CN113851618B - Method for preparing high-performance ferric phosphate/graphene composite anode material by utilizing hydrochloric acid leaching solution of iron vitriol slag and application of high-performance ferric phosphate/graphene composite anode material - Google Patents
Method for preparing high-performance ferric phosphate/graphene composite anode material by utilizing hydrochloric acid leaching solution of iron vitriol slag and application of high-performance ferric phosphate/graphene composite anode material Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 49
- 239000010405 anode material Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000002893 slag Substances 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 title claims abstract description 28
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000005955 Ferric phosphate Substances 0.000 title description 11
- 229940032958 ferric phosphate Drugs 0.000 title description 11
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 26
- -1 hydrogen ions Chemical class 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052935 jarosite Inorganic materials 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 method for preparing a high-performance iron phosphate/graphene composite anode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and application thereof. The preparation method comprises the following steps: (1) Determining the mass concentration of all iron and hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag; (2) Sequentially adding a certain amount of distilled water, graphene oxide and H into the hydrochloric acid leaching solution of the iron vitriol slag 2 O 2 And Na (Na) 3 PO 4 ·12H 2 O, standing, filtering, washing and freeze-drying after the reaction to obtain a precursor; (3) And sintering the precursor in an argon atmosphere to obtain the iron phosphate/graphene composite anode material. The method of the invention makes full use of iron resources in the iron vitriol slag, and the prepared iron phosphate/graphene composite material has better lithium storage performance as a lithium ion battery anode material, and the method of the invention is simple, low in cost, high in yield, easy to control preparation conditions and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a method for preparing a high-performance ferric phosphate/graphene composite anode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and application thereof.
Background
The high-iron sphalerite in China is very rich, generally contains 8% -20% of iron, and is an important raw material for zinc hydrometallurgy. In the zinc hydrometallurgy process, in order to realize zinc and iron separation, an iron removal process is required, and iron is removed mainly by adopting an iron vitriol method in China. The iron vitriol slag is iron slag obtained by iron removal through an iron vitriol method. Because the iron vitriol slag is difficult to meet the requirement of an iron making process, a plurality of zinc factories directly send the iron vitriol slag to a slag field for stacking, which not only occupies a large amount of land resources, but also causes huge waste of resources and environmental pollution. Therefore, research and utilization of the iron vitriol slag as a resource are urgent. In addition, nano iron phosphate has been widely studied as a positive electrode material of a lithium ion battery, but has been recently reported as a negative electrode material, and the reason for the nano iron phosphate may be related to factors such as poor conductivity and morphology. Therefore, the invention provides a method for preparing the ferric phosphate/graphene composite material by directly utilizing the hydrochloric acid leaching solution of the iron vitriol slag, and the method is used as a lithium ion battery cathode material to show better electrochemical performance.
Disclosure of Invention
The invention aims to provide a method for preparing an iron phosphate/graphene composite anode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and application thereof.
The method comprises the following specific steps:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the jarosite slag hydrochloric acid leaching solution obtained in the step (1), putting the obtained jarosite slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under normal temperature stirring, adding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the mass ratio of graphene oxide to theoretical generated ferric phosphate of 10% -40%, performing ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at the temperature of 400 ℃ to obtain the iron phosphate/graphene composite anode material.
The mass concentration of the total iron is iron ion (Fe 3+ ) And ferrous ion (Fe) 2+ ) The sum of the mass concentrations.
The prepared iron phosphate/graphene composite anode material can be applied to preparation of lithium ion batteries.
The invention has the advantages that: the invention directly utilizes the hydrochloric acid leaching solution of the iron vitriol slag to prepare the iron phosphate/graphene composite anode material for the high-performance lithium ion battery, provides a new method for recycling the industrial iron vitriol slag, and reduces the waste of resources and the pollution to the environment. Meanwhile, the method provided by the invention is simple, low in cost, high in yield and easy to control the preparation conditions, and is suitable for large-scale production, and the prepared ferric phosphate/graphene composite material has excellent rate capability and good cycle stability as a lithium ion battery anode material.
Drawings
Fig. 1 is an XRD pattern of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4.
Fig. 2 is a TGA profile of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4.
Fig. 3 is an SEM image of the iron phosphate/graphene composite anode material prepared in example 2.
Fig. 4 is a graph showing the rate performance of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4.
Fig. 5 is a cycle performance chart of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4.
Detailed Description
The present invention is further described in conjunction with the specific embodiments described below, and it should be noted that the following embodiments are provided to enable persons skilled in the art to better understand the present invention, and not to limit the scope of the present invention, and that persons skilled in the art may make some insubstantial improvements and modifications in light of the above.
Example 1:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the jarosite slag hydrochloric acid leaching solution obtained in the step (1), putting the obtained jarosite slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under normal temperature stirring, adding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the mass ratio of graphene oxide to theoretical generated ferric phosphate of 10%, performing ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at the temperature of 400 ℃ to obtain the iron phosphate/graphene composite anode material.
Example 2:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the jarosite slag hydrochloric acid leaching solution obtained in the step (1), putting the obtained jarosite slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under normal temperature stirring, adding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the mass ratio of graphene oxide to theoretical generated ferric phosphate of 20%, performing ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at the temperature of 400 ℃ to obtain the iron phosphate/graphene composite anode material.
Example 3:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the iron vitriol slag hydrochloric acid leaching solution obtained in the step (1), putting the iron vitriol slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under normal temperature stirring, and adding 1mg/m of iron phosphate into the beaker according to the mass ratio of graphene oxide to theoretical generated iron phosphate of 30%L graphene oxide dispersion, sonicated for 1 hour, then 2mL of H was added to the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at the temperature of 400 ℃ to obtain the iron phosphate/graphene composite anode material.
Example 4:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the jarosite slag hydrochloric acid leaching solution obtained in the step (1), putting the obtained jarosite slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under normal temperature stirring, adding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the mass ratio of graphene oxide to theoretical generated ferric phosphate of 40%, performing ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at the temperature of 400 ℃ to obtain the iron phosphate/graphene composite anode material.
The jarosite residue hydrochloric acid leach solutions used in examples 1-4 are for example only, and are not intended to limit the invention in any way, so that those skilled in the art will better understand the invention.
Electrochemical performance test: the iron phosphate/graphene composite anode material prepared in the embodiment is used as an active material, conductive carbon black (Super P) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, the mixture is uniformly mixed and ground according to the mass ratio of 7:2:1, a proper amount of N-methyl-2-pyrrolidone (NMP) is added, the mixture is uniformly mixed into slurry, the slurry is uniformly coated on a copper foil, the copper foil is dried in vacuum at 80 ℃ for 12 hours, and the electrode plate is obtained after punching. The punched electrode sheet is used as a working electrode, a metal lithium sheet is used as a counter electrode, a polypropylene porous membrane (Celgard 2400) is used as a diaphragm, and 1mol/L LiPF is used 6 Is a mixture of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (volume ratio, V (EC) :V (DMC) :V (DEC) =1:1:1) was used as an electrolyte, and a CR2016 type coin cell was assembled in a glove box filled with argon. A BTS-5V/10mA charge-discharge tester of Shenzhen Xinwei company is adopted to test the constant-current charge-discharge performance of the battery, and the charge-discharge voltage range is 0.01-3.0V. Current densities for the rate performance test were 0.2A g, respectively -1 、0.5A g -1 、1Ag -1 、2Ag -1 、3Ag -1 、5Ag -1 . In the cycle performance test, the catalyst is firstly prepared from 0.2Ag -1 Activated for 10 turns at current density and then continued at 0.5Ag -1 Is cycled to 100 turns.
As shown in fig. 1, XRD patterns of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4 are shown. As can be seen from the figure, the main phase of the material prepared according to the invention is amorphous iron phosphate.
As shown in fig. 2, TGA diagrams of the iron phosphate/graphene composite anode materials prepared in examples 1 to 4 are shown. From the figure, it can be analyzed that the material prepared by the invention contains graphene. The material prepared by combining the description of fig. 1 and fig. 2 is an iron phosphate/graphene composite anode material.
As shown in fig. 3, an SEM image of the iron phosphate/graphene composite anode material prepared in example 2 is shown. As can be seen from the figure, the iron phosphate/graphene composite anode material prepared by the invention is formed by dispersing nano iron phosphate particles in graphene.
As shown in FIG. 4, the iron phosphate/graphene composite anode materials prepared in examples 1-4 were prepared at different current densities (0.2, 0.5, 1, 2, 3, 5Ag -1 ) A lower rate performance curve. As can be seen from the figures, the iron phosphate/graphene composite anode materials prepared in examples 2 to 4 have very good rate capability. For example, the anode material prepared in example 2 was prepared at 0.2Ag -1 、0.5Ag -1 、1Ag -1 、2Ag -1 、3Ag -1 、5Ag -1 Specific discharge capacities under current density are 729.3mAh g respectively -1 、660.5mAh g -1 、595.8mAh g -1 、511.2mAh g -1 、461.5mAh g -1 And 403.2mAh g -1 。
As shown in FIG. 5, the iron phosphate/graphene composite anode materials prepared in examples 1-4 were prepared at 0.2Ag -1 Activated for 10 turns at current density and then continued at 0.5Ag -1 Cycle performance curve for current density cycled to 100 cycles. From the graph, the iron phosphate/graphene composite anode materials prepared in examples 2-4 have good cycling stability. For example, the specific charge/discharge capacities of the iron phosphate/graphene composite anode materials prepared in examples 2 to 4 are 590.6/600.2mAh g when the materials are recycled to 100 circles -1 、620.6/634.3mAh g -1 And 693.6/708.1mAh g -1 The specific charge/discharge capacity of the iron phosphate/graphene composite anode material prepared in example 1 under the same conditions is only 324.5/329.1mAh g -1 。
Claims (2)
1. A method for preparing an iron phosphate/graphene composite anode material by utilizing an iron vitriol slag hydrochloric acid leaching solution is characterized by comprising the following specific steps:
(1) Measuring the mass concentration of all iron and the mass concentration of hydrogen ions in the hydrochloric acid leaching solution of the iron vitriol slag, wherein the mass concentration of all iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23mol/L;
(2) Weighing 20mL of the jarosite slag hydrochloric acid leaching solution obtained in the step (1), putting the jarosite slag hydrochloric acid leaching solution into a beaker, adding 20mL of distilled water into the beaker under stirring at normal temperature, and generating phosphorus according to graphene oxide and theoryAdding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into a beaker according to the mass ratio of 10% -40% of ferric acid, performing ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker 2 O 2 And 2.9g of Na 3 PO 4 ·12H 2 O, enabling the mole ratio of phosphate ions to iron ions in the solution to be 1:1.5;
(3) Magnetically stirring the solution obtained in the step (2) at the constant temperature of 70 ℃ for reaction for 0.5 hour, then standing for 3 hours at normal temperature, and finally filtering, washing and freeze-drying the precipitate to constant weight to obtain a precursor;
(4) Transferring the precursor obtained in the step (3) into a tube furnace, heating the precursor to 400 ℃ from room temperature under argon atmosphere, heating the precursor at a heating speed of 2 ℃/min, and preserving the heat for 6 hours at 400 ℃ to obtain the iron phosphate/graphene composite anode material,
the mass concentration of the total iron is iron ion (Fe 3+ ) And ferrous ion (Fe) 2+ ) The sum of the mass concentrations.
2. The application of the iron phosphate/graphene composite anode material prepared by the preparation method of claim 1 is characterized in that the iron phosphate/graphene composite anode material can be applied to preparation of lithium ion batteries.
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Application publication date: 20211228 Assignee: Guilin Xing GUI Electrical Appliance Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044499 Denomination of invention: Method and Application of Preparing High Performance Iron Phosphate/Graphene Composite Negative Electrode Materials from Iron Alum Residue Hydrochloric Acid Leaching Solution Granted publication date: 20230623 License type: Common License Record date: 20231030 |
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