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    • 专利摘要:
    Method of obtaining nanocomposite material of graphitized matrix of carbon and metallic nanoparticles by means of cycles of galvanostatic charges and discharges under the action of magnetic fields, and material thus obtained. This material has supercapacitativas properties that improve its electrochemical activity, exhibiting increases in capacitance that can reach up to 600% higher than that obtained in the absence of the application of magnetic fields, which makes it suitable for use in electrodes for batteries or supercapacitors . (Machine-translation by Google Translate, not legally binding)
    公开号:ES2649688A1
    申请号:ES201600602
    申请日:2016-07-13
    公开日:2018-01-15
    发明作者:Eugenio Coronado Miralles；Helena PRIMA GARCÍA；Gonzalo ABELLÁN SÁEZ；Jorge ROMERO PASCUAL
    申请人:Universitat de Valencia；
    IPC主号:
    专利说明:

    Method of obtaining nanocomposite material by means of cycles of galvanic charges and discharges based on the action of magnetic fields, and material thus obtained.
    Introduction

    The rapid increase in energy demand in recent years has accelerated the search for low-cost alternatives for energy storage and conversion. Two-dimensional materials such as graphene or LDH (double laminar hydroxides) are fundamental components for the design of advanced nanomaterials as they have unique properties of electrochemical activity and energy conversion. These materials allow the development of applications that benefit from the two-dimensional nature of these systems, providing flexibility, numerous redox processes of interest and good electrical conductivity, aspects of utmost importance for the development of batteries with efficient anodes and cathodes, supercapacitors with high density of energy or fuel cells. Among others, supercapacitors are an important type of energy storage devices since they allow high energy density to be stored in short periods of time with the ability to repeat many charge-discharge cycles without losing efficiency.
    The present invention is directed to a new material and a manufacturing method thereof comprising the step of applying a series of galvanized static charges and discharges to a nanocomposite (NC) material with carbon graffiti matrix with FeNi3 nanoparticles in the presence of a magnetic field. external, producing a much more active material from the supercapacitive point of view, which is therefore capable of improving the efficiency of supercapacitors manufactured with said material. By applying the external magnetic field to the precursor nanocomposite material, a layer of nickel oxide (Ni2 +) is generated more electrochemically efficient than that obtained in the absence of the magnetic field. The most surprising thing is that this material is capable of increasing its capacitance almost 600% more than the material without the application of a magnetic field, and there is no reference in the literature for this increase.
    In WO 2013/177543 Al it is described that the application of a magnetic field to certain dielectric materials can induce a large increase in the dielectric constant of the material and therefore in the capacitance of the supercapacitor constructed therewith. In this document a variable magnetic field is used, thus increasing the difficulty of realization and the cost of the invention, unlike the present invention, which can use both electromagnets and static commercial magnets.
    In US20100302703 a thin film capacitor is described, intended to be implemented in circuits. As in the previous case, it is reported that, by applying magnetic fields, it is possible to increase the dielectric constant of dielectric materials by up to a factor x10.
    In Gua et al., NanoEnergy 2014, 6, 180 yen Gua et al., Energy Environmental Science 2013, 6, 194, the authors demonstrate a "relatively modest (less than 200%) increase in capacity when applying magnetic fields to materials nanocomposites based on Fe203 and graphene, and they have very poor cyclability, reducing capacity after less than 1000 cycles.
    In Lu et al., RSC Advances 2015, 5, 99745-99753 the influence of magnetic fields on the morphology and pseudo-capacitive properties of nanostructured nickel oxide is disclosed. It was found that the magnetic field affected the size and direction of growth of the NiO nanoplates, as well as the electrochemical performance of the NiO nanomaterial. In other words, this document shows that, when applying magnetic fields, the compaction and growth of NiO on Ni foam is better. In the case of the present invention, on the contrary, a growth reaction of the NiO nanoplates is not achieved, but of oxidation of the Ni to form Ni (OHh ...
    However, all these documents have one aspect in common: The increases observed in capacitance are due to phenomena other than the generation of electrochemically active chemical compounds; on the contrary, they are due to other phenomena such as magneto-resistance effects or the like. In contrast, in the case of the present invention the increases observed in capacitance are due, as will be explained in detail below, to a substantial increase in the nickel oxide layer (which is electrochemically active) generated, in comparison with which it is generated in the absence of the magnetic field. That is, by applying the magnetic field a chemical reaction has been favored, generating a much higher amount of nickel oxide than would be obtained in the absence of a magnetic field, a phenomenon that, until the knowledge of
    inventors, has not been described to date. This material, electrochemically very active,
    shows capacitance increases much higher than those obtained without the application of the magnetic field, capacitance increases that are also permanent and are still observed even in the absence of magnetic field after its generation, which shows that a new material and is not just a transitory phenomenon. This material has been characterized by the following techniques: HRTEM, SEM, Raman, XPS, electronic conductivity and magnetism, and from all of them it is inferred that a much higher oxide layer has been generated in the new generated material.
    In addition, in the aforementioned prior art documents, the galvanostatic cycles are applied as part of the method of characterization of the nanocomposites under study, and therefore it is not in any case methods of obtaining nanocomposite materials using said galvanostatic cycles, since that prior art materials are typically obtained by the usual autoclave hydrothermal process.
    Summary of the Invention
    Consequently, the problem to be solved in the present invention is to provide a method of obtaining a new material with magnetic properties far superior to those of the materials known to date, and that after application of a magnetic field exhibit increases in capacitance of up to 600% compared to the case of absence of the magnetic field.
    The solution to this problem is based on the fact that the inventors have identified that, by applying a magnetic field of intensity between 50 GY 6000 G, preferably between 1000 GY 6000 G, more preferably between 2000 GY, to a graphitized carbon matrix with FeNi3 nanoparticles 6000 G, and most preferably around 4000 G, a resulting material is obtained that is capable of exhibiting an increase in capacitance of up to 600% higher than that obtained in the absence of the application of a magnetic field.
    Consequently, a first aspect of the invention is directed to a method of obtaining a nanocomposite material comprising the following steps:
    by providing a precursor nanocomposite material comprising a matrix of
    carbon graffiti with FeNi3 nanoparticles, and
    b) subjecting said material to a number between 100 and 10,000 galvanostatic charge / discharge cycles at a current density between 30 and 1 Ag-1 either for load or for discharge, while applying a magnetic field of a intensity between 50 G Y6000 G.
    In preferred embodiments of the invention, the number of galvanostatic cycles to which the material is subjected will preferably be between 100 and 5,000, more preferably between 500 and 1,500, and most preferably between 700 and 1,000, since from that value the capacitance It does not increase significantly and in this way manufacturing costs are kept under control.
    In a second aspect, the invention is directed to the nanocomposite material obtained through said process, as well as to electrodes for batteries or supercapacitors comprising said material.
    In a third aspect, the invention is directed to the use of said nanocomposite material in electrodes for batteries or supercapacitors.
    Obtaining the nanocomposite material of the invention is also quite economical, since the precursor, before calcining it to obtain the graffiti matrix, is obtained at low temperatures (80 oC) and the optimum magnetic field is of low intensity (4000 G, equivalent to the field produced by a neodymium hand magnet). On the other hand, the present invention shows how using the external magnetic field can improve the behavior of a supercapacitive device.
    Brief description of the figures
    Figure 1: Scheme of the homemade electrochemical cell used in the described experiments and electromagnet that applies a magnetic field to it. The components are (A) reference electrode; (B) working electrode; (C) auxiliary electrode; (D) electrolyte; (E) electromagnet.
    Figure 2: Capacitive retention of the NC after 50 galvanostatic cycles without applying a magnetic field and applying different types of magnetic fields.
    Figure 3: Capacitive retention after 300 galvanostatic cycles with and without the magnetic field of the NC and its components separately.
    Figure 4: Capacitive retention after 1000 galvanostatic cycles of the NC with and without magnetic field.
    Figure 5: Galvanic discharge curves of the NC with magnetic field. (A) Curve of cycle 1; (S) 250 cycle curve; (e) 500 cycle curve; (D) Curve of cycle 750; (E) 1000 cycle curve.
    Figure 6: FESEM image of the NC after 1000 galvanostatic cycles with magnetic field.
    Figure 7: HRTEM images of the NC after 1000 galvanostatic cycles with magnetic field.
    Figure 8: Raman spectrum of the NC obtained with 1000 galvanostatic cycles applying a magnetic field.
    Figure 9: Raman spectrum of the precursor NC and the NC after the 1000 galvanostatic cycles with magnetic field.
    Figure 10: XPS spectrum of NC oxygen after 1000 galvanostatic cycles with and without magnetic field.
    Figure 11. 2 K low temperature hysteresis cycle. In this figure, the curve with alternate dotted lines corresponds to the initial precursor sample. The sample with dashed stripes represents the magnetism of the precursor sample after applying 1000 galvanostatic cycles without applying magnetic field. The dotted curve is applying the magnetic field to the precursor sample.
    Figure 12. Current curves of the source sample on the left and the sample after applying 1000 cycles and the magnetic field.
    Figure 13. NC stability test obtained with 1000 galvanostatic cycles with a continuous magnetic field of 4000 G, made at a current density of 20 Ag-l.
    Definitions
    By "nanoparticles" is meant, in the present invention, particles less than 100 nanometers in size.
    By "carbon graffiti matrix" is meant a carbon-rich material whose initial structure has completely derived to a graphite structure, which is an allotropic form of carbon in which carbon atoms exhibit Sp2 hybridization, which means that it forms three covalent bonds in the same plane at an angle of 120 ° (hexagonal structure) and that an orbital 1 {perpendicular to that plane is free. These 1 {delocalized orbitals are those that confer electrical properties to graphite.
    By "nanocomposite material" or "nanocomposite" is meant, in the present invention, a multiphase solid material having a bulky matrix and one or more nanodimensional phases (less than 100 nanometers) with different chemical and / or structural properties.
    Detailed description of the invention.
    So far all efforts to improve energy density and power in supercapacitive devices have been dedicated to modifying the internal configuration of the capacitor. This includes new approaches to improve electrode materials, new capacitor configurations, or custom made porous structures. In the course of our investigations with these hybrid magnetic materials, we have discovered that the application of an external magnetic field entails a significant increase in the performance of the device. In fact, by applying relatively small magnetic fields (4000 G) we have observed that the capacitance of a magnetic hybrid nanocomposite material increases by an order of magnitude in a conventional three electrode cell (from 105 F · g · 1 to 1010 F · g-1 ). The present invention is based on this magnetic approach to build prototypes of supercapacitative devices based on those magnetic materials such as two electrode batteries or other architectures.
    As a precursor, the nanocomposite (NC) material described in WO 2013124503 Al Y developed by the present inventors in 2013 was used, namely:
    Aqueous solutions of nickel and iron salts were prepared keeping the stoichiometric coefficient x = Mili / (Mil + MIli) constant for values of x of 0.20, 0.25 and 0.33, Y with a constant total metal concentration e equal to 1 M, using distilled water. A second aqueous solution of decanedioic acid and NaOH was prepared using distilled water. Both solutions were mixed by dropwise addition, which resulted in a gel of pH = 8. Subsequently, it was heated to 80 Oc under constant stirring and maintaining this temperature for five days at atmospheric pressure. The solid obtained was filtered and washed
    with plenty of water and ethanol, and finally dried under vacuum at room temperature. All the
    The procedure was performed in an inert atmosphere to prevent atmospheric CO2 contamination in the final precursor. Additionally, the pH was kept constant to avoid the formation of impurities in the final solid.
    The solids obtained in the first stage were calcined in a nitrogen atmosphere at different temperatures (400, 650 and 900 oC) for different periods of time: 3, 6 and 9 hours in a programmable oven with a heating ramp that can be 1 , 5 and 10 ° C / min and a nitrogen flow of 40-120 mL / min. For all cases, a powder, the FeNir carbon nanocomposite material, was obtained in the form of crystalline nanoparticles. The material resulting from this process is what, in this document, is called a precursor NCU "..
    Finally, these nanoparticles were subjected to an acid wash with 2M HCI for 2 hours, with magnetic stirring, which was able to eliminate the Ni and Fe nanoparticles embedded in the matrix, thus obtaining a graffiti and porous matrix with nanoparticles
    of FeNi3.
    To synthesize the NC of the invention, an ethanol suspension was made with precursor NC. Once the suspension was made, it was deposited in nickel foam (with a density of 6.6 mg · cm · 2) and allowed to dry at 80 oC for two hours, until once the nickel foam was compressed at a 10 ton pressure.
    Once the electrode was prepared, a series of galvanostatic cycles were applied at a current density of 10 and 1 Ag'l Y with a potential window between +0.4 V and -0.3 V vs Ag / AgCI. Said galvanostatic cycles were carried out in a homemade electrochemical cell, using the material of the invention as a working electrode as a stainless steel counter electrode, and an Ag / AgCIKCl3M reference electrode • The cell was interposed between the poles of a electromagnet, in order to apply different external magnetic fields (Figure 1). The following loading / unloading cycles were applied to said cell:
    one. 2000 G constant and continuous field
    2. 4000 G constant and continuous field
    3. 6000 G constant and continuous field
    Four. Ascending field, where they began with 50 G and increased 50 G every 2 cycles.
    5. No magnetic field applied.
    In general, trials show that specific capacity retention is increased
    with the number of cycles (160% without applying magnetic fields), starting with increases already noticeable from 50-100 cycles, as a consequence of the activation of the NC when generating metal oxides and oxohydroxides (NiOOH and FeOOH). In an initial optimization process, it was observed that, when applying a constant and continuous magnetic field of 2000 G, better results were obtained than without a magnetic field, increasing the difference with the number of cycles (Figure 2). However, the best results were obtained with a continuous magnetic field of 4000 G with an increase of 240% at 50 cycles, as can be seen in Figure 2. It was observed that the application of a magnetic field causes a greater increase in the specific capacity of the material of the invention, whether the field is continuous or gradual. In tests conducted with higher magnetic fields (up to 10,000 G, according to Figure 13) it was observed that the increase in capacitance was practically the same as with 4000 G, so the value of 4000 G was adopted for the tests subsequent as optimal value of the magnetic field strength. It also
    l
    They also carried out tests at different current densities between 1 and 30 Ag · for both loading and unloading, observing that greater increases in specific capacity were obtained with low current densities, the most optimal method being to cycle at
    l
    a current density of 10 Ag · for the load and 1 Ag · l for the discharge.
    To elucidate which part of the material of the invention was affected by the presence of a magnetic field, it was decided to do the same study to the two components of the material separately: the FeNi3 nanoparticles (NP) and the carbon matrix. The galvanostatic cycles show a smaller increase in capacitive retention in the presence of an external magnetic field for the separate components (NPs and carbon matrix), as can be seen in Figure 3. In order to determine how much we could increase the capacity specific to our NC was studied up to 1000 cycles. The capacity of our initial NC was 105.42
    l l
    F · g · for a current density of 1 Ag · Y after 1000 cycles was 1010.28 F · g · (958.27% higher). If we compare this result with the same experiment but without applying a magnetic field, the capacitive retention is 590% higher (Figure 4 and Figure 5).
    In order to compare these results with those obtained by Liu et al. in the RSC Advances publication cited above, saving the differences in the starting materials (NiO in Liu et al., versus FeNi3 in the present invention) and in its method of obtaining (hydrothermal with autoclaves in Liu et al., versus application of galvanostatic cycles in the present invention), we find that, applying the maximum magnetic field intensity used in said publication (12.6 mT or 126 G), and transforming the 0.4 V potential window used in the
    same at the value of 0.7 V used in the present invention, the resulting capacitance would be
    1562 F · g- to which it should be added that the measures of Liu et al. they are made at a current density of 0.5 Ag-l versus the value of 1 Ag-l used in the present invention. Since the relationship between capacitance and current density is exponential, the capacitance value obtained should be more than double the indicated 1562 F · g-l. This data is a clear indication of the enormous increases in capacitance that have been obtained surprisingly in the development of the present invention, and which have no comparison with those achieved to date in the state of the art.
    In order to reveal the processes behind this important increase in capacitance, a post-treatment structural analysis was performed by means of electron microscopy and Raman spectroscopy to the sample after applying the cycles with magnetic field. The FESEM images (Figure 6) of the sample after 1000 cycles show an open and highly corrugated surface with the presence of "flakes" of graphene. In addition, it is possible to observe some less conductive agglomerates that suggest the partial sintering of metal nanoparticles, as well as the presence of strongly oxidized surfaces.
    Figure 7 shows HRTEM images of the NC formed after applying the magnetic field. Selected images revealed highly crystalline multiple domain nanoparticles embedded in the carbon matrix. In addition, it can be seen that the redox reaction induced by the application of the magnetic field forms a rougher surface. The appearance of these rough surfaces as a result of the galvanostatic activation is believed to result in an increase in the specific surface area, a greater penetration of OH- ions, in the inner zone of the FeNi NP], and therefore , will allow a higher oxidation, forming more active species that will participate in redox reactions.
    Raman spectroscopic analysis shows, in some spectra, characteristic graphene bands (i.e., O, G, and 20), which have a smaller proportion of I / G and an acute peak 20, indicative of less aggregated flakes (Figure 8). This could be related to the massive deployment of previously formed carbon nanocells and / or a better separation of graphene layers as a result of electrolyte penetration.
    Also, Figure 9 shows a Raman spectrum of the precursor NC and the NC obtained after 1000 galvanostatic cycles under magnetic field. In this spectrum it can be seen that the Raman signal of nickel oxide is negligible for the precursor NC, but is very intense in the
    NC resulting from oxidation with galvanostatic cycles and under magnetic field,
    demonstrating again the formation of Ni oxide with the procedure proposed.
    In addition, the average spectra exhibit a morphology quite similar to that of the precursor NC, without cycles and without applying magnetic fields, which is indicative of the structural stability of the graphene counterpart. However, voltammetric cycles and galvanostatic discharge curves show the opposite.
    In order to corroborate that in the presence of a magnetic field we favor the oxide formation reaction, XPS measurements were made to the NCs obtained by means of the galvanostatic cycles with and without applying a magnetic field. As can be seen in Figure 10, the oxide signal increases for the NC obtained with a magnetic field, confirming that oxidation is favored in the presence of the magnetic field.
    Finally, the magnetic properties of the precursor NC and the resulting NC were measured after the galvanostatic cycles with and without magnetic field. The hysteresis cycles of the different NCs first show an increase in the coercive field after the galvanostatic cycles, and within these it is greater in the NC with magnetic field, demonstrating a higher oxide formation. The "exchange bias" effect also appears in the measurement of the NC with magnetic field. The presence of the "exchange bias" in the NC formed after applying a magnetic field may come from the interaction between the antiferromagnetic spins formed on the oxidized surface and the ferromagnetic spins of the FeNi3 core. • This "exchange bias" depends on the thickness of the antiferromagnetic oxide layer formed. Therefore, there is an "exchange bias" only in the sample formed after applying the cycles with magnetic field is a demonstration that the magnetic field favors the formation of the oxide layer. On the other hand, conductivity measurements were also made. For the NC synthesized with the magnetic field the resistance increases by two orders of magnitude compared to the precursor NC (from 6.54 kOhms · cm-1 to 200 Ohms · cm-1 respectively). Nickel oxide is not a good conductor, so such increased resistance confirms the formation of much more nickel oxide. Another corroboration of the oxide formation is the change of conductor type, the precursor NC being a metallic conductor and after performing the galvanostatic cycles with magnetic field, it becomes a semiconductor, as can be seen in Figure 12.
    Finally, with the idea of seeing how stable the new NC is, 10,000 loading / unloading cycles were performed to see its degradation during these cycles, in which, as can be seen in Figure 13, after 10,000 cycles the retention is greater than 90%, so after this number of charges and discharges only 10% of the material is degraded.
    In conclusion, we have synthesized a new composite material using galvanostatic cycles and an external magnetic field with very capacitive properties
    S higher than those of the precursor NC. These results open the door to an external improvement of the specific capacitance in magnetic hybrid supercapacitors, and brings us closer to the development of promising new magnetically switchable energy storage devices.
    权利要求:
    Claims (13)
    [1]
    one)   Procedure for obtaining a nanocomposite material comprising the following steps: a) providing a precursor nanocomposite material comprising a carbon graffiti matrix with FeNi3 nanoparticles, and b) subjecting said material to a number between 100 and 10,000 of galvanostatic charge cycles / discharge at a current density between 30 Ag · l and 1 Ag · l either for charging or for discharge, while applying a magnetic field with an intensity between 50 GY 6,000 G.
    2) Method according to claim 1, wherein the galvanostatic cycles are carried out at a current density of 10 Agl for the load and 1 Agl for the discharge.
    3) Method according to claims 1 or 2, wherein the galvanostatic cycles are performed in a potential window between +0.4 V and -0.3 V vs Ag / AgCI.
    4) Method according to any one of the preceding claims, wherein the magnetic field has an intensity between 1000 G and 6000 G.
    5) Method according to claim intensity between 2000 G and 6000 G.4,inhethatthe magnetic fieldhavea
    6) Procedure according to intensity of 4000 G.theclaim5,inhethathecountrysidemagnetichavea
    7) Method according to any one of the preceding claims 1 to 6, wherein the number of galvanostatic cycles is between 100 and 5000.
    8) Method according to claim 7, wherein the number of galvanostatic cycles is between 500 and 1500.
    9) Method according to claim 8, wherein the number of galvanostatic cycles is between 700 and 1000.
    10) Method according to any one of the preceding claims, wherein the field
    Magnetic is constant. 11) Method according to any one of the preceding claims 1-9, wherein the magnetic field is variable. 12) Nanocomposite material obtained through the process described in any one of claims 1 to 11 above. 10 13) Electrodes for batteries or supercapacitors comprising the material of claim 12. 14) Use of the nanocomposite material of claim 12 in battery electrodes. 15) Use of the nanocomposite material of claim 12 in electrodes for supercapacitors.
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    同族专利:
    公开号 | 公开日
    WO2018011445A1|2018-01-18|
    ES2649688B1|2018-10-24|
    EP3486348B1|2021-05-26|
    PL3486348T3|2021-10-04|
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    EP2818570A1|2012-02-23|2014-12-31|Universitat de Valéncia|Graphitized matrix nanocomposites and metal nanoparticles with supercapacitance and magnetoresistance properties|
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