CN115849321B - FePO for lithium ion battery anode material 4 Preparation method of hollow microsphere - Google Patents
FePO for lithium ion battery anode material 4 Preparation method of hollow microsphere Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 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 13
- 239000008103 glucose Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 50
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 50
- 239000005955 Ferric phosphate Substances 0.000 description 49
- 229940032958 ferric phosphate Drugs 0.000 description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a FePO used for a lithium ion battery anode material 4 A preparation method of hollow microspheres. The preparation method comprises Fe (OH) 3 Preparation of embedded carbon sphere precursor and Fe (OH) 3 Pretreatment of/C sphere precursor and FePO 4 Formation of hollow microspheres and removal of carbon spheres. The invention adopts a limited technology to obtain FePO for the anode material of the lithium ion battery 4 Hollow microsphere with structure of FePO along with removal of precursor carbon sphere 4 The nano particles form hollow microspheres in situ, the morphology is easy to control, the size is uniform, the diameter of the microspheres is smaller than 3 mu m, and FePO is prepared 4 The particle size of the nano particles is uniform and is below 50nm, the method has simple process, high product purity and easy realization of process, and FePO is obtained 4 The hollow microsphere has the characteristics of large specific surface area, low surface density, high porosity and the like, can effectively inhibit the volume effect in the charge and discharge process, and improves the rate capability of the battery.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of lithium ion batteries, and particularly relates to FePO for a positive electrode material of a lithium ion battery 4 A preparation method of hollow microspheres.
Background
With the development of the fields of environmental protection, electric automobile technology and the like, the application of the lithium ion battery as the energy storage device is more and more widespread. LiFePO 4 The material is considered as one of the best lithium ion power battery anode materials by the advantages of no toxicity, environmental protection, abundant sources of raw materials, good cycle performance and thermal stability, and the like. Ferric phosphate (FePO) 4 ) As a precursor of lithium iron phosphate as a positive electrode material of a lithium ion battery, the shape, structure and chemical composition of the precursor directly influence the performance of the lithium ion battery. Although FePO 4 The lithium ion battery has the advantages of rich raw materials, low price, large discharge capacity (170 mAh/g), no toxicity, environmental friendliness and the like, but the practical application is greatly restricted due to the defects of low conductivity, slow lithium ion diffusion and the like.
Designing specific nanostructures to enhance lithium ionAn effective strategy for the electrochemical performance of a subcell. For example, fePO 4 The hollow microsphere has the characteristics of large specific surface area, low surface density, high porosity and the like, can effectively inhibit the volume effect in the charge and discharge process, and improves the rate capability of the battery. In addition, high porosity can provide more Li + The deintercalation position shortens Li + Diffusion distance, thereby improving specific capacity and cycle performance. Currently for FePO 4 The synthesis of hollow microspheres is mostly carried out by a surfactant or a template (including hard template, soft template and self-sacrifice template) combined precipitation method, and the product is basically ferric phosphate (FePO) containing crystal water 4 ·2H 2 O), further synthesis of LiFePO 4 When the crystallization water removal treatment is needed, the long-term application of the crystallization water removal treatment is limited. In addition, most of the template methods are to generate templates first and deposit FePO 4 So that FePO 4 The particle size of the nanoparticles is not uniform enough and is prone to agglomeration. Therefore, glucose is used as a carbon source, and the carbon mosaic Fe (OH) is firstly and synchronously obtained by a hydrothermal carbonization method 3 Removing carbon spheres by solid phase calcination to obtain FePO 4 Hollow microsphere to avoid FePO 4 Problems exist in the preparation process of hollow microspheres.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides FePO for a positive electrode material of a lithium ion battery 4 A preparation method of hollow microspheres.
The invention discloses a FePO used for a lithium ion battery anode material 4 Preparation method of hollow microsphere，The method specifically comprises the following steps:
1）Fe(OH) 3 preparation of the embedded carbon sphere precursor, adding glucose and ferric salt into ionized water, stirring until the glucose and ferric salt are completely dissolved, adding urea, stirring uniformly, transferring the mixed solution into a hydrothermal reaction kettle, reacting at 140-180 ℃ for 8-16 h, and performing post-treatment to obtain Fe (OH) 3 Inlay carbon sphere precursors, i.e. Fe (OH) 3 a/C sphere precursor;
2）Fe(OH) 3 pretreatment of the ball precursor to be prepared in step 1)Fe(OH) 3 Ball milling and drying the ball precursor, phosphate, urea and grinding aid on a ball mill to obtain Fe (OH) 3 a/C sphere precursor mixture;
3）FePO 4 formation of hollow microspheres and removal of carbon spheres the Fe (OH) treated in step 2) 3 Adding the ball precursor mixture into a tube furnace, heating to calcination temperature, calcining under air atmosphere, and oxidizing carbon into Fe (OH) while removing carbon dioxide 3 Conversion to FePO by reaction with phosphate 4 Obtaining the required FePO 4 Hollow microspheres.
Further, the invention also discloses that the ferric salt in the step 1) is one of ferric trichloride, ferric nitrate, ferrous sulfate and ferrous chloride.
Further, the invention also discloses that when the ferric salt in the step 1) is ferrous salt, oxidant hydrogen peroxide is added at the same time; the molar ratio of the oxidant to the ferrous ions is 1-3: 1.
further, the invention also discloses that the molar ratio of glucose, urea and ferric salt in the step 1) is 2-10: 3-6: 1.
further, the invention also discloses that the phosphate in the step 2) is NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 One of them.
Further, the invention also discloses that the grinding aid in the step 2) is water or ethanol.
Further, the invention also discloses Fe (OH) in the step 2) 3 Fe in the ball-C precursor 3+ PO in phosphate 4 3- And urea molar ratio 1:1: 2-4.
Furthermore, the invention also discloses a heating rate in the step 3) is 3 ℃/min-8 ℃/min.
Further, the invention also discloses the calcination temperature in the step 3) is 600-800 ℃ and the calcination time is 1-5 h.
Further, the invention also discloses a post-treatment process of the step 1), which comprises the following steps: cooling to room temperature after the reaction is finished, and separating by precipitation and centrifugationSeparating, washing with water and absolute ethanol respectively, and drying at 60deg.C for 12 hr to obtain Fe (OH) 3 and/C ball precursor.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) The invention adopts a limited technology to obtain FePO for the anode material of the lithium ion battery 4 Hollow microsphere with structure of FePO along with removal of precursor carbon sphere 4 The nano particles form hollow microspheres in situ, the morphology is easy to control, the size is uniform, the diameter of the microspheres is smaller than 3 mu m, and FePO is prepared 4 The particle size of the nano particles is uniform and below 50nm, so that no agglomeration phenomenon occurs;
2) According to the invention, glucose is used as a carbon source, and carbon embedded Fe (OH) is firstly obtained synchronously by a hydrothermal carbonization method 3 The microspheres of (2) avoid the precipitation of ferric phosphate (FePO) 4 ·2H 2 O) the treatment process of further removing crystal water, and then removing carbon spheres by using a solid phase calcination method to obtain FePO 4 The hollow micro-improvement of the electrochemical performance of the lithium ion battery has simple process and high product purity, and is easy to realize the process;
3) The invention designs a special nano structure to obtain FePO 4 The hollow microsphere has the characteristics of large specific surface area, low surface density, high porosity and the like, can effectively inhibit the volume effect in the charge and discharge process, improves the rate capability of the battery, and can provide more Li with high porosity + The deintercalation position shortens Li + Diffusion distance, thereby improving specific capacity and cycle performance.
Drawings
FIG. 1 is a FePO of the invention prepared based on example 1 4 SEM image of hollow microspheres.
FIG. 2 is a FePO based on example 1 4 SEM image of hollow microspheres at high magnification.
FIG. 3 is a FePO of the invention prepared based on example 2 4 SEM image of hollow microspheres.
FIG. 4 is a FePO of the invention prepared based on example 3 4 SEM image of hollow microspheres.
FIG. 5 is a schematic diagram of a preferred embodiment of the present inventionThe invention is based on FePO prepared in example 4 4 SEM image of hollow microspheres.
FIG. 6 is a FePO of the invention prepared based on example 5 4 SEM image of hollow microspheres.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1:
(1) 5.4g of glucose and 2.25g of ferrous sulfate are dissolved in 160ml of deionized water under stirring, 1.6ml of hydrogen peroxide solution (30%) is added into the solution after complete dissolution, stirring is continued for 30min, then 2.7g of urea is added into the solution, stirring is continued for 10min, after the solution is uniformly dissolved, the mixed solution is transferred into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 180 ℃ for 8 h. Finally cooling to room temperature, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying (60 ℃ for 12 h) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 Ball precursor/C, 1.15gNH 4 H 2 PO 4 Placing 1.2g of urea and 3ml of deionized water into a steel ball milling tank for ball milling, setting the rotating speed to 220 r/min and the ball milling time to 1h, and drying the treated mixture in an oven at 80 ℃ for 12 hours;
(3) 3g of Fe (OH) after the second drying step 3 Calcining the mixture of the ball precursor and the C ball precursor in a tubular furnace under the air atmosphere condition, keeping the temperature at the heating rate of 3 ℃/min and the temperature of 600 ℃ for 5 hours, and naturally cooling to the room temperature to obtain the required FePO 4 Hollow microspheres. As shown in FIG. 1, fePO prepared according to this example 4 SEM pictures of hollow microspheres, it is evident from the pictures that the product has a spherical structure, the diameter of the sphere being less than 3 μm. And the hollow structure of the ball can be seen from the surface of the open ball. FIG. 2 is a FePO prepared according to the present example 4 From the high-power SEM image of the hollow microspheres, it can be seen that the FePO4 nanoparticles are relatively uniform in size and have an average particle size of less than 50nm. Demonstration of FePO prepared 4 The hollow microsphere is indeed hollow and FePO 4 The nanoparticles are relatively uniform.
Example 2:
(1) 5.4g of glucose and 0.48g of ferric trichloride are dissolved in 160ml of deionized water under stirring, stirring is continued for 30min, then 0.96g of urea is added into the solution, stirring is carried out for 10min, after the solution is uniformly dissolved, the mixed solution is transferred into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 140 ℃ for 16 h. Finally cooling to room temperature, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying (60 ℃ for 12 h) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 Ball precursor/C, 1.32g (NH) 4 ) 2 HPO 4 2.4g of urea and 3ml of absolute ethyl alcohol are put into a steel ball milling tank together for ball milling, the rotating speed is set to 220 r/min, the ball milling time is set to 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12 hours;
(3) 2g of Fe (OH) after the second drying step 3 Calcining the mixture of the ball precursor and the C ball precursor in a tubular furnace under the air atmosphere condition, keeping the temperature at the heating rate of 8 ℃/min and the temperature of 800 ℃ for 1h, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. As shown in FIG. 3, fePO prepared according to this example 4 SEM pictures of hollow microspheres, it is evident from the pictures that the product has a spherical structure, the diameter of the sphere being less than 3 μm. And the hollow structure of the ball can be seen from the surface of the open ball. From the figure it can also be observed that FePO 4 The size of the nano particles is uniform, and the average particle size is smaller than 50nm. Demonstration of FePO prepared 4 The hollow microsphere is indeed hollow and FePO 4 The nanoparticles are relatively uniform.
Example 3:
(1) 3.6g of glucose and 0.6g of ferrous chloride are dissolved in 100ml of deionized water under stirring, 0.5ml of hydrogen peroxide solution (30%) is added into the solution after complete dissolution, stirring is continued for 30min, then 1.8g of urea is added into the solution, stirring is continued for 10min, after the solution is uniformly dissolved, the mixed solution is transferred into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 160 ℃ for 12 h. Finally cooling to room temperature, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying (60 ℃ for 12 h) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 3gFe (OH) prepared in the first step 3 Ball precursor/C, 1.79g (NH) 4 ) 3 PO 4 Placing 1.8g of urea and 3ml of deionized water into a steel ball milling tank for ball milling, setting the rotating speed to 220 r/min and the ball milling time to 1h, and drying the treated mixture in an oven at 80 ℃ for 12 hours;
(3) 2g of Fe (OH) after the second drying step 3 Calcining the mixture of the ball precursor and the C ball precursor in a tube furnace under the air atmosphere condition, keeping the temperature at the temperature rising rate of 5 ℃/min and the temperature of 700 ℃ for 2.5 hours, and naturally cooling to the room temperature to obtain the required FePO 4 Hollow microspheres. As shown in FIG. 4, fePO prepared according to this example 4 SEM pictures of hollow microspheres, it is evident from the pictures that the product has a spherical structure, the diameter of the sphere being less than 3 μm. And the hollow structure of the ball can be seen from the surface of the open ball. From the figure it can also be observed that FePO 4 The size of the nano particles is uniform, and the average particle size is smaller than 50nm. Demonstration of FePO prepared 4 The hollow microsphere is indeed hollow and FePO 4 The nanoparticles are relatively uniform.
Example 4:
(1) 1.8g of glucose and 0.5g of ferric nitrate are dissolved in 60ml of deionized water under stirring, stirring is continued for 30min, then 0.6g of urea is added into the solution, stirring is carried out for 10min, after the solution is uniformly dissolved, the mixed solution is transferred into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 170 ℃ for 10 h. Finally cooling to room temperature, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying (60 ℃ for 12 h) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 1gFe (OH) prepared in the first step 3 Ball precursor/C, 0.46g NH 4 H 2 PO 4 Placing 0.9g of urea and 1ml of deionized water into a steel ball milling tank for ball milling, setting the rotating speed to 220 r/min and the ball milling time to 1h, and drying the treated mixture in an oven at 80 ℃ for 12 hours;
(3) Drying 1g Fe (OH) in the second step 3 Calcining the ball precursor mixture in the air atmosphere condition in a tube furnace, keeping the temperature at a heating rate of 4 ℃/min and 700 ℃ for 2 hours, and naturally cooling to room temperature to obtain the ball precursorObtaining the required FePO 4 Hollow microspheres. As shown in FIG. 5, fePO prepared according to this example 4 SEM pictures of hollow microspheres, it is evident from the pictures that the product has a spherical structure, the diameter of the sphere being less than 3 μm. And the hollow structure of the ball can be seen from the surface of the open ball. From the figure it can also be observed that FePO 4 The size of the nano particles is uniform, and the average particle size is smaller than 50nm. Demonstration of FePO prepared 4 The hollow microsphere is indeed hollow and FePO 4 The nanoparticles are relatively uniform.
Example 5:
(1) 2.7g of glucose and 1.17g of ferrous sulfate are dissolved in 80ml of deionized water under stirring, 1.2ml of hydrogen peroxide solution (30%) is added into the solution after complete dissolution, stirring is continued for 30min, then 1.7g of urea is added into the solution, stirring is continued for 10min, after the solution is uniformly dissolved, the mixed solution is transferred into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at 150 ℃ for 14 h. Finally cooling to room temperature, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying (60 ℃ for 12 h) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 Ball precursor/C, 1.32g (NH) 4 ) 2 HPO 4 2.4g of urea and 3ml of absolute ethyl alcohol are put into a steel ball milling tank together for ball milling, the rotating speed is set to 220 r/min, the ball milling time is set to 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12 hours;
(3) Drying 1g Fe (OH) in the second step 3 Calcining the mixture of the ball precursor and the C ball precursor in a tubular furnace under the air atmosphere condition, keeping the temperature rising rate of 6 ℃/min and the temperature of 650 ℃ for 4 hours, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. As shown in FIG. 6, fePO prepared according to this example 4 SEM pictures of hollow microspheres, it is evident from the pictures that the product has a spherical structure, the diameter of the sphere being less than 3 μm. Moreover, fePO can also be seen from the figure 4 The size of the nano particles is uniform, and the average particle size is smaller than 50nm. Demonstration of FePO prepared 4 The hollow microsphere is indeed hollow and FePO 4 The nanoparticles are relatively uniform.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (10)
1. FePO for lithium ion battery anode material 4 Preparation method of hollow microsphere，The method is characterized by comprising the following steps of:
1）Fe(OH) 3 preparation of the embedded carbon sphere precursor, adding glucose and ferric salt into ionized water, stirring until the glucose and ferric salt are completely dissolved, adding urea, stirring uniformly, transferring the mixed solution into a hydrothermal reaction kettle, reacting at 140-180 ℃ for 8-16 h, and performing post-treatment to obtain Fe (OH) 3 Inlay carbon sphere precursors, i.e. Fe (OH) 3 a/C sphere precursor;
2）Fe(OH) 3 pretreatment of the ball precursor Fe (OH) prepared in step 1) 3 Ball milling and drying the ball precursor, phosphate, urea and grinding aid on a ball mill to obtain Fe (OH) 3 a/C sphere precursor mixture;
3）FePO 4 formation of hollow microspheres and removal of carbon spheres the Fe (OH) treated in step 2) 3 Adding the ball precursor mixture into a tube furnace, heating to calcination temperature, calcining under air atmosphere, and oxidizing carbon into Fe (OH) while removing carbon dioxide 3 Conversion to FePO by reaction with phosphate 4 Obtaining the required FePO 4 Hollow microspheres.
2. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，The method is characterized in that the ferric salt in the step 1) is one of ferric trichloride, ferric nitrate, ferrous sulfate and ferrous chloride.
3. FePO for positive electrode material of lithium ion battery according to claim 2 4 Preparation method of hollow microsphere，It is characterized in that when the ferric salt in the step 1) is ferrous salt, oxidant hydrogen peroxide is added at the same time; the molar ratio of the oxidant to the ferrous ions is 1-3: 1.
4. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，The method is characterized in that the molar ratio of glucose to urea to ferric salt in the step 1) is 2-10: 3-6: 1.
5. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，Characterized in that the phosphate in step 2) is NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 One of them.
6. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，The method is characterized in that the grinding aid in the step 2) is water or ethanol.
7. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，Characterized in that Fe (OH) in step 2) 3 Fe in the ball-C precursor 3+ PO in phosphate 4 3- And urea molar ratio 1:1: 2-4.
8. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，The method is characterized in that the heating rate in the step 3) is 3-8 ℃ per minute.
9. FePO for positive electrode material of lithium ion battery according to claim 1 4 Preparation method of hollow microsphere，The method is characterized in that the calcination temperature in the step 3) is 600-800 ℃ and the calcination time is 1-5 h.
10. A method according to any one of claims 1 to 9 for lithium ionFePO of battery positive electrode material 4 Preparation method of hollow microsphere，The method is characterized in that the post-treatment process of the step 1) is as follows: cooling to room temperature after the reaction is finished, precipitating, centrifugally separating, washing with water and absolute ethyl alcohol respectively, and drying at 60 ℃ for 12 hours to obtain Fe (OH) 3 and/C ball precursor.
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