CN112909235B - Battery negative electrode material of binuclear molybdenum cluster compound and preparation method thereof - Google Patents
Battery negative electrode material of binuclear molybdenum cluster compound and preparation method thereof Download PDFInfo
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- CN112909235B CN112909235B CN201911217338.1A CN201911217338A CN112909235B CN 112909235 B CN112909235 B CN 112909235B CN 201911217338 A CN201911217338 A CN 201911217338A CN 112909235 B CN112909235 B CN 112909235B
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention relates to the technical field of energy, and discloses a binuclear molybdenum cluster compound serving as a battery cathode material and a preparation method thereof, wherein the preparation process of the binuclear molybdenum cluster compound comprises the following steps: firstly, uniformly stirring and mixing ammonium molybdate and a surfactant, then heating and dropwise adding thiourea at a certain speed, and reacting for a certain time to obtain the binuclear molybdenum cluster compound. And finally, sintering the product at a certain temperature to realize in-situ carbon coating. Compared with sulfides, the binuclear molybdenum cluster compound has the characteristics of higher capacity, better cycle performance, more excellent rate performance and the like. And the preparation process is simple, the performance is controllable, and the universality and the scalability are realized.
Description
Technical Field
The invention relates to the technical field of energy, in particular to a battery cathode material of a binuclear molybdenum cluster compound and a preparation method thereof.
Background
As is well known, energy production and storage technologies have attracted considerable attention for everyday use in recent decades. Advances in Lithium Ion Battery (LIB) technology have improved global living conditions, and rechargeable Lithium Ion Batteries (LIBs) have revolutionized portable electronic devices, including cell phones, notebook computers, and digital cameras, by researchers as the most promising energy storage systems, currently having a global market value of up to 100 billion dollars. At the same time, due to the limited lithium resources, researchers are looking to find alternative sources for next generation Electrical Energy Storage (EES) devices. Recently, Sodium Ion Batteries (SIBs) have become one of the most promising candidates because of the high content of sodium-containing compounds and the inexpensive raw materials.
The performance of the lithium ion battery mainly depends on the performance of positive and negative electrode materials, the current lithium ion battery negative electrode material is mainly a carbon material, but the theoretical specific capacity of the lithium ion battery negative electrode material is only 372 mA.h/g, and the lithium ion battery negative electrode material cannot meet the requirements of the current development of high-energy density lithium ion batteries. Currently, many layered metal sulfides MS2(M ═ Mo, W, Ga, Nb, and Ta) are also used as anode materials for lithium ion batteries. However, in the lithium ion deintercalation process, the metal sulfide anode material can generate huge volume expansion, so that the structural stability of the metal sulfide anode material is damaged, and finally, the material is pulverized, so that the cycle performance of the anode is seriously influenced.
Disclosure of Invention
Objects of the invention
The invention provides a simple wet chemical method for preparing a binuclear molybdenum cluster compound, which can be used as a negative electrode material of a lithium ion battery.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a binuclear molybdenum cluster compound used as a battery negative electrode material is formed by regularly agglomerating twenty to two hundred nanometer particles.
Preferably, the diameter of the binuclear molybdenum cluster compound particles is 20-200 nm.
The invention also provides a preparation method of the binuclear molybdenum cluster compound battery cathode material, which is characterized by comprising the following steps of:
the first step is as follows: dissolving ammonium molybdate and polyvinylpyrrolidone (PVP) in glycol, and magnetically stirring for 8 h;
the second step is that: heating the solution prepared in the first step until the temperature of the system reaches the boiling point;
the third step: slowly dripping thiourea solution into the solution obtained in the second step by using a constant-pressure separating funnel, and reacting for one hour;
the fourth step: after the solution obtained in the third step is naturally cooled, cleaning the product after liquid centrifugation for three times by using alcohol and deionized water, and drying the cleaned product in a drying oven at the temperature of 60-80 ℃;
the fifth step: and sintering the powder obtained in the fourth step at the temperature of 400-700 ℃ under the protection of Ar gas to obtain the binuclear molybdenum cluster compound serving as the lithium ion battery cathode material.
Preferably, the mass ratio of ammonium molybdate to polyvinylpyrrolidone (PVP) in the first step is in the range of 0.25 to 5.
Preferably, the boiling point of the system is reached in the second step and is maintained for a period of time until the liquid in the system turns brown.
Preferably, the rate of adding thiourea in the third step is controlled to be 0.8mL/min-2mL/min, and the reaction time is calculated from the beginning of adding thiourea.
Preferably, the heating conditions in the fifth step are as follows: argon is used as an inert gas source, inert gas is introduced at the flow rate of 200-.
(III) advantageous effects
Compared with the prior art, the invention provides a battery cathode material of a binuclear molybdenum cluster compound and a preparation method thereof, and the battery cathode material has the following beneficial effects:
the nano-scale binuclear molybdenum cluster compound prepared by the invention is limited by polyvinylpyrrolidone in the forming process, and a large-space three-dimensional reticular porous material regularly formed by particles smaller than 200nm is gradually formed. The meshes between the constituent particles greatly buffer the volume change of the negative electrode material during the process of lithium ion desorption. And the smaller particles and the porous network structure greatly increase the number of active sites of the anode material.
Meanwhile, the preparation method of the material is simple and easy to implement, and the experimental instrument is simple. The prepared three-dimensional reticular dual-core molybdenum cluster compound lithium ion battery composite negative electrode material has relatively uniform particle size, a formed reticular structure is very stable, the specific capacity of the battery negative electrode material is high, the cycle performance is very stable, and the rate capability is excellent.
Drawings
FIG. 1 is an SEM image of a binuclear molybdenum cluster compound material obtained in example 1;
FIG. 2 is an XRD spectrum of the binuclear molybdenum cluster compound material obtained in example 1;
FIG. 3 is a graph showing the charge-discharge cycle and rate performance of a negative electrode of a lithium ion battery prepared from the binuclear molybdenum cluster compound material obtained in example 1;
FIG. 4 is an SEM image of a binuclear molybdenum cluster compound material obtained in example 2;
FIG. 5 is an XRD spectrum of the binuclear molybdenum cluster compound material obtained in example 2;
FIG. 6 is a graph of the charge-discharge cycle and rate performance of a lithium ion battery cathode made of the binuclear molybdenum cluster compound material obtained in example 2;
FIG. 7 is an SEM image of a binuclear molybdenum cluster compound material obtained in example 3;
FIG. 8 is an XRD spectrum of the binuclear molybdenum cluster compound material obtained in example 3;
FIG. 9 is a graph of the charge-discharge cycle and rate performance of a lithium ion battery cathode made of the binuclear molybdenum cluster compound material obtained in example 3;
FIG. 10 is an SEM image of a binuclear molybdenum cluster compound material obtained in example 4;
FIG. 11 is an XRD spectrum of the binuclear molybdenum cluster compound material obtained in example 4;
fig. 12 is a graph showing charge-discharge cycle and rate performance of a negative electrode of a lithium ion battery prepared from the binuclear molybdenum cluster compound material obtained in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 0.5g of ammonium molybdate and 0.1g of polyvinylpyrrolidone (PVP) and placing the ammonium molybdate and the PVP in a 250mL three-neck flask on a heating sleeve, weighing 150mL of ethylene glycol by using a measuring cylinder, adding the ethylene glycol into the three-neck flask, and stirring for 8 hours by magnetic force to fully and uniformly mix the raw materials; heating until the temperature of the system reaches the boiling point, after boiling for five minutes, slowly dropwise adding 25mL of thiourea (0.5m/L) solution into the solution by using a 100mL constant-pressure separating funnel, and reacting for one hour; after the solution is naturally cooled, the liquid is centrifuged, the centrifuged product is washed three times by alcohol and deionized water, and then the washed product is completely dried in an oven at the temperature of 60-80 ℃. Taking out the dried powder, fully grinding the powder, putting the powder into a quartz boat, and carrying out heat treatment in a tube furnace. The heat treatment conditions are as follows: and (5) under the protection of Ar gas, heating to 100 ℃ in the first 5min, preserving heat for 5min, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace. The lithium ion battery cathode material with a large-range net structure consisting of the binuclear molybdenum cluster compounds with the particle size of 50-150nm can be obtained, and the diameter of each net hole is about 50-300 nm.
As shown in the SEM image of the binuclear molybdenum cluster compound shown in figure 1, the unique three-dimensional network structure of the material can be seen from the SEM image, which is formed by stacking relatively dispersed nano-scale small particles, and the XRD pattern of the compound shown in figure 2 basically corresponds to a standard card of the binuclear molybdenum cluster compound, so that the obtained compound can be determined to be the binuclear molybdenum cluster compound. As shown in the charge-discharge cycle performance and rate performance graphs of the lithium ion battery cathode prepared from the binuclear molybdenum cluster compound shown in FIG. 3, the charge-discharge capacity of the first circle is 927.3 and 542.9mAh/g respectively, and then is slightly reduced, the charge-discharge capacity of the first circle is increased until the 31 st circle (the charge-discharge capacity is 876.7 and 886.4mAh/g respectively), and the charge-discharge capacity of the second circle is 944.2 and 955.4mAh/g respectively. The product has good rate performance, and the capacity of the product is slightly increased compared with the initial capacity after the product is circulated back to mAh/g by 100,200,500, 1000 and 2000mAh/g for ten circles respectively.
Example 2
Weighing 0.5g of ammonium molybdate and 0.5g of polyvinylpyrrolidone (PVP) and placing the ammonium molybdate and the PVP in a 250mL three-neck flask on a heating sleeve, weighing 150mL of ethylene glycol by using a measuring cylinder, adding the ethylene glycol into the three-neck flask, and stirring for 8 hours by magnetic force to fully and uniformly mix the raw materials; heating until the temperature of the system reaches the boiling point, after boiling for five minutes, slowly dropwise adding 25mL of thiourea (0.5m/L) solution into the solution by using a 100mL constant-pressure separating funnel, and reacting for one hour; after the solution is naturally cooled, the liquid is centrifuged, the centrifuged product is washed three times by alcohol and deionized water, and then the washed product is completely dried in an oven at the temperature of 60-80 ℃. Taking out the dried powder, fully grinding the powder, putting the powder into a quartz boat, and carrying out heat treatment in a tube furnace. The heat treatment conditions are as follows: and (5) under the protection of Ar gas, heating to 100 ℃ in the first 5min, preserving heat for 5min, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace. The lithium ion battery cathode material with the small-range net structure consisting of the binuclear molybdenum cluster compound with the particle size of 20-200nm can be obtained, and the diameter of each net hole is about 100-500 nm.
As shown in the SEM image of the binuclear molybdenum cluster compound shown in fig. 4, the three-dimensional network structure of the material can be seen from the image: as shown in fig. 5, the XRD spectrum of the compound is substantially consistent with that of the standard card of the binuclear molybdenum cluster compound, and it can be known that the obtained material is indeed the binuclear molybdenum cluster compound: as shown in a charge-discharge cycle performance and rate performance diagram of a lithium ion battery cathode prepared from the binuclear molybdenum cluster compound shown in FIG. 6, the charge-discharge cycle performance diagram shows that the first reversible capacity is 841mAh/g under the current density of 100mA/g, the capacity of 732mAh/g is still remained after 80 cycles of circulation, the specific capacity of the lithium ion battery cathode is very stable under different current densities, and the lithium ion battery cathode still has the high capacity of 634mAh/g even under the current density of 2Ag & lt-1 & gt.
Example 3
Weighing 0.5g of ammonium molybdate and 1g of polyvinylpyrrolidone (PVP) and placing the ammonium molybdate and the PVP in a 250mL three-neck flask on a heating sleeve, weighing 150mL of ethylene glycol by using a measuring cylinder, adding the ethylene glycol into the three-neck flask, and stirring by magnetic force for 8 hours to fully and uniformly mix the raw materials; heating until the temperature of the system reaches the boiling point, after boiling for five minutes, slowly dropwise adding 25mL of thiourea (0.5m/L) solution into the solution by using a 100mL constant-pressure separating funnel, and reacting for one hour; after the solution is naturally cooled, the liquid is centrifuged, the centrifuged product is washed three times by alcohol and deionized water, and then the washed product is completely dried in an oven at the temperature of 60-80 ℃. Taking out the dried powder, fully grinding the powder, putting the powder into a quartz boat, and carrying out heat treatment in a tube furnace. The heat treatment conditions are as follows: and (5) under the protection of Ar gas, heating to 100 ℃ in the first 5min, preserving heat for 5min, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace. The lithium ion battery cathode material with a large-range net structure consisting of the binuclear molybdenum cluster compound with the particle size of 20-100nm can be obtained, and the diameter of each net hole is about 50-300 nm.
As shown in the SEM image of the binuclear molybdenum cluster compound shown in fig. 7, it can be seen from the SEM image that the three-dimensional network structure of the material is composed of relatively compact nanoparticles, and as shown in the XRD spectrum of the binuclear molybdenum cluster compound shown in fig. 8, it can be seen that the obtained material is indeed the binuclear molybdenum cluster compound. As shown in fig. 9, it can be seen from the charge-discharge cycle performance and rate performance graphs of the lithium ion battery cathode prepared from the binuclear molybdenum cluster compound, that the first reversible capacity is 907mAh/g under the current density of 100mA/g, and the capacity (capacity retention rate 79.6%) of 721.8mAh/g is still left after 80 cycles, and the rate performance is stable through the rate performance test.
Example 4
Weighing 0.5g of ammonium molybdate and 2g of polyvinylpyrrolidone (PVP) and placing the ammonium molybdate and the PVP in a 250mL three-neck flask on a heating sleeve, weighing 150mL of ethylene glycol by using a measuring cylinder, adding the ethylene glycol into the three-neck flask, and stirring by magnetic force for 8 hours to fully and uniformly mix the raw materials; heating until the temperature of the system reaches the boiling point, after boiling for five minutes, slowly dropwise adding 25mL of thiourea (0.5m/L) solution into the solution by using a 100mL constant-pressure separating funnel, and reacting for one hour; after the solution is naturally cooled, the liquid is centrifuged, the centrifuged product is washed three times by alcohol and deionized water, and then the washed product is completely dried in an oven at the temperature of 60-80 ℃. Taking out the dried powder, fully grinding the powder, putting the powder into a quartz boat, and carrying out heat treatment in a tube furnace. The heat treatment conditions are as follows: and (5) under the protection of Ar gas, heating to 100 ℃ in the first 5min, preserving heat for 5min, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace. The relatively firm lithium ion battery cathode material with a large-range network structure and composed of the binuclear molybdenum cluster compound with the particle size of 50-150nm can be obtained, and the diameter of each network is about 50-200 nm.
As shown in the SEM image of the binuclear molybdenum cluster compound shown in fig. 10, it can be seen from the SEM image that the material is a compact three-dimensional network structure composed of closely-connected nanoparticles, and as shown in the XRD spectrum of the binuclear molybdenum cluster compound shown in fig. 11, it can be seen that the obtained material is indeed the binuclear molybdenum cluster compound. As shown in fig. 12, the charge-discharge cycle performance and rate performance diagram of the lithium ion battery cathode prepared from the binuclear molybdenum cluster compound shows that the first reversible capacity is 715.4mAh/g under the current density of 100mA/g and the capacity of 441.4mAh/g (the capacity retention rate is 61.7%) is still remained after 80 cycles, and the charge-discharge rate performance diagram shows that when the current densities are 100,200,500, 1000 and 2000mA/g, the corresponding specific capacities are 534.4, 488.2, 6.6, 354 and 186.2mAh/g, respectively. High capacity of 186.2mAh/g was obtained even at a current density of 2000 mA/g.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (6)
1. A preparation method of a binuclear molybdenum cluster compound used as a battery cathode material is characterized in that the cathode material is formed by regularly agglomerating twenty to two hundred nanometer particles; the preparation method of the compound comprises the following steps:
the first step is as follows: dissolving ammonium molybdate and polyvinylpyrrolidone PVP in ethylene glycol, and magnetically stirring for 8 h;
the second step is that: heating the solution prepared in the first step until the temperature of the system reaches the boiling point;
the third step: slowly dripping thiourea solution into the solution obtained in the second step by using a constant-pressure separating funnel, and reacting for one hour;
the fourth step: after the solution obtained in the third step is naturally cooled, cleaning the product after liquid centrifugation for three times by using alcohol and deionized water, and drying the cleaned product in a drying oven at the temperature of 60-80 ℃;
the fifth step: and sintering the powder obtained in the fourth step at the temperature of 400-700 ℃ under the protection of Ar gas to obtain the binuclear molybdenum cluster compound serving as the lithium ion battery cathode material.
2. The method according to claim 1, wherein the diameter of the binuclear molybdenum cluster compound particles is 20 to 200 nm.
3. The method according to claim 1, wherein the mass ratio of ammonium molybdate to polyvinylpyrrolidone PVP in the first step is in the range of 0.25 to 5.
4. The method according to claim 1, wherein the boiling point of the system is reached in the second step and the boiling point is maintained for a certain period of time until the liquid in the system turns brown.
5. The method according to claim 1, wherein the rate of addition of thiourea in the third step is controlled to be 0.8mL/min to 2mL/min, and the reaction time is calculated from the start of addition of thiourea.
6. The production method according to claim 1, wherein the heating conditions in the fifth step are: argon is used as an inert gas source, inert gas is introduced at the flow rate of 200-.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232264B1 (en) * | 1998-06-18 | 2001-05-15 | Vanderbilt University | Polymetallic precursors and compositions and methods for making supported polymetallic nanocomposites |
| CN101486733A (en) * | 2009-03-09 | 2009-07-22 | 华南师范大学 | Oxygen-containing bridge dinuclear molybdenum cluster compound, and preparation and use thereof |
| CN107946592A (en) * | 2017-10-22 | 2018-04-20 | 曲靖师范学院 | A kind of preparation method of polyoxometallate lithium ion battery electrode material |
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| US20140050947A1 (en) * | 2012-08-07 | 2014-02-20 | Recapping, Inc. | Hybrid Electrochemical Energy Storage Devices |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232264B1 (en) * | 1998-06-18 | 2001-05-15 | Vanderbilt University | Polymetallic precursors and compositions and methods for making supported polymetallic nanocomposites |
| CN101486733A (en) * | 2009-03-09 | 2009-07-22 | 华南师范大学 | Oxygen-containing bridge dinuclear molybdenum cluster compound, and preparation and use thereof |
| CN107946592A (en) * | 2017-10-22 | 2018-04-20 | 曲靖师范学院 | A kind of preparation method of polyoxometallate lithium ion battery electrode material |
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