calcining the spherical precursor in a nitrogen atmosphere box furnace for 6 hours, and naturally cooling to room temperature. As shown in fig. 2 to 4, the prepared lithium iron phosphate material has a uniform distribution of primary particles of 80 to 100nm in a 10000-fold SEM picture, and a spherical secondary particle with a particle size distribution of 1 to 30 μm in a 100-fold SEM picture, and the loose packed density of the large and small ball-packed lithium iron phosphate is 0.88g/cm as shown by a loose packed density test 3 . The material is sieved, and then a pole piece is manufactured by adopting a stirring and pulping process and assembled into a button cell, wherein the 0.2C discharge capacity reaches 162.7mAh/g and the 1C discharge capacity reaches 154.6mAh/g within the voltage range of 2.0-3.75V.
Example 2
1000g of hydrated ammonium ferric phosphate (iron-phosphorus ratio is 1.00), 198g of lithium carbonate (purity is 99.6 percent), 15g of lithium dihydrogen phosphate and 2.1g of nano magnesium oxide are accurately weighed and then sequentially added into 1000g of pure water, 75g of anhydrous glucose is added in the stirring process, full grinding is carried out in a superfine sand mill in a single-machine double-barrel mode, the granularity and the pH value of the slurry are measured by once grinding and sampling in the process, when the granularity D50 of the slurry reaches 0.95 mu m, 20g of salicylic acid is weighed and slowly added into the slurry, the slurry is continuously ground until the granularity D50 of the slurry is 100nm, and at the moment, the pH value of the slurry is 10.42.
The slurry is dried and granulated by using LPG-5 type centrifugal spray drying equipment, and is sprayed, dried and granulated by using an atomizing disc in a hole combination form with a large hole diameter of 4.8mm and a small hole diameter of 1.5mm to obtain a ball stacking precursor with a spherical particle size of 1-30 mu m. The apparent density of the precursor is 0.79g/cm as shown by a loose density test 3 。
Calcining the spherical composite particle precursor in a nitrogen atmosphere box furnace for 8 hours, naturally cooling to room temperature, uniformly distributing the primary particles of the prepared lithium iron phosphate material in a 10000-time SEM picture to be 100nm, showing that the particles are spherical particles in a 100-time SEM picture, and distributing the particle size of the particles between 1 and 30 mu m, wherein the loose packing density test shows that the loose packing density of the lithium iron phosphate filled with the large and small balls is 0.95g/cm 3 . Sieving the material, preparing pole pieces by stirring and pulping process, and assemblingThe 0.2C discharge capacity of the button cell reaches 163.6mAh/g and the 1C discharge capacity reaches 155.6mAh/g within the voltage range of 2.0 to 3.75V.
Comparative example
1000g of ferric phosphate dihydrate (with an iron-phosphorus ratio of 0.99), 200g of lithium carbonate (with a purity of 99.6%), 9g of lithium dihydrogen phosphate and 2.1g of nano-magnesium oxide are accurately weighed and then added into 1000g of pure water in sequence, 75g of anhydrous glucose is added in the stirring process, and the mixture is fully ground in a superfine sand mill in a single-machine double-barrel mode until the granularity D50 of the slurry reaches 80nm, and the pH value of the slurry is 10.78 at the moment.
Drying, granulating and separating the slurry by using LPG-5 type centrifugal spray drying equipment, and performing spray drying and granulation on the slurry by using an atomizing disc with a round hole diameter of 4.8mm to obtain a precursor with spherical particles of 20-30 mu m, wherein the apparent density test of the precursor shows that the apparent density of the precursor is 0.65g/cm 3 。
Calcining the precursor in a nitrogen atmosphere box furnace for 6 hours, naturally cooling to room temperature, wherein the primary particles of the prepared lithium iron phosphate material are 80-300 nm in a 10000-time SEM picture and are not uniformly distributed, the primary particles are spherical particles in a 100-time SEM picture, the particle size distribution is 20-30 mu m, and the loose packing density test shows that the loose packing density of the lithium iron phosphate material is 0.71g/cm 3 . The material is sieved, and then a pole piece is manufactured by adopting a stirring pulping process and assembled into a button cell, wherein the 0.2C discharge capacity is 155.8mAh/g and the 1C discharge capacity is 146mAh/g within the voltage range of 2.0-3.75V.
As can be seen from the comparison between examples 1 and 2 and the comparative example, the lithium iron phosphate prepared by the slurry without pH adjustment in the comparative example has low apparent density and discharge capacity.
Hereinbefore, specific embodiments of the present application are described with reference to the drawings. However, those skilled in the art will appreciate that various modifications and substitutions can be made to the specific embodiments of the present application without departing from the scope of the present application. Such modifications and substitutions are intended to be within the scope of the present application.
Claims (10)
1. A preparation method of spherical nano lithium iron phosphate is characterized by comprising the following steps:
step S1: adding an iron source, a phosphorus source, a lithium source, a carbon source and a doping substance into a dispersion medium, and grinding the slurry by using a superfine grinding machine;
step S2: adding a slurry pH value regulator into the slurry to regulate the pH value of the slurry when the granularity D50 of the slurry reaches below 1 mu m in the process of grinding the slurry by using an ultra-fine grinding machine, and controlling the pH value of the slurry to be in a range of 9.5 to 10.5, wherein the slurry pH value regulator is an organic acid with a carboxyl group;
and step S3: carrying out spray drying granulation on the slurry after the pH adjustment is finished to obtain a spherical precursor mixed by large balls and small balls;
and step S4: and calcining the spherical precursor in an inert gas atmosphere protection furnace to obtain the spherical lithium iron phosphate anode material mixed by large balls and small balls.
2. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein the iron source comprises one or two of ferric phosphate dihydrate and ferric ammonium phosphate monohydrate; the phosphorus source comprises one or two of ammonium dihydrogen phosphate, ferric phosphate dihydrate, ferric ammonium phosphate monohydrate and lithium dihydrogen phosphate; the lithium source comprises one or two of lithium carbonate, lithium hydroxide, lithium phosphate and lithium acetate; the carbon source comprises one or more of glucose, sucrose and fructose; the doping substance comprises one or more of zirconium, titanium, manganese, magnesium, vanadium and compounds thereof; the dispersion medium is pure water with the conductivity less than 10 us/cm.
3. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein the ratio of iron to phosphorus in the iron source and the phosphorus source is in the range of 0.96 to 1.05, the ratio of lithium iron in the lithium source and the iron source is in the range of 1.00 to 1.03, the carbon source is cracked and then accounts for 1.0% to 2.0%, and the doping material is cracked and accounts for 0.01% to 1%.
4. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein the particle size of the slurry is in the range of 30 to 150nm after the slurry is ground by an ultra-fine grinder.
5. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein the slurry pH value regulator comprises one or two of citric acid, malic acid and salicylic acid.
6. The preparation method of spherical nano lithium iron phosphate according to claim 1, wherein the addition amount of the slurry pH regulator is from 0.01 to 0.03 molar ratio of hydrogen ions to lithium ions.
7. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein in step 3, the slurry is subjected to spray drying granulation by using a centrifugal spray drying device, and an atomizing disc of the centrifugal spray drying device adopts a structure of combining a large circular hole and a small circular hole.
8. The method for preparing spherical nano lithium iron phosphate according to claim 7, wherein in an atomizing disk of the centrifugal spray drying equipment, the ratio of the cross-sectional area of the large circular hole to the cross-sectional area of the small circular hole is (10% to 50%): (50% to 90%) of the diameter of the large circular hole is 2 to 5 times the diameter of the small circular hole.
9. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein in step 4, the inert gas atmosphere protection furnace comprises at least one of a tube furnace, a box furnace, a tunnel furnace and a rotary furnace capable of circulating nitrogen or argon, the calcination temperature is 700 to 750 ℃, the calcination holding time is 4 to 10 hours, the calcination process adopts a step-by-step temperature rise rate, the temperature rise rate of 200 to 550 ℃ is 0 to 2 ℃/min, and the temperature rise rate of other temperature intervals is 3 to 10 ℃/min.
10. The method for preparing spherical nano lithium iron phosphate according to claim 1, wherein in the spherical precursor mixed by the large spheres and the small spheres, the diameter of the large spheres ranges from 10 to 20 μm, and the diameter of the small spheres ranges from 1 to 10 μm; the particle size distribution range of the large and small ball mixed spherical lithium iron phosphate anode material is 1-30 mu m, and the apparent density is more than 0.85g/cm 3 。
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