CN109786684B - High-performance porous Sn3O4Base carbon composite material and preparation method and application thereof - Google Patents
High-performance porous Sn3O4Base carbon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses high-performance porous Sn3O4A carbon-based composite material is prepared from micron-class SnO through adding P @ F-127 and silica gel to aqueous solution, ultrasonic mixing, dispersing aniline monomer in it, adding ammonium persulfate to initiate polymerization reaction under ice bath condition, washing, drying, and Ar/H passing through it2Performing heat treatment on the mixed gas, and finally removing silicon dioxide by hydrofluoric acid aqueous solution to prepare the high-performance porous Sn3O4A base carbon composite material. The invention also discloses the high-performance porous Sn3O4A base carbon composite material and applications thereof. According to the characteristic that the volume effect is easy to occur in the charge-discharge cycle of the lithium battery and the sodium battery cathode material, the low-price commercial micron-sized SnO is used as the starting material, and the micron-sized SnO is subjected to ultrasonic and high-temperature reassembly and dispersion to form the nano-sized Sn3O4The material is fully dispersed in the porous carbon material doped with the heteroatom.
Description
Technical Field
The invention relates to the technical field of lithium/sodium ion battery cathode materials, in particular to high-performance porous Sn3O4A base carbon composite material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high open circuit voltage, large energy density, long service life, no memory effect, less pollution, small self-discharge rate and the like, is superior to other traditional secondary batteries in overall performance, and is considered as the most ideal power supply for various portable electronic equipment and electric automobiles. Although the traditional lithium ion battery cathode material graphite has good cycling stability and higher cost performance, the traditional lithium ion battery cathode material graphite has lower charge-discharge specific capacity and no advantage in volume specific capacity, and is difficult to meet the requirement of a power system, particularly an electric vehicle and a hybrid electric vehicle on high capacity of the battery. Therefore, the development of a novel lithium ion battery cathode material with high specific capacity, high charge and discharge efficiency and long cycle life is extremely urgent.
Among the tin oxides, Sn3O4Has very high theoretical lithium storage capacity (twice of graphite), can effectively improve the energy density of the lithium ion battery when being used as a negative electrode material of the lithium ion battery, and has good safetyThe lithium ion battery has rich resource reserve, and is one of the lithium ion battery cathode materials which have the most development potential and can replace graphite. However, the main problem which hinders the practical application of the metal oxide is that the metal oxide has large volume change (300%) during the cyclic charge and discharge process, the anode material is easy to be pulverized, and the cycle performance is poor, and in addition, the metal oxide also has the general problem of poor conductivity, which is also an important factor influencing the practical application of the metal oxide.
At present, the tin monoxide material can be produced on a large scale. However, due to the large particle size (micron size), the cycling performance and rate capability are poor when the material is applied to a battery material. How to expand the application range of commercial tin oxide has become a bottleneck restricting the development of the tin oxide.
Disclosure of Invention
In view of the disadvantages of the prior art, it is a first object of the present invention to provide a high performance porous Sn3O4A preparation method of the base carbon composite material;
it is a second object of the present invention to provide a high performance porous Sn3O4A base carbon composite;
it is a third object of the present invention to provide a high performance porous Sn3O4The application of the base carbon composite material in the aspect of lithium ion batteries.
The technical scheme adopted by the invention for solving the technical problems is as follows:
high-performance porous Sn3O4The preparation method of the base carbon composite material is characterized in that SiO is introduced to the surface of a high-capacity nanometer negative electrode material2Taking a commercial micron-sized SnO as a sacrificial layer, adding P @ F-127 and silica gel in an aqueous solution, sufficiently mixing with ultrasound, dispersing aniline monomer in the aqueous solution, adding ammonium persulfate to initiate polymerization under ice bath conditions, washing and drying the reacted product, and passing the product through Ar/H2Performing heat treatment on the mixed gas, and finally removing silicon dioxide by hydrofluoric acid aqueous solution to prepare the high-performance porous Sn3O4A base carbon composite material.
Further, the preparation method specifically comprises the following steps:
(1) dispersing P @ F-127 in deionized water, ultrasonically stirring until the P @ F-127 is completely dissolved, dissolving silica gel in the deionized water, and ultrasonically stirring for 20 minutes to completely dissolve the silica gel;
(2) adding commercial SnO into the solution in the step (1), performing ultrasonic treatment to uniformly disperse the commercial SnO, then dropwise adding an aniline monomer, performing ultrasonic stirring to uniformly disperse the aniline monomer, transferring the solution into a round-bottom flask, and stirring for 20 minutes under an ice bath condition; dropwise adding concentrated hydrochloric acid, and continuously stirring under an ice bath condition;
(3) preparing an aqueous solution containing ammonium persulfate, and adding the aqueous solution into the solution obtained in the step (2); keeping ice bath condition, stirring and reacting for 12 h; after the reaction is finished, carrying out suction filtration, washing for three times, and carrying out vacuum drying;
(4) putting the composite material of the step (3) in Ar/H2Treating the mixture at high temperature, and treating the mixture with dilute HF acid to obtain the composite material.
The particle diameter of the SnO is 5-50 mu m; the particle size range of the silicon dioxide gel is 5-40nm, and the mass ratio of the silicon dioxide gel to water is 0.5: 100-5: 100; the mass ratio of SnO to water is 0.1: 100-1: 100; the mass ratio of the P @ F-127 to the water is 0.1: 100-1: 100; the mass concentration ranges of the concentrated hydrochloric acid and the aniline are 0.01-0.24 mM/mL and 0.01-0.22 mM/mL respectively; the adding amount of the ammonium persulfate in the aqueous solution of the ammonium persulfate is 1.5-3 times of the mass of the aniline monomer.
Further, the high-temperature treatment condition is 400-700 ℃ for 0.5-6 h.
Further, the amount of the HF acid is 5-30%, and the treatment time is 0.5-12 h.
Furthermore, the porous structure is mesoporous carbon, and the hollow pore gap is 5-40 nm.
Further, the porous Sn3O4Preparation method of base carbon composite material by using carbon and Sn3O4The mass ratio of the carbon to the metal oxide is 1: 5-1: 1, and the carbon can not only play a role in improving the conductivity and inhibiting the volume expansion of the carbon in the composite material, but also ensure that the prepared composite electrode has higher specific capacity.
The high-performance porous Sn prepared by the preparation method3O4A base carbon composite material.
The above high-performance porous Sn3O4The application of the base carbon composite material in the preparation of composite electrodes.
Advantageous effects
According to the characteristics of the lithium battery cathode material in charge-discharge circulation, the method takes commercial micron-sized SnO as an initial raw material to prepare the heteroatom-rich doped porous carbon-nano Sn by a one-step method3O4A composite material. The composite structure is beneficial to the conduction of electrons and the quick diffusion of lithium electrolyte, can greatly improve the characteristics of quick attenuation, low reversible capacity and the like of commercial micron-sized SnO, and is suitable for a negative electrode material of a power battery material.
The preparation method disclosed by the invention is environment-friendly, simple in operation process, high in yield, excellent in charge and discharge performance of the material and convenient for industrial production.
Drawings
FIG. 1 is an XRD pattern of samples prepared in examples 1-4, wherein a, b, c, d correspond to examples 1-4;
FIG. 2 is an SEM photograph of samples prepared in examples 1-4: (a) a commercial SnO material, (b) the sample of example 1, (c/d) the sample of example 2, (e) the sample of example 3, (f) the sample of example 4;
FIG. 3 shows the conditions of 500mA g for the lithium battery electrode prepared from the composite material prepared in examples 1-4-1The cycle performance test curve under the charge-discharge current density of (1), wherein a, b, c, d correspond to examples 1 to 4;
FIG. 4 shows the results of the preparation of the composite material and the related electrode in example 2 at 1 A.g for a sodium ion battery electrode-1The cycle performance test curve under the charge-discharge current density.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Example 1
Dispersing 0.5g P @ F-127 in 100mL deionized water, ultrasonically stirring until the solution is completely dissolved, dissolving 0.5g of silica gel (40nm) in the solution, and ultrasonically stirring for 20 minutes to completely dissolve the silica gel; then 0.5g of commercial SnO (5-50 μm) was added, sonicated for 1h to disperse it uniformly, then 0.4mL of aniline monomer was added dropwise, sonicated to disperse it uniformly, the solution was transferred to a round-bottom flask, stirred under ice bath conditions for 20 minutes, 0.5mL of concentrated hydrochloric acid was added, and stirring in an ice-water bath was continued. In addition, 10mL of a solution containing 1g of (NH)4)2S2O8Adding the aqueous solution of (1) to the mixed solution. The ice bath condition was maintained and the reaction was stirred for 12 h. And after the reaction is finished, carrying out suction filtration, washing for three times, and carrying out vacuum drying to obtain the composite material. The composite material is placed in Ar/H2High-temperature treatment is carried out for 6h at 500 ℃ under mixed gas. Treating with dilute 10% HF acid for 5h, washing with a large amount of deionized water, and vacuum drying to obtain high-performance porous Sn with hollow pore gap of about 40nm3O4A base carbon composite material. Porous Sn3O4Preparation method of base carbon composite material by using carbon and Sn3O4The mass ratio of (A) to (B) is 1: 3.0.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 4 hours to prepare the composite electrode. Placing the electrode in 2025 battery case, using lithium sheet as counter electrode, polyethylene film as separator, and 1M LiPF6EC/DEC (v/v: 1/1) was a constant current charge and discharge test performed for the electrolyte assembled cell.
Example 2
Dispersing 0.3g P @ F-127 in 100mL deionized water, ultrasonically stirring until the solution is completely dissolved, dissolving 1g of silicon dioxide gel (5nm) in the solution, and ultrasonically stirring for 20 minutes to completely dissolve the silicon dioxide gel; then 0.6g of commercial SnO (10-30 μm) was added, sonicated for 1h to disperse it uniformly, then 0.4mL of aniline monomer was added dropwise, sonicated to disperse it uniformly, the solution was transferred to a round-bottom flask, stirred under ice bath conditions for 20 minutes, 0.5mL of concentrated hydrochloric acid was added, and stirring in an ice-water bath was continued. In addition, 10mL of a solution containing 1.2g of (NH)4)2S2O8An aqueous solution of (A) to (B)Adding it into the above mixed solution. The ice bath condition was maintained and the reaction was stirred for 12 h. And after the reaction is finished, carrying out suction filtration, washing for three times, and carrying out vacuum drying to obtain the composite material. The composite material is placed in Ar/H2Treating at 600 deg.C for 3h under mixed gas. Treating with dilute 30% HF acid for 0.5h, washing with large amount of deionized water, and vacuum drying to obtain high-performance porous Sn with hollow pore gap of about 5nm3O4A base carbon composite material. Porous Sn3O4Preparation method of base carbon composite material by using carbon and Sn3O4The mass ratio of (A) to (B) is 1: 3.3.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 4 hours to prepare the composite electrode. Placing the electrode in 2025 battery case, using lithium sheet as counter electrode, polyethylene film as separator, and 1M LiPF6EC/DEC (v/v: 1/1) was a constant current charge and discharge test performed for the electrolyte assembled cell.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 60 ℃ for 4 hours to prepare the composite electrode. The electrode was placed in a 2025 cell can, with a sodium sheet as the counter electrode, a polyethylene film as the separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 3
Dispersing 0.1g P @ F-127 in 100mL deionized water, ultrasonically stirring until the solution is completely dissolved, dissolving 0.5g of silica gel (40nm) in the solution, and ultrasonically stirring for 20 minutes to completely dissolve the silica gel; then 0.1g of commercial SnO (5-50 μm) was added, sonicated for 1h to disperse it uniformly, then 0.4mL of aniline monomer was added dropwise, sonicated to disperse it uniformly, the solution was transferred to a round-bottom flask, stirred under ice bath conditions for 20 minutes, 0.1mL of concentrated hydrochloric acid was added, and stirring in an ice-water bath was continued. In addition, 10mL of a solution containing 1g of (NH)4)2S2O8Adding the aqueous solution of (1) to the mixed solution. The ice bath condition was maintained and the reaction was stirred for 12 h. After the reaction is finished, the mixture is filtered, washed for three times and dried in vacuumAnd (5) obtaining the composite material. The composite material is placed in Ar/H2High-temperature treatment is carried out for 0.5h at 700 ℃ under mixed gas. Treating with dilute 10% HF acid for 12h, washing with a large amount of deionized water, and vacuum drying to obtain high-performance porous Sn with hollow pore gap of about 40nm3O4A base carbon composite material. Porous Sn3O4Preparation method of base carbon composite material by using carbon and Sn3O4The mass ratio of (A) to (B) is 1: 1.1.
And fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, coating, and performing vacuum drying at 70 ℃ for 4 hours to prepare the composite electrode. Placing the electrode in 2025 battery case, using lithium sheet as counter electrode, polyethylene film as separator, and 1M LiPF6EC/DEC (v/v: 1/1) was a constant current charge and discharge test performed for the electrolyte assembled cell.
Example 4
Dispersing 1g P @ F-127 in 100mL deionized water, ultrasonically stirring until the solution is completely dissolved, dissolving 5g of silicon dioxide gel (5nm) in the solution, and ultrasonically stirring for 20 minutes to completely dissolve the silicon dioxide gel; then 1g of commercial SnO (5-50 μm) is added and dispersed uniformly by ultrasonic treatment for 1h, then 2mL of aniline monomer is added dropwise and dispersed uniformly by ultrasonic stirring, the solution is transferred to a round-bottom flask and stirred for 20 minutes under ice bath conditions, 2mL of concentrated hydrochloric acid is added, and stirring in ice water bath is continued. In addition, 10mL of a solution containing 3g of (NH)4)2S2O8Adding the aqueous solution of (1) to the mixed solution. The ice bath condition was maintained and the reaction was stirred for 12 h. And after the reaction is finished, carrying out suction filtration, washing for three times, and carrying out vacuum drying to obtain the composite material. The composite material is placed in Ar/H2High-temperature treatment is carried out for 6h at 400 ℃ under mixed gas. Treating with dilute 10% HF acid for 5h, washing with a large amount of deionized water, and vacuum drying to obtain high-performance porous SnO with hollow pore gap of about 5nmxA base carbon composite material. Porous Sn3O4Preparation method of base carbon composite material by using carbon and Sn3O4The mass ratio of (1): 4.5.
fully grinding the sintered material, uniformly mixing the ground material with carbon black and carboxymethyl cellulose according to the proportion of 70: 15, and coating a filmAnd (4) vacuum drying at 70 ℃ for 4h to prepare the composite electrode. Placing the electrode in 2025 battery case, using lithium sheet as counter electrode, polyethylene film as separator, and 1M LiPF6EC/DEC (v/v: 1/1) was a constant current charge and discharge test performed for the electrolyte assembled cell.
Material characterization and electrochemical Performance testing
The morphology structure of the composite material and the electrochemical performance of the composite material prepared by the method are tested and characterized by phase tests and cycle performance tests.
XRD analysis
FIG. 1 is an XRD pattern of examples 1-4. As can be seen from the figure, the samples prepared in examples 1-4 are all Sn3O4The structure of (1).
2. Topography analysis
FIG. 2 is an SEM photograph of samples prepared in examples 1-4: (a) the commercial SnO material can show that particles are in a spherical structure, and the sizes of the particles are different from 5-50 mu m; (b-f) SEM of samples in examples 1 to 4, it can be seen from the figure that the prepared material has a large number of hollow structures on the surface, and spherical SnO with a structure of 5 to 50 μm does not exist any more, so that a uniform composite phase structure is obtained.
3. Cycle performance test
FIG. 3 shows the conditions of 500mA g for the lithium battery electrode prepared by the composite negative electrode material prepared in examples 1-4-1The cycle performance test curve under the charge-discharge current density; as can be seen from the figure, the samples prepared in the examples are used as the negative electrode of the lithium battery and all show better cycle performance, and can maintain 400 mAh.g after 100 cycles-1The above reversible capacity is greatly improved compared to commercial SnO and carbon materials.
FIG. 4 shows that the composite negative electrode material prepared in example 2 and the sodium ion battery electrode prepared from the relevant electrode are at 1 A.g-1The cycle performance test curve under the charge-discharge current density; as can be seen from the figure, the samples prepared in the examples are used as the negative electrode of the sodium battery and all show better cycle performance, and can maintain 300 mAh.g after 100 cycles-1The reversible capacity is greatly improved compared with commercial SnO and carbon materialsAnd improvements.
In conclusion, the invention realizes the preparation of porous Sn3O4The prepared material of the base carbon composite material has a uniform porous structure, and the structure can fully solve the problems of volume effect and the like of a tin oxide material serving as a lithium/sodium battery cathode material in the circulating process, greatly reduce polarization and greatly improve the circulating performance of the battery.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (4)
1. High-performance porous Sn3O4The preparation method of the base-carbon composite material is characterized in that commercial micron-sized SnO is used as a starting raw material, P @ F-127 and silica gel are added into an aqueous solution and are sufficiently ultrasonically mixed, an aniline monomer is dispersed in the aqueous solution, ammonium persulfate is added under the ice bath condition to initiate polymerization reaction, and a product after the reaction is washed, dried and then passes through Ar/H2Treating the mixed gas at high temperature, and finally removing silicon dioxide by hydrofluoric acid aqueous solution to prepare the high-performance porous Sn3O4A base carbon composite; the preparation method specifically comprises the following steps:
(1) dispersing P @ F-127 in 100mL of deionized water, ultrasonically stirring until the P @ F-127 is completely dissolved, dissolving silica gel in the deionized water, and ultrasonically stirring for 20 minutes to completely dissolve the silica gel to obtain a mixed solution A;
(2) adding commercial SnO into the mixed solution A obtained in the step (1), performing ultrasonic treatment for 1h to uniformly disperse the mixed solution A, then dropwise adding an aniline monomer, performing ultrasonic stirring to uniformly disperse the aniline monomer, transferring the solution into a round-bottom flask, and stirring for 20 minutes under the ice bath condition; dropwise adding concentrated hydrochloric acid, and stirring under an ice bath condition to obtain a mixed solution B;
(3) preparing an aqueous solution containing ammonium persulfate, and adding the aqueous solution into the mixed solution B obtained in the step (2); keeping ice bath condition, stirring and reacting for 12 h; after the reaction is finished, carrying out suction filtration, washing for three times, and carrying out vacuum drying to obtain a composite material A;
(4) putting the composite material A obtained in the step (3) in Ar/H2Treating the mixture for 0.5 to 6 hours at the high temperature of 400 to 700 ℃ under the mixed gas, and then treating the mixture for 0.5 to 12 hours by using HF acid with the volume percentage of 5 to 30 percent to obtain the composite material.
In the step (1), the particle size range of the silica gel is 5-40nm, the mass ratio of the silica gel to water is 0.5: 100-5: 100, and the mass ratio of P @ F-127 to water is 0.1: 100-1: 100; in the step (2), the particle diameter of the SnO is 5-50 mu M, the mass ratio of the SnO to water is 0.1: 100-1: 100, and the mass concentration ranges of the concentrated hydrochloric acid and the aniline are 0.01-0.24M and 0.01-0.22M respectively; in the step (3), the adding amount of ammonium persulfate in the aqueous solution of ammonium persulfate is 1.5-3 times of the mass of the aniline monomer;
the high performance porous Sn3O4The porous structure of the base carbon composite material is mesoporous carbon, and the hollow pore gap is 5-40 nm.
2. The high performance porous Sn of claim 13O4The preparation method of the base carbon composite material is characterized in that the porous Sn3O4Carbon and Sn in base carbon composite material3O4The mass ratio of (A) to (B) is 1: 5-1: 1.
3. High-performance porous Sn prepared by the preparation method of claim 13O4A base carbon composite material.
4. The high performance porous Sn of claim 33O4The application of the base carbon composite material in the preparation of lithium ion battery and sodium ion battery composite electrodes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916829A (en) * | 2015-04-20 | 2015-09-16 | 长春理工大学 | Nitrogen-doped porous nanometer carbon-tin composite lithium ion battery negative electrode material and preparation method thereof |
| EP2991136A1 (en) * | 2014-08-29 | 2016-03-02 | Centre National De La Recherche Scientifique | Method for manufacturing a miniaturized electrochemical cell |
| CN107369819A (en) * | 2017-07-05 | 2017-11-21 | 合肥国轩高科动力能源有限公司 | Egg-shaped double-carbon-shell tin-based lithium ion battery cathode material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2991136A1 (en) * | 2014-08-29 | 2016-03-02 | Centre National De La Recherche Scientifique | Method for manufacturing a miniaturized electrochemical cell |
| CN104916829A (en) * | 2015-04-20 | 2015-09-16 | 长春理工大学 | Nitrogen-doped porous nanometer carbon-tin composite lithium ion battery negative electrode material and preparation method thereof |
| CN107369819A (en) * | 2017-07-05 | 2017-11-21 | 合肥国轩高科动力能源有限公司 | Egg-shaped double-carbon-shell tin-based lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Understanding the thermodynamic pathways of SnO-to-SnOx phase transition";Pranab Sarker;《Computational Materials Science 111 (2016) 359–365》;20151018;全文 * |
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