CN112993247A - High-surface-capacity self-supporting hard carbon cathode and preparation and application thereof - Google Patents
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Abstract
The invention provides a self-supporting hard carbon cathode with high surface capacity and preparation and application thereof, wherein the cathode is a self-supporting hard carbon cathode with a three-dimensional porous framework, and no adhesive is contained in the cathode; the three-dimensional porous skeleton is internally provided with meshes which are mutually communicated in nano and micron scale, the aperture range is 1 nm-500 mu m, and the porosity of the three-dimensional porous hard carbon skeleton is 5% -90%, namely the volume fraction of the meshes is 5% -90%. On one hand, the self-supporting three-dimensional porous carbon skeleton has higher electron transmission capacity and accelerates the electron transmission in the cathode; on the other hand, the porous structure is beneficial to the infiltration of electrolyte and ion transmission.
Description
Technical Field
The invention belongs to the field of secondary alkali metal ion batteries; in particular to a self-supporting hard carbon cathode with a spongy three-dimensional porous framework and high surface capacity, a preparation method and application thereof.
Background
In recent years, efficient utilization of renewable energy has necessitated new and inexpensive energy storage technologies. Among the energy storage technologies, secondary batteries are receiving attention due to their portability and flexibility. Currently, lithium ion batteries have already occupied the major market in portable electronic device products due to their advantages of high energy density, long cycle life, and the like; meanwhile, the development potential of the lithium ion battery as the best choice of the power battery of the electric automobile is increasingly strong. With the widespread use of lithium ion batteries in electric vehicles, the cost and the reserves of the relevant raw materials are facing serious problems. Although the energy density and development maturity of the sodium/potassium ion battery are not as good as those of the lithium ion battery, the advantages of abundant reserves and low cost are greatly beneficial to the development of large-scale energy storage, and the sodium/potassium ion battery is expected to be a beneficial supplement of the lithium ion battery in related fields.
Research and development of electrode materials are one of the keys of the development and application of alkali metal ion battery technology, and carbon-based negative electrode materials have the advantages of rich raw materials, low cost, large reversible capacity, good rate capability and the like, and are concerned by experts and scholars at home and abroad. The carbon negative electrode material comprises graphite and non-graphite, wherein the graphite negative electrode has the advantages of low potential, high capacity, good conductivity, high safety, low price and the like, and is the mainstream negative electrode of the current commercial lithium ion battery. However, the graphite negative electrode material has poor matching with the electrolyte due to structural defects of the graphite negative electrode material, and is easy to generate a co-intercalation reaction with an acrylic carbonate organic solvent in the electrolyte in the charging and discharging process to cause structural damage, so that the cycle stability and the charging and discharging efficiency of the battery are influenced. Meanwhile, graphite cannot be used as a negative electrode material of a sodium-ion battery due to mismatch of the radius of sodium ions and lattice parameters of graphite. The hard carbon as one of carbon cathode materials has the characteristics of isotropic structure, larger interlamellar spacing than graphite, and high ion diffusion speed in the charging process, so that the hard carbon has better rate performance. Meanwhile, the hard carbon material also has the advantages of good cycle performance, low price (2 ten thousand yuan/ton lower than that of a graphite cathode material for a power battery), high safety and the like, so that the hard carbon material is attracted by people in the field of alkali metal ion cathode materials. However, the hard carbon electrode prepared by the existing slurry coating method has low surface capacity and poor rate capability.
Disclosure of Invention
The invention aims to provide a preparation method and application of a self-supporting hard carbon negative electrode with a spongy three-dimensional porous skeleton.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a hard carbon cathode, which is provided with a self-supporting three-dimensional porous hard carbon skeleton; the electrode has no adhesive; the three-dimensional porous skeleton is internally provided with meshes which are mutually communicated in nano and micron scale, the aperture range is 1 nm-500 mu m, and the porosity of the self-supporting three-dimensional porous hard carbon skeleton is 5% -90%, namely the volume fraction of the meshes is 5% -90%, preferably 40% -60%.
Based on the technical scheme, preferably, the growth amount of the self-supporting three-dimensional porous hard carbon skeleton is 1-40mg cm-2That is, the weight of the three-dimensional porous hard carbon skeleton per unit area is 1 to 40 mg.
Based on the technical scheme, preferably, the self-supporting three-dimensional porous hard carbon skeleton is obtained by carbonizing a porous polymer film at high temperature; porous polymer membranes are prepared from polymers by a phase inversion process.
Based on the technical scheme, preferably, the polymer is one or more than two of polybenzimidazole, polyacrylonitrile, phenolic resin, polyethersulfoneketone, polyvinylidene chloride and derivatives thereof, and polyimide and derivatives thereof;
the phase inversion method comprises one or more of thermal phase inversion, immersion phase inversion, vapor phase inversion and solvent evaporation induced phase inversion.
Based on the technical scheme, preferably, the polymer is one or more than two of polybenzimidazole, polyacrylonitrile, phenolic resin, polyethersulfoneketone, polyvinylidene chloride and derivatives thereof, and polyimide and derivatives thereof;
the phase inversion method comprises one or more of thermal phase inversion, immersion phase inversion, vapor phase inversion and solvent evaporation induced phase inversion.
In another aspect, the invention provides a preparation method of the self-supporting hard carbon negative electrode with the three-dimensional porous framework, which comprises the following steps:
(1) dissolving a polymer in an organic solvent according to the mass fraction of 1-50% to obtain a precursor solution;
(2) pouring the precursor solution prepared in the step (1) on a glass plate, and blade-coating to form a film;
(3) carrying out phase inversion treatment on the polymer film prepared in the step (2) to obtain a porous polymer film;
(4) and (4) calcining the porous polymer film prepared in the step (3) at high temperature to prepare the self-supporting hard carbon cathode with a three-dimensional porous framework.
Based on the above technical scheme, preferably, the organic solvent comprises one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran.
Based on the technical scheme, preferably, the self-supporting hard carbon negative electrode can be used for lithium ion batteries, sodium ion batteries and potassium ion batteries.
Based on the above technical scheme, preferably, the thickness of the polymer film in the step (2) is between 50 and 2000 μm.
Based on the above technical scheme, preferably, the porous polymer membrane in the step (4) is calcined at 1000-2000 ℃ for 2-20 h. Calcination at 1500 ℃ for 2-8h is preferred.
In the step (4), the high-temperature calcination is to heat the porous polymer film from room temperature to a set temperature, and the heating speed is 0.5-3 ℃/min.
The invention also provides an alkali metal ion battery which comprises a negative electrode, wherein the negative electrode is the hard carbon electrode.
The invention also provides an application of the hard carbon electrode, and the hard carbon electrode is applied to the negative electrode side of the alkali metal ion battery.
Based on the technical scheme, preferably, the alkali metal ion battery is a lithium ion battery, a sodium ion battery or a potassium ion battery.
Advantageous effects
(1) Compared with the commercial hard carbon material, the self-supporting hard carbon cathode prepared by the invention has a self-supporting three-dimensional porous framework: on one hand, the self-supporting three-dimensional porous carbon skeleton has higher electron transmission capacity and accelerates the electron transmission in the cathode; on the other hand, the porous structure is beneficial to the infiltration of electrolyte and ion transmission.
(2) The self-supporting electrode can still show excellent electrochemical performance under higher area capacity due to the rapid electron/ion transmission capability.
Drawings
Fig. 1 is an SEM image of a self-supporting hard carbon anode prepared in example 1.
Fig. 2 is an SEM image of a self-supporting hard carbon anode prepared in example 2.
Fig. 3 is a graph comparing the rate performance of the button cells of comparative example 1 and example 1.
Fig. 4 is a graph comparing the rate performance of the button cells of comparative example 2 and example 2.
Fig. 5 is a graph comparing the rate performance of the button cells of comparative example 3 and example 3.
Fig. 6 is a graph comparing the rate performance of the button cells of comparative example 4 and example 4.
Fig. 7 is a rate performance graph of the button cell battery of example 5.
Detailed Description
Thermally induced phase inversion: dissolving the polymer in a solvent with high boiling point and low volatility to form a homogeneous solution above the melting point of the polymer; then blade-coating to form a film, and cooling to separate the film from the film; and finally, selecting a proper volatile extractant to extract the solvent to obtain the polymer membrane with the porous structure.
Immersion phase inversion: dissolving a polymer in a proper solvent to form a uniform polymer solution, and then blade-coating to form a film; the obtained polymer film is immersed in a suitable non-solvent and taken out after a suitable time to obtain a polymer film having a porous structure.
Vapor phase inversion: dissolving a polymer in a proper solvent to form a uniform polymer solution, and then blade-coating to form a film; and putting the obtained polymer membrane into a constant temperature and humidity box filled with steam, and taking out the polymer membrane after a proper time to obtain the polymer membrane with a porous structure.
Solvent evaporation induced phase inversion: dissolving the polymer in a mixture of a solvent and a non-solvent (the solvent has higher volatility), and inducing the phase inversion by controlling the volatilization process of the solvent; the porous morphology is formed by thermal removal of non-solvent rich droplets.
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example 1
The commercially available Colorado (5 microns) is used as an electrode active material, super P is used as a conductive agent, and polyvinylidene fluoride (PVDF) is used as a binder to prepare slurry, wherein the composition ratio of the slurry to the PVDF is 8:1: 1. Copper foil is used as a current collector, an electrode is coated by blade coating with the thickness of 100 microns, and the electrode is dried at 60 ℃. The electrode supporting amount at this time was about 1mg cm-2. Using a sodium sheet with a diameter of 1.6mm, a glass fiber membrane as a diaphragm, and 1M NaPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1) of EC/DMC serving as a solvent is used as an electrolyte, and the Na | hard carbon half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Comparative example 2
The commercially available Colorado (5 microns) is used as an electrode active material, super P is used as a conductive agent, and polyvinylidene fluoride (PVDF) is used as a binder to prepare slurry, wherein the composition ratio of the slurry to the PVDF is 8:1: 1. Copper foil is used as a current collector, an electrode is coated by blade coating with the thickness of 100 microns, and the electrode is dried at 60 ℃. The electrode supporting amount at this time was about 1mg cm-2. A lithium sheet with a diameter of 1.6mm and a celgard 2325 diaphragm were used, with 1M LiPF6And (3) as a supporting electrolyte, using a mixed solution (volume ratio is 1:1:1) of EC/DMC/EMC as an electrolyte to assemble the lithium | hard carbon half cell. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Comparative example 3
Using commercially available Colorado (5 micron) as electrode active material, super P as conductive agent, and polyVinylidene fluoride (PVDF) is used as a binder to prepare slurry, and the composition ratio of the PVDF is 8:1: 1. Taking copper foil as a current collector, coating an electrode with the thickness of 300 microns by blade coating, and drying at 60 ℃. The electrode supporting amount at this time was about 3mg cm-2. Using a sodium sheet with a diameter of 1.6mm, a glass fiber membrane as a diaphragm, and 1M NaPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1) of EC/DMC serving as a solvent is used as an electrolyte, and the Na | hard carbon half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Comparative example 4
The commercially available Colorado (5 microns) is used as an electrode active material, super P is used as a conductive agent, and polyvinylidene fluoride (PVDF) is used as a binder to prepare slurry, wherein the composition ratio of the slurry to the PVDF is 8:1: 1. Taking copper foil as a current collector, coating an electrode with the thickness of 300 microns by blade coating, and drying at 60 ℃. The electrode supporting amount at this time was about 3mg cm-2. A lithium sheet with a diameter of 1.6mm and a celgard 2325 diaphragm were used, with 1M LiPF6And (3) as a supporting electrolyte, using a mixed solution (volume ratio is 1:1:1) of EC/DMC/EMC as an electrolyte to assemble the lithium | hard carbon half cell. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Example 1
0.6g of PBI (polybenzimidazole) was weighed out and completely dissolved in 9.4g of N, N-dimethylformamide, the resulting polymer solution was stirred for 10 hours and spread on a glass plate (thickness 250 μm), and then the glass plate was transferred to an ethanol nonsolvent and immersed for 30 minutes. The glass plate was taken out, and the prepared film was cut into a disk having a diameter of 14 mm. The wafer is put in a tube furnace and carbonized at 1200 ℃ for 4h to obtain the self-supporting hard carbon electrode with a 3D porous structure (figure 1). At this time, the supporting amount of the self-supporting hard carbon negative electrode was about 1mg cm-2. Using a sodium sheet with a diameter of 1.6mm, a glass fiber membrane as a diaphragm, and 1M NaPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1) of EC/DMC serving as a solvent is used as an electrolyte, and the Na | hard carbon half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Example 2
0.6g of PBI (polybenzimidazole) was weighed out and completely dissolved in 9.4g of N, N-dimethylformamide, the resulting polymer solution was stirred for 10 hours and spread on a glass plate (thickness 250 μm), and then the glass plate was transferred to an ethanol nonsolvent and immersed for 30 minutes. The glass plate was taken out, and the prepared film was cut into a disk having a diameter of 14 mm. The wafer is put in a tube furnace and carbonized at 1000 ℃ for 4h to obtain the self-supporting hard carbon electrode with a 3D porous structure (figure 1). At this time, the supporting amount of the self-supporting hard carbon negative electrode was about 1mg cm-2. With 1M LiPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1:1) of EC/DMC/EMC as a solvent is used as an electrolyte, and the lithium | self-supporting hard carbon electrode half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Example 3
0.6g of PBI (polybenzimidazole) was weighed out and completely dissolved in 9.4g of N, N-dimethylformamide, the resulting polymer solution was stirred for 10 hours and spread on a glass plate (thickness 750 μm), and then the glass plate was transferred to an ethanol nonsolvent and immersed for 30 minutes. The glass plate was taken out, and the prepared film was cut into a disk having a diameter of 14 mm. And (3) putting the wafer in a tube furnace, and carrying out carbonization treatment at 1000 ℃ for 4h to obtain the self-supporting hard carbon battery with the 3D porous structure. At this time, the supporting amount of the self-supporting hard carbon negative electrode was about 3mg cm-2. Using a sodium sheet with a diameter of 1.6mm, a glass fiber membrane as a diaphragm, and 1M NaPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1) of EC/DMC serving as a solvent is used as an electrolyte, and the Na | hard carbon half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Example 4
0.6g of PBI (polybenzimidazole) was weighed out and completely dissolved in 9.4g of N, N-dimethylformamide, the resulting polymer solution was stirred for 10 hours and spread on a glass plate (thickness 750 μm), and then the glass plate was transferred to an ethanol nonsolvent and immersed for 30 minutes. The glass plate was taken out, and the prepared film was cut into a disk having a diameter of 14 mm. The wafer is processedAnd putting the carbon electrode in a tubular furnace, and carrying out carbonization treatment at 1000 ℃ for 4h to obtain the self-supporting hard carbon electrode with a 3D porous structure. At this time, the supporting amount of the self-supporting hard carbon negative electrode was about 3mg cm-2. With 1M LiPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1:1) of EC/DMC/EMC as a solvent is used as an electrolyte, and the lithium | self-supporting hard carbon electrode half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
Example 5
0.6g of PBI (polybenzimidazole) was weighed out and completely dissolved in 9.4g of N, N-dimethylformamide, the resulting polymer solution was stirred for 10 hours and spread on a glass plate (thickness 3000 μm), and then the glass plate was transferred to an ethanol nonsolvent and immersed for 60 minutes. The glass plate was taken out, and the prepared film was cut into a disk having a diameter of 14 mm. And (3) putting the wafer in a tube furnace, and carrying out carbonization treatment at 1000 ℃ for 4h to obtain the self-supporting hard carbon electrode with the 3D porous structure. At this time, the supporting amount of the self-supporting hard carbon negative electrode was about 15mg cm-2. Using a sodium sheet with a diameter of 1.6mm, a glass fiber membrane as a diaphragm, and 1M NaPF6And (3) as a supporting electrolyte, a mixed solution (the volume ratio is 1:1) of EC/DMC serving as a solvent is used as an electrolyte, and the Na | hard carbon half cell is assembled. At a theoretical specific capacity of 300mAh g-1Charge and discharge tests were performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C.
The commercial hard carbon electrode prepared by the slurry coating method has the problems of active material falling off, cracking and the like, and the battery performance is seriously influenced when the hard carbon electrode is used in a sodium ion battery, so that the electrode supporting amount in the comparative example is up to 3mg cm-2。
As can be seen from FIGS. 1 and 2, the porous membrane prepared by the high-temperature carbonization phase conversion method of the invention can obtain a porous three-dimensional carbon skeleton, and the pore size distribution is 50-1000 nm.
As can be seen from fig. 3 to 7, compared with the electrode prepared by the slurry coating method, the self-supporting electrode has excellent rate performance, and the effect is more obvious under high load; the main reasons are that:
1) the self-supporting hard carbon negative electrode of the invention has a spongy three-dimensional porous skeleton: on one hand, the three-dimensional porous carbon skeleton has higher electron transmission capacity and accelerates the electron transmission in the cathode; on the other hand, the porous structure is beneficial to the infiltration of electrolyte and ion transmission.
2) The electronic/ionic conduction network of the electrode prepared by the slurry coating method is discontinuous, so that the rate capability of the electrode is poor.
Claims (10)
1. A hard carbon electrode, wherein the electrode is a self-supporting three-dimensional porous hard carbon skeleton; the self-supporting three-dimensional porous hard carbon skeleton is obtained by carbonizing a porous polymer film at high temperature; the porous polymer film is prepared from a polymer by a phase inversion method;
the self-supporting three-dimensional porous carbon skeleton is internally provided with meshes which are mutually communicated in nano and micron scales, the aperture range is 1 nm-500 mu m, and the porosity is 5% -90%, preferably 20-50%.
2. The hard carbon electrode according to claim 1, wherein the amount of growth of the self-supporting three-dimensional porous hard carbon skeleton is 1-40mg cm-2。
3. The hard carbon electrode according to claim 1,
the polymer is one or more than two of polybenzimidazole, polyacrylonitrile, phenolic resin, polyethersulfone ketone, polyvinylidene chloride and derivatives thereof, and polyimide and derivatives thereof;
the phase inversion method comprises one or more of thermal phase inversion, immersion phase inversion, vapor phase inversion and solvent evaporation induced phase inversion.
4. A method of making a hard carbon electrode according to claim 1, comprising the steps of:
(1) dissolving a polymer in an organic solvent to obtain a precursor solution; the mass fraction of the polymer in the precursor solution is 1-50%;
(2) pouring the precursor solution prepared in the step (1) on a glass plate, and blade-coating to form a film to obtain a polymer film;
(3) carrying out phase inversion treatment on the polymer film prepared in the step (2) to obtain a porous polymer film;
(4) and (4) calcining the porous polymer film prepared in the step (3) at high temperature to prepare the hard carbon electrode.
5. The method of claim 4, wherein:
the organic solvent is one or more than two of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran.
6. The method of claim 4, wherein: the thickness of the porous polymer film in the step (2) is 50-2000 μm.
7. The method of claim 4, wherein: the high-temperature calcination in the step (4) is set at the temperature of 1000-2000 ℃ for 1-20 h.
8. The method of claim 7, wherein: in the step (4), the high-temperature calcination is to heat the porous polymer film from room temperature to the calcination temperature, and the heating speed is 0.5-5 ℃/min.
9. An alkali metal ion battery comprising a negative electrode, wherein the negative electrode is a hard carbon electrode according to any one of claims 1 to 3.
10. Use of a hard carbon electrode according to any one of claims 1 to 3, wherein the hard carbon electrode is applied to the negative electrode side of an alkali metal ion battery; the alkali metal ion battery is a lithium ion battery, a sodium ion battery or a potassium ion battery.
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