CN107195897B - Nano FeNbO4Graphene composite material and preparation and application thereof - Google Patents
Nano FeNbO4Graphene composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a nano FeNbO4A/graphene composite material and preparation and application thereof belong to the technical field of new energy. Nano FeNbO4The preparation method of the/graphene e composite material comprises the step of mixing C10H5O20Nb、Fe(NO3)3·9H2Carrying out hydrothermal reaction on O and graphene in a reaction kettle, and roasting the obtained particles, wherein the hydrothermal reaction conditions are as follows: preserving the heat for 20-24 hours at 180-240 ℃ to obtain particles; the roasting conditions are as follows: heating the particles obtained by the hydrothermal reaction to 950-1000 ℃ at a speed of 3-5 ℃/min under an argon atmosphere, and preserving heat for 6-10 h; cooling to room temperature at the speed of 2-3 ℃/min to obtain the nano FeNbO4A graphene composite material. The obtained nano FeNbO4Electrochemical performance of/graphene composite material is higher than that of nano FeNbO synthesized by hydrothermal method4And micron FeNbO synthesized by solid phase sintering method4All are improved.
Description
Technical Field
The invention relates to a nano FeNbO4A/graphene composite material and preparation and application thereof belong to the technical field of new energy.
Background
With the increasing exhaustion of non-renewable resources such as petroleum and natural gas, the increasing importance of people on the environment, and the increasing high efficiency of the production of electrical energy with strong renewability, lithium ion batteries as reserve electrical energy are being further applied to strategic emerging industries such as new energy vehicles and smart power grids from portable electrical devices. Both smart grids and new energy vehicles put higher requirements on the safety, power, capacity and other performances of the lithium ion battery.
The lithium ion battery cathode materials which are commercialized at present comprise carbon cathode materials such as artificial graphite and natural modified graphite with hexagonal or rhombic layered structures, and lithium titanate (LTO, Li) with cubic spinel structure4Ti5O12). However, when graphite is used as the negative electrode material, the electrolyte is decomposed during the first charge and discharge process, which is seriousAnd also easily causes volume change of the carbon negative electrode material with de-intercalation of lithium ions and intercalation of solvent molecules into graphite during charge-discharge cycles, resulting in collapse of graphite layers. In addition, the diffusion rate of lithium ions in the graphite layer is low, so that the rate performance is poor, and lithium dendrites are easily formed on the surface of the graphite during overcharge to cause internal short circuit of the battery. Although the LTO material has the advantages of zero strain, stable cycling performance, high thermal stability and the like, the electron conductivity and the ion conductivity are very low (the inherent conductivity is only 10) because the LTO material is an insulator-9S/cm) resulting in poor high rate performance. In order to meet the requirements of power batteries on high energy density, long service life and safety of electrode materials, researchers continuously improve the performance of the currently commercialized anode materials on one hand and continuously research and explore novel anode materials on the other hand. Among them, silicon-based and tin-based negative electrode materials are receiving wide attention due to their extremely high theoretical capacities. Wherein the silicon-based material has the highest specific capacity and is lithiated to Li4.4When Si is used, the theoretical capacity of the material reaches 4200mAh/g, which is more than ten times of that of the existing commercial graphite cathode material. However, when silicon is used as the negative electrode material of the lithium ion battery, during the charging and discharging processes, the silicon and the lithium ions are combined and alloyed, so that a large volume effect is generated, the volume change reaches 400%, the structure of the material is easy to damage, the electrodes are easy to pulverize, and the cycle efficiency of the material is greatly reduced. At present, the research on silicon-based negative electrode materials mainly focuses on Si/M (M is a metal element) and Si/C composite materials, and the volume expansion of the composite materials is relieved by adopting nano synthesis. The tin-based negative electrode material mainly includes metallic tin, tin-based oxide, and tin-based alloy. The theoretical capacity of the lithium ion battery is higher than that of a graphite cathode by more than 500mAh/g, but a huge volume effect exists in the lithium extraction and insertion process, the volume change reaches about 260%, the cycle performance of the lithium ion battery is seriously deteriorated, the irreversible capacity of the lithium ion battery is large for the first time, and the application of the lithium ion battery in practical production is greatly limited.
The niobium-based negative electrode material mainly comprises niobium oxide, titanium niobium oxide and the like. The potential of the niobium-based negative electrode material for lithium ions is high because the fermi level of lithium ions therein is large. Niobium element has a lot of valence changes, so niobium-based negative electrode materials generally have higher theoretical specific capacity. At present, the synthesis methods of niobium-based negative electrode materials mainly comprise a solid-phase method and a hydrothermal method. The traditional solid phase method synthesized material often has the phenomena of overlarge particle size, uneven dispersion, serious agglomeration and the like, which directly causes that the specific surface area of the material is too small and the material is not contacted with an electrolyte sufficiently, and the cracking-pulverization-falling process of the material is easily aggravated in the charging and discharging process, and meanwhile, the particles with large particle size can increase the length of a diffusion path of lithium ions and reduce the number of the diffusion path, thereby seriously worsening the performances of the material such as the circulation rate and the like. And the hydrothermal method alone can relieve the adverse effect caused by oversize particles to a certain extent, but the improvement degree of the electrochemical performance of the material is relatively limited.
Disclosure of Invention
In order to solve the technical problem, the invention provides nano FeNbO for a lithium ion battery cathode4Preparation method of/graphene (FNO/Gra) composite material, and electrochemical performance of material obtained by using method is higher than that of nano FeNbO synthesized by hydrothermal method4(Nano FNO) and micron FeNbO synthesized by solid phase sintering method4(Micro FNO) was increased.
Nano FeNbO4The preparation method of the/graphene composite material comprises the step of mixing C10H5O20Nb (niobium oxalate), Fe (NO)3)3·9H2Carrying out hydrothermal reaction on O and graphene in a reaction kettle, roasting the obtained particles, wherein,
the hydrothermal reaction conditions are as follows: preserving the heat for 20-24 hours at 180-240 ℃ to obtain particles;
the roasting conditions are as follows: heating the particles obtained by the hydrothermal reaction to 950-1000 ℃ at a speed of 3-5 ℃/min under an argon atmosphere, and preserving heat for 6-10 h; cooling to room temperature at the speed of 2-3 ℃/min to obtain the nano FeNbO4A graphene composite material.
The hydrothermal and roasting process can be carried out in the equipment disclosed by the prior art, such as a polytetrafluoroethylene reaction kettle, a muffle furnace, a tubular furnace and the like.
Further, it is characterized byC is10H5O20Nb and Fe (NO)3)3·9H2The molar ratio of O is 1: 1.
Further, the graphene and the target obtained FeNbO4In a weight ratio of 15-18: 100, wherein the FeNbO obtained by the target4The weight of (B) is represented by C10H5O20Nb and Fe (NO)3)3·9H2FeNbO obtained by taking O as raw material according to proportion complete reaction theory4The weight of (c).
Further, completely dispersing the graphene by dissolving the graphene in deionized water and performing ultrasonic treatment in an ultrasonic cleaning machine for 30min to obtain a graphene dispersion liquid; further, the weight ratio of graphene to water in the dispersion liquid is preferably 0.213-0.255: 100.
Further, C is10H5O20Nb and Fe (NO)3)3·9H2Dissolving O in water respectively and then mixing to obtain mixed solution; still further, it is preferable that C is10H5O20The concentration of Nb is 0.08-0.1 mol/L, Fe (NO)3)3·9H2The concentration of O is 0.08-0.1 mol/L.
Further, the mixed solution and the dispersion liquid of graphene are subjected to ultrasonic treatment in an ultrasonic cleaning machine for at least 2 hours to be completely mixed.
Furthermore, the mixture synthesized by the hydrothermal method is washed with deionized water and absolute ethyl alcohol for three times respectively, then is placed in a drying box at the temperature of 80 ℃ to be dried, the dried product is ground, and the ground particles are roasted again.
A preferred technical scheme of the invention is as follows: electrode material nano FeNbO for lithium ion battery cathode4A preparation method of/Graphene composite material comprises the following process steps:
① FeNbO obtained according to graphene and target4Weighing graphene according to the weight ratio of 15-18: 100, and carrying out ultrasonic treatment for 30min to uniformly disperse the graphene in deionized water to obtain a graphene dispersion liquid;
② weighing C according to the mole ratio of Nb to Fe being 1:110H5O20Nb and Fe (NO)3)3·9H2O, respectively dissolving the weighed materials in ionized water, mixing and stirring the weighed materials at 60 ℃ for 30min after the weighed materials are completely dissolved so as to promote the weighed materials to be fully mixed, and carrying out ultrasonic treatment for 30min to obtain a brownish yellow clear solution, wherein C10H5O20The concentration of Nb is 0.08-0.1 mol/L, Fe (NO)3)3·9H2The concentration of O is 0.08-0.1 mol/L;
③ mixing the dispersion of graphene with C10H5O20Nb and Fe (NO)3)3·9H2Mixing the uniform solution of O and performing ultrasonic treatment in an ultrasonic cleaning machine for 2 hours to completely disperse the O to obtain a black mixed solution; carrying out hydrothermal reaction on the black mixed solution in a reaction kettle, wherein the hydrothermal reaction conditions are as follows: preserving the heat for 20-24 hours at 180-240 ℃ to obtain a product;
④ centrifuging, washing with deionized water and anhydrous ethanol for 3 times, oven drying at 80 deg.C, and grinding to obtain black powder;
⑤ placing the obtained black powder into a corundum crucible, placing the corundum crucible in a tube furnace with high-purity argon as protective gas, heating to 950-1000 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-10 h, cooling to room temperature at the speed of 2-3 ℃/min, and finally obtaining black FeNbO4Graphene material (FNO/Gra).
The invention also aims to provide the nano FeNbO prepared by the method4The material is nano FeNbO4The particles are distributed in an irregular grid formed by interweaving single-layer graphene e to form the composite material, wherein the nano FeNbO4The average particle diameter of the particles is 50-80 nm.
The invention has the beneficial effects that: FeNbO prepared by the method4Graphene composite material, in which FeNbO4The particles are monoclinic nanoparticles and are distributed in an irregular grid formed by interweaving single-layer graphene so as to form FeNbO4A graphene composite material. The FeNbO4Graphene composite materialAs a lithium ion cathode material, performing charge and discharge tests, and synthesizing the lithium ion cathode material with a solid phase method to obtain micron FeNbO4(synthesis process: weighing appropriate amount of Nb according to the molar ratio of Nb: Fe ═ 1: 1)2O5And Fe2O3Putting the weighed materials into a 100ml agate ball-milling tank, ball-milling for 4h on a planetary ball mill at the rotating speed of 600r/min, putting the powder obtained by ball-milling into a corundum crucible, roasting in a muffle furnace at 1100 ℃ in air for 24h) and synthesizing the nano FeNbO by a hydrothermal method4(Synthesis Process and preparation of FeNbO4Graphene composites were identical except that graphene, high purity argon and a tube furnace were not used and were sintered in a muffle furnace); the range of the charging and discharging test voltage is 0.01-3V, the test currents are four types, namely 40mA/g, 80mA/g, 200mA/g and 400mA/g, and the test temperature is 25 ℃. Test results show that not only the first discharge capacity, the charge capacity 865.7mAh/g and the first discharge and charge capacity 599.1mAh/g are improved compared with micron (483.9mAh/g and 378.7mAh/g) and nanometer (751.7mAh/g and 576.3mAh/g), but also the cycle performance and the rate performance are better.
Drawings
FIG. 1 is an XRD map of Micro FNO, Nano FNO and FNO/Gra, and the XRD map shows that the peaks of Micro FNO, Nano FNO and FNO/Gra are sharp and almost no impurity peak appears, and main diffraction peaks are similar to monoclinic system FeNbO4The diffraction peak of (PDF-70-2275) corresponds to each other. Therefore, the synthesized material can be judged to be highly crystalline and has no impurity phase;
FIG. 2 is a first charging and discharging map of Micro FNO, Nano FNO and FNO/Gra under the charging and discharging test voltage range of 0.01-3V and the current of 40 mA/g;
FIG. 3 is a cycle performance map of Micro FNO, Nano FNO and FNO/Gra according to the present invention, the capacity retention rates of Micro FNO, Nano FNO and FNO/Gra are 82.94%, 92.83% and 95.75% in sequence from the tenth time to the fifty times when the cycle tends to be stable, and the capacity fading of each cycle is 1.01mAh/g, 0.6875mAh/g and 0.495 mAh/g. Therefore, the FNO/Gra cycle performance can be judged to be the best;
FIG. 4 is a graph of multiplying power performance of Micro FNO, Nano FNO and FNO/Gra of the present invention;
FIGS. 5(a), (b) and (c) are SEM images of Micro FNO, Nano FNO and FNO/Gra, respectively, and it can be seen from the SEM images that the prepared Micro FNO and Nano FNO materials have good crystal form development, uniform size, good dispersion degree and no obvious agglomeration phenomenon. The sizes of Micro FNO particles are mostly distributed between 0.5-1 um, and the sizes of Nano FNO particles are mainly distributed between 50-80 nm. The Gra/FNO material has a fuzzy surface due to the nanoscale FeNbO4The particles are wound and wrapped in the sheet layer of the graphene with smooth surface, so that the original particles lose clear edges and corners;
FIGS. 6(a), (b) and (c) are TEM spectra of FNO/Gra under different magnification according to the present invention, respectively.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Electrode material nano FeNbO for lithium ion battery cathode4The preparation method of the/graphene (FNO/Gra) composite material comprises the following steps:
step 1, preparing FeNbO4Graphene precursor:
(1) weighing 0.0638g of graphene, and ultrasonically dispersing the graphene in 30mL of deionized water for 30min to obtain a graphene dispersion liquid;
(2) weighing C10H5O20Nb1.076g、Fe(NO3)3·9H2O0.808g, dissolving in 20mL deionized water respectively, mixing the two solutions, mixing and stirring the two solutions at 60 ℃ for 30min to promote the complete mixing, and performing ultrasonic treatment for 30min to obtain a brownish yellow clear solution;
(3) mixing the dispersion liquid of graphene with C10H5O20Nb and Fe (NO)3)3·9H2Mixing the uniform solution of O and performing ultrasonic treatment in an ultrasonic cleaning machine for 2 hours to completely disperse the O to obtain a black mixed solution;
(4) placing the obtained black mixed solution in a polytetrafluoroethylene reaction kettle lining, fixing the black mixed solution in the reaction kettle, placing the black mixed solution in an oven, preserving the heat for 24 hours at the temperature of 200 ℃, and naturally cooling the black mixed solution to the room temperature to obtain a layered substance;
(5) removing upper layer liquid of layered substance, washing lower layer substance with deionized water and anhydrous ethanol for three times, oven drying the obtained product at 80 deg.C, and grinding the dried product to obtain black powder, i.e. FeNbO4A graphene precursor.
Putting the precursor powder obtained in the step 1 into a corundum crucible, and roasting in a tubular furnace at 1000 ℃ for 6 hours by taking high-purity argon as protective gas, wherein the heating speed is 5 ℃/min; and cooling to room temperature at the speed of 3 ℃/min to finally obtain a black electrode material FeNbO 4/graphene composite material (FNO/Gra).
The composite material FNO/Gra is synthesized by a hydrothermal method, and Nb is weighed according to the molar ratio of Nb to Fe of 1:1 compared with micron MicroFNO synthesized by a traditional solid phase method (synthesis process)2O5And Fe2O3Putting weighed materials into a 100ml agate ball-milling tank, ball-milling for 4h on a planetary ball mill at the rotating speed of 600r/min, putting powder obtained by ball-milling into a corundum crucible, and roasting in a muffle furnace at 1100 ℃ for 24h) compared with the Nano FNO synthesized by a hydrothermal method (synthesis process and preparation of FeNbO)4The graphene composite material is consistent, but the raw material does not contain graphene, and the graphene is roasted in a muffle furnace without argon protection), so that the electrochemical performance of the graphene composite material is improved to different degrees. The range of the charging and discharging test voltage is 0.01-3V, the test currents are four types, namely 40mA/g, 80mA/g, 200mA/g and 400mA/g, the test temperature is 25 ℃, and the specific figure is shown in figure 4.
As shown in figure 2, the charging and discharging tests are carried out under the conditions that the charging and discharging test voltage range is 0.01-3V and the current is 40mA/g, and the test results show that not only the first discharging capacity, the charging capacity of 865.7mAh/g, the first discharging and charging capacity of 599.1mAh/g are improved for micrometers (483.9mAh/g and 378.7mAh/g) and the first discharging and charging capacity of nanometers (751.7mAh/g and 576.3mAh/g), but also the cycle performance and the rate performance are better.
Claims (7)
1. Nano FeNbO4The preparation method of the/graphene composite material is characterized by comprising the following steps: is to mix C10H5O20Nb、Fe(NO3)3·9H2Carrying out hydrothermal reaction on O and graphene in a reaction kettle, roasting the obtained particles, wherein,
the hydrothermal reaction conditions are as follows: preserving the heat for 20-24 hours at 180-240 ℃ to obtain particles;
the roasting conditions are as follows: heating the particles obtained by the hydrothermal reaction to 950-1000 ℃ at a speed of 3-5 ℃/min under an argon atmosphere, and preserving heat for 6-10 h; cooling to room temperature at the speed of 2-3 ℃/min to obtain the nano FeNbO4The obtained material is nano FeNbO4The particles are distributed in an irregular grid formed by interweaving single-layer graphene, wherein the nano FeNbO4The average particle diameter of the particles is 50-80 nm, and the particles are FeNbO4Are monoclinic nanoparticles.
2. The method of claim 1, wherein: the graphene and FeNbO obtained by the target4The weight ratio of (A) to (B) is 15-18: 100.
3. The method of claim 1, wherein: said C is10H5O20Nb and Fe (NO)3)3·9H2The molar ratio of O is 1: 1.
4. The method of claim 1, wherein: c is to be10H5O20Nb and Fe (NO)3)3·9H2Respectively dissolving O in water, mixing the mixed solution with the dispersion liquid in which the graphene is dispersed, and ultrasonically dispersing for at least 2h after mixing, wherein C10H5O20The concentration of Nb is 0.08-0.1 mol/L, Fe (NO)3)3·9H2The concentration of O is 0.08-0.1 mol/L, and the stone in the dispersion liquidThe weight ratio of the graphene to the water is 0.213-0.255: 100.
5. The method of claim 1, wherein: washing the mixture synthesized by the hydrothermal method with deionized water and absolute ethyl alcohol for three times respectively, then placing the mixture in a drying box at 80 ℃ for drying, grinding the dried product, and roasting the ground particles.
6. The method of claim 1, wherein the FeNbO is prepared as a nano-scale product4The graphene composite material is characterized in that: the material is nano FeNbO4The particles are distributed in an irregular grid formed by interweaving single-layer graphene, wherein the nano FeNbO4The average particle diameter of the particles is 50-80 nm.
7. The nano FeNbO of claim 64The graphene composite material is applied as a negative electrode of a lithium ion battery.
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| Hydrothermal synthesis and electrochemical properties of FeNbO4 nanospheres;Hyuu-Woo SHIM，等;《journal of the ceramic society of japan》;20120229;第120卷(第1398期);第82页右栏第2节、第83页左栏第3段 * |
| Photophysical,bandstructural,and textural properties of o-FeNbO4 in relation to its cocatalyst-assisted photoactivity for water oxidation;Robin Babu,等;《RSC Advances》;20140721;第63卷(第4期);第33436页左栏第2.1节 * |
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