CN115849321A - FePO for lithium ion battery anode material 4 Preparation method of hollow microspheres - Google Patents
FePO for lithium ion battery anode material 4 Preparation method of hollow microspheres 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 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010405 anode material Substances 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 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
- 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
- 238000001035 drying 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
- 238000001816 cooling Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 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
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 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
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 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 1
- 239000002105 nanoparticle Substances 0.000 abstract description 15
- 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 49
- 239000005955 Ferric phosphate Substances 0.000 description 48
- 229940032958 ferric phosphate Drugs 0.000 description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004090 dissolution 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
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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 invention discloses FePO for a lithium ion battery anode material 4 A method for preparing hollow microspheres. The preparation method comprises Fe (OH) 3 Preparation of precursor of inlaid carbon ball, fe (OH) 3 Pretreatment of/C ball precursor and FePO 4 Forming hollow microspheres and removing carbon spheres. The invention adopts the limited technology to obtain FePO for the anode material of the lithium ion battery 4 The hollow microsphere has a structure of FePO along with the removal of the carbon spheres as the precursor 4 The nano particles form hollow microspheres in situ, the appearance is easy to control, the size is uniform, the diameter of the microspheres is less than 3 mu m, and the FePO is 4 The grain diameter of the nano-particles is uniform and is below 50nm, the method has simple process and high product purity, and the process is easy to realize to obtain FePO 4 The hollow microsphere hasThe specific surface area is large, the surface density is low, the porosity is high, and the like, so that the volume effect in the charge and discharge process can be effectively inhibited, and the rate performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to FePO for a lithium ion battery anode material 4 A method for preparing 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 energy storage equipment is more and more extensive. LiFePO 4 The material is non-toxic and environment-friendly, has rich raw material sources, and has cycle performance and thermal stabilityThe performance is good, and the like, and is considered to be one of the best positive electrode materials of the lithium ion power battery. Iron phosphate (FePO) 4 ) The morphology, structure and chemical composition of the precursor of lithium iron phosphate as the anode material of the lithium ion battery directly influence the performance of the lithium ion battery. Although FePO 4 Has the advantages of rich raw materials, low price, large discharge capacity (170 mAh/g), no toxicity, environmental protection and the like, however, the practical application of the lithium ion secondary battery is greatly restricted due to the defects of low conductivity, slow lithium ion diffusion and the like.
Designing special nanostructures is an effective strategy for improving the electrochemical performance of lithium ion batteries. For example, fePO 4 The hollow microspheres have the characteristics of large specific surface area, low surface density, high porosity and the like, can effectively inhibit the volume effect in the charging and discharging process, and improve the rate capability of the battery. In addition, high porosity can provide more Li + Position of deintercalation, shortening of Li + Diffusion distance, thereby improving the specific capacity and the cycle performance of the composite material. For FePO at present 4 The synthesis of hollow microspheres mostly adopts a surfactant or template (including a hard template, a soft template and a self-sacrificial template) combined precipitation method, and the method is characterized in that the generated product is basically ferric phosphate (FePO) containing crystal water 4 ·2H 2 O), further synthesizing LiFePO 4 The crystal water removal treatment is needed, and the long-term application of the crystal water removal treatment is limited. In addition, most of the template methods are to firstly generate a template and then deposit FePO 4 So that FePO is formed 4 The nanoparticles are not uniform enough in particle size and are prone to agglomeration. Therefore, the invention utilizes glucose as a carbon source, and the carbon-embedded Fe (OH) is firstly synchronously obtained by a hydrothermal carbonization method 3 The microspheres are removed by a solid-phase calcination method to obtain FePO 4 Hollow microspheres to circumvent FePO 4 The problems existed in the preparation process of the hollow microsphere.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides FePO for a positive electrode material of a lithium ion battery 4 A method for preparing hollow microspheres.
The invention discloses a lithium ion batteryFePO of positive electrode material 4 Preparation method of hollow microspheres，The method specifically comprises the following steps:
1）Fe(OH) 3 the preparation method of the embedded carbon sphere precursor comprises the steps of adding glucose and ferric salt into ionized water, stirring until the glucose and the ferric salt are completely dissolved, adding urea, stirring uniformly, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 8-16 h at 140-180 ℃, and carrying out aftertreatment to obtain Fe (OH) 3 Studded carbon sphere precursor, i.e. Fe (OH) 3 a/C ball precursor;
2）Fe(OH) 3 pretreatment of C ball precursor Fe (OH) prepared in step 1) 3 Performing ball milling on the/C ball precursor, phosphate, urea and grinding aid in a ball mill, and drying to obtain Fe (OH) 3 a/C ball precursor mixture;
3）FePO 4 formation of hollow microspheres and removal of carbon spheres Fe (OH) treated in step 2) 3 Adding the/C ball precursor mixture into a tubular furnace, heating to the calcining temperature, calcining in air atmosphere, and removing Fe (OH) while oxidizing carbon into carbon dioxide 3 Reacting with phosphate to convert into FePO 4 To obtain 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, hydrogen peroxide serving as an oxidant is added; the molar ratio of the oxidant to the ferrous ions is 1 to 3:1.
further, the invention also discloses that the molar ratio of the glucose, the urea and the ferric salt in the step 1) is 2 to 10:3 to 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 kind of (1).
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 C ball precursor 3+ PO in phosphate 4 3- And urea in a molar ratio of 1:1:2 to 4.
Further, the invention also discloses that the heating rate in the step 3) is 3-8 ℃/min.
Further, the invention also discloses that the calcining temperature in the step 3) is 600-800 ℃, and the calcining time is 1-5h.
Further, the invention also discloses 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 12h to obtain Fe (OH) 3 a/C ball precursor.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) The invention adopts the limited technology to obtain FePO for the anode material of the lithium ion battery 4 The hollow microsphere has the structure of FePO with the removal of the precursor carbon spheres 4 The nano particles form hollow microspheres in situ, the appearance is easy to control, the size is uniform, the diameter of the microspheres is less than 3 mu m, and the FePO is 4 The nano particles have uniform particle size, and no agglomeration phenomenon occurs below 50 nm;
2) The invention adopts glucose as carbon source, and firstly synchronously obtains carbon-embedded Fe (OH) by a hydrothermal carbonization method 3 The microsphere avoids ferric phosphate (FePO) obtained by a precipitation method 4 ·2H 2 O) further removing crystal water, removing carbon spheres by using a solid-phase calcination method and obtaining FePO 4 The electrochemical performance of the lithium ion battery is improved in a hollow mode, the method is simple in process, the product purity is high, and the process is easy to realize;
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 by high porosity + Position of deintercalation, shortening of Li + Diffusion distance, thereby improving the specific capacity and the cycle performance of the material.
Drawings
FIG. 1 is a FePO prepared according to the invention based on example 1 4 SEM image of hollow microspheres.
FIG. 2 is FePO based on example 1 4 High power SEM images of hollow microspheres.
FIG. 3 is FePO prepared according to the invention based on example 2 4 SEM image of hollow microspheres.
FIG. 4 is FePO prepared according to the invention based on example 3 4 SEM image of hollow microspheres.
FIG. 5 is FePO prepared according to the invention based on example 4 4 SEM image of hollow microspheres.
FIG. 6 is FePO prepared based on example 5 in accordance with the present invention 4 SEM image of hollow microspheres.
Detailed Description
The invention is described in further detail below with reference to the following figures and detailed description.
Example 1:
(1) Dissolving 5.4g of glucose and 2.25g of ferrous sulfate in 160ml of deionized water under the stirring condition, adding 1.6ml of hydrogen peroxide solution (30%) into the solution after complete dissolution, continuously stirring for 30min, then adding 2.7g of urea into the solution, stirring for 10min to dissolve uniformly, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 8 h. Cooling to room temperature, precipitating, centrifuging, washing with water and anhydrous ethanol respectively, and drying (60 deg.C, 12 hr) to obtain Fe (OH) 3 a/C sphere precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 C ball precursor, 1.15gNH 4 H 2 PO 4 1.2g of urea and 3ml of deionized water are put into a steel ball milling tank together for ball milling, the rotating speed is set to be 220 r/min, the ball milling time is set to be 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12h;
(3) Drying the second step, and then adding 3g of Fe (OH) 3 Calcining the/C ball precursor mixture in a tubular furnace under the air atmosphere condition, heating at the rate of 3 ℃/min, keeping the temperature at 600 ℃ for 5h, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. Shown as root in FIG. 1FePO prepared according to this example 4 The SEM image of the hollow microsphere shows that the product has a spherical structure, and the diameter of the sphere is less than 3 μm. And the hollow structure of the ball can also be seen from the surface of the open ball. FIG. 2 is a FePO prepared according to this example 4 The high-power SEM image of the hollow microsphere shows that the FePO4 nano-particles are relatively uniform in size and have an average particle size of less than 50nm. Demonstration of the FePO prepared 4 The hollow microspheres are indeed hollow structure and FePO 4 The nanoparticles are relatively uniform.
Example 2:
(1) Dissolving 5.4g of glucose and 0.48g of ferric trichloride in 160ml of deionized water under the condition of stirring, continuously stirring for 30min, then adding 0.96g of urea into the solution, stirring for 10min, uniformly dissolving, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 16 h at 140 ℃. Cooling to room temperature, precipitating, centrifuging, washing with water and anhydrous ethanol respectively, and drying (60 deg.C, 12 hr) to obtain Fe (OH) 3 a/C ball precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 C ball precursor, 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 be 220 r/min, the ball milling time is set to be 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12h;
(3) 2g of Fe (OH) dried in the second step 3 Calcining the/C ball precursor mixture in a tubular furnace under the condition of air atmosphere, wherein the heating rate is 8 ℃/min, keeping the temperature at 800 ℃ for 1h, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. FePO prepared according to this example is shown in FIG. 3 4 The SEM image of the hollow microsphere shows that the product has a spherical structure, and the diameter of the sphere is less than 3 μm. And the hollow structure of the ball can also be seen from the surface of the open ball. From the figure, fePO can also be observed 4 The nano particles are uniform in size, and the average particle size is less than 50nm. Demonstration of the FePO prepared 4 The hollow microspheres are indeed hollow structure and FePO 4 The nanoparticles are relatively uniform.
Example 3:
(1) Dissolving 3.6g of glucose and 0.6g of ferrous chloride in 100ml of deionized water under the stirring condition, adding 0.5ml of hydrogen peroxide solution (30%) into the solution after complete dissolution, continuously stirring for 30min, then adding 1.8g of urea into the solution, stirring for 10min to dissolve uniformly, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 12 h. Cooling to room temperature, precipitating, centrifuging, washing with water and anhydrous ethanol respectively, and drying (60 deg.C, 12 hr) to obtain Fe (OH) 3 a/C ball precursor;
(2) Mixing the 3gFe (OH) prepared in the first step 3 C ball precursor, 1.79g (NH) 4 ) 3 PO 4 1.8g of urea and 3ml of deionized water are put into a steel ball milling tank for ball milling, the rotating speed is set to be 220 r/min, the ball milling time is set to be 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12h;
(3) 2g of Fe (OH) dried in the second step 3 Calcining the/C ball precursor mixture in a tubular furnace under the condition of air atmosphere, wherein the heating rate is 5 ℃/min, the temperature is kept at 700 ℃ for 2.5h, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. FIG. 4 shows FePO prepared according to this example 4 The SEM image of the hollow microsphere shows that the product has a spherical structure, and the diameter of the sphere is less than 3 μm. And the hollow structure of the ball can also be seen from the surface of the open ball. From the figure, fePO can also be observed 4 The nano particles are relatively uniform in size, and the average particle size is less than 50nm. Demonstration of the FePO prepared 4 The hollow microspheres are indeed hollow structure and FePO 4 The nanoparticles are relatively uniform.
Example 4:
(1) Dissolving 1.8g of glucose and 0.5g of ferric nitrate in 60ml of deionized water under the condition of stirring, continuously stirring for 30min, then adding 0.6g of urea into the solution, stirring for 10min to dissolve uniformly, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 10 h at 170 ℃. Cooling to room temperature, precipitating, centrifuging, washing with water and anhydrous ethanol respectively, and drying (60 deg.C, 12 hr) to obtain Fe (OH) 3 a/C ball precursor;
(2) The first stepPreparation of 1gFe (OH) 3 C ball precursor, 0.46g NH 4 H 2 PO 4 0.9g of urea and 1ml of deionized water are put into a steel ball milling tank for ball milling, the rotating speed is set to be 220 r/min, the ball milling time is set to be 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12h;
(3) Drying the second step to obtain 1g of Fe (OH) 3 Calcining the/C ball precursor mixture in a tubular furnace under the air atmosphere condition, keeping the temperature for 2h at 700 ℃ with the heating rate of 4 ℃/min, and naturally cooling to room temperature to obtain the required FePO 4 Hollow microspheres. FIG. 5 shows FePO prepared according to this example 4 The SEM image of the hollow microsphere shows that the product has a spherical structure, and the diameter of the sphere is less than 3 μm. And the hollow structure of the ball can also be seen from the surface of the open ball. From the figure, fePO can also be observed 4 The nano particles are relatively uniform in size, and the average particle size is less than 50nm. Demonstration of the FePO prepared 4 The hollow microspheres are indeed hollow structure and FePO 4 The nanoparticles are relatively uniform.
Example 5:
(1) Dissolving 2.7g of glucose and 1.17g of ferrous sulfate in 80ml of deionized water under the stirring condition, adding 1.2ml of hydrogen peroxide solution (30%) into the solution after complete dissolution, continuously stirring for 30min, then adding 1.7g of urea into the solution, stirring for 10min to dissolve uniformly, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 14 h. Cooling to room temperature, precipitating, centrifuging, washing with water and anhydrous ethanol respectively, and drying (60 deg.C, 12 hr) to obtain Fe (OH) 3 a/C ball precursor;
(2) 2.5g of Fe (OH) prepared in the first step 3 C ball precursor, 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 be 220 r/min, the ball milling time is set to be 1h, and then the treated mixture is dried in an oven at 80 ℃ for 12h;
(3) Drying the second step to obtain 1g of Fe (OH) 3 Calcining the/C ball precursor mixture in a tubular furnace under the air atmosphere condition, keeping the temperature for 4h at 650 ℃ with the heating rate of 6 ℃/min, and naturally coolingCooling to room temperature to obtain the required FePO 4 Hollow microspheres. FIG. 6 shows FePO prepared according to this example 4 The SEM image of the hollow microsphere shows that the product has a spherical structure, and the diameter of the sphere is less than 3 μm. Further, fePO was observed from the graph 4 The nano particles are relatively uniform in size, and the average particle size is less than 50nm. Demonstration of the FePO prepared 4 The hollow microspheres are indeed hollow structure 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 all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (10)
1. FePO for lithium ion battery anode material 4 Preparation method of hollow microspheres，The method is characterized by comprising the following steps:
1）Fe(OH) 3 the preparation method of the embedded carbon sphere precursor comprises the steps of adding glucose and ferric salt into ionized water, stirring until the glucose and the ferric salt are completely dissolved, adding urea, stirring uniformly, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 8-16 h at 140-180 ℃, and carrying out aftertreatment to obtain Fe (OH) 3 Studded carbon sphere precursor, i.e. Fe (OH) 3 a/C sphere precursor;
2）Fe(OH) 3 pretreatment of/C ball precursor Fe (OH) prepared in step 1) 3 Performing ball milling on the/C ball precursor, phosphate, urea and grinding aid in a ball mill, and drying to obtain Fe (OH) 3 A C ball precursor mixture;
3）FePO 4 formation of hollow microspheres and removal of carbon spheres Fe (OH) treated in step 2) 3 Adding the/C ball precursor mixture into a tubular furnace, heating to the calcining temperature, calcining in air atmosphere, and removing Fe (OH) while oxidizing carbon into carbon dioxide 3 Reacting with phosphate to convert into FePO 4 To obtain the required FePO 4 Hollow microspheres.
2. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheresMethod of making，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 lithium ion battery positive electrode material according to claim 2 4 Preparation method of hollow microspheres，The method is characterized in that when the ferric salt in the step 1) is ferrous salt, hydrogen peroxide serving as an oxidant is added at the same time; the molar ratio of the oxidant to the ferrous ions is 1 to 3:1.
4. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheres，The method is characterized in that the molar ratio of glucose, urea and ferric salt in the step 1) is 2-10: 3 to 6:1.
5. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheres，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 kind of (1).
6. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheres，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 microspheres，It is characterized in that Fe (OH) in the step 2) 3 Fe in C ball precursor 3+ PO in phosphate 4 3- And urea in a molar ratio of 1:1:2 to 4.
8. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheres，Characterized by the temperature increase in step 3)The speed is 3 ℃/min-8 ℃/min.
9. FePO for lithium ion battery positive electrode material according to claim 1 4 Preparation method of hollow microspheres，The method is characterized in that the calcining temperature in the step 3) is 600-800 ℃, and the calcining time is 1-5h.
10. FePO for use in a positive electrode material for lithium ion batteries according to any one of claims 1 to 9 4 Preparation method of hollow microspheres，The method is characterized in that the post-treatment process of the step 1) comprises the following steps: cooling to room temperature after the reaction is finished, precipitating, centrifugally separating, respectively washing with water and absolute ethyl alcohol, and drying at 60 ℃ for 12h to obtain Fe (OH) 3 a/C ball precursor.
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