CN112499617B - Preparation method of N and S co-doped hollow carbon nanocube and potassium ion battery - Google Patents
Preparation method of N and S co-doped hollow carbon nanocube and potassium ion battery Download PDFInfo
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- CN112499617B CN112499617B CN202011176376.XA CN202011176376A CN112499617B CN 112499617 B CN112499617 B CN 112499617B CN 202011176376 A CN202011176376 A CN 202011176376A CN 112499617 B CN112499617 B CN 112499617B
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a preparation method of an N and S co-doped hollow carbon nanocube, which comprises the following steps: dissolving citric acid monohydrate, a compound containing N and S and sodium chloride in water, then freeze-drying at-70 to-80 ℃, calcining for 1.5 to 4 hours at 700 to 800 ℃ in an inert atmosphere, cooling to room temperature, washing with water, filtering and drying to obtain the N and S co-doped hollow carbon nanocube. The N and S co-doped hollow carbon nanocubes are used as the negative electrode material of the potassium ion battery, the long-time circulation of the lithium ion battery can be realized under different current densities, the specific capacity is almost not attenuated, and the circulation stability of the potassium ion battery is greatly improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a preparation method of an N and S co-doped hollow carbon nanocube and a potassium ion battery.
Background
In the face of fossil fuel depletion and environmental crisis problems, the need for new and advanced battery technology is pressing. Since 1991, well-known Lithium Ion Batteries (LIBs) have been used in various electronic devices and electric vehicles. However, the widespread use of LIBs is still limited by disadvantages such as insufficient lithium resources and relatively low specific capacity. Sodium Ion Batteries (SIBs) are candidates that have attracted much attention due to their abundant sodium resources and chemical properties similar to lithium. Unfortunately, sodium ions have the disadvantages of large radius and high redox potential making it difficult to intercalate into graphite, making commercial application difficult.Potassium, a more excellent candidate, has a lower redox potential and can be intercalated into graphite, achieving 273mA h g, compared to sodium -1 High specific capacity of (2). In general, Potassium Ion Batteries (PIBs) have the following advantages: i) compared with lithium, the storage capacity is rich, and the cost is lower; ii) K + Are weaker and form smaller solvated ions, and therefore are more prevalent than Li + And Na + The ionic conductivity is better; iii) Al foil can be used as the current collector instead of Cu foil, thereby reducing the cost.
The search for high performance PIBs still relies on rationally designed anode materials, among which carbon materials of various morphologies are popular for their low cost, non-toxic, and harmless advantages. However, due to the large radius of potassium ions, it is difficult to achieve rapid intercalation/deintercalation in carbon materials, resulting in low rate performance, low specific capacity and poor cycle stability.
Disclosure of Invention
Aiming at the problem of poor performance of the potassium ion battery, the invention provides the N and S co-doped hollow carbon nanocube as the negative electrode material of the potassium ion battery, so that the long-time circulation of the potassium ion battery can be realized under different current densities, the specific capacity is almost not attenuated, and the circulation stability of the potassium ion battery is greatly improved.
One purpose of the invention is realized by the following technical scheme:
a preparation method of an N and S co-doped hollow carbon nanocube comprises the following steps:
dissolving citric acid monohydrate, a compound containing N and S and sodium chloride in water, then freeze-drying at-70 to-80 ℃, calcining for 1.5 to 4 hours at 700 to 800 ℃ in an inert atmosphere, cooling to room temperature, washing with water, filtering and drying to obtain the N and S co-doped hollow carbon nanocube.
According to the preparation method of the N and S co-doped hollow carbon nanocube, sodium chloride is used as a template for preparing a hollow cubic structure, citric acid monohydrate is used as a carbon source, and after high-temperature calcination, the citric acid monohydrate is carbonized, and the sodium chloride is removed, so that the hollow carbon nanocube structure is formed. Compared with other carbon sources such as glucose and the like, the citric acid monohydrate can be better compounded with the sodium chloride template and uniformly coated on the sodium chloride template, so that a more uniform hollow carbon nanocube structure is formed, and the improvement of the cycle stability and the specific capacity of the potassium ion battery is facilitated.
The N and S containing compound is preferably one or more of trithiocyanuric acid, thiourea, allylthiourea, L-cysteine and mercaptoethylamine, and more preferably thiourea.
Preferably, the molar ratio of citric acid monohydrate, N-and S-containing compound, sodium chloride is 1: (0.8-1.5): (15-30). Further preferably, the molar ratio of citric acid monohydrate, N-and S-containing compounds, sodium chloride is 1: (1.0-1.3): (20-25). The reasonable proportion of the citric acid monohydrate and the sodium chloride can ensure that the citric acid monohydrate is well coated on the sodium chloride template to form a more uniform and uniform hollow carbon nanocube structure. The proportion of the compound containing N and S is controlled, so that the co-doping amount of N and S on the hollow carbon nanocube is proper, and the improvement of electrochemical properties such as specific capacity of the material is facilitated.
The inert atmosphere during the calcination is preferably one of argon, helium and nitrogen, and the purity is preferably 99.99%.
The other purpose of the invention is realized by the following technical scheme:
the utility model provides a hollow carbon nanocube base potassium ion battery of N and S codope, potassium ion battery includes positive pole, negative pole, diaphragm and electrolyte, the positive pole is metal potassium, the negative pole includes the hollow carbon nanocube of N and S codope that above-mentioned preparation method prepared.
The hollow cubic structure of the N and S co-doped hollow carbon nanocube can relieve volume change caused by an electrochemical reaction process, the stability of the battery is improved, a large number of active sites can be introduced and interlayer spacing can be enlarged by double doping of the N and S to the hollow carbon nanocube, the specific capacity of the material is improved, and the rapid deintercalation of potassium ions is promoted. According to the invention, the N and S co-doped hollow carbon nanocube is used as the negative electrode material of the potassium ion battery, so that the specific capacity and other electrochemical performance parameters of the potassium ion battery can be improved, and the good cycle life of the electrode material can be maintained.
Preferably, the preparation method of the negative electrode of the N and S co-doped hollow carbon nanocube-based potassium ion battery comprises the following steps: and dissolving the N and S co-doped hollow carbon nanocubes, the conductive material and the binder in a mixed solution of water and ethanol, uniformly mixing, coating on a current collector, and drying to obtain the negative electrode.
Preferably, the mass ratio of the N-S co-doped hollow carbon nanocube to the conductive material to the binder is (80-90): (5-10): (5-10).
The conductive material can be common conductive material in the potassium ion battery, such as one or more of acetylene black, conductive carbon black, graphene, carbon nanotubes and carbon fibers. The binder can be a common binder material in the preparation of potassium ion battery electrodes, such as one or a plurality of compounds of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethyl cellulose, polyvinyl alcohol and fluorinated rubber. The current collector is an aluminum foil or a copper foil.
Preferably, the mass ratio of water to ethanol in the mixture of water and ethanol is (3-5): 1; the mass ratio of the mixed liquid of water and ethanol to the N and S co-doped hollow carbon nanocube is preferably (8-12): 1, uniform and viscous slurry can be obtained, so that the loading capacity of the active material of the potassium ion battery can be improved, and the performance of the potassium ion battery is improved.
The higher the load capacity of the N and S co-doped hollow carbon nanocube on a current collector is, the higher the specific capacity of the battery is, but with the increase of the load capacity, the thickness of the electrode becomes thicker, the diffusion of ions becomes slower, and the rate capability becomes lower. Therefore, the load capacity of the N and S co-doped hollow carbon nanocubes on the current collector is controlled to be 0.5-1.2 mg/cm 2 。
Preferably, the separator is a cellulose paper separator. The cellulose paper diaphragm can not deform in the electrochemical reaction process of the potassium ion battery and can not react with electrolyte.
Preferably, the electrolyte is 2-4mol/L of ethylene glycol dimethyl ether (DME) solution of potassium bis (fluorosulfonyl) imide (KFSI). The ethylene glycol dimethyl ether (DME) solution of potassium bis (fluorosulfonyl) imide (KFSI) selected by the invention is beneficial to the transmission of metal cations, and the concentration of 2-4mol/L is beneficial to the formation of a uniform solid electrolyte interface film and the transfer of the metal cations, so that the performance of a potassium ion battery is improved. The preparation of the DME solution containing 2-4mol/L KFSI is carried out in a glove phase, 2-4mol KFSI is dissolved in 1L ethylene glycol dimethyl ether, and the mixture is stirred uniformly.
The N and S co-doped hollow carbon nanocube-based potassium ion battery can be a button potassium ion battery, and the preparation method comprises the following steps:
(1) cutting a metal potassium block to be used as a positive electrode;
(2) dissolving N and S co-doped hollow carbon nanocubes, a conductive material and a binder in a mixed solution of water and ethanol, uniformly mixing, coating on a current collector, and drying to prepare a negative pole piece by using a punching machine;
(3) and then sequentially putting the button cell negative electrode cover, the potassium block, the cellulose paper diaphragm, the electrolyte, the negative electrode, the elastic sheet and the button cell positive electrode cover in sequence for assembly to prepare the button potassium ion cell. The entire assembly process must be carried out in a glove box with water and oxygen content below 0.1ppm, since the electrolyte and metallic potassium are extremely sensitive to water and oxygen, which in turn has a great influence on the performance of the battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the preparation of N and S double-doped and excellent hollow carbon nanocube structure can be successfully realized by freeze-drying and high-temperature calcining citric acid monohydrate, N and S-containing compounds and sodium chloride;
(2) according to the invention, citric acid monohydrate is used as a carbon source, has a better compound degree with sodium chloride, and is uniformly coated on a sodium chloride template, so that a more uniform hollow carbon nanocube structure is formed, and the improvement of the cycle stability and specific capacity of the potassium ion battery is facilitated;
(3) according to the invention, the N and S co-doped hollow carbon nanocube is used as the negative electrode material of the potassium ion battery, so that the specific capacity of the potassium ion battery is improved, the potassium ion battery obtains astonishing ultra-long circulation stability, long circulation of 9 months can be carried out under a small current, and the capacity is not attenuated.
Drawings
Fig. 1 (a) is a Scanning Electron Microscope (SEM) image of the N and S co-doped hollow carbon nanocube prepared in example 1, and fig. 1 (b) is a High Resolution Scanning Electron Microscope (HRSEM) image of the N and S co-doped hollow carbon nanocube prepared in example 1;
fig. 2 (a) is a Transmission Electron Microscope (TEM) image of the N and S co-doped hollow carbon nanocube prepared in example 1, and fig. 2 (b-d) is a High Resolution Transmission Electron Microscope (HRTEM) image of the N and S co-doped hollow carbon nanocube prepared in example 1;
fig. 3 (a) is an X-ray photoelectron spectrum (XPS) of the N and S co-doped hollow carbon nanocube prepared in example 1; FIG. 3 (b-d) is an XPS peak plot of the elements of the N and S co-doped hollow carbon nanocube prepared in example 1;
fig. 4 is a raman spectrum of the N and S co-doped hollow carbon nanocube prepared in example 1;
FIG. 5 is a High Resolution Transmission Electron Microscopy (HRTEM) image of N and S co-doped hollow carbon nanocubes prepared in example 1;
FIG. 6 (a) shows a 2032 type button potassium ion battery constructed from N and S co-doped hollow carbon nanocubes of example 1 at a sweep rate of 0.2mV S -1 Cyclic voltammogram under (b) of fig. 6 is the N and S co-doped hollow carbon nanocubes prepared in example 1 at a current density of 50mA g -1 A constant current charge-discharge curve is obtained;
FIG. 7 shows a 2032 type button potassium ion battery constructed from N and S co-doped hollow carbon nanocubes of example 1 at different current densities (50mA g) -1 To 500mA g -1 Then return to 50mA g -1 ) Multiplying power of (a);
FIG. 8 (a) is a 2032 type potassium ion button cell constructed from N and S co-doped hollow carbon nanocubes of example 1 at a low current density of 50mA g -1 Cycling stability and coulombic efficiency, FIG. 8 (b) shows the N and S co-produced in example 1The doped hollow carbon nanocubes have a high current density of 1000mA g -1 Cyclic stability and coulombic efficiency.
FIG. 9 (a) shows a 2032 type button-type potassium ion battery constructed from the hollow carbon nanocube of comparative example 1 at a low current density of 50mA g -1 Circulation stability and coulombic efficiency, fig. 9 (b) shows that the 2032 type button type potassium ion battery constructed from the hollow carbon nanocube of comparative example 1 has a high current density of 1000mA g -1 Cyclic stability and coulombic efficiency.
FIG. 10 (a) shows a 2032 type button-type potassium ion battery constructed from the nanocarbon material of comparative example 2 at a low current density of 50mA g -1 Circulation stability and coulombic efficiency, fig. 10 (b) shows that the 2032 type button type potassium ion battery constructed from the nanocarbon material of comparative example 2 has a high current density of 1000mA g -1 Cyclic stability and coulombic efficiency.
FIG. 11 (a) is a 2032 type potassium ion button cell constructed from the N and S co-doped hollow carbon nanocubes of comparative example 3 at a low current density of 50mA g -1 Circulation stability and coulombic efficiency, fig. 11 (b) is a 2032 type button type potassium ion battery constructed of the N and S co-doped hollow carbon nanocubes of comparative example 3 at a high current density of 1000mA g -1 Cycling stability and coulombic efficiency.
Detailed Description
The technical solution of the present invention will be further described and explained with reference to the following embodiments and the accompanying drawings. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
The preparation method of the N and S co-doped hollow carbon nanocube of example 1 includes the following steps:
dissolving citric acid monohydrate, thiourea and sodium chloride in deionized water, wherein the molar ratio of the citric acid monohydrate to the thiourea to the sodium chloride is 0.0146:0.017:0.342, and the deionized water is added in an amount such that the concentration of the sodium chloride is 200 g/L. Then, the resulting solution was freeze-dried at-80 ℃, and then transferred to a quartz tube furnace to be calcined at 750 ℃ for 2 hours in an argon atmosphere, followed by natural cooling to room temperature. Subsequently, the produced powder was washed with deionized water to remove excess sodium chloride from the product. And finally, carrying out vacuum filtration on the solution, and drying the filtered solid at 80 ℃ to obtain the N and S co-doped hollow carbon nanocube.
Comparative example 1
Comparative example 1 a hollow carbon nanocube was prepared, the preparation method comprising the steps of:
citric acid monohydrate and sodium chloride are dissolved in deionized water to be uniformly dispersed, the molar ratio of the citric acid monohydrate to the sodium chloride is 0.0146:0.342, and the deionized water is added in an amount to ensure that the concentration of the sodium chloride is 200 g/L. The subsequent experimental steps are the same as those in example 1 and are not described herein.
Comparative example 2
Comparative example 2 a nanocarbon material was prepared, the preparation method comprising the steps of:
dissolving citric acid monohydrate in deionized water, and uniformly dispersing, wherein the addition amount of the deionized water is such that the concentration of the citric acid monohydrate is 30 g/L. Secondly, the obtained solution is frozen and dried at-80 ℃, and then transferred to a quartz tube furnace to be calcined for 2 hours at 750 ℃ in argon atmosphere, and then naturally cooled to room temperature to obtain the nano carbon material.
Comparative example 3
The preparation method of the N and S co-doped hollow carbon nanocube of comparative example 3 includes the following steps:
dissolving glucose, thiourea and sodium chloride in deionized water, uniformly dispersing, wherein the molar ratio of the glucose to the thiourea to the sodium chloride is 0.0146:0.017:0.342, and the addition amount of the deionized water is such that the concentration of the sodium chloride is 200 g/L. The subsequent experimental steps are the same as those in example 1 and are not described herein.
Fig. 1 (a) is a Scanning Electron Microscope (SEM) image of the N and S co-doped hollow carbon nanocubes prepared in example 1, and fig. 1 (b) is a High Resolution Scanning Electron Microscope (HRSEM) image of the N and S co-doped hollow carbon nanocubes prepared in example 1, indicating that the prepared carbon material has a hollow cubic nanostructure and mass synthesis of the structure can be achieved.
Fig. 2 (a-d) are Transmission Electron Microscope (TEM) images of N and S co-doped hollow carbon nanocubes prepared in example 1, further showing that example 1 prepares hollow carbon nanocubes and the hollow carbon nanocubes are uniformly distributed.
Fig. 3 (a) is an X-ray photoelectron spectrum (XPS) of the N and S co-doped hollow carbon nanocube prepared in example 1, indicating successful doping of N and S into the hollow carbon nanocube. Fig. 3 (b-d) is an XPS peak chart of each element of the N and S co-doped hollow carbon nanocube prepared in example 1, and further shows that the prepared carbon material contains N and S, and nitrogen mainly exists in the form of pyridine N and pyrrole N, which introduces a large number of active sites to the carbon nanomaterial and increases the specific capacity of the potassium ion battery.
FIG. 4 is a Raman spectrum of N and S co-doped hollow carbon nanocubes prepared in example 1, I D /I G Values greater than 1 are sufficient to illustrate that co-doping of N and S introduces many active sites and defects.
Fig. 5 is a high-resolution transmission electron microscope (HRTEM) image of the N and S co-doped hollow carbon nanocube prepared in example 1, which fully illustrates that co-doping of N and S can expand the interlayer spacing (the interlayer spacing of undoped N and S is 0.3637nm), and expansion of the interlayer spacing of the carbon material is beneficial to de-intercalation of potassium ions in the electrochemical reaction process, so that change of volume can be alleviated, the structure is prevented from being damaged, and further, the cycle stability of the potassium ion battery can be improved.
The N and S co-doped hollow carbon nanocube prepared in example 1 is used as a negative electrode material to construct a 2032 type button potassium ion battery, and the preparation method of the 2032 type button potassium ion battery comprises the following steps:
(1) cutting a metal potassium block to be used as a positive electrode;
(2) dissolving N and S co-doped hollow carbon nanocubes, acetylene black and sodium carboxymethylcellulose in a mass ratio of 8:1:1 in a mixed solution of deionized water and ethanol (the mass ratio of water to ethanol in the mixture of water and ethanol is 4: 1), and mixing the mixed solution of water and ethanol with the N and S co-doped hollow carbon nanocubesThe mass ratio of the rice cubes is 10: 1, uniformly mixing and coating the mixture on a copper foil, wherein the loading capacity of the N and S co-doped hollow carbon nanocube on the copper foil is 0.8mg/cm 2 After drying, preparing a round pole piece with the diameter of 12mm as a negative pole by using a punching machine;
(3) and then sequentially putting a button cell negative electrode cover, a potassium block, a cellulose paper diaphragm, 3mol/L of ethylene glycol dimethyl ether solution of potassium bifluoride sulfimide, a negative electrode circular pole piece, an elastic piece and a button cell positive electrode cover in sequence for assembly to prepare the button potassium ion cell, wherein 40 microliter of the 3mol/L ethylene glycol dimethyl ether solution of the potassium bifluoride sulfimide is taken as electrolyte for each button cell. The entire assembly process must be carried out in a glove box with water and oxygen content below 0.1 ppm.
And simultaneously, respectively using the hollow carbon nanocube in the comparative example 1, the nanocarbon material in the comparative example 2 and the N and S co-doped hollow carbon nanocube in the comparative example 3 as cathode materials to construct a 2032 type button type potassium ion battery, wherein the preparation method of the button type potassium ion battery is the same as that of the cathode materials.
The electrochemical performance of the type 2032 button type potassium ion battery constructed in example 1 and comparative examples 1-3 was tested at room temperature. FIG. 6 (a) is a 2032 type potassium ion button cell constructed from the N and S co-doped hollow carbon nanocubes of example 1 at a sweep rate of 0.2mV S -1 Cyclic voltammogram under, fig. 6 (b) is a 2032 type button type potassium ion battery constructed from the N and S co-doped hollow carbon nanocubes of example 1 at a current density of 50mA g -1 The first curve is different from the later curves because irreversible boundary reaction occurs for the first time and a stable solid electrolyte interface film is generated, and the later curves are basically superposed to show that the battery has good cycling stability. FIG. 7 shows a 2032 type button potassium ion battery constructed from N and S co-doped hollow carbon nanocubes of example 1 at different current densities (50mA g) -1 To 500mA g -1 Then return to 50mA g -1 ) No matter the current density, the specific capacity of the battery is very stable, which shows that the battery hasThe electrode material has good cycling stability, and when the current density returns to the low current density from the high current density again, the battery can still carry out long cycling for 9 months without obvious capacity attenuation, which fully shows that the electrode material has good electrochemical stability and can adapt to different current changes. FIG. 8 (a) shows a 2032 type button potassium ion battery constructed of N and S co-doped hollow carbon nanocubes of example 1 at a low current density of 50mA g -1 Cyclic stability and coulombic efficiency, fig. 8 (b) is a 2032 type button type potassium ion battery constructed of the N and S co-doped hollow carbon nanocubes of example 1 at a high current density of 1000mA g -1 The circulation stability and the coulombic efficiency of the prepared potassium ion battery can fully show that the prepared potassium ion battery can realize super-strong circulation stability under the conditions of large current density and small current density, the retention rate of specific capacity reaches 99.9 percent, and the potassium ion battery can stably circulate for 9 months (50mA g) especially under the condition of small current density -1 The time for 600 cycles is about 9 months), which is the potassium ion battery with the best cycle life at the low current density reported so far.
FIG. 9 (a) is a 2032 type button potassium ion battery constructed from the hollow carbon nanocube of comparative example 1 at a low current density of 50mA g -1 Circulation stability and coulombic efficiency, fig. 9 (b) shows that the 2032 type button type potassium ion battery constructed from the hollow carbon nanocube of comparative example 1 has a high current density of 1000mA g -1 Cycling stability and coulombic efficiency. In the preparation process of the hollow carbon nanocube of the comparative example 1, thiourea is not added, so that the specific capacity of the constructed 2032 type button type potassium ion battery is reduced, because N and S doping brought by the thiourea introduces a plurality of active sites and defects, and the specific capacity of the potassium ion battery can be improved.
FIG. 10 (a) shows a 2032 type button-type potassium ion battery constructed from the nanocarbon material of comparative example 2 at a low current density of 50mA g -1 Circulation stability and coulombic efficiency, fig. 10 (b) shows that the 2032 type button type potassium ion battery constructed from the nanocarbon material of comparative example 2 has a high current density of 1000mA g -1 Cyclic stability and coulombic efficiency.The nano carbon material prepared in the comparative example 2 lacks N and S co-doping and an excellent hollow cubic structure, so that the specific capacity of the potassium ion battery is sharply attenuated, and the cycling stability is poor.
FIG. 11 (a) is a 2032 type potassium ion button cell constructed from the N and S co-doped hollow carbon nanocubes of comparative example 3 at a low current density of 50mA g -1 (b) of fig. 11 is a 2032 type button type potassium ion battery constructed of the N and S co-doped hollow carbon nanocube of comparative example 3 at a high current density of 1000mA g -1 Cyclic stability and coulombic efficiency. Comparative example 3 adopts glucose as a carbon source, and the degree of the combination of the glucose and sodium chloride is not as good as that of citric acid monohydrate and sodium chloride, so that the glucose is not uniformly coated on a sodium chloride template to form an inhomogeneous hollow carbon nanocube structure, and the specific capacity and the cycling stability of the potassium ion battery constructed in comparative example 3 are reduced.
The specific embodiments described herein are merely illustrative of the spirit of the invention and do not limit the scope of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of an N and S co-doped hollow carbon nanocube is characterized by comprising the following steps:
dissolving citric acid monohydrate, thiourea and sodium chloride in water, wherein the molar ratio of the citric acid monohydrate to the thiourea to the sodium chloride is 0.0146:0.017:0.342, wherein the concentration of the sodium chloride is 200g/L, freeze-drying the obtained solution at-80 ℃, calcining the solution at 750 ℃ for 2h in an argon atmosphere, cooling to room temperature, washing with water, vacuum-filtering to obtain a solid, and finally drying at 80 ℃ to obtain the N and S co-doped hollow carbon nanocube.
2. An N and S co-doped hollow carbon nanocube-based potassium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is metal potassium, and the negative electrode comprises the N and S co-doped hollow carbon nanocube prepared by the preparation method of claim 1.
3. The N and S co-doped hollow carbon nanocube-based potassium ion battery according to claim 2, wherein the preparation method of the negative electrode comprises the following steps: and dissolving the N and S co-doped hollow carbon nanocubes, the conductive material and the binder in a mixed solution of water and ethanol, uniformly mixing, coating on a current collector, and drying to obtain the negative electrode.
4. The N and S co-doped hollow carbon nanocube-based potassium ion battery according to claim 3, wherein the mass ratio of the N and S co-doped hollow carbon nanocube to the conductive material to the binder is (80-90): (5-10): (5-10).
5. The N and S co-doped hollow carbon nanocube-based potassium ion battery according to claim 3, wherein the mass ratio of water to ethanol in the mixture of water and ethanol is (3-5): 1, the mass ratio of the mixed liquid of water and ethanol to the N and S co-doped hollow carbon nanocube is (8-12): 1.
6. the N and S co-doped hollow carbon nanocube-based potassium ion battery according to claim 3, wherein the loading amount of the N and S co-doped hollow carbon nanocube on the current collector is 0.5-1.2 mg/cm 2 。
7. The N and S co-doped hollow carbon nanocube-based potassium ion battery according to claim 2, wherein the membrane is a cellulose paper membrane.
8. The N and S co-doped hollow carbon nanocube-based potassium ion battery of claim 2, wherein the electrolyte is 2-4mol/L of ethylene glycol dimethyl ether solution of potassium bis-fluorosulfonylimide.
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