CN114335478A - Magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density as well as preparation method and application thereof - Google Patents
Magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density as well as preparation method and application thereof Download PDFInfo
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- CN114335478A CN114335478A CN202111670338.4A CN202111670338A CN114335478A CN 114335478 A CN114335478 A CN 114335478A CN 202111670338 A CN202111670338 A CN 202111670338A CN 114335478 A CN114335478 A CN 114335478A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 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 60
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000004005 microsphere Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000004576 sand Substances 0.000 claims abstract description 31
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 31
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 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 22
- 239000008103 glucose Substances 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
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 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 8
- 238000007599 discharging Methods 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000005955 Ferric phosphate Substances 0.000 claims 1
- 229940032958 ferric phosphate Drugs 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims 1
- 239000007790 solid phase Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 24
- 239000000523 sample Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PTZOLXYHGCJRHA-UHFFFAOYSA-L azanium;iron(2+);phosphate Chemical compound [NH4+].[Fe+2].[O-]P([O-])([O-])=O PTZOLXYHGCJRHA-UHFFFAOYSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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Images
Abstract
The invention discloses a magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, a preparation method and application thereof, belonging to the technical field of lithium batteries and comprising the following preparation steps: (1) weighing a proper amount of iron source, phosphorus source, lithium source, magnesium hydroxide, PEG-400 and carbon source A, mixing in a solid phase to obtain a mixture, adding the mixture into deionized water containing zircon sand for ball milling, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished; (2) carrying out spray drying treatment on the slurry obtained in the step (1) to obtain yellowish-brown precursor powder; (3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas for high-temperature sintering to obtain the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, and a preparation method and application thereof.
Background
Under the international background of resource shortage and energy conservation and emission reduction, the lithium ion battery is internationally recognized as an ideal energy storage and output power supply due to higher volume energy density, mass energy density and excellent cycle performance, and increasingly plays an important role in various fields. As an important component of the lithium ion battery, the performance of the anode material of the lithium battery directly affects various performance indexes of the lithium battery and occupies the core position of the lithium ion battery. At present, there are many kinds of positive electrode materials for lithium ion batteries in the market, wherein lithium iron phosphate is a preferred positive electrode material for lithium ion batteries because of its advantages of large discharge capacity, long service life, low price, no toxicity, no environmental pollution, wide raw material sources, stable voltage platform, excellent safety performance, excellent cycle performance, and the like.
The lithium iron phosphate positive electrode material has many excellent properties, but has significant disadvantages. A huge gap exists between primary particles of the commonly prepared lithium iron phosphate, so that the tap density of the lithium iron phosphate is low, and the volume energy density of the lithium iron phosphate is low; in addition, the lithium iron phosphate anode material belongs to an olivine crystal structure, and the structure causes extremely low electronic conductivity and ion diffusivity, thereby greatly influencing the discharge capacity under high rate. By combining the reasons, the application range of the lithium iron phosphate cathode material is limited to a certain extent due to the defects of low tap density, low electronic conductivity and low ion diffusivity.
At present, people make a series of progress in the field of solving the problems of low electronic conductivity and low ion diffusivity, and people mainly adopt means of carbon coating, ion doping and particle nanocrystallization to improve the electronic conductivity and the ion diffusivity of the lithium iron phosphate anode material in the prior art, but improper carbon coating treatment can influence the exertion of material capacity and the improvement of rate capability, and too thick carbon layer can influence the tap density of the material; the metal particle doping needs to control the components and content of doped metal ions, and the doped metal particles cannot damage the crystal structure of the material, otherwise, the material capacity is reduced; too small a particle size of the nanoparticles will reduce the tap density of the material and is not conducive to increasing the volumetric energy density.
Disclosure of Invention
The invention aims to provide a magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, a preparation method and application thereof, and solves the problems of low tap density, low electronic conductivity and low ion diffusivity of a lithium iron phosphate material in the prior art.
The technical scheme of the invention is as follows:
a preparation method of magnesium-doped lithium iron phosphate/carbon composite microspheres with high tap density comprises the following steps:
(1) weighing a proper amount of iron source, phosphorus source, lithium source, magnesium hydroxide, PEG-400 and carbon source A, mixing in a solid phase to obtain a mixture, adding the mixture into deionized water containing zircon sand for ball milling, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished; wherein the molar ratio of the iron element, the phosphorus element, the lithium element and the magnesium element in the mixture is 1:1:1.01:0.01-0.05, the mass of the PEG-400 accounts for 2-5% of the mixture, and the mass of the carbon source accounts for 8-16% of the mixture.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas for high-temperature sintering, and collecting a product after the tube furnace is cooled to room temperature, namely the magnesium-doped lithium iron phosphate/carbon composite microsphere.
Preferably, the iron source in the step (1) is any one of iron phosphate, ferrous oxalate, ferric oxide, ammonium iron phosphate and ferrous phosphate, the phosphorus source is one or a combination of more of iron phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, the lithium source is one or a combination of two of lithium carbonate and lithium hydroxide, and the carbon source a is any one or a combination of more of glucose, sucrose and starch;
still preferably, in the step (1), the iron source and the phosphorus source are iron phosphate, the lithium source is lithium carbonate, and the carbon source a is glucose.
Preferably, the ball milling frequency in the step (1) is 40-60Hz, and the time is 20-40 min; the mass ratio of the deionized water to the mixture is 1-3:1, and the mass ratio of the zircon sand to the mixture is 8-16: 1.
Preferably, the ball milling frequency in the step (1) is 50Hz, and the time is 30 min; the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
Preferably, the feeding rate of the spray drying in the step (2) is 30mL/min, the frequency of the atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃.
Preferably, the sintering temperature in the step (3) is 700-.
The second purpose of the invention is to provide a magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, which is prepared by adopting the preparation method.
The third purpose of the invention is to provide application of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, wherein the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density is used for manufacturing a lithium ion battery anode material.
The invention has the beneficial effects that:
1. the magnesium-doped lithium iron phosphate/carbon composite material prepared by the preparation method has high electronic conductivity and ion diffusivity, good rate capability and cycle performance and high tap density, can be used for producing high-capacity and medium-high power lithium ion batteries, and has better specific capacity and longer service life;
2. according to the invention, by accurately controlling the addition of magnesium hydroxide, magnesium ions are successfully doped into lithium iron phosphate lattices on the premise of not changing the crystal structure, and are modified together by combining a carbon coating comprehensive method, so that the electronic conductivity and the ion diffusivity of the lithium iron phosphate composite material are improved, and the discharge capacity of the lithium iron phosphate composite material under high rate is further improved;
3. according to the invention, PEG-400 is added into the raw material, so that the PEG-400 can be used as a morphology control agent to cooperate with a spray forming technology to effectively regulate the sphericity of material particles, thereby improving the tap density of the material;
4. the flame retardance of magnesium hydroxide is fully utilized, the sintering temperature is stabilized by absorbing latent heat through thermal decomposition of the magnesium hydroxide and carrying away heat by generated steam, the sintering temperature is further increased to 790 ℃ in the lithiation process, thermal decomposition of a carbon source is facilitated, the graphitization degree is improved, the electronic conductivity and the ion diffusivity of the material are further improved, the carbon content in a magnesium-doped lithium iron phosphate product is reduced through the thermal decomposition of the carbon source, and the tap density of the material is further improved;
5. according to the invention, the growth of material grains is effectively inhibited through the synergistic effect of PEG-400 and a carbon source in the pyrolysis process, so that the transmission distance of lithium ions is shortened, the low electronic conductivity and the ion diffusivity of the lithium iron phosphate composite material are improved, and the discharge capacity of the lithium iron phosphate composite material under high rate is further improved;
6. the precursor powder can generate water vapor and carbon dioxide in the sintering process, and micropores can be formed when the water vapor and the carbon dioxide are separated, so that the prepared spherical lithium iron phosphate product has a porous structure, the porous structure is beneficial to full contact and infiltration of electrolyte and active substances, and the condition that the active substances are not fully infiltrated with the electrolyte to cause discharge capacity loss is avoided;
7. the preparation method is simple, easy to operate, free of special harsh devices, low in preparation condition requirements, low in cost and easy for large-scale production.
Drawings
FIG. 1 is an X-ray diffraction pattern of sample materials obtained in examples 1 to 3 and comparative example 1;
FIG. 2 is a scanning electron micrograph of sample materials obtained in examples 1 to 3 and comparative example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure. In the following examples, reagents and instruments not specifically described are commercially available, and experimental procedures not specifically described are carried out according to manufacturer's instructions or ordinary skill in the art, and unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the practice of the present invention.
The embodiment of the invention provides a preparation method of magnesium-doped lithium iron phosphate/carbon composite microspheres with high tap density, which comprises the following steps:
(1) weighing a proper amount of iron source, phosphorus source, lithium source, magnesium hydroxide, PEG-400 and carbon source A, mixing in a solid phase to obtain a mixture, adding the mixture into deionized water containing zircon sand for ball milling, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished; wherein the molar ratio of the iron element, the phosphorus element, the lithium element and the magnesium element in the mixture is 1:1:1.01:0.01-0.05, the mass of the PEG-400 accounts for 2-5% of the mass of the mixture, and the mass of the carbon source accounts for 8-16% of the mass of the mixture.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas for high-temperature sintering, and collecting a product after the tube furnace is cooled to room temperature to obtain the magnesium-doped lithium iron phosphate/carbon composite microsphere.
In some preferred embodiments of the present invention, the molar ratio of the iron element, the phosphorus element, the lithium element and the magnesium element in the mixture in step (1) can also be selected from 1:1:1.01:0.02, 1:1:1.01:0.03, 1:1:1.01: 0.04.
In some preferred embodiments of the present invention, the mass ratio of PEG-400 to the mixture in step (1) may be selected to be 2.5%, 3%, 3.5%, 4%, 4.5%, and the mass ratio of the carbon source to the mixture may be selected to be 9%, 10%, 11%, 12%, 13%, 14%, 15%.
In some preferred embodiments of the present invention, in step (1), the ball milling frequency may also be selected from 45Hz, 50Hz, and 55Hz, and the ball milling time may also be selected from 25min, 30min, and 35 min.
In some preferred embodiments of the present invention, the mass ratio of the deionized water to the mixture in step (1) may also be selected from 1.5:1, 2:1, and 2.5:1, and the mass ratio of the zircon sand to the mixture may also be selected from 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, and 15: 1.
In some preferred embodiments of the present invention, the sintering temperature in step (3) may be 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, and the sintering time may be 8.5h, 9h, 9.5 h.
The magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density is prepared by the preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density.
The magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density can be used for manufacturing a lithium ion battery anode material.
The following are specific examples:
example 1
A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, magnesium hydroxide, glucose and PEG-400, mixing the iron phosphate, the lithium carbonate, the magnesium hydroxide, the glucose and the PEG-400 to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron, phosphorus and lithium to magnesium in the mixture is 1:1:1.01:0.03, the mass of the PEG-400 is 2% of the mass of the mixture, the mass of the glucose is 10% of the mass of the mixture, the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 730 ℃ and the gas flow of 0.1mL/s for 8 hours at a high temperature to finally obtain a magnesium-doped lithium iron phosphate/carbon composite microsphere sample with high tap density.
Example 2
A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, magnesium hydroxide, glucose and PEG-400, mixing the iron phosphate, the lithium carbonate, the magnesium hydroxide, the glucose and the PEG-400 to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron, phosphorus and lithium to magnesium in the mixture is 1:1:1.01:0.01, the mass of the PEG-400 is 2% of the mass of the mixture, the mass of the glucose is 10% of the mass of the mixture, the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 730 ℃ for 8h under the condition that the gas flow is 0.1mL/s, thereby finally obtaining the magnesium-doped lithium iron phosphate/carbon composite microsphere sample with high tap density.
Example 3
A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, magnesium hydroxide, glucose and PEG-400, mixing the iron phosphate, the lithium carbonate, the magnesium hydroxide, the glucose and the PEG-400 to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron, phosphorus and lithium to magnesium in the mixture is 1:1:1.01:0.05, the mass of the PEG-400 is 2% of the mass of the mixture, the mass of the glucose is 10% of the mass of the mixture, the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 730 ℃ for 8h under the condition that the gas flow is 0.1mL/s, thereby finally obtaining the magnesium-doped lithium iron phosphate/carbon composite microsphere sample with high tap density.
Example 4
A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, magnesium hydroxide, glucose and PEG-400, mixing the iron phosphate, the lithium carbonate, the magnesium hydroxide, the glucose and the PEG-400 to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron, phosphorus and lithium to magnesium in the mixture is 1:1:1.01:0.03, the mass of the PEG-400 is 2% of the mass of the mixture, the mass of the glucose is 10% of the mass of the mixture, the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 790 ℃ and the gas flow rate of 0.1mL/s for 8 hours at a high temperature to finally obtain a magnesium-doped lithium iron phosphate/carbon composite microsphere sample with high tap density.
Comparative example 1
A lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, glucose and PEG-400, mixing the iron phosphate, the lithium carbonate, the glucose and the PEG-400 to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron element, phosphorus element and lithium element in the mixture is 1:1:1.01, the mass of the PEG-400 is 2% of the mass of the mixture, the mass of the glucose is 10% of the mass of the mixture, the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 730 ℃ for 8h under the condition that the gas flow is 0.1mL/s, thereby finally obtaining the lithium iron phosphate/carbon composite microsphere sample.
Comparative example 2
A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density and a preparation method thereof comprise the following steps:
(1) weighing a proper amount of iron phosphate, lithium carbonate, magnesium hydroxide and glucose, mixing the iron phosphate, the lithium carbonate, the magnesium hydroxide and the glucose to obtain a mixture in a solid phase manner, placing the mixture in deionized water containing zircon sand for ball milling, carrying out ball milling at the frequency of 50Hz for 30min, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished, wherein the molar ratio of iron element, phosphorus element, lithium element and magnesium element in the mixture is 1:1:1.01:0.03, the mass of the glucose is the addition amount corresponding to the carbon content of the obtained product of 1.6%, the mass ratio of the deionized water to the mixture consisting of the iron source, the phosphorus source, the lithium source, the magnesium hydroxide and the carbon source A is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) under the conditions that the feeding rate is 30mL/min, the frequency of an atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃ to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas, and sintering at the sintering temperature of 730 ℃ for 8h under the condition that the gas flow is 0.1mL/s, thereby finally obtaining the magnesium-doped lithium iron phosphate/carbon composite microsphere sample.
Test example 1
The inventors performed physicochemical property and button cell tests on samples prepared in examples 1 to 4 and comparative examples 1 to 2, and the results are shown in table 1 below, wherein the physicochemical property tests include a carbon content test and a tap density test;
the button cell testing method comprises the following steps: and (2) mixing the following components in percentage by mass: 15: sample No. 5: SP: PVDF is assembled into a buckle and tested under the condition that the cut-off voltage is 2.2V; the tap density is measured by a tap density meter, and the carbon content is measured by a carbon-sulfur analyzer.
TABLE 1 test results of sample materials of examples 1-4 and comparative examples 1-2
As can be seen from table 1 above:
the difference between examples 1-3 and comparative example 1 is in the magnesium content, and it can be seen that the optimum ratio of the mixture is: the molar ratio of the iron element, the phosphorus element, the lithium element and the magnesium element is 1:1:1.01:0.03, and too much or too little can cause the rate capability and the cycle performance of the material to be reduced, because too much magnesium ions are doped into the material to cause the lattice distortion of the material to be more serious, the reversibility of the material to be reduced, and the cycle performance to be reduced; the excessively low magnesium ion doping has limited improvement on the electronic conductivity and the ion diffusivity of the material, and is not enough to improve the rate capability and the cycle performance, so the optimal magnesium ion doping amount is 0.03 percent through the comparison experiment test; the difference between example 1 and example 4 is the difference in sintering temperature, and as can be seen from table 1, the sintering temperature was increased from 730 ℃ to 790 ℃, and the sample prepared in example 4 had a higher tap density.
The difference between the example 1 and the comparative example 2 is that the PEG-400 is added or not, and the table shows that the tap density of the sample material prepared by the comparative example 2 without adding PEG-400 is obviously lower than that of the example 1, which indicates that the PEG-400 can effectively improve the tap density of the synthetic material, and the discharge capacity and the cycle performance of the example 1 are higher than those of the comparative example 2, which indicates that the PEG-400 can play a synergistic effect with a carbon source, and the electronic conductivity and the ion diffusion rate of the lithium iron phosphate composite material are improved.
Test example 2
(1) The sample materials obtained in examples 1-3 and comparative example 1 were subjected to an X-ray diffraction test, and the XRD test results are shown in fig. 1, where diffraction peaks of samples prepared with different magnesium doping contents correspond to diffraction peaks of standard lithium iron phosphate uniformly and in a one-to-one manner, and no impurity peak is present, indicating that the samples conform to the olivine-type lithium iron phosphate structure; further illustrates that the crystal structure of the lithium iron phosphate is not changed by the doping of the magnesium ions. In addition, no diffraction peak of carbon was observed in the figure, indicating that carbon was in an amorphous state or contained in a low amount.
(2) The sample materials obtained in examples 1-3 and comparative example 1 are subjected to electron microscope scanning, and SEM test is shown in FIG. 2, and it can be seen that particles of the sample are all spherical and have holes on the surface, which indicates whether the addition of magnesium hydroxide does not affect the spherical porous morphology of the material, the spherical porous morphology is a result of the synergistic effect of PEG-400 and spray forming technology, and is independent of whether the magnesium hydroxide is added, and the spherical porous structure can improve the tap density of the material and is beneficial to the infiltration of electrolyte and electrode active substances.
In summary, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited too much, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that the technical solutions described in the foregoing embodiments can be easily deduced, replaced, or substituted for some technical features without departing from the spirit of the present invention, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of magnesium-doped lithium iron phosphate/carbon composite microspheres with high tap density is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing a proper amount of iron source, phosphorus source, lithium source, magnesium hydroxide, PEG-400 and carbon source, mixing the iron source, the phosphorus source, the lithium source, the magnesium hydroxide, the PEG-400 and the carbon source to obtain a mixture, adding the mixture into deionized water containing zircon sand for ball milling, and filtering and separating the zircon sand by using a screen to obtain slurry after the ball milling is finished; wherein the molar ratio of the iron element, the phosphorus element, the lithium element and the magnesium element in the mixture is 1:1:1.01:0.01-0.05, the mass of the PEG-400 accounts for 2-5% of the mass of the mixture, and the mass of the carbon source accounts for 8-16% of the mass of the mixture.
(2) Carrying out spray drying treatment on the slurry obtained in the step (1) to obtain yellowish-brown precursor powder;
(3) and (3) placing the yellowish-brown precursor powder obtained in the step (2) into a tube furnace rich in inert gas for high-temperature sintering, and collecting a product after the tube furnace is cooled to room temperature to obtain the magnesium-doped lithium iron phosphate/carbon composite microsphere.
2. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 1, which is characterized by comprising the following steps: the iron source in the step (1) is any one of iron phosphate, ferrous oxalate, ferric oxide, ammonium ferric phosphate and ferrous phosphate, the phosphorus source is one or a combination of more of iron phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, the lithium source is one or a combination of two of lithium carbonate and lithium hydroxide, and the carbon source A is any one or a combination of more of glucose, sucrose and starch.
3. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 2, characterized by comprising the following steps: in the step (1), the iron source and the phosphorus source are iron phosphate, the lithium source is lithium carbonate, and the preferred carbon source A is glucose.
4. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 1, which is characterized by comprising the following steps: the ball milling frequency in the step (1) is 40-60Hz, and the time is 20-40 min; the mass ratio of the deionized water to the mixture is 1-3:1, and the mass ratio of the zircon sand mixture is 8-16: 1.
5. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 4, characterized by comprising the following steps: the ball milling frequency in the step (1) is 50Hz, and the time is 30 min; the mass ratio of the deionized water to the mixture is 1.5:1, and the mass ratio of the zircon sand to the mixture is 12: 1.
6. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 1, which is characterized by comprising the following steps: in the step (2), the feeding rate of spray drying is 30mL/min, the frequency of the atomizing disc is 300Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃.
7. The preparation method of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 1, which is characterized by comprising the following steps: the sintering temperature in the step (3) is 700-790 ℃, the sintering time is 8-10h, and the inert gas flow is 0.1 mL/s.
8. A magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density, which is prepared by the preparation method of any one of claims 1 to 7.
9. The use of the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density according to claim 8, wherein: the magnesium-doped lithium iron phosphate/carbon composite microsphere with high tap density is used for manufacturing the anode material of the lithium ion battery.
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