CN107093731B - Polyvanadyl compound, preparation method and application thereof, and lithium ion battery containing same - Google Patents
Polyvanadyl compound, preparation method and application thereof, and lithium ion battery containing same Download PDFInfo
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Abstract
The invention provides a poly-vanadium-oxygen cluster compound, a preparation method and application thereof, and a lithium ion battery containing the same. The poly-vanadium-oxygen cluster compound provided by the invention has a stable structure, has high capacity and rapid charge and discharge performance, can be used as a negative electrode material to be applied to a lithium ion battery, and the further prepared lithium ion battery also has excellent theoretical capacity and good cycle performance. In the method, the poly-vanadium-oxygen cluster compound is prepared by raw material mixing and a solvothermal method, and the method has the characteristics of convenience and quickness in preparation method, simplicity in operation, stable structure of the prepared poly-vanadium-oxygen cluster compound, excellent electrical properties and the like.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a poly-vanadium-oxygen cluster compound, a preparation method and application thereof, and a lithium ion battery containing the same.
Background
Energy and environment are two of the most serious problems facing the human being entering the century, and the development of new energy and renewable clean energy is one of the most decisive technical fields in the world economy. With the development of microelectronic technology, miniaturized devices are increasing, and high-performance chemical power sources enter a large-scale application stage.
The lithium ion battery is the most ideal rechargeable chemical battery in the world at present, and compared with the traditional nickel-cadmium battery or nickel-hydrogen battery, the lithium ion battery has the advantages of high voltage, large capacity, low self-discharge rate and the like. Because each performance of the lithium ion battery is more excellent, the lithium ion battery is widely applied to the communication and automobile fields at present, and the popularization and the use of the electric automobile also enable the demand of the lithium ion battery to be increased day by day.
The performance of lithium ion batteries depends mainly on the electrodesThe performance of the material is good and bad. The basic requirements for electrode materials in lithium ion batteries mainly include the following: the lithium ion battery has the advantages of high reversible capacity, good structural flexibility and stability, rapid lithium ion diffusion rate, long cycle life, good safety, low production cost and environmental friendliness. In commercial lithium ion batteries, the positive electrode is predominantly a Li-containing material with a higher redox potential, such as LiCoO2，LiMn2O4And LiFePO that has been developed and used in recent years4. Graphite is the most commonly used commercial negative electrode material because of its low cost of production, low and smooth operating voltage, and long life. However, most of the lithium intercalation compounds formed by Li ion intercalation into graphite have a composition of LiC6This stoichiometric ratio of lithium carbide corresponds to a smaller theoretical capacity (372 mAhg)-1) And a smaller actual energy density. Meanwhile, the transport rate of Li ions in graphite electrodes is generally less than 10-6cm2s-1Since the electrochemical diffusion coefficient of Li ions is closely related to the power density of the battery, the battery using graphite as the negative electrode has a low power density. In order to increase the energy and power density of lithium ion batteries, it is very necessary to develop a negative electrode material having a large capacity and a high lithium ion transport rate.
Polyacids, also known as Polyoxometalates (abbreviated as POMs), are Metal-Oxygen cluster (Metal-Oxygen Clusters) compounds constructed from early transition elements such as Mo, W, V, Nb, and Ta in the framework structure. POMs have attracted considerable attention because of the various advantageous properties exhibited by polyacids, such as fluorescence, catalytic activity, and single molecule magnets, among others. From a structural and electronic perspective, their molecular structures can be thought of as nanosized metal oxides, which are also the most diverse molecular-based clusters. In recent years, POMs have been studied as positive or negative electrode materials for lithium ion batteries because of their unique structures and excellent multi-electron redox characteristics.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a multi-vanadium-oxygen cluster compound, which has a stable structure, higher capacity and rapid charge and discharge performance, and can be further used as a negative electrode material to be applied to a lithium ion battery.
The second purpose of the invention is to provide a preparation method of the poly-vanadium-oxygen cluster compound, in the method, the poly-vanadium-oxygen cluster compound is prepared by raw material mixing and a solvothermal method, and the preparation method has the characteristics of convenience and simplicity in operation, stable structure of the prepared poly-vanadium-oxygen cluster compound, excellent electrical properties and the like.
The third purpose of the present invention is to provide an application of the poly-vanadium-oxygen cluster compound, wherein the poly-vanadium-oxygen cluster compound has excellent electrical properties such as high capacity, rapid charge and discharge properties, and the like, and thus can be applied to lithium ion batteries.
The fourth purpose of the invention is to provide a lithium ion battery, which takes the poly vanadium oxide cluster compound as a negative electrode material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a polyoxovanadiumo compound having the structural formula: [ M ] Ax(H2O)y]a[V15O36(NO3)z]b·cH2O；
Wherein M is a metal ion;
wherein X is 1-3, y is 6-10, and z is 1-3;
wherein a is 1-3, b is 1-2, and c is 12-15.
Optionally, in the present invention, in the polyoxovanadiumoxide cluster compound, M is an alkali metal or alkaline earth metal cation;
preferably, M is an alkali metal cation.
Optionally, in the present invention, in the polyoxovanadium compound: x is 2-3, y is 8-10, and z is 1-2;
and/or, a is 2-3, b is 1, and c is 13-15.
OptionalIn the invention, the structural formula of the poly-vanadyl compound is as follows: [ M ] A2(H2O)9]2[V15O36(NO3)]·15H2O；
Wherein M is an alkali metal cation.
Meanwhile, the invention also provides a preparation method of the poly-vanadium-oxygen cluster compound, which comprises the following steps:
and dissolving vanadate and sulfite into the mixed solvent, stirring, heating the obtained mixed system in a reaction kettle for reaction, cooling and filtering to obtain the vanadium-oxygen cluster compound.
Optionally, in the present invention, the vanadate is metavanadate, and the sulfite is an alkali metal or alkaline earth metal sulfite.
Optionally, in the present invention, the mixed solvent is a mixed solution of water and an alkaline organic solvent.
Optionally, in the present invention, the heating reaction in the reaction kettle specifically comprises: reacting for 12-36 h at the temperature of 150-200 ℃.
Similarly, the invention also provides the application of the poly-vanadium-oxygen cluster compound in photoelectric materials.
Further, the invention also provides a lithium ion battery containing the poly vanadium oxide cluster compound.
Compared with the prior art, the invention has the beneficial effects that:
(1) the poly-vanadium-oxygen cluster compound has excellent electrical properties such as higher capacity, rapid charge and discharge performance and the like, and can be further used as a negative electrode material of a lithium ion battery; meanwhile, the further prepared lithium ion battery also has excellent theoretical capacity and better cycle performance;
(2) the preparation method is convenient and fast, the operation is simple, and the prepared poly-vanadium-oxygen cluster compound has the characteristics of stable structure, excellent electrical property and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a structural diagram of a molecular single crystal and a structural diagram of a bulk structure of a metal vanadyl cluster compound provided in example 1 of the present invention; FIG. 1 a) is a view showing a structure of a molecular single crystal, and FIG. 1 b) is a view showing a structure of a stack;
FIG. 2 is a graph comparing powder diffraction data (XRD) and theoretical simulation values of a metal vanadyl cluster compound provided in example 1 of the present invention;
FIG. 3 is a scheme of synthesis and technique in example 1 of the present invention;
fig. 4 is a cycle performance test chart of the lithium ion battery provided in experimental example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The vanadium-oxygen cluster compound provided by the invention is a novel vanadium-oxygen cluster compound which takes pentadeca-nucleus metal vanadium-oxygen cluster as a core and is provided with counter cations and crystal water, and the unit structural molecular formula of the vanadium-oxygen cluster compound is as follows: [ M ] Ax(H2O)y]a[V15O36(NO3)z]b·cH2O；
Wherein, in the poly-vanadyl compound, the central metal V has two valence states, one is tetravalent vanadium, and the other is pentavalent vanadium;
wherein M is a metal ion;
preferably, the metal ion is an alkali metal or alkaline earth metal cation, which may be, for example, Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+Or Ba2+An isometalated cation;
more preferably, the metal ion is an alkali metal cation, which may be, for example, Li+、Na+、K+、Rb+、Cs+An isometalated cation;
further preferably, the metal ion is Na+Or K+Ions;
wherein X is 1-3, y is 6-10, and z is 1-3;
preferably, X, Y, Z are integers of 1-3, 6-10, and 1-3, respectively, such as: x may be 1, 2, or 3; y may be 6, 7, 8, 9, or 10; z can be 1, 2, or 3;
wherein a is 1-3, b is 1-2, and c is 12-15;
preferably, a, b and c are integers of 1-3, 1-2 and 12-15 respectively, such as: a may be 1, 2, or 3; b may be 1 or 2; c may be 12, 13, 14, or 15, provided that the parameters are selected to ensure charge balance of the compound.
Further preferably, the structural formula of the poly-vanadyl compound provided by the invention is as follows: [ M ] A2(H2O)9]2[V15O36(NO3)]·15H2O；
Wherein M is an alkali metal cation, such as Li+、Na+、K+、Rb+、Cs+Alkali metal cations;
further preferably, the alkali metal ion is Na+Or K+Ions, i.e., M is Na or K;
meanwhile, in the preferred poly-vanadium oxy-cluster compound provided by the invention, the central metal V also comprises two valence states, one is tetravalent vanadium, and the other is pentavalent vanadium;
thus, based on the principle of charge balance, the structural formula of the poly-vanadyl compound provided by the invention further should be as follows: [ M ] A2(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O。
The preparation method of the poly vanadium oxide cluster compound comprises the following steps: and dissolving vanadate and sulfite into the mixed solvent, stirring, heating the obtained mixed system in a reaction kettle for reaction, cooling and filtering to obtain the vanadium-oxygen cluster compound.
The preparation method comprises the following steps:
preferably, the vanadate is metavanadate;
further preferably, the vanadate is ammonium metavanadate, potassium metavanadate, sodium metavanadate or the like;
more preferably, the vanadate is ammonium metavanadate.
Preferably, the sulfite is metal sulfite with a molecular formula of Mx(SO3)y；
Further preferably, the sulfite is an alkali metal or alkaline earth metal sulfite;
more preferably, the sulfite is an alkali metal sulfite, such as lithium sulfite, sodium sulfite, potassium sulfite, or rubidium sulfite;
most preferably, the sulfite is sodium sulfite or potassium sulfite.
More preferably, the molar ratio of the metavanadate and the metal sulfite as raw materials in the invention is (1-15): for example, but not limited to, 1 may be 3:1, 5:1, 8:1, 10:1, or 12: 1.
Preferably, the mixed solvent is a mixed solution of water and an alkaline organic solvent;
more preferably, the basic organic solvent is an aliphatic amine, an aromatic amine or a nitrogen heterocyclic compound, and the basic organic solvent may be, for example, an aliphatic amine compound such as ethylamine, propylamine, butylamine, ethylenediamine or triethylamine, an aromatic amine such as aniline or phenylenediamine, or a nitrogen heterocyclic compound such as pyridine, substituted pyridine, imidazole, substituted imidazole, pyrrole or substituted pyrrole;
more preferably, the basic organic solvent is a nitrogen heterocyclic compound, and may be, for example, but not limited to, pyridine, pyrrole, imidazole, N-methylimidazole, N-ethylimidazole, and the like.
Further preferably, the volume ratio of the water-alkaline organic solvent is (1-10): (1-5); for example, but not limited to, 2:1, 3:1, 5:1, 7:2, 8:3, 8:5, 1:2, 2:5, or 3: 4, etc.
Preferably, the stirring temperature is room temperature, and the stirring time is 1-5 h, for example, 2, 3 or 4 h.
Preferably, the temperature for heating in the reaction kettle is 150-200 ℃, for example, but not limited to 160, 170, 180, 190 ℃ or the like; the heating time is 12-36 h, for example, but not limited to, 18, 24 or 32 h.
Preferably, after the product poly vanadium oxide cluster compound is obtained by filtration, the method further comprises a step of drying the product, wherein the drying temperature can be controlled to be 120-180 ℃, and the drying time can be 12-24 hours.
The preparation method of the poly vanadium oxide cluster compound can be summarized as follows:
the molar ratio is (1-15): 1, dissolving vanadate and sulfite into the mixture according to the volume ratio of (1-10): (1-5) stirring the mixed solution of water and an alkaline organic solvent for 1-5 hours at room temperature, heating the obtained mixed system in a reaction kettle at the temperature of 150-200 ℃ for 12-36 hours, cooling and filtering to obtain a poly-vanadium-oxygen cluster compound, and drying the product at the temperature of 120-180 ℃ for 12-24 hours.
The poly vanadium oxide cluster compound provided by the invention has multi-electron reduction reaction and rapid lithium ion diffusion performance, so that the poly vanadium oxide cluster compound has higher capacity and rapid charge and discharge performance, and can be further used as a functional material to be applied to photoelectric devices such as lithium ion batteries and the like.
The cathode material of the lithium ion battery provided by the invention is the poly vanadium-oxygen cluster compound, and the poly vanadium-oxygen cluster compound has excellent electrical properties, so that the lithium ion battery provided by the invention has high theoretical capacity and better cycle performance.
Example 1
10 millimoles (mmol) of ammonium metavanadate and 1 mmol of anhydrous sodium sulfite are dissolved inStirring the mixture for 3 hours at normal temperature in a mixed solvent of 70 ml of water and 20 ml of N-ethylimidazole, then putting the mixture into a 100 ml reaction kettle to react for 24 hours at 180 ℃, and filtering the mixture to obtain black crystals, wherein the crystals are resolved through a single crystal structure and show a novel 15-nuclear metal vanadium oxygen cluster with a sodium ion as a counter cation, and the molecular formula of the crystals is as follows: [ Na ]2(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O。
The structure diagram and the stacking structure diagram of the molecular single crystal of the metal vanadium oxide cluster are respectively shown as a) in figure 1 and b) in figure 1, and the powder diffraction data (XRD) and the comparison graph of theoretical simulation values are shown as figure 2;
the crystallographic data are shown in table 1 below:
TABLE 1[ Na ]2(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O crystallographic data
Further, the vanadium-oxygen cluster is dried for 12 hours in a vacuum drying oven at 120 ℃ and used as a lithium ion battery cathode material.
Example 1 the synthesis and technical route is shown in figure 3.
Experimental example 1
Taking the vanadium-oxygen cluster dried in the embodiment 1 as a negative electrode material, adding the vanadium-oxygen cluster, a binder polyvinylidene fluoride and a conductive agent acetylene black into a grinding container according to the mass ratio of 75:15:10, adding N-methylpyrrolidone as a solvent, mixing, and fully and uniformly grinding; then, uniformly coating the copper foil with a scraper, drying the copper foil in a vacuum drying oven at 100 ℃ for 12 hours, and cutting the copper foil into a wafer with the diameter of 8mm to prepare a negative pole piece;
meanwhile, a button-shaped lithium ion battery is assembled in a glove box by taking a lithium sheet as a counter electrode, polyethylene as a diaphragm material, 1mol/L lithium hexafluorophosphate as an electrolyte and ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 1:1:1 as electrolytes.
Then, the prepared lithium ion battery is subjected to electrochemical test to detect the performance of the electrode, and the specific test content and method are as follows:
and (3) cycle testing: placing the button-shaped lithium battery at room temperature for 12 hours, and then carrying out electrochemical performance test: the voltage range is 0.01V-3V when the cycle performance is tested, the current density is 100mA/g, and the capacity is still as high as 569mAh/g after the cycle times are 100 times; the cycle reaches 300 circles at 300mA/g, the battery capacity still reaches 332mAh/g, and the battery is still in the cycle. Fig. 4 shows a cycle performance test chart of the lithium ion battery.
The poly-vanadium-oxygen cluster compound has stable structure, higher capacity and good cycle stability, and can be further used as a functional material to be applied to devices such as lithium ion batteries and the like.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. A polyoxovanadiumo compound, wherein the polyoxovanadiumo compound has a structural formula as follows: [ M ] Ax(H2O)y]a[V15O36(NO3)z]b·cH2O；
Wherein M is an alkali metal or alkaline earth metal cation;
wherein x is 2-3, y is 8-10, and z is 1-2;
wherein a is 2-3, b is 1, and c is 13-15.
2. The polyoxovanadiumoxy cluster compound of claim 1, wherein M is an alkali metal cation.
3. The polyoxovanadiumoxy cluster compound of any one of claims 1-2, wherein the polyoxovanadiumoxy cluster compound has a structural formula as follows: [ M ] A2(H2O)9]2[V15O36(NO3)]·15H2O；
Wherein M is an alkali metal cation.
4. A method for preparing the polyvanadyl compound of any one of claims 1 to 3, wherein the method comprises the steps of:
dissolving ammonium metavanadate and sulfite in a mixed solvent, stirring, heating the obtained mixed system in a reaction kettle for reaction, cooling and filtering to obtain the poly-vanadium-oxygen cluster compound.
5. The method according to claim 4, wherein the sulfite is an alkali metal or alkaline earth metal sulfite.
6. The production method according to claim 4, wherein the mixed solvent is a mixed solution of water and a basic organic solvent.
7. The preparation method according to claim 4, wherein the heating reaction in the reaction kettle specifically comprises: reacting for 12-36 h at the temperature of 150-200 ℃.
8. Use of the polyvanadyl compound of any one of claims 1 to 3 in photovoltaic materials.
9. A lithium ion battery comprising the polyvanadyl compound of any one of claims 1 to 3.
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| CN103382210A (en) * | 2013-07-03 | 2013-11-06 | 吉林化工学院 | Structure of isopolyoxovanadate hybrid compound and preparation method of isopolyoxovanadate hybrid compound |
| CN106582815A (en) * | 2016-12-20 | 2017-04-26 | 聊城大学 | Vanadium-based oxygen cluster compound catalyst, preparation method and application |
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| JP2002241333A (en) * | 2001-02-20 | 2002-08-28 | Nissan Chem Ind Ltd | Method of producing aromatic hydroxy compound |
| CN103382210A (en) * | 2013-07-03 | 2013-11-06 | 吉林化工学院 | Structure of isopolyoxovanadate hybrid compound and preparation method of isopolyoxovanadate hybrid compound |
| CN106582815A (en) * | 2016-12-20 | 2017-04-26 | 聊城大学 | Vanadium-based oxygen cluster compound catalyst, preparation method and application |
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