CN118461309B - A method for preparing a carbon-based negative electrode material for a sodium ion battery - Google Patents
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Abstract
本发明公开一种钠离子电池用碳基负极材料的制备方法，属于电池及电池材料技术领域。首先，本发明采用N、P对氧化石墨烯进行共掺杂改性，材料界面稳定性更好，阻抗更低；其次，本发明将复合碳纤维和改性石墨烯等比例混合后进行高效球磨，有效的抑制了石墨烯的层状结构的堆叠和塌陷，提供了快速的钠传输路径，负极材料电化学性能得到明显提升。使用本发明负极材料制备得到的钠离子电池首次充放电循环后的比容量在700mAh/g以上（0.1A/g），循环1000圈后，容量保持率在90%以上，电化学性能得到有效提升。
The present invention discloses a method for preparing a carbon-based negative electrode material for a sodium ion battery, and belongs to the technical field of batteries and battery materials. First, the present invention adopts N and P to co-dope and modify graphene oxide, and the material interface stability is better and the impedance is lower; secondly, the present invention mixes the composite carbon fiber and the modified graphene in equal proportions and then conducts efficient ball milling, which effectively inhibits the stacking and collapse of the layered structure of the graphene, provides a fast sodium transmission path, and significantly improves the electrochemical performance of the negative electrode material. The specific capacity of the sodium ion battery prepared using the negative electrode material of the present invention after the first charge and discharge cycle is above 700mAh/g (0.1A/g), and after 1000 cycles, the capacity retention rate is above 90%, and the electrochemical performance is effectively improved.
Description
Technical Field
The invention belongs to the technical field of batteries and battery materials, and particularly relates to a preparation method of a carbon-based negative electrode material for a sodium ion battery.
Background
Electrochemical energy storage is considered to be an efficient energy storage technology because of its high energy conversion efficiency, relatively compact size, and fast response speed. However, due to the progressive lack of lithium resources, lithium Ion Batteries (LIBs), which are prominent in electrochemical energy storage, are urgently needed to find new generation energy storage batteries that can take over their position. Sodium has the advantages of abundant resources, low cost, environmental friendliness and the like, and is therefore paid attention to by researchers.
The negative electrode materials of sodium ion batteries are various, and currently mainly comprise carbon-based materials, titanium-based materials, alloy materials, organic materials and the like, wherein the carbon-based materials are considered as candidate materials with the most application prospect due to easy availability and low cost. The carbon-based material mainly comprises crystalline carbon and amorphous carbon, the crystalline carbon is natural graphite and artificial graphite, and the lithium ion battery mainly adopts the negative electrode material of the type. However, when graphite is used as the negative electrode of a sodium ion battery, intercalation of sodium ions cannot be realized, the specific capacity is too low, and the requirements cannot be met. Amorphous carbon materials mainly include both hard carbon and soft carbon types. The hard carbon has higher initial discharge capacity, good multiplying power performance and structural stability, has certain electrochemical performance advantages, and is the first choice of the anode material at present.
However, the existing hard carbon material has the defects of higher cost, high price, low first effect, poor cycle stability and the like.
For example, chinese patent application CN202210872497.0 discloses a negative electrode material of a sodium ion battery, a pole piece and a sodium ion battery, wherein the negative electrode material comprises a negative electrode main material, a conductive agent and a binder, the mass ratio of the negative electrode main material to the conductive agent to the binder is 100 (1-5): (1-5), the negative electrode main material comprises a mixture of at least two of graphite, soft carbon and hard carbon, and the mass ratio of the graphite, the soft carbon and the hard carbon is 0-5): (0-15): (80-98).
The method uses hard carbon as a main negative electrode material, and is doped with partial soft carbon and graphene so as to overcome the defect of the hard carbon material. However, the battery performance of the prepared battery is not obviously improved, and the inherent defects of the existing hard carbon negative electrode can not be effectively overcome by simple doping.
Therefore, the new material is continuously explored and the new morphology structure is built, so that the negative electrode material with high energy density and good cycle performance is obtained, and the method is one of the key research directions of the current negative electrode material of the sodium ion battery.
Disclosure of Invention
Aiming at the problems in the prior art, the novel carbon anode material with an interpenetrating network structure is obtained through element doping and high-efficiency ball milling, the three-dimensional structure of the novel carbon anode material effectively solves stacking and collapse of graphene, and simultaneously provides a rapid transmission path for sodium ions, so that the capacity performance and the cycle performance of the battery are effectively improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 100-200mg of graphene oxide in 100-200mL of deionized water, and carrying out ultrasonic treatment for 1-2 hours to obtain graphene dispersion liquid;
(2) Adding a modifier with the same mass as graphene oxide into graphene dispersion liquid, performing ultrasonic dispersion for 10-20min, mixing uniformly, then placing the mixture into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 2-5 ℃ per min under nitrogen or argon atmosphere, and keeping for 2h, and naturally cooling to obtain modified graphene;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 10-12 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 10-15%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a modified graphene-carbon fiber composite material;
(5) And after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
Further, the modifier in the step (2) is obtained by mixing urea and ammonium dihydrogen phosphate according to a mass ratio of 1:1.
Further, the average particle size of the nano silicon dioxide in the step (2) is 20-30nm, and the addition amount is 1% of the mass of the polyacrylonitrile.
Further, the organic solvent in the step (3) is one or more of N, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylacetamide.
The electrostatic spinning parameters of the step (3) are that the spinning voltage is 15-30KV, the advancing speed is 1-2 mL/h, the receiving distance is 10-18cm, water bath is adopted for receiving, the oxidation and carbonization method comprises the steps of placing the dried composite fiber into an alumina porcelain boat, placing the alumina porcelain boat into a tubular furnace, introducing oxygen into the tubular furnace, heating to 280 ℃ at the heating rate of 1 ℃ per minute, keeping the temperature constant for 2h, naturally cooling to obtain an oxidized product, introducing protective gas nitrogen into the tubular furnace, heating to 650 ℃ from room temperature at the heating rate of 1 ℃ per minute, heating to 1000 ℃ at the heating rate of 3 ℃ per minute, preserving heat for 30min, naturally cooling in the protective gas, and grinding to obtain the composite carbon fiber.
The high-energy ball milling treatment method in the step (4) comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, putting the mixture and the grinding balls into a grinding tank together, charging 1-5bar of nitrogen or argon for protection, wherein the ball-material ratio is (20-30): 1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward and reverse rotation for 5 minutes, then stopping for 1 minute and then reversing for 5 minutes to form a period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 100-200 rotations per minute.
Furthermore, the grinding pot and the grinding balls are made of agate.
Further, the drying temperature in the step (5) is 50-100 ℃ and the drying time is 5-10h.
The raw materials of the invention are all commercially available.
The beneficial effects are that:
(1) Firstly, the invention adopts N, P to carry out co-doping modification on graphene oxide, and doping N and P elements, and after the two elements are mixed in equal proportion, the synergistic effect is achieved, on one hand, the interlayer spacing can be improved, the diffusion of sodium ions can be promoted, on the other hand, more defect sites can be generated, the adsorption capacity can be increased, the electronic conductivity of the material can be improved, the interface stability of the material is better, and the impedance is lower;
(2) Secondly, the composite carbon fiber and the modified graphene are mixed in equal proportion and then subjected to high-efficiency ball milling, a proper amount of carbon fiber and the modified graphene are combined, and the low-speed ball milling is carried out through forward and reverse alternation, so that the carbon fiber effectively breaks up the lamellar structure of the graphene to realize conversion from a two-dimensional structure to a three-dimensional structure of the graphene, thereby effectively inhibiting stacking and collapse of the lamellar structure of the graphene, providing a rapid sodium transmission path, greatly increasing the specific surface area of the carbon material, greatly enhancing the wettability of the carbon material to electrolyte, and greatly improving the electrochemical performance of the cathode material;
(3) Finally, the specific capacity of the sodium ion battery prepared by using the negative electrode material is more than 700mAh/g (0.1A/g) after the first charge and discharge cycle, the capacity retention rate is more than 90% after 1000 cycles of cycle, and the electrochemical performance is effectively improved.
Drawings
FIG. 1 is a first-turn charge-discharge curve of a negative electrode material according to embodiment 3 of the present invention;
FIG. 2 is a scanning electron micrograph of the negative electrode material obtained in example 3 and comparative examples 4 to 6 of the present invention, in which the scale size is 10. Mu.m;
FIG. 3 is a graph showing the cycle performance of a sodium ion battery obtained from the negative electrode material obtained in example 3 of the present invention;
FIG. 4 shows the AC impedance spectra of the electrode materials of example 3 and comparative examples 1-3 of the present invention.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 100mg of graphene oxide in 200mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain graphene dispersion liquid;
(2) Adding a modifier with the same mass as graphene oxide into graphene dispersion liquid, carrying out ultrasonic dispersion for 10min, mixing uniformly, then placing the mixture into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 2 ℃ per min under nitrogen or argon atmosphere, and keeping for 2h, and naturally cooling to obtain modified graphene;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 10 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 10%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a modified graphene-carbon fiber composite material;
(5) And after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
The modifier is obtained by mixing urea and ammonium dihydrogen phosphate according to a mass ratio of 1:1.
The average particle diameter of the nano silicon dioxide in the step (2) is 20-30nm, and the addition amount is 1% of the mass of the polyacrylonitrile.
The organic solvent in the step (3) is N, N-dimethylformamide.
The electrostatic spinning parameters of the step (3) are that the spinning voltage is 15KV, the advancing speed is 1mL/h, the receiving distance is 10cm, water bath is adopted for receiving, the method of oxidization and carbonization comprises the steps of placing the dried composite fiber into an alumina porcelain boat, then placing the alumina porcelain boat into a tubular furnace, introducing oxygen into the tubular furnace, heating to 280 ℃ at the heating rate of 1 ℃ per minute, keeping the temperature for 2h, naturally cooling to obtain an oxidized product, introducing protective gas nitrogen into the tubular furnace, heating to 650 ℃ from room temperature at the heating rate of 1 ℃ per minute, heating to 1000 ℃ at the heating rate of 3 ℃ per minute, preserving heat for 30min, naturally cooling in the protective gas, and grinding to obtain the composite carbon fiber.
The high-energy ball milling treatment method in the step (4) comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, putting the mixture and the grinding balls into a grinding tank together, charging 1bar of nitrogen or argon for protection, wherein the ball material ratio is 20:1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward rotation for 5 minutes, then stopping for 1 minute, and then reversing for 5 minutes to be a period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 100 revolutions per minute.
The grinding pot and the grinding ball are made of agate.
And (5) drying at 50 ℃ for 10 hours.
Example 2
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 150mg of graphene oxide in 100mL of deionized water, and carrying out ultrasonic treatment for 1.5 hours to obtain graphene dispersion liquid;
(2) Adding a modifier with the same mass as graphene oxide into graphene dispersion liquid, carrying out ultrasonic dispersion for 20min, mixing uniformly, then placing the mixture into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 3 ℃ per min under nitrogen or argon atmosphere, and keeping for 2h, and naturally cooling to obtain modified graphene;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 10 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 13%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a modified graphene-carbon fiber composite material;
(5) And after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
The modifier is obtained by mixing urea and ammonium dihydrogen phosphate according to a mass ratio of 1:1.
The average particle diameter of the nano silicon dioxide in the step (2) is 20-30nm, and the addition amount is 1% of the mass of the polyacrylonitrile.
The organic solvent in the step (3) is dimethyl sulfoxide.
The electrostatic spinning parameters of the step (3) are that the spinning voltage is 20KV, the advancing speed is 1mL/h, the receiving distance is 15cm, water bath is adopted for receiving, the method of oxidization and carbonization comprises the steps of placing the dried composite fiber into an alumina porcelain boat, then placing the alumina porcelain boat into a tubular furnace, introducing oxygen into the tubular furnace, heating to 280 ℃ at the heating rate of 1 ℃ per minute, keeping the temperature for 2h, naturally cooling to obtain an oxidized product, introducing protective gas nitrogen into the tubular furnace, heating to 650 ℃ from room temperature at the heating rate of 1 ℃ per minute, heating to 1000 ℃ at the heating rate of 3 ℃ per minute, preserving heat for 30min, naturally cooling in the protective gas, and grinding to obtain the composite carbon fiber.
The high-energy ball milling treatment method in the step (4) comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, putting the mixture and the grinding balls into a grinding tank together, charging 3bar of nitrogen or argon for protection, wherein the ball material ratio is 25:1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward rotation for 5 minutes, then stopping for 1 minute, and then reversing for 5 minutes to be a period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 100 revolutions per minute.
The grinding pot and the grinding ball are made of agate.
And (5) drying at 100 ℃ for 5 hours.
Example 3
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 200mg of graphene oxide in 120mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain graphene dispersion liquid;
(2) Adding a modifier with the same mass as graphene oxide into graphene dispersion liquid, carrying out ultrasonic dispersion for 20min, mixing uniformly, then placing the mixture into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 5 ℃ per min under nitrogen or argon atmosphere, and keeping for 2h, and naturally cooling to obtain modified graphene;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 12 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 15%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a modified graphene-carbon fiber composite material;
(5) And after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
The modifier is obtained by mixing urea and ammonium dihydrogen phosphate according to a mass ratio of 1:1.
The organic solvent in the step (3) is N, N-dimethylacetamide.
The average particle diameter of the nano silicon dioxide in the step (2) is 20-30nm, and the addition amount is 1% of the mass of the polyacrylonitrile.
The electrostatic spinning parameters of the step (3) are that the spinning voltage is 30KV, the advancing speed is 2mL/h, the receiving distance is 18cm, water bath is adopted for receiving, the method of oxidization and carbonization comprises the steps of placing the dried composite fiber into an alumina porcelain boat, then placing the alumina porcelain boat into a tubular furnace, introducing oxygen into the tubular furnace, heating to 280 ℃ at the heating rate of 1 ℃ per minute, keeping the temperature for 2h, naturally cooling to obtain an oxidized product, introducing protective gas nitrogen into the tubular furnace, heating to 650 ℃ from room temperature at the heating rate of 1 ℃ per minute, heating to 1000 ℃ at the heating rate of 3 ℃ per minute, preserving heat for 30min, naturally cooling in the protective gas, and grinding to obtain the composite carbon fiber.
The high-energy ball milling treatment method in the step (4) comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, putting the mixture and the grinding balls into a grinding tank together, charging 5bar of nitrogen or argon for protection, wherein the ball material ratio is 30:1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward rotation for 5 minutes, then stopping for 1 minute, and then reversing for 5 minutes to be a period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 200 revolutions per minute.
The grinding pot and the grinding ball are made of agate.
And (5) drying at 80 ℃ for 8 hours.
Comparative example 1
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 200mg of graphene oxide in 120mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain graphene dispersion liquid;
(2) Adding a modifier with the same mass as graphene oxide into graphene dispersion liquid, carrying out ultrasonic dispersion for 20min, mixing uniformly, then placing the mixture into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 5 ℃ per min under nitrogen or argon atmosphere, and keeping for 2h, and naturally cooling to obtain modified graphene;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 12 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 15%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a modified graphene-carbon fiber composite material;
(5) And after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
The modifier is urea.
In this comparative example, the procedure of example 3 was followed except that only urea was used as the modifier.
Comparative example 2
In this comparative example, the procedure of example 3 was followed except that only monoammonium phosphate was used as the modifier.
Comparative example 3
The preparation method of the carbon-based negative electrode material for the sodium ion battery comprises the following preparation steps:
(1) Dispersing 200mg of graphene oxide in 120mL of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain graphene dispersion liquid;
(2) Placing the graphene dispersion liquid into a crucible, then placing the crucible into a muffle furnace, heating to 1050-1100 ℃ at a heating rate of 5 ℃ per minute under nitrogen or argon atmosphere, and keeping for 2 hours, and obtaining graphene subjected to high-temperature treatment after natural cooling;
(3) Dissolving polyacrylonitrile in an organic solvent, magnetically stirring for 12 hours at 50-60 ℃ to obtain a polyacrylonitrile spinning solution with the mass fraction of 15%, pumping the spinning solution into a syringe, and preparing composite fibers by an electrostatic spinning method;
(4) Mixing the composite carbon fiber and the graphene obtained in the step (2) according to the mass ratio of 1:1, and then adding the mixture into a ball milling tank for high-energy ball milling treatment to obtain a graphene-carbon fiber composite material;
and after ball milling is finished, cooling the modified graphene-carbon fiber composite material to room temperature, and drying to finally obtain a powdery final product.
In this comparative example, the raw materials and the preparation method were the same as in example 3, except that the modification treatment of graphene was not performed.
Comparative example 4
This comparative example was the same as example 3 except that the composition ratio of the composite carbon fiber and the modified graphene was changed.
The high-energy ball milling treatment method comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 2:1, putting the mixture and the grinding balls into a grinding tank, filling 5bar of nitrogen or argon for protection, wherein the ball-material ratio is 30:1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward and reverse rotation for 5 minutes, then stop for 1 minute and reverse rotation for 5 minutes for one period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 200 revolutions per minute.
Comparative example 5
This comparative example was the same as example 3 except that the composition ratio of the composite carbon fiber and the modified graphene was changed.
The high-energy ball milling treatment method comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:2, putting the mixture and the grinding balls into a grinding tank, filling 5bar of nitrogen or argon for protection, wherein the ball-material ratio is 30:1, the ball milling process adopts a forward and reverse rotation mode, the forward and reverse rotation mode is set to be forward and reverse rotation for 5 minutes, then stop for 1 minute and reverse rotation for 5 minutes for one period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 500 rotations per minute.
Comparative example 6
The comparative example was conducted in the same manner as in example 3 except that the ball milling was conducted in a single direction.
The high-energy ball milling treatment method comprises the steps of mixing the composite carbon fiber and the modified graphene according to the mass ratio of 1:1, putting the mixture and the grinding ball into a grinding tank, filling 5bar of nitrogen or argon for protection, wherein the ball-material ratio is 30:1, the ball milling process adopts a forward rotation mode, the forward rotation mode is set to be forward rotation for 5 minutes, then stopping for 1 minute, and then stopping forward rotation for 5 minutes for one period, the ball milling process is operated for 30 periods, and the revolution of the ball mill is 200 revolutions per minute.
Performance testing
Material morphology the material morphology was characterized analytically using a SU8010 cold field emission Scanning Electron Microscope (SEM) from hitachi.
Battery assembly the negative electrode materials obtained in the examples and comparative examples were used as experimental samples, respectively, and batteries were prepared for performance testing. The cathode material is taken as an active substance, mixed and ground with conductive agent acetylene black and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1 to prepare slurry, uniformly coated on a current collector copper foil, and vacuum-dried for 12 hours at 120 ℃ to prepare the working electrode.
An electrochemical experiment was performed using a standard CR2032 type cell with pure sodium metal sheet as the counter electrode and glass fiber as the separator, and the electrolyte was 1mol/L sodium hexafluorophosphate dissolved in a mixture of ethylene carbonate and dimethyl carbonate (volume ratio 1:1). The cells were aged for 12 hours prior to electrochemical testing. And adopting a CT2001 blue battery test system to perform constant current charge and discharge tests at different current densities in a voltage window of 0.01-3.00V. Electrochemical Impedance Spectroscopy (EIS) was measured using the same electrochemical workstation by applying an alternating voltage with an amplitude of 10mV in the frequency range of 100kHz-100 MHz.
TABLE 1 Performance test results
From the data in table 1, we can also see that the anode material of the embodiment of the invention has good specific capacity and cycle performance, because the carbon fiber and the graphene are mixed in proper proportion, and the carbon fiber and the graphene are fully combined by combining a positive and negative combination high-efficiency ball milling mode, the carbon fiber plays a role in supporting the lamellar structure of the graphene, the formed three-dimensional structure effectively relieves the stacking and collapse of the lamellar structure of the graphene, and provides a rapid sodium transmission path, and meanwhile, the co-doping of N, P can generate more defect sites and increase adsorption capacity due to interaction of the two, so that the interface stability is good, and the impedance of the material is reduced macroscopically, and the electrochemical performance is improved. While comparative examples 1-6, in which the process parameters were changed, exhibited significant impairment of both capacity and cycle performance. Comparative examples 1-3, in which the doping of the element was changed, did not significantly affect the microstructure, and more so, the surface properties of the material were affected, and the lack of N, P doped anode material resulted in an increase in charge transfer resistance and a decrease in interfacial stability, thereby resulting in a decrease in electrochemical properties of the material (see fig. 4). In comparative examples 4 to 6, in which the composition of the graphene of carbon fiber and the ball milling method were changed, the improvement effect of the carbon fiber on the lamellar structure of graphene was reduced, and an effective supporting effect could not be achieved, thus resulting in a reduction in the material performance (as shown in fig. 2).
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
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