CN110734077A - hierarchical-pore Prussian-blue nanospheres wrapped by iodine-doped graphene as well as preparation method and application of nanospheres - Google Patents
hierarchical-pore Prussian-blue nanospheres wrapped by iodine-doped graphene as well as preparation method and application of nanospheres Download PDFInfo
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Abstract
The invention provides hierarchical pore Prussian blue nanospheres coated on basis of iodine-doped graphene as well as a preparation method and application thereof6Adding inorganic acid into the nanosphere precursor for etching reaction to prepare FeFe (CN) with a hollow hierarchical pore structure6Nanospheres are added with iodine-doped graphene for uniform and dense coating through the ultrasonic and freezing composite drying process to obtain doped grapheneHetero-graphene-encapsulated hierarchical pore prussian blue nanospheres (i.e., fefe (cn))6@ IG) by the preparation method, steps can be further added to form hollow grading holes FeFe (CN)6The nanosphere has the conductive performance, and can improve the performance of the nanosphere after multiple charging and discharging. The lithium ion battery cathode material prepared from the material has good capacity, good stable cyclicity, capacity maintenance rate of more than 90 percent, simple preparation method process and convenient operation, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of battery application, in particular to hierarchical-pore Prussian-blue nanospheres wrapped by iodine-doped graphene and a preparation method and application thereof.
Background
With the rapid development of intelligent robots and new energy electric vehicles, Lithium Ion Batteries (LIBs) are widely used as main energy storage devices by , and the existing lithium ion batteries mostly adopt graphite as a negative electrode material due to relatively low theoretical capacity (LiC) of the graphite6Is 372 mAh g-1) The practical application of the lithium battery is limited, particularly in new energy electric vehicles, so that the development of new -generation lithium battery electrode materials is imminent.
Prussian blue (Fe) as an artificially synthesized polymer of th4[Fe(CN)6]3·14H2O, Prussianblue, PB for short) has the advantages of excellent electrochemical reversibility, high stability, easiness in preparation and the like, so that the method has a great application prospect in the aspects of chemically modified electrodes, electrochromism, secondary batteries and the like.
However, for the reported application of prussian blue to the negative electrode of the lithium ion battery, the research of the prussian blue generally has the characteristics of poor conductivity, low charge and discharge capacity, unstable cycle and the like. Thus, the prior art is yet to be improved and enhanced.
Disclosure of Invention
The invention aims to provide graded-pore Prussian-blue nanospheres coated on the basis of iodine-doped graphene as well as a preparation method and application thereof, and aims to solve the technical problems of poor conductivity, low charge and discharge capacity and unstable cycle of lithium batteries in the prior art.
The technical scheme of the invention comprises the following steps:
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps of A, adding K3[Fe(CN)6]Dissolving in deionized water, adding surfactant, ultrasonic stirringAdding inorganic acid solution into the clear solution, stirring, heating to 70-90 ℃ under magnetic stirring, reacting for 22-26h, and cooling to room temperature; centrifuging to collect precipitate, washing with distilled water and ethanol several times, and vacuum drying at 50-70 deg.C for 10-14 h to obtain solid FeFe (CN)6A nanosphere precursor;
B. solid FeFe (CN) prepared above6Respectively adding the nanosphere precursor and the surfactant into an inorganic acid solution, uniformly stirring, heating to 120 ℃ in a sealed environment, continuously reacting for 4-6h, and gradually cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres;
C. iodine doped graphene and the prepared FeFe (CN) with graded pores6Adding the nanosphere into ionized water, performing ultrasonic treatment for 1-2h, and freeze-drying for 46-50h to obtain iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanospheres.
The preparation method of the hierarchical pore Prussian blue nanospheres based on iodine-doped graphene coating comprises the step A of preparing the K3[Fe(CN)6]And the surfactant in a mass ratio of 1:15 to 1:30, wherein the concentration of the inorganic acid solution is 0.5M.
The preparation method of the graded-pore Prussian blue nanospheres coated on the basis of iodine-doped graphene comprises the step B of solid FeFe (CN)6The mass ratio of the nanosphere precursor to the surfactant is 1:3-1:5, the concentration of the inorganic acid solution is 1.0-2.0M, the reaction time of temperature rise is 4.5-5h, the temperature rise rate is 2-5 ℃/min, the temperature drop rate is 0.2-2 ℃/min, and the nanosphere precursor and the surfactant have hierarchical pores FeFe (CN)6The particle size of the nanosphere is 100-200 nm.
The preparation methods of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene comprise the step of preparing the hierarchical pore Prussian blue nanospheres, wherein the surfactant is any of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or polyvinylidene fluoride.
According to the preparation method of the graded-hole Prussian blue nanospheres wrapped by the iodine-doped graphene, the inorganic acid solution is any of hydrochloric acid, sulfuric acid and nitric acid.
The preparation method of the hierarchical pore Prussian blue nanospheres based on iodine-doped graphene wrapping comprises the step C of adding iodine-doped graphene and FeFe (CN) with hierarchical pores6The mass ratio of the nanospheres is 1:5-1:10, ultrasonic treatment is carried out for 1.0-1.5h, and freeze drying is carried out for 48-50 h.
The preparation method of the hierarchical pore Prussian blue nanospheres based on iodine-doped graphene wrapping comprises the following steps of A1 and K3[Fe(CN)6]Dissolving in deionized water, adding polyvinylpyrrolidone, ultrasonically stirring to obtain clear solution, adding HCl solution, stirring, heating to 80 deg.C under magnetic stirring, reacting for 24 hr, and cooling to room temperature; the precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6A nanosphere precursor;
b1, solid FeFe (CN) prepared by the above method6Respectively adding the nanosphere precursor and the surfactant into an inorganic acid solution, uniformly stirring, heating to 120 ℃ in a sealed environment, continuously reacting for 5 hours, and then gradually cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres;
c1, doping iodine with graphene and FeFe (CN) with hierarchical pore prepared by the method6Adding the nanosphere into ionized water, performing ultrasonic treatment for 1.5h, and freeze-drying for 48h to obtain iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanospheres.
hierarchical pore Prussian blue nanospheres based on iodine doped graphene encapsulation prepared by the Nian method described above, wherein the iodine doped graphene encapsulated hierarchical pore FeFe (CN)6The nanosphere is a dark blue powder structure, and the spherical particle size is 150-200 nm.
applications of the hierarchical pore Prussian blue nanospheres based on iodine doped graphene wrapping as described above, which are applied to the negative electrode of the lithium electronic battery.
According to the application of the iodine-doped graphene-coated hierarchical pore Prussian blue nanospheres, the working electrode of the lithium electronic battery is prepared from the following components in percentage by mass of 80: 10: 10 graded pore based on iodine doped graphene encapsulation FeFe (CN)6Nanosphere, acetylene black and polyvinylidene fluoride.
The technical scheme of the invention has the following beneficial effects:
1. the invention firstly mixes the iodine doped graphene (IG for short) with a large amount of electrochemical active sites and enhanced conductivity with FeFe (CN) with uniformly graded pores6The iodine-doped graphene-coated hierarchical pore Prussian blue nanospheres prepared by the method have the advantages of small and uniform size of and high reaction yield, and have the characteristics of strong crystallinity, good stability and the like of reaction products after being etched by inorganic acid solutions (particularly HCl solutions) with different temperatures and proper concentrations.
2. The hierarchical pore Prussian blue nanospheres coated by the iodine-doped graphene, which are obtained by the invention, are used as main cathode materials in lithium ion batteries, wherein FeFe (CN)6The nanospheres have the characteristic of hierarchical pores, can be mutually communicated and have hierarchical porous structures with pores of different scales, are favorable for improving the electrochemical performance of the cathode, keep good appearance before and after reaction, do not collapse or deform at all, can achieve the electrochemical effect superior to the existing product, and show the characteristics of difficult attenuation of the cathode capacity of the lithium ion battery, good rate capability and the like.
By the preparation method, Prussian blue FeFe (CN) can be effectively added6The conductivity of the nanospheres can be improved, and Prussian blue FeFe (CN)6The nanosphere still keeps better performance after being charged and discharged for many times. The lithium ion battery cathode material prepared from the material has the advantages of good capacity, low attenuation tendency and long service life. And the preparation method of the embodiment has simple process and convenient operation, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows iodine doped graphene, solid FeFe (CN) in the preparation process of examples 1 to 7 of the present invention6Nanosphere precursor, FeFe (CN) with hierarchical pores6Nanosphere and iodine doped graphene coated hierarchical pores FeFe (CN)6Nano meterBall (i.e. FeFe (CN))6@ IG);
FIG. 2 shows FeFe (CN) having graded pores in the preparation processes of examples 1 to 7 of the present invention6A nanosphere XRD spectrogram;
FIG. 3 shows FeFe (CN) having graded pores in the preparation processes of examples 1 to 7 of the present invention6Nanosphere element distribution images;
FIG. 4 shows the iodine doped graphene and the iodine doped graphene coated hierarchical pore FeFe (CN) during the preparation of the embodiments 1 to 7 of the present invention6X-ray photoelectron spectroscopy of nanospheres;
FIG. 5 shows the iodine doped graphene coated hierarchical pore FeFe (CN) during the preparation of examples 1 to 7 of the present invention6The nanospheres have electrochemical performance as electrode materials;
FIG. 6 shows the iodine doped graphene coated hierarchical pore FeFe (CN) during the preparation of examples 1 to 7 of the present invention6A nanosphere circulating CV curve and a first-circle discharging platform;
FIG. 7 shows the iodine doped graphene coated hierarchical pore FeFe (CN) during the preparation of examples 1 to 7 of the present invention6Nanosphere at 2000mA g-1Current density of (a);
FIG. 8 shows the iodine doped graphene coated hierarchical pore FeFe (CN) during the preparation of examples 1 to 7 of the present invention6Nanosphere (FeFe (CN)6@ IG) as electrode material before and after reaction.
Detailed Description
The specific implementation process of the iodine-doped graphene-coated hierarchical pore prussian blue nanosphere, the preparation method and the application thereof is described below.
The embodiment provides a preparation method of hierarchical pore Prussian blue nanospheres based on iodine-doped graphene wrapping, which comprises the following steps of firstly, adding K3[Fe(CN)6]Dissolving in deionized water, adding surfactant, ultrasonic stirring to obtain clear solution, adding inorganic acid solution, stirring, heating, magnetically stirring, heating to 70-90 deg.C, reacting for 22-26 hr, and cooling to room temperature; centrifuging to collect precipitate, washing with distilled water and ethanol for several times, and vacuum drying at 50-70 deg.CDrying for 10-14 h to obtain solid FeFe (CN)6And (5) a nanosphere precursor. In this step, K is3[Fe(CN)6]And a surfactant at a mass ratio of preferably 1:15 to 1:30, and the concentration of the inorganic acid solution is 0.5M, and it is possible to prepare a hierarchical pore FeFe (CN) having a size of only by using the above experimental conditions in the present invention6The concentration of the inorganic acid solution in the embodiment is relatively high, if the concentration of the inorganic acid (such as hydrochloric acid) is too high, the etched cavity is too large, no action constraint is imposed on the migration of lithium ion of the lithium ion battery, if the concentration of the inorganic acid is too low, the etching is incomplete, and a sample with graded holes cannot be obtained, so that the optimal concentration of the inorganic acid solution in the embodiment is about 0.5M, and the optimal preparation effect is achieved.
Next, the solid FeFe (CN) prepared above was mixed6Respectively adding the nanosphere precursor and the surfactant into an inorganic acid solution, uniformly stirring, heating to 120 ℃ in a sealed environment, continuously reacting for 4-6h, and gradually cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres. In this step, the solid FeFe (CN)6The mass ratio of the nanosphere precursor to the surfactant is 1:3-1:5, the concentration of the inorganic acid solution is 1.0-2.0M, the reaction time of temperature rise is 4.5-5h, the temperature rise rate is 2-5 ℃/min, the temperature drop rate is 0.2-2 ℃/min, and the nanosphere precursor and the surfactant have hierarchical pores FeFe (CN)6The particle size of the nanosphere is 100-200 nm.
Finally, iodine doped graphene and the prepared FeFe (CN) with hierarchical pores6Adding the nanosphere into ionized water, performing ultrasonic treatment for 1-2h, and freeze-drying for 46-50h to obtain iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanospheres. Preferably, in this step, the iodine doped graphene and the FeFe (CN) having hierarchical pores6The mass ratio of the nanospheres is 1:5-1:10, ultrasonic treatment is carried out for 1.0-1.5h, and freeze drying is carried out for 48-50 h.
In the preferred embodiment, PVP is adopted as the surfactant, which is synthetic water-soluble polymer surfactants, the molecule contains hydrophobic methylene carbon chain and strong polar internal acyl group, and the PVP can be adsorbed on the surface of the nano particle in various ways to ensure that the PVP can be adsorbed on the surface of the nano particle in various waysRemarkably reduced surface tension, and has effect in preventing FeFe (CN)6The effect of particle agglomeration. In addition, the inorganic acid solution adopted by the invention is hydrochloric acid (HCl) or sulfuric acid (H)2SO4) And nitric acid (HNO)3) Among , hydrochloric acid solution is particularly preferable, and it is advantageous that Cl is dissociated in the solution-Minimal anion volume, cause FeFe (CN)6The change of agglomeration on the particle surface is minimal.
The iodine-doped graphene-coated hierarchical pore FeFe (CN) can be prepared by the preparation method6Nanospheres (i.e. FeFe (CN))6@ IG) having a spherical particle diameter of 150-. The FeFe (CN) thus prepared6The @ IG is applied to the negative electrode of the lithium-ion battery, is favorable for improving the electrochemical performance of the negative electrode, keeps good appearance before and after reaction, does not collapse or deform, can achieve the electrochemical effect superior to the existing product, and shows the characteristics that the capacity of the negative electrode of the lithium-ion battery is not easy to attenuate and the rate capability is good.
The technical solution of the present invention is further illustrated by through the following specific examples.
Example 1
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 80 ℃ under magnetic stirring, reacting the mixture for 24 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.45g) into a 1.0M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 115 ℃ at a speed of 2 ℃/min, and continuously reacting for 4.5h, then gradually cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (2.5 g) into 30 mL of ionized water, performing ultrasonic treatment for 1.0 h, and freeze-drying for 48h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 2
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 80 ℃ under magnetic stirring, reacting the mixture for 24 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.45g) into a 1.0M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 115 ℃ at a speed of 2 ℃/min, continuously reacting for 4.5h, and then gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (3.0g) into 30 mL of ionized water, performing ultrasonic treatment for 1.0 h, and freeze-drying for 48h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 3
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, carrying out programmed temperature rise to 70 ℃ under magnetic stirring, reacting for 22 hours, and then cooling to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 50 ℃ for 10 h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.60g) into a 1.5M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 120 ℃ at a speed of 2 ℃/min, reacting for 4h, and gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (3.5 g) into 30 mL of ionized water, performing ultrasonic treatment for 1.0 h, and freeze-drying for 46h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 4
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 90 ℃ under magnetic stirring, reacting the mixture for 26 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 70 ℃ for 14 h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6The nanosphere precursor (0.15g) and surfactant PVP (0.75g) were added to 1.5M HCl solution separatelyStirring, placing in a sealed stainless steel autoclave, heating to 120 deg.C at a speed of 2 deg.C/min, reacting for 6h, and gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (3.5 g) into 30 mL of ionized water, performing ultrasonic treatment for 2.0 h, and freeze-drying for 50h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 5
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 80 ℃ under magnetic stirring, reacting the mixture for 24 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.75g) into a 2.0M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 120 ℃ at a speed of 2 ℃/min, reacting for 5h, and gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (4.0 g) into 30 mL of ionized water, performing ultrasonic treatment for 1.0 h, and freeze-drying for 49h to obtain a loose dark blue powder iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 6
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 80 ℃ under magnetic stirring, reacting the mixture for 24 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Solid FeFe (CN) prepared in the step (1)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.75g) into a 2.0M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 120 ℃ at a speed of 2 ℃/min, reacting for 5h, and gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (4.5 g) into 30 mL of ionized water, performing ultrasonic treatment for 1.0 h, and freeze-drying for 50h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Example 7
preparation method of hierarchical pore Prussian blue nanospheres wrapped by iodine-doped graphene, which comprises the following steps:
(1) will K3[Fe(CN)6](0.1g) was dissolved in deionized water, surfactant PVP (3.0g) was added, the mixture was stirred with ultrasound to a clear solution, 0.5M HCl solution was added, and after stirring for 60 min, a pale yellow solution was formed and transferred to a 100 mL flask. Then putting the mixture into a water bath kettle, heating the mixture to 80 ℃ under magnetic stirring, reacting the mixture for 24 hours, and then cooling the mixture to room temperature. The precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6And (5) a nanosphere precursor.
(2) Mixing the rice prepared in the step (1)Core FeFe (CN)6Respectively adding a nanosphere precursor (0.15g) and a surfactant PVP (0.75g) into a 2.0M HCl solution, stirring uniformly, placing in a sealed stainless steel autoclave, heating to 120 ℃ at a speed of 2 ℃/min, reacting for 5h, and gradually cooling to room temperature to obtain FeFe (CN) with graded holes6Nanospheres.
(3) Iodine-doped graphene IG (0.5g) and the hierarchical pore FeFe (CN) prepared in the step (2)6Adding the nanosphere (5.0 g) into 30 mL of ionized water, performing ultrasonic treatment for 1.5h, and freeze-drying for 50h to obtain loose dark blue powder iodine-doped graphene-coated hierarchical pores FeFe (CN)6Nanosphere (FeFe (CN)6@IG）。
Iodine doped graphene coated hierarchical pore FeFe (CN) of preparation Processes of inventive examples 1 to 76Nanosphere (FeFe (CN)6@ IG), the spherical particle diameter is 150-200 nm.
As shown in fig. 1, it was confirmed in fig. 1a that the IG sheet exhibited a fluffy and wavy morphology with more wrinkles and folded areas. Highly folded IGs retain their two-dimensional (2D) lamellar structure and randomly aggregate to form disordered solids. FIGS. 1a and 1b contain hierarchical pores FeFe (CN)6After the nanospheres were etched with HCl, the surfaces became significantly rougher, pores were created, the basic shape of the nanospheres was certainly preserved, the spherical particle size was 150-200nm, FIG. 1c contains graded pores FeFe (CN)6The nanospheres are tightly located on the IG layer, and the dispersion can enhance the conductivity of the composite material and buffer FeFe (CN)6Volume change of the nano-ball in the process of charging and discharging. Furthermore, this layered FeFe (CN)6The surface-to-point close contact between the @ IG composite materials forms a highly interconnected conductive network, which is beneficial to improving the conductivity of the composite materials.
As shown in FIG. 2, all diffraction peaks of the etching precursor in the X-ray diffraction pattern (XRD) are directed to typical FeFe (CN)6(JCPDS 01-0239) XRD analysis showed solid FeFe (CN) after HCl etching6Nanosphere precursors and FeFe (CN) with hierarchical pores6The crystal phase of the nano-spherical particles is not changed and corresponds to a {100} crystal plane, a {110} crystal plane, a {200} crystal plane and a {210} crystal planeA {211} crystal plane, a {220} crystal plane, a {300} crystal plane, a {310} crystal plane, a {320} crystal plane, a {321} crystal plane. FeFe (CN) having hierarchical pores6The crystallinity of the nano-sphere particles is enhanced, and the nano-sphere particles have hierarchical pores FeFe (CN)6The size of the nanospheres is slightly reduced to about 230 nm.
As shown in FIG. 3, the element distribution image shows that there are hierarchical pores FeFe (CN)6The even distribution of elements Fe, C and N in the heterostructure of the nanosphere can be observed by TEM to confirm the effectiveness of the etching process at step .
As shown in fig. 4, the iodine doped graphene raman spectrum showed two different D peaks (1357 cm)-1) And G peak (1588 cm)-1) And weak 2D peaks (2590-3060 cm)-1). D and G peaks respectively correspond to defects and sp of the crystal structure of the iodine-doped graphene2Degree of hybrid graphitization. Calculating the D/G intensity ratio (I) of the iodine-doped grapheneD/IG) Is about 1.10. The carbon lattice structure of iodine doped graphene is more disordered than the original graphene due to edge deformation and cracking during doping. It can be seen from XPS that iodine in iodine-doped graphene is pentaiodide (I)5-) And triiodide (I)3-) The polyanion exists in a form, and the positive charge density of the graphene is increased in a surface charge transfer mode. Therefore, iodine doped graphene (IG) has better conductivity.
The invention also protects the iodine doped graphene coated hierarchical pore FeFe (CN)6Nanospheres (i.e. FeFe (CN))6@ IG) as a negative electrode material in lithium ion batteries.
The FeFe (CN)6The preparation method of the @ IG composite material as the negative electrode material of the lithium ion battery can adopt any method known in the field. The method adopted in the embodiment of the invention is as follows: in an Ar glove box, an active material for a working electrode (i.e., FeFe (CN) prepared in the above example)6@ IG), acetylene black (AB for short) and polyvinylidene fluoride (PVDF for short) at 80: 10: 10, grinding and mixing uniformly. In the test cells, lithium sheets were used as the counter electrode and the reference electrode, and Celgard 2400 membrane manufactured by Celgard corporation, USA was used as the separator. The electrolyte has a concentration of 10M lithium hexafluorophosphate (i.e. LiPF)6) The material is dissolved in a mixture of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a mass ratio of 1:1:1 to assemble the material into the lithium ion battery.
The above lithium ion battery discharge/charge test was performed at voltage intervals of 0.001 to 3.0V at room temperature (25 ℃). Electrochemical Impedance Spectroscopy (EIS) was performed using the electrochemical workstation CHI760E, an AC signal with a frequency in the range of 10 kHz to 100 mHz and an amplitude of 5 mV. Electrochemical workstation using CHI760E at 1 mV s-1The sweep rate of (c) was measured between 0.001 and 3.0V using Cyclic Voltammetry (CV).
As shown in FIG. 5, FIG. 5a shows FeFe (CN) at room temperature6@ IG electrode at 1 mVs between 0.001 and 3.0V-1The first four Cyclic Voltammetry (CV) curves performed at the sweep rate of (c). From this we can see FeFe (CN)6@ IG first shows a clear discharge plateau at 1.6V, which means Fe coordinated to the C and N atoms3+Reduction of ions and Li+Embedding in FeFe (CN)6In the lattice, a strong reduction peak was observed at 0.45V for the th discharge period, which is attributable to a side reaction occurring on a Solid Electrolyte Interphase (SEI) film formed on the electrode surface from the second period onward, CV curves almost overlapped, indicating FeFe (CN)6The stability and excellent electrochemical reversibility of @ IG. The peak at 0.76V during the second discharge indicates Li+Is inserted into FeFe (CN)6Without phase decomposition. FIG. 5b shows FeFe (CN)6The discharging/charging platform curve of the first 50 cycles of the @ IG negative electrode material and the current density of 100mA g-1And the charge and discharge voltage is between 0.001V and 3.0V. In FIGS. 5c and 5d, from FeFe (CN)6@ IG prepared electrode at 1000 mA g-1Current density of 709.5 mAh g after 250 cycles-1And at a specific discharge capacity of 2000mA g-1Current density of 448.0 mAh g after 300 cycles-1Specific discharge capacity of (2). These results demonstrate that FeFe (CN)6The @ IG negative electrode material has excellent cycle stability under a large current. FIG. 5e shows different currentsMultiplying factor of FeFe (CN)6Rate capability and cycling capability of the @ IG electrode as the current density was gradually increased from 100 to 200, 500, 1000 and 2000mA g-1When the discharge capacity is increased, the corresponding discharge specific capacity is respectively reduced from 987 to 804.8, 731.9, 591 and 507.7 mAh g-1. When the current density is recovered to 100mA g-1The specific discharge capacity is recovered to 758.1 mAh g-1This indicates FeFe (CN)6The @ IG electrode also has excellent electrochemical properties and structural stability after undergoing high current cycling.
As shown in FIG. 6, the step discharge occurred in the 0.001-1.4V range, first with Fe coordinated with low spin CIIIReduction to FeIIThen FeIIIs further reduced by .
As shown in FIG. 7, at 2000mA g-1At a current density of FeFe (CN)6The @ IG composite showed 189.7 mAh g after 300 cycles-1Specific discharge capacity of (2).
As shown in FIG. 8, for further understanding of FeFe (CN)6According to the relationship between the cycle performance and the structural characteristics of @ IG, the shape change of the negative electrode material under different current densities after 100 times of charge and discharge cycles is observed under SEM. With the original FeFe (CN)6At 100mA g compared with the @ IG electrode-1At current density, FeFe (CN) was also observed after 100 cycles6Is substantially unchanged and is FeFe (CN)6The @ IG electrode maintains its integrity. Furthermore, FeFe (CN)6@ IG was uniformly distributed in a composite of polyvinylidene fluoride (PVDF) and acetylene black, and steps further confirmed that the structure prepared in this example can effectively alleviate pulverization, prevent particle aggregation, and ensure long-term stability when the charge/discharge current density was 1000 mA g-1While the electrode after cycling still can maintain the complete structure, FeFe (CN)6The @ IG nano structure can adapt to volume expansion of multiple charging and discharging and prevent agglomeration of Prussian blue nanospheres. FIGS. 8g and 8h are transmission electron microscopy images of the electrode material after 10 cycles, showing that FeFe (CN)6The nanospheres are clearly visible and in close contact with the iodine-doped graphene, and no shedding phenomenon occurs.
Iodine doped graphene coated hierarchical pores FeFe (CN) prepared in examples 1-76Nanospheres (i.e. FeFe (CN))6@ IG) as the negative electrode of the lithium ion battery, the electrochemical test is carried out, and the lithium ion battery is at 100mAhg-1The results of the capacity and the capacity maintenance rate after the current density is cycled for 300 times are shown in table 1, the lithium ion battery has good test repeatability and good cycle stability, and the capacity maintenance rate after the current density is cycled for 300 times is up to more than 90%.
In the discharge process of the lithium ion battery, the volume expansion of the cathode material can be caused by the lithium intercalation, and the FeFe (CN) prepared by the invention6@ IG will alleviate this volume expansion. In addition, the hierarchical pore structure is beneficial to the rapid transmission of lithium ions, and the compounding of iodine-doped graphene greatly improves FeFe (CN)6The conductivity of the nanospheres.
Hierarchical pore FeFe (CN) coated with iodine-doped graphene prepared in example 26Nanospheres (i.e. FeFe (CN))6@ IG) was compared to the reported electrochemical performance of prussian blue and its derived materials, as shown in table 2. FeFe (CN)6The electrochemical performance of the @ IG electrode is superior. For example, graphene foam-wrapped Prussian blue is reported to have a current density of 100mA g-1In the case of (1), about 514 mAh g can be maintained after 150 cycles-1Specific capacity of, and single crystal Mn [ Fe (CN)6]0.6667·nH2O cubes (about 600 nm) at 200 mA g-1The specific capacity of the alloy after 100 cycles under the current density is kept to be about 295.7 mAh g-1. In addition to high porosity, two factors may cause example 2 to exhibit excellent lithium ion battery performance. Firstly, wrapping iodine doped graphene hierarchical pore FeFe (CN)6Nanospheres can withstand volume changes during cycling and improve their conductivity. Secondly, in terms of theoretical specific capacity, with mixed-valence Mx[Fe(CN)6]y(M = Fe, Mn and Co) vs FeFe (CN)6Nanospheres based mainly on Fe3+Contribute to discharge, allow at dischargeMore Li in electric time+Embedded FeFe (CN)6In the unit cell structure, thus FeFe (CN)6Has higher theoretical specific capacity.
It should be understood that the foregoing description of specific embodiments is in some detail, and not for the purposes of limiting the invention as defined by the appended claims.
Claims (10)
1, preparation methods of hierarchical pore Prussian blue nanospheres wrapped on iodine-doped graphene, which comprise the following steps:
A. will K3[Fe(CN)6]Dissolving in deionized water, adding surfactant, ultrasonic stirring to obtain clear solution, adding inorganic acid solution, stirring, heating, magnetically stirring, heating to 70-90 deg.C, reacting for 22-26 hr, and cooling to room temperature; centrifuging to collect precipitate, washing with distilled water and ethanol several times, and vacuum drying at 50-70 deg.C for 10-14 h to obtain solid FeFe (CN)6A nanosphere precursor;
B. solid FeFe (CN) prepared above6Mixing the nanosphere precursor and a surfactant, adding the mixture into an inorganic acid solution, uniformly stirring, heating to 120 ℃ in a sealed environment, continuously reacting for 4-6h, and gradually cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres;
C. iodine doped graphene and the prepared FeFe (CN) with graded pores6Adding the nanosphere into ionized water, performing ultrasonic treatment for 1-2h, and freeze-drying for 46-50h to obtain iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanospheres.
2. The method for preparing graded-pore Prussian-blue nanospheres based on iodine-doped graphene coating according to claim 1, wherein in step A, K is3[Fe(CN)6]And the amount of surfactantThe ratio is 1:15-1:30, and the concentration of the inorganic acid solution is 0.5M.
3. The method for preparing graded-pore prussian blue nanospheres based on iodine-doped graphene coating according to claim 2, wherein in step B, solid FeFe (CN)6The mass ratio of the nanosphere precursor to the surfactant is 1:3-1:5, the concentration of the inorganic acid solution is 1.0-2.0M, the reaction time of temperature rise is 4.5-5h, the temperature rise rate is 2-5 ℃/min, the temperature drop rate is 0.2-2 ℃/min, and the nanosphere precursor and the surfactant have hierarchical pores FeFe (CN)6The particle size of the nanosphere is 100-200 nm.
4. The preparation method of graded-pore Prussian-blue nanospheres based on iodine-doped graphene wrapping according to claim 3, wherein the surfactant is any of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or polyvinylidene fluoride.
5. The method for preparing graded-hole Prussian-blue nanospheres based on iodine-doped graphene wrapping according to claim 3, wherein the inorganic acid solution is any of hydrochloric acid, sulfuric acid and nitric acid.
6. The method for preparing Prussian blue nanospheres based on iodine-doped graphene wrapping classification holes according to claim 3, wherein in step C, the iodine-doped graphene and the Prussian blue nanospheres with classification holes are FeFe (CN)6The mass ratio of the nanospheres is 1:5-1:10, ultrasonic treatment is carried out for 1.0-1.5h, and freeze drying is carried out for 48-50 h.
7. The preparation method of graded-pore prussian blue nanospheres based on iodine-doped graphene coating according to claim 3, which comprises the following steps:
a1, mixing K3[Fe(CN)6]Dissolving in deionized water, adding polyvinylpyrrolidone, ultrasonic stirring to obtain clear solution, adding HCl solution, stirring, heating to 80 deg.C under magnetic stirring, reacting for 24 hr,then cooling to room temperature; the precipitate was collected by centrifugation, washed several times with distilled water and ethanol and dried under vacuum at 60 ℃ for 12h to obtain solid FeFe (CN)6A nanosphere precursor;
b1, solid FeFe (CN) prepared by the above method6Respectively adding the nanosphere precursor and the surfactant into an inorganic acid solution, uniformly stirring, carrying out programmed heating to 120 ℃ in a sealed environment, continuously reacting for 5 hours, and gradually carrying out programmed cooling to room temperature to obtain FeFe (CN) with graded pores6Nanospheres;
c1, doping iodine with graphene and FeFe (CN) with hierarchical pore prepared by the method6Adding the nanosphere into ionized water, performing ultrasonic treatment for 1.5h, and freeze-drying for 48h to obtain the iodine-doped graphene-coated hierarchical pore FeFe (CN)6Nanospheres.
8, graded-pore prussian blue nanospheres based on iodine-doped graphene wrapping prepared by the method of claims 1-6- , characterized in that the iodine-doped graphene wrapping graded-pore fefe (cn)6The nanosphere is a dark blue powder structure, and the spherical particle size is 150-200 nm.
applications of iodine doped graphene coated based hierarchical pore prussian blue nanospheres according to claim 8, characterized in that said iodine doped graphene coated based hierarchical pore fefe (cn)6The nanospheres are applied to the negative electrode of a lithium electronic battery.
10. The use of iodine doped graphene coated hierarchical pore prussian blue nanospheres according to claim 9, wherein: the working electrode of the lithium ion battery is prepared from the following components in percentage by mass of 80: 10: iodine doped graphene coated hierarchical pores FeFe (CN) of 106Nanosphere, acetylene black and polyvinylidene fluoride.
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