CN114975927B - Graphene oxide-sodium iron phosphate composite positive electrode material and preparation method thereof - Google Patents
Graphene oxide-sodium iron phosphate composite positive electrode material and preparation method thereof Download PDFInfo
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- CN114975927B CN114975927B CN202210581846.3A CN202210581846A CN114975927B CN 114975927 B CN114975927 B CN 114975927B CN 202210581846 A CN202210581846 A CN 202210581846A CN 114975927 B CN114975927 B CN 114975927B
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- graphene oxide
- iron phosphate
- positive electrode
- sodium iron
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 239000011734 sodium Substances 0.000 title claims abstract description 44
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 41
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 41
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011812 mixed powder Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 11
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 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
- 238000004321 preservation Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 159000000000 sodium salts Chemical class 0.000 abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 235000011008 sodium phosphates Nutrition 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention discloses a graphene oxide-sodium iron phosphate composite anode material and a preparation method thereof, comprising the following steps of ultrasonically dispersing graphene oxide in deionized water to form graphene oxide dispersion liquid; adding sodium salt, ferric salt and phosphorus source into the graphene oxide dispersion liquid, and continuously magnetically stirring to obtain a uniformly mixed solution; transferring the uniformly mixed solution into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, repeatedly centrifuging and washing a product obtained by the hydrothermal reaction by using a solvent, drying to obtain uniformly mixed powder, and placing the uniformly mixed powder into a tubular furnace for heat treatment to obtain the graphene oxide-sodium iron phosphate composite anode material. The prepared composite positive electrode material has excellent electrochemical performance, multiplying power performance and reversibility, is simple to operate, has low raw material cost and can be prepared in a large scale.
Description
Technical Field
The invention relates to a graphene oxide-sodium iron phosphate composite positive electrode material and a preparation method thereof, and belongs to the technical field of sodium ion battery positive electrode materials.
Background
In recent years, with the increasing tension of energy resources and the increasing increase of environmental pollution, the development of renewable clean energy has become an urgent requirement for realizing energy diversification, coping with climate change and realizing sustainable development. As an important energy storage means, various systems including nickel-hydrogen, nickel-chromium, lead-acid, lithium ion batteries, sodium ion batteries, etc. have been developed over the years, and the applications thereof are spread over various fields.
Compared with a lithium ion battery, the sodium ion battery has the advantages of low cost, environmental friendliness and the like. At present, in the preparation process of the sodium ion battery, a carbon material is generally selected as a negative electrode, and a positive electrode material is relatively abundant. The sodium iron phosphate has the advantages of higher theoretical specific capacity (154 mAh/g), low cost, good safety, environmental friendliness and the like, and is a very promising sodium ion battery anode material. However, the capacity and cycling stability of sodium ion batteries are limited to some extent due to the poor electronic conductivity of the sodium iron phosphate material. Therefore, improving the conductivity of the sodium iron phosphate material is a technical problem to be solved.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the graphene oxide-sodium iron phosphate composite anode material and the preparation method thereof, which have excellent electrochemical performance, rate capability and reversibility, simple operation and low raw material cost, and can be prepared in a large scale.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
on one hand, the invention discloses a preparation method of a graphene oxide-sodium iron phosphate composite positive electrode material, which comprises the following steps,
ultrasonically dispersing graphene oxide in deionized water to form graphene oxide dispersion liquid;
adding sodium salt, ferric salt and phosphorus source into the graphene oxide dispersion liquid, and continuously magnetically stirring to obtain a uniformly mixed solution;
transferring the uniformly mixed solution into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, repeatedly centrifuging and washing a product obtained by the hydrothermal reaction by using a solvent, and drying to obtain uniformly mixed powder; wherein the uniformly mixed powder comprises graphene oxide and sodium iron phosphate;
and placing the uniformly mixed powder in a tube furnace for heat treatment to obtain the graphene oxide-sodium iron phosphate composite anode material.
Further, the graphene oxide is prepared by a modified Hummers method.
Further, the sodium salt comprises one or more of sodium phosphate, sodium citrate and sodium hydrogen phosphate.
Further, the iron salt comprises one or more of ferrous oxalate, ferric nitrate and ferrous ammonium sulfate hexahydrate.
Further, the phosphorus source comprises one or more of phosphoric acid, diammonium hydrogen phosphate and monoammonium hydrogen phosphate.
Further, the reaction temperature of the hydrothermal reaction condition is 140-180 ℃, and the heat preservation time is 2-8 h.
Further, the solvent comprises one or more of deionized water and absolute ethyl alcohol.
Further, the tube furnace is filled with inert gas; the heating rate of the tube furnace is 5 ℃/min-10 ℃/min, the target temperature is 500 ℃ to 700 ℃, and the heat treatment time is 3 to 8 hours.
Further, the content of the graphene oxide is 0.5-8 wt.% of the content of the generated sodium iron phosphate.
On the other hand, the invention discloses a graphene oxide-sodium iron phosphate composite positive electrode material prepared based on the preparation method of the graphene oxide-sodium iron phosphate composite positive electrode material, wherein the graphene oxide-sodium iron phosphate composite positive electrode material comprises a positive electrode active material and a conductive agent, the positive electrode active material is sodium iron phosphate, and the conductive agent is graphene oxide.
Compared with the prior art, the invention has the beneficial effects that:
the graphene oxide-sodium iron phosphate composite positive electrode material prepared by the invention is used as a positive electrode of a room-temperature sodium ion half-cell, has excellent electrochemical performance and has a specific capacity of 138mAh/g under the current density of 0.1C. Meanwhile, the material has excellent multiplying power performance and reversibility, and in the multiplying power test, the material always maintains higher coulombic efficiency after 200 charge and discharge cycles.
The preparation method of the graphene oxide-sodium iron phosphate composite positive electrode material is simple to operate, can be used for mass preparation, is low in raw material cost, has better environmental friendliness, and has a wide application prospect in the field of energy storage materials.
The sodium iron phosphate is prepared by a hydrothermal synthesis method, so that the prepared sodium iron phosphate has smaller grain size of about 30 nm. The reduction of the size of the crystal grain of the sodium iron phosphate can increase the specific surface area of the sodium iron phosphate, so that the rate of oxidation-reduction reaction of the anode material is increased, and better electrochemical performance is obtained.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a graphene oxide-sodium iron phosphate composite positive electrode material prepared in example I;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the graphene oxide-sodium iron phosphate composite positive electrode material prepared in example one;
FIG. 3 is an alternating current impedance spectrum (EIS) chart of the graphene oxide-sodium iron phosphate composite positive electrode material prepared in example I;
fig. 4 is a graph showing the results of the rate performance test of the graphene oxide-sodium iron phosphate composite cathode material prepared in example one at a current density of 0.1C.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1:
the embodiment 1 provides a preparation method of a graphene oxide-sodium iron phosphate composite positive electrode material, which comprises the following steps:
firstly, 0.03g of graphene oxide (3 wt.% of the content of sodium iron phosphate is generated) is ultrasonically dispersed in deionized water to form graphene oxide dispersion liquid; then, 5.75mmol of ferrous ammonium sulfate and 5.75mmol of sodium phosphate are dissolved in 60mL of graphene oxide dispersion liquid, and magnetic stirring is carried out to obtain a uniformly mixed solution; transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, setting the temperature of an oven to 160 ℃, preserving heat for 3 hours, naturally cooling the product, and centrifugally washing for several times to obtain a wet product; the wet product after centrifugation is kept warm by a blast drier at the temperature of 70 ℃ until water is completely evaporated, so as to obtain evenly mixed powder; and finally, placing the uniformly mixed powder into a tube furnace, heating the uniformly mixed powder to 650 ℃ at a heating rate of 5 ℃/min under the condition of inert gas, and performing heat treatment for 6 hours to obtain the graphene oxide-sodium iron phosphate composite anode material powder.
The XRD pattern of the sample prepared in example 1 is shown in FIG. 1, illustrating that a material of high purity is obtained; the TEM image of the prepared sample is shown in FIG. 2, and it can be seen that the sample particles are uniformly distributed, and the average grain size is about 30 nm; the alternating current impedance spectrum is shown in figure 3, and the charge transfer resistance of the graphene oxide-sodium iron phosphate composite battery anode material is about 200 omega; the cycle performance is shown in fig. 4, and the higher coulombic efficiency (more than 95%) is maintained after 200 charge-discharge cycles.
And (3) battery assembly: 0.2g of graphene oxide-sodium iron phosphate composite anode powder prepared in the embodiment 1 is weighed as an active agent, 0.025g of acetylene black is used as a conductive agent, and 0.025g of polyvinylidene fluoride (PVDF) is used as a binder; 1mL of N-methylpyrrolidone (NMP) is added to fully mix the positive electrode active material, the conductive agent and the adhesive into uniform and sticky slurry, the slurry is coated on an aluminum foil and cut into positive electrode plates, metal sodium is used as a negative electrode, sodium perchlorate is used as electrolyte, and a CR2032 button cell is assembled in a glove box.
The test result shows that the discharge capacity of the graphene oxide-sodium iron phosphate composite battery anode material prepared in the example 1 reaches 138mAh/g at the room temperature of 0.1C current density.
Example 2:
the embodiment 2 provides a preparation method of a graphene oxide-sodium iron phosphate composite positive electrode material, which comprises the following steps:
firstly, performing ultrasonic dispersion on 0.01g of graphene oxide (1% of generated sodium iron phosphate content) in deionized water to form graphene oxide dispersion liquid; then, 5.75mmol of ferrous ammonium sulfate and 5.75mmol of sodium phosphate are dissolved in 60mL of graphene oxide dispersion liquid, and magnetic stirring is carried out to obtain a uniformly mixed solution; transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, setting the temperature of an oven to 160 ℃, preserving heat for 3 hours, naturally cooling the product, and centrifugally washing for several times to obtain a wet product; the wet product after centrifugation is kept warm by a blast drier at the temperature of 70 ℃ until water is completely evaporated, so as to obtain evenly mixed powder; and finally, placing the uniformly mixed powder into a tube furnace, heating the uniformly mixed powder to 650 ℃ at a heating rate of 5 ℃/min under the condition of inert gas, and performing heat treatment for 6 hours to obtain the graphene oxide-sodium iron phosphate composite anode material powder.
And (3) battery assembly: 0.2g of graphene oxide-sodium iron phosphate composite positive electrode material powder prepared in the embodiment 2 is weighed as a positive electrode active material, 0.025g of acetylene black is used as a conductive agent, and 0.025g of polyvinylidene fluoride (PVDF) is used as a binder; 1mL of N-methylpyrrolidone (NMP) is added to fully mix the positive electrode active material, the conductive agent and the adhesive into uniform and sticky slurry, the slurry is coated on an aluminum foil and cut into positive electrode plates, metal sodium is used as a negative electrode, sodium perchlorate is used as electrolyte, and the CR2032 button cell is assembled in a vacuum glove box.
The test result shows that the discharge capacity of the graphene oxide-sodium iron phosphate composite battery anode material prepared in the example 2 reaches 130mAh/g at the room temperature under the current density of 0.1C.
Example 3:
the embodiment 3 provides a graphene oxide-sodium iron phosphate composite positive electrode material and a preparation method thereof, and the preparation method comprises the following steps:
firstly, performing ultrasonic dispersion on 0.05g of graphene oxide (5% of generated sodium iron phosphate content) in deionized water to form graphene oxide dispersion liquid; then, 5.75mmol of ferrous ammonium sulfate and 5.75mmol of sodium phosphate are dissolved in 60mL of graphene oxide dispersion liquid, and magnetic stirring is carried out to obtain a uniformly mixed solution; transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, setting the temperature of an oven to 160 ℃, preserving heat for 3 hours, naturally cooling the product, and centrifugally washing for several times to obtain a wet product; the wet product after centrifugation is kept warm by a blast drier at the temperature of 70 ℃ until water is completely evaporated, so as to obtain evenly mixed powder; and finally, placing the uniformly mixed powder into a tube furnace, heating the uniformly mixed powder to 650 ℃ at a heating rate of 5 ℃/min under the condition of inert gas, and performing heat treatment for 6 hours to obtain the graphene oxide-sodium iron phosphate composite anode material powder.
And (3) battery assembly: 0.2g of graphene oxide-sodium iron phosphate composite positive electrode material powder of example 3 was weighed as a positive electrode active material, 0.025g of acetylene black was used as a conductive agent, 0.025g of polyvinylidene fluoride (PVDF) was used as a binder, 1mL of N-methylpyrrolidone (NMP) was added to thoroughly mix the positive electrode active material, the conductive agent and the binder into a uniform and viscous slurry, the slurry was coated on an aluminum foil and cut into a positive electrode sheet, metallic sodium was used as a negative electrode, sodium perchlorate was used as an electrolyte, and a CR2032 type button cell was assembled in a vacuum glove box.
The test result shows that the discharge capacity of the graphene oxide-sodium iron phosphate composite battery anode material prepared in the example 3 reaches 120mAh/g at the room temperature under the current density of 0.1C.
From the comparison of examples 1 to 3, it can be seen that the graphene oxide-sodium iron phosphate composite positive electrode material added with graphene oxide as a conductive agent has excellent electrochemical performance. Wherein, the graphene oxide-sodium iron phosphate composite cathode material added with 0.03g of graphene oxide in the embodiment 1 has a specific capacity of 138mAh/g at a current density of 0.1C.
Example 4
The embodiment 4 provides a battery positive electrode material without graphene oxide and a preparation method thereof, and the battery positive electrode material comprises the following steps:
dissolving 5.75mmol of ferrous ammonium sulfate and 5.75mmol of sodium phosphate in 60mL of deionized water, and magnetically stirring to obtain a uniformly mixed solution; transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, setting the temperature of an oven to 160 ℃, preserving heat for 3 hours, naturally cooling the product, and centrifugally washing for several times to obtain a wet product; the wet product after centrifugation is kept warm by a blast drier at the temperature of 70 ℃ until water is completely evaporated, so as to obtain evenly mixed powder; and (3) placing the uniformly mixed powder into a tube furnace, heating the uniformly mixed powder to 650 ℃ at a heating rate of 5 ℃/min under the condition of inert gas, and performing heat treatment for 6 hours to obtain the pure sodium iron phosphate powder.
The CR2032 type button sodium ion battery assembled in this example 4 was used, and the discharge capacity at a current density of 0.1C was 90mAh/g. The electrochemical properties of the material are clearly reduced.
Example 5
The example 5 provides a graphene oxide-sodium iron phosphate composite positive electrode material and a preparation method thereof, which are different from the example 2 only in the annealing treatment temperature of the tube furnace.
Ultrasonically dispersing 0.01g of graphene oxide in deionized water to form graphene oxide dispersion liquid; dissolving 5.75mmol of ferrous ammonium sulfate and 5.75mmol of sodium phosphate in 60mL of graphene oxide dispersion liquid, and magnetically stirring to obtain a uniformly mixed solution; transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, setting the temperature of an oven to 160 ℃, preserving heat for 3 hours, naturally cooling the product, and centrifugally washing for several times to obtain a wet product; the wet product after centrifugation is kept warm by a blast drier at the temperature of 70 ℃ until water is completely evaporated, so as to obtain evenly mixed powder; placing the uniformly mixed powder into a tube furnace, heating the uniformly mixed powder to 800 ℃ at a heating rate of 5 ℃/min under the condition of inert gas, and performing heat treatment for 6 hours, and performing XRD test on the obtained product, wherein the sodium iron phosphate generates a heterogeneous phase at the temperature, and the phase purity is reduced. The material is obtained through a large number of experiments, and the target temperature of the tube furnace, namely the annealing treatment temperature, is the best in the range of 500-700 ℃.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (5)
1. The preparation method of the graphene oxide-sodium iron phosphate composite positive electrode material is characterized by comprising the following steps of,
ultrasonically dispersing graphene oxide in deionized water to form graphene oxide dispersion liquid;
adding sodium phosphate and ferric salt into the graphene oxide dispersion liquid, and continuously magnetically stirring to obtain a uniformly mixed solution; the ferric salt comprises one or more of ferrous oxalate, ferric nitrate and ferrous ammonium sulfate hexahydrate;
transferring the uniformly mixed solution into a polytetrafluoroethylene reaction kettle for hydrothermal reaction, repeatedly centrifuging and washing a product obtained by the hydrothermal reaction by using a solvent, and drying to obtain uniformly mixed powder; wherein the uniformly mixed powder comprises graphene oxide and sodium iron phosphate; the hydrothermal reaction conditions: the reaction temperature is 140-180 ℃, and the heat preservation time is 2-8 hours;
placing the uniformly mixed powder in a tube furnace for heat treatment to obtain a graphene oxide-sodium iron phosphate composite anode material; the tube furnace is filled with inert gas; the heating rate of the tube furnace is 5-10 ℃/min, the target temperature is 500-700 ℃, and the heat treatment time is 3-8 h.
2. The method for preparing a graphene oxide-sodium iron phosphate composite positive electrode material according to claim 1, wherein the graphene oxide is prepared by a modified Hummers method.
3. The method for preparing a graphene oxide-sodium iron phosphate composite positive electrode material according to claim 1, wherein the solvent comprises one or more of deionized water and absolute ethyl alcohol.
4. The method for preparing a graphene oxide-sodium iron phosphate composite positive electrode material according to claim 1, wherein the content of graphene oxide is 0.5-8 wt.% of the content of generated sodium iron phosphate.
5. The graphene oxide-sodium iron phosphate composite positive electrode material prepared by the preparation method of the graphene oxide-sodium iron phosphate composite positive electrode material according to any one of claims 1 to 4, wherein the graphene oxide-sodium iron phosphate composite positive electrode material comprises a positive electrode active material and a conductive agent, the positive electrode active material is sodium iron phosphate, and the conductive agent is graphene oxide.
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| CN107017395A (en) * | 2017-05-22 | 2017-08-04 | 中南大学 | A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application |
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| US10797313B2 (en) * | 2017-12-05 | 2020-10-06 | Global Graphene Group, Inc. | Method of producing anode or cathode particulates for alkali metal batteries |
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| CN107017395A (en) * | 2017-05-22 | 2017-08-04 | 中南大学 | A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application |
| CN109103442A (en) * | 2018-09-18 | 2018-12-28 | 四川省有色冶金研究院有限公司 | A kind of preparation method of graphene-coated lithium iron phosphate positive electrode |
| CN110299528A (en) * | 2019-07-02 | 2019-10-01 | 中南大学 | Fluorinated phosphate ferric sodium pyrophosphate@C@RGO composite material and its preparation and the application in sodium-ion battery |
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