CN114335523A - Preparation method of hard carbon negative electrode for high-energy-density sodium ion battery - Google Patents
Preparation method of hard carbon negative electrode for high-energy-density sodium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a hard carbon cathode for a high-energy-density sodium ion battery with excellent sodium storage performance, wherein the hard carbon cathode comprises porous carbon and chemical vapor deposition carbon for adjusting the size of a surface orifice; the hard carbon cathode reserves a coherent pore channel structure in the porous carbon. The invention designs a carbon-coated carbon-carbon composite structure through chemical vapor deposition, realizes the regulation and control of the pore size of the porous carbon surface, simultaneously combines the particle size, the specific surface area, the pore diameter, the gas source concentration and the influence of a catalyst on the sodium storage performance of precursor particles, designs the hard carbon cathode which has excellent performances on the first coulombic efficiency, the rate capability and the platform capacity, and has guiding significance for promoting the commercialization process of the high-energy density sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a hard carbon cathode for a high-energy-density sodium ion battery with excellent sodium storage performance.
Background
With the rapid advance of the information-based society and the scientific development of civilization, the energy pattern is undergoing an important revolution. It is well known that the large consumption of fossil energy brings about numerous environmental problems such as deterioration of urban air and global warming, and its consequences are worried. In addition, the resource characteristics of lean oil and less gas enable the dependence of China on foreign fossil energy to be high, and the continuous high energy safety risk is brought. Under the background, green energy represented by wind energy, water energy and solar energy becomes an important breakthrough for our country to get rid of energy crisis. With the promotion of the current electric Chinese policy, energy storage as an indispensable link in the smart grid brings huge market demands. Although the lithium ion battery is still the main system of electrochemical energy storage nowadays, the lithium ion battery is limited by the uneven storage and distribution of lithium resources, and is difficult to independently bear the pressure of large-scale development of the energy storage industry in the future. In contrast, sodium resources are rich in reserves, widely distributed and low in cost, so that the sodium ion battery which is produced in the same period as the lithium ion battery returns to the visual field of people again, becomes an energy storage technology competitively developed by various countries, and is also an important opportunity for our country to lead the world in the new energy industry.
Among the cathode materials available for sodium ion batteries, carbon cathodes have lower potential, higher capacity, stable physicochemical properties and low cost, and become the first choice cathode material for the commercial development of sodium ion batteries. However, the graphite negative electrode, which has contributed to the commercialization of lithium ion batteries, cannot be used as a negative electrode for sodium ion batteries because the low-order intercalation compound with sodium is thermodynamically unstable. The hard carbon material has larger interlayer spacing, abundant defects and a nano-pore structure formed by disordered stacking of graphite microcrystals, which become active sites for sodium ion storage, and thus becomes a negative electrode material which is most hopeful to promote sodium ion industrialization. However, since the use of hard carbon as a sodium-electric negative electrode in 2000 to date, the storage mechanism of sodium ions in the disordered structure of hard carbon still cannot be completely understood, and most of the hard carbon materials selected as the negative electrode in research have low coulombic efficiency for the first time, short platform capacity and high synthesis cost, so that the commercialization process of the sodium-ion battery is difficult to further advance.
In view of the above, there is a need to provide a method for preparing a hard carbon negative electrode for a high-energy density sodium ion battery, which has excellent sodium storage performance, in which a layer of carbon material is coated on the surface of porous carbon particles by a chemical vapor deposition method to realize the regulation and control of the pore size of the surface of the porous carbon, and the particle size and pore size of the porous carbon particles and the specific surface area of the porous carbon precursor have a great influence on the performance of the hard carbon negative electrode, so that an optimal choice is made. The method has important guiding significance for promoting the commercialization process of the hard carbon cathode of the sodium ion battery.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the preparation method of the hard carbon cathode for the high-energy-density sodium ion battery with excellent sodium storage performance is provided, the structure that porous carbon particles are coated by chemical vapor deposition carbon is adopted, the continuity of an internal pore channel can be kept while the pore size of the surface is adjusted, and the rapid diffusion and storage of sodium ions in the pore channel are facilitated; meanwhile, the selected precursor has a proper particle size, which is beneficial to accelerating the solid-phase diffusion rate of ions; the internal pore volume of the material can provide sufficient sodium storage space and realize rapid ion transmission. By integrating the design requirements, the designed structure can further improve the platform capacity, the first coulombic efficiency and the rate capability of the hard carbon cathode, and promote the commercialization of the sodium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a hard carbon anode for a high energy density sodium ion battery, the hard carbon anode comprising porous carbon and chemical vapor deposition carbon for adjusting the pore size of the surface; the hard carbon negative electrode reserves a coherent pore channel structure inside the porous carbon particles; the preparation method of the hard carbon negative electrode at least comprises the following steps:
firstly, grinding a porous carbon precursor to obtain porous carbon powder with proper particle size and rich nanopores inside;
secondly, putting the porous carbon powder into a tubular furnace, introducing protective gas, and heating to a target temperature at a certain heating rate;
thirdly, introducing a carbon-containing gas source, and performing chemical vapor deposition at a target temperature; this temperature causes rapid cracking of the carbon-containing gas source and an increase in the concentration of carbon-containing small molecules in the atmosphere.
Fourthly, reacting for a period of time at constant temperature, closing the carbon-containing element gas source, and reducing the temperature to the room temperature at a certain cooling rate; and the high-concentration carbon-containing micromolecules are quickly polymerized and deposited on the surfaces of the porous carbon particles, so that the porous carbon particles are completely coated.
The target temperature is 1000 ℃ to 1200 ℃, and the third step can be added with catalyst. The low constant temperature can cause the deposition rate of carbon-containing micromolecules to be slowed down, so that carbon deposition can be developed more deeply to a precursor, the continuity of an internal pore channel is influenced, the rate capability of the material is further influenced, the low constant temperature can cause insufficient methane cracking, particles cannot be fully coated, and further the first coulombic efficiency and the platform capacity are reduced; higher isothermal temperatures lead to severe methane cracking, resulting in excessive deposition and increased inefficient energy consumption. The addition of the catalyst can shorten the chemical vapor deposition time and improve the particle coating effect.
As an improvement of the preparation method of the hard carbon cathode for the high-energy-density sodium ion battery, the particle size of the porous carbon particles is 1-4 mu m, the particle size is too large, the diffusion rate of sodium ions in a solid phase is slow, and the rate capability and the platform capacity of the material are influenced; the particle size is too small, more exposed surfaces lead to more severe irreversible decomposition of the electrolyte, and the coulombic efficiency and the cycle stability of the material are reduced.
As an improvement of the preparation method of the hard carbon cathode for the high-energy density sodium-ion battery, the specific surface of the porous carbon precursor is 500-3800 m2A too low specific surface area results in a lower platform capacity, which is not advantageous compared to commercially available hard carbon materials; too high a specific surface reduces the structural stability and the compacted density of the material. The pore diameter of the porous carbon is 0.5-9 nm. Larger pore sizes lead to increased metallicity of the deposited sodium, which risks shorting the cell, and larger pore sizes lead to a reduction in the specific surface area of the material, which leads to a reduction in the sodium storage capacity; smaller pore sizes can affect ion transport in the solid phase, with loss of rate capability and sodium storage capacity.
As an improvement of the preparation method of the hard carbon cathode for the high-energy density sodium ion battery, the specific surface of the hard carbon cathode material is close to 0 m measured by nitrogen gas at 77K2(ii)/g; the specific surface area and the pore diameter obtained by the small angle X-ray scattering test are the same as those of the porous carbon precursor, which indicates that the hard carbon retains the pore channel structure inside the porous carbon (the small angle X-ray scattering test detects the internal pore channel).
In the first step, the porous carbon precursor is at least one of microporous activated carbon, hierarchical porous activated carbon, template porous carbon, porous graphene and the like.
As an improvement of the preparation method of the hard carbon negative electrode for the high energy density sodium ion battery, in the second step, the protective gas is at least one of argon, nitrogen and hydrogen. The hydrogen is preferably selected as the hydrogen is an atmosphere with reducibility, so that the oxygen content of the hard carbon negative electrode material is favorably reduced, and the low potential plateau capacity and the rate capability of the hard carbon negative electrode material are favorably improved.
As an improvement of the preparation method of the hard carbon cathode for the high-energy-density sodium-ion battery, in the second step, the flow of the protective gas is 10-100 mL/min, the heating rate is 0.1-20 ℃/min, and the tubular furnace can be replaced by a microwave reactor. The reduction of the flow rate and the temperature rise rate of the protective gas is beneficial to reducing the production cost. The microwave reactor can reduce the reaction time and is beneficial to reducing the production cost.
As an improvement of the preparation method of the hard carbon negative electrode for the high energy density sodium ion battery, in the third step, the carbon-containing gas source is at least one of methane, ethane, propane, ethylene, acetylene, propyne, benzene, toluene, carbon monoxide, cyclohexane, and the like. Different carbon-containing element gas sources can generate carbon-containing micromolecules with different components and sizes during final temperature cracking, and the orifice modification effect on the hard carbon material is different during deposition; in addition, the cheap carbon-containing gas source is selected, so that the production cost of the hard carbon cathode material is reduced.
As an improvement of the preparation method of the hard carbon cathode for the high-energy density sodium-ion battery, the flow of the carbon-containing element gas source is 5-50 mL/min. The flow of the carbon-containing gas source is too small, the deposition amount is insufficient, and the particle coating effect is not obvious; the excessive flow of the carbon-containing gas source can generate excessive carbon deposition during deposition, and the low potential platform capacity of the hard carbon cathode material is reduced.
As an improvement of the method for preparing the hard carbon negative electrode for the high energy density sodium ion battery, in the first step, the catalyst is at least one of Fe, Co, Ni, Cu, Au, Ag, Pt and Pb.
As an improvement of the preparation method of the hard carbon cathode for the high energy density sodium ion battery, in the fourth step, the duration time of the constant temperature reaction is 0.1-10 h; the cooling rate is 0.1-20 ℃/min. The constant temperature time is insufficient, the deposition amount is insufficient, and the particle coating effect is not obvious; the constant temperature time is too long, excessive carbon deposition can be generated during deposition, and the low potential platform capacity of the hard carbon cathode material is reduced. The deposition amount is too large due to too high cooling rate, and the particle coating effect is not controllable; too slow cooling rate can cause too long production time of the hard carbon cathode material and increase production cost.
The method has the following advantages:
first, the precursor of the method has wide source, and the activated carbon products are cheap and easily available on the market.
Second, the method is simple to operate, large-scale ball milling (grinding) and chemical vapor deposition methods have been widely used industrially, and the target structure is easily achieved by controlling the parameters of the reaction.
Thirdly, the method has low energy consumption, the chemical vapor deposition temperature (less than 1200 ℃) is lower than the preparation temperature (higher than 1400 ℃) of common hard carbon, and the energy consumption and the pollutant emission can be reduced.
Fourthly, the method maximizes the capacity of the porous carbon cathode, the capacity reaches 350-490 mAh/g under the current density of 0.1C (50 mA/g), which is the highest value of the current hard carbon cathode material, the capacity retention rate reaches more than 70% under the current density of 1C, the power characteristic is obviously improved, and the electrochemical performance is superior to that of the hard carbon cathode material sold in the market.
The invention adopts the structure of coating porous carbon particles with chemical vapor deposition carbon, can keep the continuity of an internal pore passage while adjusting the size of a surface pore opening, and is beneficial to the rapid diffusion and storage of sodium ions in the pore passage; meanwhile, the selected precursor has a proper particle size, which is beneficial to accelerating the solid phase diffusion rate of ions; the internal pore volume of the material can provide sufficient sodium storage space and realize rapid ion transmission. By integrating the design requirements, the designed structure can further improve the platform capacity, the first coulombic efficiency and the rate capability of the hard carbon cathode, so that the hard carbon cathode for the high-energy-density sodium-ion battery with excellent sodium storage performance is obtained, and the commercialization of the sodium-ion battery is promoted.
In the present invention, the positive electrode active material may be at least one of a transition metal layered oxide, a sodium polyanion compound, prussian blue, prussian white, and the like.
The negative electrode includes a negative electrode active material, a conductive agent, a binder, and the like, wherein the negative electrode active material is a porous carbon material in the present invention; the conductive agent can be at least one of SUPER-P, KS-6, conductive graphite, carbon nano tube, graphene, carbon fiber VGCF, acetylene black, Ketjen black and the like; the binder may be at least one of PVDF, CMC, SBR, PTFE, SA, PAA, PAN, etc.
The electrolyte comprises an organic solvent, sodium salt and the like, wherein the organic solvent can be at least one of EC, PC, DMC, DEC, EMC, EA, FEC, VC and the like; the sodium salt can be NaClO4、NaPF6、NaBF4At least one of NaFSI, NaTFSI, etc.
Compared with the prior art, the invention further considers the optimal design method of the hierarchical structure of the porous carbon, and the sodium storage performance of the cathode material is improved to the maximum extent by optimizing the position of the carbon coating layer (controlling the deposition of the coated carbon on the surface of the porous carbon and reducing the deposition in the pore structure), the particle size, the specific surface, the pore diameter and the like of the cathode material, thereby providing guiding significance for promoting the commercialization of the hard carbon cathode of the high-energy density sodium ion battery.
Drawings
The invention and its advantageous effects are explained in detail below with reference to the accompanying drawings and the detailed description.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the porous carbon precursor in example 1 of the present invention.
Fig. 2 is a nitrogen (77K) adsorption/desorption curve of the porous carbon precursor in example 1 of the present invention.
FIG. 3 is a pore size distribution curve of the porous carbon precursor in example 1 of the present invention.
Fig. 4 is a nitrogen (77K) adsorption/desorption curve of the hard carbon negative electrode material in example 1 of the present invention.
Fig. 5 is a small angle X-ray scattering curve of the hard carbon negative electrode material in example 1 of the present invention.
Fig. 6 is a first-turn charge-discharge curve of the hard carbon negative electrode material in example 1 of the present invention.
Fig. 7 is a Raman curve of the hard carbon anode material in example 2 of the present invention.
Fig. 8 is a Raman curve of the hard carbon anode material in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention are described below with specific examples, but the scope of the present invention is not limited thereto.
Example 1
The embodiment provides a preparation method of a hard carbon cathode for a high-energy-density sodium-ion battery, wherein the hard carbon cathode comprises porous carbon particles and chemical vapor deposition carbon for adjusting the size of a surface orifice, and a coherent pore channel structure in the porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, grinding microporous activated carbon YP80 to the particle size of 4 mu m to obtain porous carbon powder with rich nanopores inside;
secondly, putting the porous carbon powder in the first step into a tubular furnace, introducing protective gas argon with the flow of 64 mL/min, and heating to the final temperature of 1000 ℃ at the speed of 5 ℃/min;
thirdly, introducing methane gas with the flow rate of 14 mL/min at the final temperature of 1000 ℃ to perform chemical vapor deposition;
and fourthly, after reacting for 4 hours at constant temperature, cutting off methane gas, and cooling to room temperature at a cooling rate of 5 ℃/min to obtain the hard carbon cathode material of the sodium-ion battery.
The SEM image of the milled activated carbon material of example 1 is shown in fig. 1, and it can be seen that: the particle size of the milled activated carbon particles was about 4 μm.
The nitrogen (77K) desorption curve of the milled activated carbon material of example 1 is shown in fig. 2, and it can be seen that: the specific surface area of the activated carbon is 2021 m2/g。
The pore size distribution curve of the milled activated carbon material of example 1 is shown in fig. 3, and it can be seen that: the aperture of the active carbon has micropores and mesopores, and is distributed in the range of 0.5-4 nm.
The nitrogen (77K) adsorption and desorption curve of the hard carbon anode material of the sodium-ion battery provided in example 1 is shown in fig. 4, and it can be seen that: the pore structure of the prepared sodium ion battery cathode material cannot be detected by nitrogen, and the specific surface area is about 0 m2/g。
The small-angle X-ray scattering curve of the hard carbon anode material of the sodium-ion battery provided in example 1 is shown in fig. 5, and it can be seen that: the specific surface area of the prepared sodium-ion battery negative electrode material is 2519 m2And/g, indicating that the pore environment inside the porous material is reserved.
The first-turn charge-discharge curve of the hard carbon negative electrode material of the sodium-ion battery provided in example 1 is shown in fig. 6, and it can be seen that: the prepared hard carbon cathode material of the sodium ion battery has the first coulombic efficiency of 81 percent and the reversible specific capacity of 485 mAh/g, wherein the specific capacity of a low-potential platform is 375 mAh/g.
Example 2
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, microporous Activated Carbon Fiber (ACF) is ground and put into a tube furnace, and after constant temperature reaction for 2 hours, methane gas is cut off; the rest is the same as embodiment 1, and the description is omitted here.
The Raman spectrum of the hard carbon anode of the sodium-ion battery provided in example 2 is shown in fig. 7, and it can be seen that: the prepared sodium ion battery hard carbon cathode material has the same surface phase structure and deposited carbon measured under 325 nm laser, and has the same bulk phase structure and microporous activated carbon fiber measured under 532 nm laser, which indicates that the deposited carbon only covers the particle surface.
Example 3
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, microporous activated carbon CEP21KSN is ground and placed in a tubular furnace, and after reacting for 4 hours at constant temperature, methane gas is cut off; the rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is:
in the preparation method of the hard carbon negative electrode material, the hierarchical pore activated carbon is ground to the particle size of 1 μm, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 5
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the final temperature is 1200 ℃, and the rest is the same as that of the embodiment 1, and the description is omitted.
Example 6
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the protection gas source is nitrogen, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 7
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the protection gas source is hydrogen, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 8
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the carbon-containing element gas source is benzene, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 9
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the protection gas source is ethane, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 10
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the protection gas source is propane, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 11
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the protection gas source is cyclohexane, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 12
The embodiment provides a preparation method of a hard carbon cathode for a high-energy-density sodium-ion battery, wherein the hard carbon cathode comprises template porous carbon particles and chemical vapor deposition carbon for adjusting the size of a surface orifice, and a coherent pore channel structure in the porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, grinding template porous carbon to the particle size of 4 mu m to obtain activated carbon powder with rich nano-pore channels inside;
secondly, putting the activated carbon powder in the first step into a tubular furnace, introducing protective gas argon with the flow of 45 mL/min, and heating to the final temperature of 1100 ℃ at the speed of 4 ℃/min;
thirdly, introducing methane gas with the flow rate of 45 mL/min at the final temperature of 1100 ℃ to perform chemical vapor deposition;
and fourthly, after reacting for 4.5 hours at constant temperature, cutting off methane gas, and cooling to room temperature at a cooling rate of 4 ℃/min to obtain the hard carbon cathode material of the sodium-ion battery.
Example 13
The embodiment provides a preparation method of a hard carbon cathode for a high-energy-density sodium-ion battery, wherein the hard carbon cathode comprises porous graphene and chemical vapor deposition carbon for adjusting the pore size of a surface, and a coherent pore channel structure in porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, grinding porous graphene to the particle size of 4 microns to obtain activated carbon powder with rich nanopores inside;
secondly, putting the activated carbon powder in the first step into a tubular furnace, introducing protective gas argon with the flow of 30 mL/min, and heating to a final temperature of 1150 ℃ at the speed of 3 ℃/min;
thirdly, introducing methane gas with the flow rate of 30 mL/min under the condition of the final temperature of 1150 ℃ to carry out chemical vapor deposition;
fourthly, after 5 hours of constant temperature reaction, cutting off methane gas, and cooling to room temperature at a cooling rate of 3 ℃/min to obtain the hard carbon cathode material of the sodium ion battery
Example 14
The embodiment provides a preparation method of a hard carbon cathode for a high-energy-density sodium-ion battery, wherein the hard carbon cathode comprises porous carbon particles and chemical vapor deposition carbon for adjusting the size of a surface orifice, and a coherent pore channel structure in the porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, mixing and grinding porous carbon and a catalyst (transition metal Cu) to obtain active carbon and catalyst mixed powder with rich nano-pore channels inside;
secondly, putting the mixed powder in the first step into a tubular furnace, introducing protective gas argon with the flow of 64 mL/min, and heating to the final temperature of 1050 ℃ at the speed of 5 ℃/min;
thirdly, introducing methane gas with the flow rate of 14 mL/min under the condition of the final temperature of 1050 ℃ to carry out chemical vapor deposition;
and fourthly, after reacting at constant temperature for 30 min, cutting off methane gas, and cooling to room temperature at a cooling rate of 20 ℃/min to obtain the hard carbon cathode material of the sodium-ion battery.
Example 15
The difference from example 14 is:
in the preparation method of the hard carbon cathode material, the catalyst is noble metal Pt, the constant-temperature reaction time is 15 min, and the rest is the same as that in the embodiment 1, and the description is omitted.
Example 16
The embodiment provides a preparation method of a hard carbon cathode for a high-energy-density sodium-ion battery, wherein the hard carbon cathode comprises porous carbon particles and chemical vapor deposition carbon for adjusting the size of a surface orifice, and a coherent pore channel structure in the porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, grinding microporous activated carbon YP80 to the particle size of 4 mu m to obtain porous carbon powder with rich nanopores inside;
secondly, placing the porous carbon powder in the first step into a microwave reactor, and introducing protective gas argon with the flow rate of 64 mL/min;
thirdly, introducing methane gas with the flow rate of 14 mL/min to carry out chemical vapor deposition;
fourthly, after reacting for 0.1h, cutting off methane gas to obtain the hard carbon cathode material of the sodium ion battery.
Comparative example 1
The difference from example 2 is:
in the preparation method of the hard carbon cathode material, the final temperature is 900 ℃; the rest is the same as embodiment 2, and the description is omitted here.
The Raman spectrum of the hard carbon anode of the sodium ion battery provided in comparative example 1 is shown in fig. 8, and it can be seen that: the surface phase structure of the prepared hard carbon cathode material of the sodium ion battery measured under 325 nm laser and the bulk phase structure measured under 532 nm laser are the same as those of the microporous activated carbon fiber, which shows that carbon deposition extends into the inner holes of the particles.
Comparative example 2
The hard carbon negative electrode comprises porous carbon particles and chemical vapor deposition carbon for adjusting the size of a surface orifice, and a coherent pore channel structure in the porous carbon particles is reserved; the preparation method of the hard carbon negative electrode comprises the following steps:
firstly, simply grinding the microporous activated carbon fiber ACF, wherein the particle size of the microporous activated carbon fiber ACF is about 10 mu m;
secondly, putting the ACF powder in the first step into a tube furnace, introducing protective gas with the flow of 64 mL/min, and heating to the final temperature of 1000 ℃ at the speed of 5 ℃/min;
thirdly, introducing a carbon-containing gas source with the flow rate of 14 mL/min at the final temperature of 1000 ℃ to perform chemical vapor deposition;
and fourthly, after the reaction is carried out for 2 hours at constant temperature, cutting off a carbon-containing gas source, and cooling to room temperature at a cooling rate of 5 ℃/min to obtain the hard carbon cathode material of the sodium-ion battery.
Comparative example 3
The difference from example 2 is:
in the preparation method of the hard carbon cathode material, the microporous activated carbon fiber ACF is ground to the particle size of 4 μm and then put into a tube furnace, and the rest is the same as the embodiment 1, and the details are not repeated.
Comparative example 4
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, porous graphene PGM is ground and placed in a tubular furnace, and after a constant temperature reaction for 10 hours, methane gas is cut off; the rest is the same as embodiment 1, and the description is omitted here.
Comparative example 5
The difference from example 1 is:
in the preparation method of the hard carbon cathode material, the hierarchical pore activated carbon is ground and put into a tube furnace, and after reacting for 2 hours at constant temperature, methane gas is cut off; the rest is the same as embodiment 1, and the description is omitted here.
Comparative example 6
The difference from example 1 is:
the negative electrode material is commercially available hard carbon.
In examples 1 to 16 and comparative examples 1 to 6, the negative electrode conductive additive wasThe Super-P and the negative binder are PVDF, the mass ratio of the active substance to the conductive additive to the binder is 8:1:1, and the negative current collector is copper foil. In the electrolyte, the electrolyte is NaClO4The solvent is a solvent with the volume ratio of 1: EC and DEC of 1, with sodium sheet as the counter electrode, electrochemical performance tests were performed on the batteries of examples 1-16 and comparative examples 1-4 to test the rate capability (1C) and specific mass capacity (0.1C, 50 mA/g) of the electrode composite, and the results are shown in Table 1.
Table 1: test results of examples 1 to 16 and comparative examples 1 to 6.
As can be seen from table 1: the regulation and control of the pore size of the porous carbon are realized by controlling the structure of the carbon-coated particles obtained at the final temperature during the chemical vapor deposition, the specific mass capacity (350-490 mAh/g under 0.1C) and the rate capability (the capacity retention rate is higher than 70% under 1C) of the hard carbon cathode can be remarkably improved, and the chemical vapor deposition time (10-30 min) can be greatly shortened after the catalyst is introduced; the regulation and control result of the particle size shows that the size of the particle size greatly influences the performance of the material, and the superior sodium storage capacity, coulombic efficiency and rate characteristic of the material can be ensured when the particle size is kept to be 4 mu m or below; the pore structure of the precursor is also crucial to the performance of the material, the larger specific surface area can bring about the capacity improvement, and the surface area reaches 1000 m2The performance of the material exceeds that of the commercially available hard carbon when the material is more than g, the influence of the pore size on the rate performance is obvious, and when pores with the size of more than 4 nm appear in the material, the large-current discharge capacity of the hard carbon negative electrode is obviously improved. By adjusting the hard carbon hierarchical structure, including the carbon coating position (only the deposition coating is on the surface of the porous carbon, but not in the porous structure), the particle size, the specific surface of the precursor and the aperture of the precursor, the sodium storage performance of the hard carbon can be further optimized.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a hard carbon negative electrode for a high-energy-density sodium-ion battery is characterized by comprising the following steps: the hard carbon negative electrode comprises porous carbon and chemical vapor deposition carbon for adjusting the size of the surface pore; the hard carbon negative electrode reserves a coherent pore channel structure inside the porous carbon particles; the preparation method of the hard carbon negative electrode at least comprises the following steps:
firstly, grinding a porous carbon precursor to obtain porous carbon powder with proper particle size and rich nanopores inside;
secondly, putting the porous carbon powder into a tubular furnace, introducing protective gas, and heating to a target temperature at a certain heating rate;
thirdly, introducing a carbon-containing gas source, and performing chemical vapor deposition at a target temperature;
and fourthly, reacting for a period of time at constant temperature, closing the carbon-containing element gas source, and reducing the temperature to the room temperature at a certain cooling rate.
2. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: the specific surface of the porous carbon precursor is 500-3800 m2The pore diameter of the porous carbon is 0.5-9 nm.
3. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: the specific surface of the hard carbon negative electrode material is close to 0 m when tested by nitrogen at 77K2(ii)/g; the specific surface area and the pore diameter obtained by a small-angle X-ray scattering test are basically the same as those of the porous carbon precursor.
4. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the first step, the porous carbon precursor is at least one of microporous activated carbon, hierarchical porous activated carbon, template porous carbon, porous graphene and the like.
5. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the second step, the protective gas is at least one of argon, nitrogen and hydrogen.
6. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the second step, the flow rate of the protective gas is 10-100 mL/min, and the heating rate is 0.1-20 ℃/min; the target temperature is 1000-1200 ℃; the tube furnace may be replaced with a microwave reactor.
7. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the third step, the carbon-containing gas source is at least one of methane, ethane, propane, ethylene, acetylene, propyne, benzene, toluene, carbon monoxide and cyclohexane.
8. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: the flow rate of the carbon-containing element gas source is 5-50 mL/min.
9. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the first step, a catalyst is also added, wherein the catalyst is at least one of Fe, Co, Ni, Cu, Au, Ag, Pt and Pb.
10. The method of making a hard carbon anode for a high energy density sodium ion battery of claim 1, wherein: in the fourth step, the duration time of the constant temperature reaction is 0.1-10 h; the cooling rate is 0.1-20 ℃/min.
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