CN113851618A - Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application - Google Patents
Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application 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 53
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 53
- 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
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000002893 slag Substances 0.000 title claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 title claims abstract description 29
- 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 28
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- -1 hydrogen ions Chemical class 0.000 claims abstract description 22
- 239000002243 precursor Substances 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 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910000406 trisodium phosphate Inorganic materials 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
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid 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
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052935 jarosite Inorganic materials 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
- 239000000243 solution Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 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
- 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
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 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
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 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
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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
- 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
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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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a high-performance iron phosphate/graphene composite negative electrode material by using an iron vitriol slag hydrochloric acid leaching solution and application thereof. The preparation method comprises the following steps: (1) and (3) measuring the mass concentrations of total iron and hydrogen ions in the alcanite slag hydrochloric acid leaching solution. (2) Sequentially adding a certain amount of distilled water, graphene oxide and H into the hydrochloric acid leaching solution of the jarosite slag2O2And Na3PO4·12H2And O, standing, filtering, washing and freeze-drying after reaction to obtain a precursor. (3) And sintering the precursor in an argon atmosphere to obtain the iron phosphate/graphene composite negative electrode 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 the lithium ion battery cathode material, and the method of the invention is simple, low in cost, high in yield, easy to control the preparation conditions, and suitable for large-scale lithium ion batteriesAnd (4) large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a method for preparing a high-performance iron phosphate/graphene composite cathode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and application thereof.
Technical Field
The high-iron sphalerite is rich in China, generally contains 8-20% of iron, and is an important raw material for zinc hydrometallurgy. In the process of zinc hydrometallurgy, in order to realize the separation of zinc and iron, an iron removal process is required, and China mainly adopts an iron vitriol method to remove iron. The iron vitriol slag is iron slag obtained by removing iron by an iron vitriol method. Since the iron vitriol slag can hardly meet the requirements of the iron making process, a plurality of zinc smelters directly send the iron vitriol slag to a slag yard for stacking, which not only occupies a large amount of land resources, but also causes huge waste of resources and environmental pollution. Therefore, the research and utilization of the iron vitriol slag are urgent. In addition, nanometer iron phosphate has been widely studied as a positive electrode material of a lithium ion battery, but the nanometer iron phosphate is only reported as a negative electrode material, and the reason of the nanometer iron phosphate may be related to factors such as poor conductivity and morphology of the nanometer iron phosphate. Therefore, the invention provides a method for preparing an iron phosphate/graphene composite material by directly utilizing an iron vitriol slag hydrochloric acid leaching solution, and the iron phosphate/graphene composite material is used as a lithium ion battery negative electrode material and shows better electrochemical performance.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance iron phosphate/graphene composite negative electrode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and application thereof.
The method comprises the following specific steps:
(1) and (3) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L.
(2) Measuring 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, adding a graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the proportion that the mass ratio of the graphene oxide to theoretically generated iron phosphate is 10% -40%, carrying out ultrasonic treatment for 1 hour, and adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2And O, wherein the molar ratio of phosphate ions to iron ions in the solution is 1: 1.5.
(3) And (3) carrying out magnetic stirring reaction on the solution obtained in the step (2) at the constant temperature of 70 ℃ for 0.5 hour, then standing at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor.
(4) And (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
The mass concentration of the total iron is iron ions (Fe)3+) And ferrous ion (Fe)2+) Sum of mass concentration.
The prepared ferric phosphate/graphene composite negative electrode material can be applied to the preparation of high-performance lithium ion batteries.
The invention has the advantages that: according to the invention, the ferric phosphate/graphene composite negative electrode material for the high-performance lithium ion battery is prepared by directly utilizing the iron vitriol slag hydrochloric acid leaching solution, a new method is provided for resource utilization of industrial iron vitriol slag, and resource waste and environmental pollution are reduced. Meanwhile, the method is simple, low in cost, high in yield, easy to control preparation conditions and suitable for large-scale production, and the prepared iron phosphate/graphene composite material serving as the lithium ion battery cathode material has excellent rate performance and good cycle stability.
Drawings
Fig. 1 is an XRD spectrum of the iron phosphate/graphene composite negative electrode material prepared in examples 1-4.
Fig. 2 is a TGA diagram of the iron phosphate/graphene composite negative electrode materials prepared in examples 1 to 4.
Fig. 3 is an SEM image of the iron phosphate/graphene composite negative electrode material prepared in example 2.
Fig. 4 is a rate performance graph of the iron phosphate/graphene composite negative electrode materials prepared in examples 1 to 4.
Fig. 5 is a cycle performance diagram of the iron phosphate/graphene composite negative electrode material prepared in examples 1 to 4.
Detailed Description
The present invention is further described with reference to the following specific examples, which are intended to provide those skilled in the art with a better understanding of the present invention, and are not intended to limit the scope of the present invention, which is to be construed as limited thereby.
Example 1:
(1) and (3) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L.
(2) Measuring 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, adding a graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the proportion that the mass ratio of the graphene oxide to theoretically generated iron phosphate is 10%, carrying out ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2And O, wherein the molar ratio of phosphate ions to iron ions in the solution is 1: 1.5.
(3) And (3) carrying out magnetic stirring reaction on the solution obtained in the step (2) at the constant temperature of 70 ℃ for 0.5 hour, then standing at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor.
(4) And (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
Example 2:
(1) and (3) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L.
(2) Measuring 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, adding a graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the proportion that the mass ratio of the graphene oxide to theoretically generated iron phosphate is 20%, carrying out ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2And O, wherein the molar ratio of phosphate ions to iron ions in the solution is 1: 1.5.
(3) And (3) carrying out magnetic stirring reaction on the solution obtained in the step (2) at the constant temperature of 70 ℃ for 0.5 hour, then standing at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor.
(4) And (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
Example 3:
(1) and (3) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L.
(2) Measuring 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, adding a graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the proportion that the mass ratio of the graphene oxide to the theoretically generated iron phosphate is 30%, carrying out ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2And O, wherein the molar ratio of phosphate ions to iron ions in the solution is 1: 1.5.
(3) And (3) carrying out magnetic stirring reaction on the solution obtained in the step (2) at the constant temperature of 70 ℃ for 0.5 hour, then standing at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor.
(4) And (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
Example 4:
(1) and (3) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L.
(2) Measuring 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 then according to the mass ratio of the graphene oxide to the theoretically generated iron phosphateAdding graphene oxide dispersion liquid with the mass concentration of 1mg/mL into a beaker according to the proportion of 40%, carrying out ultrasonic treatment for 1 hour, and then adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2And O, wherein the molar ratio of phosphate ions to iron ions in the solution is 1: 1.5.
(3) And (3) carrying out magnetic stirring reaction on the solution obtained in the step (2) at the constant temperature of 70 ℃ for 0.5 hour, then standing at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor.
(4) And (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
The hydrochloric acid leaching solution of the jarosite slag used in the examples 1 to 4 is only an example, and the present invention is not limited to the above-mentioned one, so that the present invention can be better understood by those skilled in the art.
And (3) electrochemical performance testing: the iron phosphate/graphene composite negative electrode 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 materials are 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 materials are uniformly mixed and coated on a copper foil after being uniformly mixed, the materials are dried in vacuum at the temperature of 80 ℃ for 12 hours, and electrode plates are obtained after blanking. Taking the electrode slice obtained after blanking as a working electrode, a metal lithium slice as a counter electrode, a polypropylene porous membrane (Celgard 2400) as a diaphragm and 1mol/L LiPF6Mixed solution (volume ratio, V) of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC)(EC):V(DMC):V(DEC)1:1:1) was used as an electrolyte and assembled into a CR2016 type button cell in a glove box filled with argon. And testing the constant-current charge and discharge performance of the battery by adopting a BTS-5V/10mA type charge and discharge tester of Shenzhen Xinwei company, wherein the charge and discharge voltage range is 0.01-3.0V. The current density of the multiplying power performance test is 0.2A g respectively-1、0.5A g-1、1A g-1、2A g-1、3A g-1、5A g-1. Cyclicity ofWhen tested, the test time is first 0.2A g-1Activated for 10 cycles at current density and then continued at 0.5A g-1Is cycled up to 100 cycles.
As shown in fig. 1, the XRD patterns of the iron phosphate/graphene composite negative electrode materials prepared in examples 1 to 4 are shown. As can be seen from the figure, the main phase of the material prepared by the invention is amorphous iron phosphate.
As shown in fig. 2, TGA diagrams of the iron phosphate/graphene composite negative electrode 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 prepared material is the iron phosphate/graphene composite negative electrode material which is illustrated by combining the figure 1 and the figure 2.
As shown in fig. 3, is an SEM image of the iron phosphate/graphene composite negative electrode material prepared in example 2. As can be seen from the figure, the iron phosphate/graphene composite negative electrode 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 negative electrode materials prepared in examples 1 to 4 were prepared at different current densities (0.2, 0.5, 1, 2, 3, 5A g)-1) Rate performance curve below. As can be seen from the figure, the iron phosphate/graphene composite negative electrode materials prepared in examples 2 to 4 have very good rate capability. For example, the negative electrode material prepared in example 2 was at 0.2A g-1、0.5A g-1、1A g-1、2A g-1、3A g-1、5A g-1The discharging specific capacities under current densities are 729.3mAh g respectively-1、660.5mAh g-1、595.8mAh g-1、511.2mAh g-1、461.5mAh g-1And 403.2mAh g-1。
As shown in fig. 5, the content of the iron phosphate/graphene composite negative electrode material prepared in examples 1 to 4 was 0.2A g-1Activated for 10 cycles at current density and then continued at 0.5A g-1Cycling performance curves at current density to 100 cycles. As can be seen from the figure, the iron phosphate/graphene composite negative electrode materials prepared in the embodiments 2-4 have good cycling stability. For example, the iron phosphate/graphene composite negative electrode material prepared in examples 2 to 4 is charged/discharged when the cycle reaches 100 cyclesThe specific capacity is 590.6/600.2mAh g respectively-1、620.6/634.3mAh g-1And 693.6/708.1mAh g-1The specific charge/discharge capacity of the iron phosphate/graphene composite negative electrode material prepared in the example 1 under the same condition is only 324.5/329.1mAh g-1。
Claims (2)
1. A method for preparing a high-performance iron phosphate/graphene composite negative electrode material by utilizing an iron vitriol slag hydrochloric acid leaching solution and an application thereof are characterized by comprising the following specific steps:
(1) measuring the mass concentration of total iron and the mass concentration of hydrogen ions in the alcanite slag hydrochloric acid leaching solution, wherein the mass concentration of the total iron is 0.255mol/L, and the mass concentration of the hydrogen ions is 1.23 mol/L;
(2) measuring 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, adding a graphene oxide dispersion liquid with the mass concentration of 1mg/mL into the beaker according to the proportion that the mass ratio of the graphene oxide to theoretically generated iron phosphate is 10% -40%, carrying out ultrasonic treatment for 1 hour, and adding 2mL of H into the beaker2O2And 2.9g of Na3PO4·12H2O, enabling the molar 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 at the normal temperature for 3 hours, and finally filtering, washing and freeze-drying the precipitate until the weight is constant to obtain a precursor;
(4) and (4) transferring the precursor obtained in the step (3) to a tube furnace, heating the precursor to 400 ℃ from room temperature under the argon atmosphere, raising the temperature at the speed of 2 ℃/min, and preserving the heat at 400 ℃ for 6 hours to obtain the iron phosphate/graphene composite negative electrode material.
The mass concentration of the total iron is iron ions (Fe)3+) And ferrous ion (Fe)2+) Sum of mass concentration.
2. The application of the iron phosphate/graphene composite negative electrode material prepared by the preparation method according to claim 1 is characterized in that the iron phosphate/graphene composite negative electrode material can be applied to the preparation of high-performance lithium ion batteries.
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| CN202110915591.5A CN113851618B (en) | 2021-08-10 | 2021-08-10 | 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 |
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| CN202110915591.5A CN113851618B (en) | 2021-08-10 | 2021-08-10 | 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 |
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| CN113851618B CN113851618B (en) | 2023-06-23 |
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| RU2810612C1 (en) * | 2022-01-04 | 2023-12-28 | Пролоджиум Текнолоджи Ко., Лтд. | Lithium batteries |
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Application publication date: 20211228 Assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045027 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: 20231101 Application publication date: 20211228 Assignee: GUANGXI BINYANG COUNTY RONGLIANG AGRICULTURAL TECHNOLOGY CO.,LTD. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044910 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: 20231101 |
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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 |