CN114094073A - Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof - Google Patents
Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a tin dioxide @ carbon foam self-supporting composite material and a preparation method and application thereof. According to the preparation method, melamine foam is used as a raw material, a carbon three-dimensional skeleton is synthesized through one-step hydrothermal synthesis, stannous chloride dihydrate is further used as a raw material, and granular tin dioxide is loaded on the surface of the carbon foam through a hydrothermal method to form the tin dioxide @ carbon foam self-supporting negative electrode. The second hydrothermal reaction has lower temperature, and does not cause collapse of the carbon skeleton structure. The electrode material can be directly used as a lithium ion battery cathode material without adding a conductive agent and a binder, the preparation method provided by the invention is simple, the raw material price is low, meanwhile, the porous carbon foam can effectively inhibit the volume expansion in the electrochemical reaction of the tin dioxide particles, and meanwhile, the three-dimensional conductive network structure also ensures the charge transmission in the electrochemical process of the electrode.
Description
Technical Field
The invention relates to the technical field of lithium battery electrode materials, in particular to a tin dioxide @ carbon foam self-supporting composite material and a preparation method and application thereof.
Background
In the existing electrochemical energy storage technology, the lithium ion battery has the advantages of high energy density, high power density, long cycle life, small self-discharge and the like, and is widely applied to the fields of portable electronic equipment and new energy automobiles. However, with the trend of miniaturization and light weight development of electronic devices and the trend of new energy vehicles towards higher driving range and shorter charging time, higher requirements are put forward on lithium ion batteries. The current lithium ion battery takes a ternary transition metal compound as a positive electrode and graphite as a negative electrode, and the energy density can reach 260 Wh/kg. Further improving the energy density of the battery needs to find positive and negative electrode materials with higher specific capacity. Tin dioxide (SnO)2) Is a tin-based oxide with high theoretical specific capacity (782 mAhg)-1) The negative electrode material, which has been considered as promising, receives a wide range of attention from both academic and industrial fields. Dahn et al (Journal of the Electrochemical Society,1997,144(6):2045-2052) studied the Electrochemical lithium storage mechanism by XRD at the earliest and can be simply expressed as a one-step conversion process (Li + SnO)2/SnO→Li2O + Sn) and further alloying process
The first conversion step is generally irreversible, resulting in a large first irreversible capacity of tin dioxide. However, Li2O can relieve the volume change of tin to a certain extent in the inert matrix. However, the second alloying reaction has a large volume change, which easily causes pulverization of the material and seriously affects the electrochemical performance of the battery. Therefore, the pure block tin dioxide has the problems of low irreversible capacity, capacity attenuation and poor cycle stability for the first time.
Currently, a method for solving the above problems of the tin dioxide anode material includes: (1) nanocrystallization of materials, e.g. SnO by low-pressure chemical vapour deposition2A film; electrodeposition method, microwave solution growth methodPreparation of nanosized SnO2Particles; or preparing hollow SnO by adopting a template method2Balls, SnO2Nanotubes, and the like. (2) The tin dioxide/carbon composite material is prepared by compounding tin dioxide and a carbon material, so that the volume change of the tin dioxide material in the de-intercalation process is buffered by using the carbon material, and the agglomeration phenomenon of the tin dioxide in the growth process is inhibited. These carbon materials include zero-dimensional carbon nanospheres, carbon dots, one-dimensional carbon nanofibers, carbon nanotubes, two-dimensional graphene, three-dimensional porous carbon, mesoporous carbon, and the like. The prepared stannic oxide/carbon composite structure comprises a carbon-coated stannic oxide nano structure, a hollow stannic oxide/carbon composite structure, a graphene/carbon nano tube/carbon fiber loaded stannic oxide nano structure, a multi-stage stannic oxide/carbon composite structure and the like. Most of the prepared stannic oxide/carbon composite structures are powder materials, and a conductive agent and a binder are further added to prepare slurry, and the slurry is coated on a current collector to prepare an electrode. Therefore, the mass of inactive substances such as a conductive agent, a binder and a current collector in the electrode is relatively large, and the energy density of the battery is greatly reduced.
The invention application with publication number CN109671921A discloses a preparation method and application of a tin dioxide/carbon flexible self-supporting composite material, wherein the preparation method comprises the following steps: (1) calcining the melamine foam at high temperature for a certain time under protective gas to obtain a carbon flexible self-supporting framework material; (2) the carbon flexible self-supporting framework material and the tin salt aqueous solution are soaked in vacuum for a period of time according to a certain proportion and then dried to obtain the tin salt/carbon flexible self-supporting composite material; (3) and calcining the tin salt/carbon flexible self-supporting composite material in a protective gas condition to obtain the tin dioxide/carbon flexible self-supporting composite material. Wherein the calcination time in the step (3) is 1-3h, the calcination temperature is 700-900 ℃, and the heating rate is 5-10 ℃/min. However, in the technical scheme, except for preparing the carbon flexible self-supporting framework material by high-temperature calcination in the step (1), after the carbon flexible self-supporting framework material is immersed in the tin salt aqueous solution, the high-temperature calcination is carried out again in the step (3), wherein the calcination temperature is 700-; and the carbon skeleton supports fewer tin dioxide particles.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a tin dioxide @ carbon foam self-supporting composite material and a preparation method and application thereof.
A preparation method of a tin dioxide @ carbon foam self-supporting composite material comprises the following steps:
(1) carbonizing melamine foam at 600-800 ℃ under the protection of inert atmosphere to form carbon foam, washing and drying;
(2) dissolving stannous chloride dihydrate in water to obtain a tin precursor solution;
(3) soaking the carbon foam prepared in the step (1) in the tin precursor solution in the step (2);
(4) and (3) carrying out hydrothermal reaction on the mixed solution obtained after the reaction in the step (3) at 160-220 ℃, washing and drying a product after the reaction is finished, and thus obtaining the tin dioxide @ carbon foam self-supporting composite material. In the application, carbon needs to be soaked in the stannous chloride dihydrate aqueous solution for soaking load, so that in the step (1), the dosage of the stannous chloride dihydrate is excessive, and the stannous chloride dihydrate is hydrolyzed to generate the basic stannous chloride and hydrochloric acid.
Preferably, in the step (1), the carbonization time is 1-3h, and the temperature rise speed is 2-5 ℃/min.
Preferably, in the step (1), the carbon skeleton formed by the carbonization is subjected to an acidification treatment. The amount of acid used in the acidification treatment is excessive so that the acidification treatment can be completed. The acidification treatment can enhance the hydrophilicity of the carbon skeleton surface.
More preferably, the acid used in the acidification treatment is nitric acid, sulfuric acid or hydrochloric acid, the concentration is 0.5-2 mol/L, and the acidification treatment time is 1-2 h.
Preferably, in the step (2), the carbon foam prepared in the step (1) is cut into a thickness of 40-60 μm and then soaked in the tin precursor solution.
Preferably, in the step (2), when the tin precursor solution is prepared, stannous chloride dihydrate is added, wherein the concentration of the stannous chloride dihydrate is 0.04-0.08 mol/L.
Preferably, in the step (3), the soaking time is 1-3 h.
Preferably, in the step (4), the hydrothermal reaction time is 4-8 h.
The invention also provides the tin dioxide @ carbon foam self-supporting composite material prepared by the preparation method.
The invention also provides application of the tin dioxide @ carbon foam self-supporting composite material in preparation of a lithium battery cathode material.
The invention has the beneficial effects that:
the invention relates to a preparation method of a tin dioxide @ carbon foam self-supporting lithium battery negative electrode material. The method comprises the steps of taking melamine foam as a raw material, carrying out one-step hydrothermal synthesis on a carbon three-dimensional skeleton, further taking stannous chloride dihydrate as a raw material, and loading granular stannic oxide on the surface of the carbon foam by adopting a hydrothermal method to form the stannic oxide @ carbon foam self-supporting negative electrode. The second hydrothermal reaction has lower temperature, and does not cause collapse of the carbon skeleton structure.
The electrode material can be directly used as a lithium ion battery cathode material without adding a conductive agent and a binder, the preparation method provided by the invention is simple, the raw material price is low, meanwhile, the porous carbon foam can effectively inhibit the volume expansion in the electrochemical reaction of the tin dioxide particles, and meanwhile, the three-dimensional conductive network structure also ensures the charge transmission in the electrochemical process of the electrode.
Drawings
Figure 1 is an SEM image of the tin dioxide @ carbon foam electrode material prepared in example 1.
Figure 2 is an SEM image of a tin dioxide @ carbon foam electrode material prepared from carbon foam without acid treatment.
Figure 3 is a photograph of the tin dioxide @ carbon foam electrode sheet prepared in example 1.
FIG. 4 is a graph of the thermal weight loss of the tin dioxide @ carbon foam prepared in example 1.
Figure 5 is an SEM image of the tin dioxide @ carbon foam electrode material prepared in example 1 after further high temperature calcination in an inert atmosphere.
Figure 6 is an XRD pattern of the tin dioxide @ carbon foam prepared in example 1.
FIG. 7 shows the tin dioxide @ carbon foam electrode material prepared in example 1 at a current density of 0.2Ag-1Cyclic stability curve of time.
Figure 8 is an SEM image of the tin dioxide @ carbon foam electrode material prepared in example 2.
FIG. 9 shows the tin dioxide @ carbon foam electrode material prepared in example 2 at a current density of 0.2Ag-1Cyclic stability curve of time.
FIG. 10 shows the tin dioxide @ carbon foam electrode material prepared in example 3 at a current density of 0.2Ag-1Cyclic stability curve of time.
Detailed Description
Example 1
And (3) placing the melamine foam in a tube furnace, heating to 800 ℃ at a speed of 5 ℃/min under the argon protection atmosphere, and preserving heat for 2h to obtain the carbon foam. Further, 10mg of the carbon foam was immersed in 200mL of a 1mol/L nitric acid solution for 2 hours, and then the carbon foam was taken out, washed with deionized water and ethanol for 3 times, and dried in an oven at 60 ℃. The dried carbon foam was cut into 40 μm thick disks.
Dissolving stannous chloride dihydrate in water to obtain a tin precursor solution, wherein the concentration of the added stannous chloride dihydrate is 0.06mol/L when the tin precursor solution is prepared.
Soaking 4 carbon foam wafers with the same thickness in 30mL of tin precursor solution for 1 hour, pouring the solution and the carbon foam wafers into a 50mL hydrothermal reaction kettle, transferring the hydrothermal reaction kettle into an oven, heating the oven to 180 ℃, preserving heat for 4 hours, taking out substances in the inner container after natural cooling, performing suction filtration and washing with deionized water and absolute ethyl alcohol for three times, putting the materials into the oven at 60 ℃, and drying and taking out the materials to obtain the tin dioxide @ carbon foam cathode material.
Phase characterization is carried out on the tin dioxide @ carbon foam prepared in the example, fig. 1 is an SEM image of the tin dioxide @ carbon foam, it can be seen that the carbon foam is a three-dimensional porous structure, and on the surface of the three-dimensional carbon foam, it can be clearly seen that granular substances are coated on the surface of the foam, and the bonding is tight.
In comparison to tin dioxide @ carbon prepared from carbon foam without surface acid treatment (fig. 2), it is evident that carbon foam without acid treatment has a smoother surface and no significant loading of tin dioxide particles.
As can be seen from a macroscopic photograph of the prepared tin dioxide @ carbon foam (figure 3), the material has certain mechanical property, does not break when bent, has good flexibility, and can be directly used as an electrode plate.
As can be seen from the thermogravimetric curve (figure 4), the curve drop between 300 and 700 ℃ represents the oxidative decomposition of carbon, and further analysis shows that SnO in the material2The content of (B) is 42%. Further, the temperature of the flexible electrode is raised to 650 ℃ at 5 ℃/min under the protection of inert atmosphere (argon), and after the flexible electrode material is calcined for 2 hours, the mechanical property of the flexible electrode material cannot be maintained, and the framework structure of the carbon foam is damaged as can be seen from an SEM (figure 5).
From the XRD pattern (figure 6), it can be analyzed that obvious diffraction peaks appear at 26.6 °, 33.7 ° and 51.8 °, corresponding to SnO2The crystal faces of the tetragonal crystal forms (110), (101) and (310) have a broadened diffraction peak between 20 and 25 degrees, and the broadened diffraction peak corresponds to the diffraction peak of the carbon foam, so that the carbon foam is amorphous carbon.
The electrode plate is used as a working electrode, a lithium ion half-cell is assembled in a glove box, metal lithium is used as a counter electrode, Celgard2400 is used as a diaphragm, and 1M LiPF is adopted6Dissolving in ethyl carbonate/diethyl carbonate/dimethyl carbonate (1: 1(v/v/v)) as electrolyte to assemble CR2032 button cell; performing constant current charge and discharge test at room temperature with voltage range of 0.01-3V and current density of 0.2Ag-1As a result, as shown in FIG. 7, it can be seen that the material had a specific first discharge capacity of 2074mAhg-1The first charging specific capacity is 994mAhg-1The first coulombic efficiency was 47.9%. After 50 times of circulation, the charging specific capacity of the material is 712mAhg-1The capacity retention was first 72%.
Example 2
And (3) placing the melamine foam in a tube furnace, heating to 600 ℃ at the speed of 2 ℃/min under the argon protection atmosphere, and preserving heat for 1h to obtain the carbon foam. Further, 20mg of the carbon foam was immersed in 150mL of a 2mol/L hydrochloric acid solution for 1 hour, and then the carbon foam was taken out, washed with deionized water and ethanol for 3 times, and dried in an oven at 60 ℃. The dried carbon foam was cut into disks having a thickness of 60 μm.
Dissolving stannous chloride dihydrate in water to obtain a tin precursor solution, wherein the concentration of the added stannous chloride dihydrate is 0.04mol/L when the tin precursor solution is prepared.
Soaking 4 carbon foam wafers with the same thickness in 30mL of tin precursor solution for 1 hour, pouring the solution and the carbon foam wafers into a 50mL hydrothermal reaction kettle, transferring the solution and the carbon foam wafers into an oven, heating the oven to 180 ℃, preserving heat for 8 hours, taking out substances in the inner container after natural cooling, performing suction filtration and washing with deionized water and absolute ethyl alcohol for three times, putting the materials into the oven at 60 ℃, and drying and taking out the materials to obtain the tin dioxide @ carbon foam cathode material.
Fig. 8 is an SEM of the tin dioxide @ carbon foam produced, and it can be seen that there is a coarse and uneven distribution of particulate matter on the surface of the carbon foam.
The electrode plate is used as a working electrode, a lithium ion half-cell is assembled in a glove box, metal lithium is used as a counter electrode, Celgard2400 is used as a diaphragm, and 1M LiPF is adopted6Dissolving in ethyl carbonate/diethyl carbonate/dimethyl carbonate (1: 1(v/v/v)) as electrolyte to assemble CR2032 button cell; performing constant current charge and discharge test at room temperature with voltage range of 0.01-3V and current density of 0.2Ag-1As a result, as shown in FIG. 9, the first discharge specific capacity of the material was 2866mAhg-1First charge specific capacity of 1032mAhg-1The first coulombic efficiency was 36%. After 35 times of circulation, the charging specific capacity of the material is 630mAhg-1The capacity retention was 61% of the first time.
Example 3
And (3) placing the melamine foam in a tube furnace, heating to 700 ℃ at a speed of 2 ℃/min under the argon protection atmosphere, and preserving heat for 3h to obtain the carbon foam. Further, after 15mg of the carbon foam was immersed in 200mL of a 0.5mol/L sulfuric acid solution for 1 hour, the carbon foam was taken out, washed 3 times with deionized water and ethanol, and then dried in an oven at 60 ℃. The dried carbon foam was cut into disks having a thickness of 60 μm.
Dissolving stannous chloride dihydrate in water to obtain a tin precursor solution, wherein the concentration of the added stannous chloride dihydrate is 0.08mol/L when the tin precursor solution is prepared.
Soaking 4 carbon foam wafers with the same thickness in 30mL of tin precursor solution for 3 hours, then pouring the solution and the carbon foam wafers into a 50mL hydrothermal reaction kettle, transferring the solution and the carbon foam wafers into an oven, raising the temperature of the oven to 180 ℃, preserving the heat for 6 hours, taking out substances in the inner container after natural cooling, carrying out suction filtration and washing three times by adopting deionized water and absolute ethyl alcohol, then putting the materials into the oven at 60 ℃, and drying and taking out the materials to obtain the tin dioxide @ carbon foam cathode material.
The electrode plate is used as a working electrode, a lithium ion half-cell is assembled in a glove box, metal lithium is used as a counter electrode, Celgard2400 is used as a diaphragm, and 1M LiPF is adopted6Dissolving in ethyl carbonate/diethyl carbonate/dimethyl carbonate (1: 1(v/v/v)) as electrolyte to assemble CR2032 button cell; performing constant current charge and discharge test at room temperature with voltage range of 0.01-3V and current density of 0.2Ag-1As a result, as shown in FIG. 10, the specific first discharge capacity of the material was 2613mAhg-1The first charging specific capacity is 1003mAhg-1The first coulombic efficiency was 38%. After 50 times of circulation, the charging specific capacity of the material is 697mAhg-1The capacity retention was 69% of the first time.
According to the embodiment, the tin dioxide @ carbon foam self-supporting lithium battery cathode material provided by the invention has the advantages that the carbon foam plays a role in supporting a three-dimensional conductive network and a framework, the nano tin dioxide is tightly coated on the surface of the carbon foam, the electrolyte is fully soaked on the surface of the tin dioxide in the charging and discharging processes of the battery, the tin dioxide is promoted to fully participate in electrochemical reaction, and the good circulation stability is kept.
Claims (10)
1. A preparation method of a tin dioxide @ carbon foam self-supporting composite material is characterized by comprising the following steps:
(1) carbonizing melamine foam at 600-800 ℃ under the protection of inert atmosphere to form carbon foam, washing and drying;
(2) dissolving stannous chloride dihydrate in water to obtain a tin precursor solution;
(3) soaking the carbon foam prepared in the step (1) in the tin precursor solution in the step (2);
(4) and (3) carrying out hydrothermal reaction on the mixed solution obtained after the reaction in the step (3) at 160-220 ℃, washing and drying a product after the reaction is finished, and thus obtaining the tin dioxide @ carbon foam self-supporting composite material.
2. The method according to claim 1, wherein in the step (1), the carbonization time is 1 to 3 hours, and the temperature rise rate is 2 to 5 ℃/min.
3. The production method according to claim 1, wherein in the step (1), the carbon skeleton formed by the carbonization is subjected to an acidification treatment.
4. The method according to claim 3, wherein the acid used in the acidification treatment is nitric acid, sulfuric acid or hydrochloric acid, the concentration is 0.5 to 2mol/L, and the acidification treatment time is 1 to 2 hours.
5. The method according to claim 1, wherein in the step (3), the carbon foam prepared in the step (1) is cut into a thickness of 40 to 60 μm and then soaked in the tin precursor solution.
6. The preparation method according to claim 1, wherein in the step (2), the concentration of the added stannous chloride dihydrate is 0.04-0.08 mol/L during preparation of the tin precursor solution.
7. The method according to claim 1, wherein in the step (3), the soaking time is 1 to 3 hours.
8. The preparation method according to claim 1, wherein in the step (4), the hydrothermal reaction time is 4-8 h.
9. Tin dioxide @ carbon foam self-supporting composite material prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the tin dioxide @ carbon foam self-supporting composite material as defined in claim 9 for the preparation of a negative electrode material for a lithium battery.
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| M.Y. WANG ET AL.: "Molybdenum-doped tin oxide nanoflake arrays anchored on carbon foam as flexible anodes for sodium-ion batteries", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| SHENGGAO WANG ET AL.，: "Preparation and properties of SnO2/nitrogen-doped foamed carbon as anode materials for lithium ion batteries", 《IONICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115020704A (en) * | 2022-06-15 | 2022-09-06 | 李致朋 | Self-supporting negative electrode material, preparation method thereof and sodium ion battery |
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