CN111933893A - Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof - Google Patents

Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof Download PDF

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CN111933893A
CN111933893A CN202010734786.5A CN202010734786A CN111933893A CN 111933893 A CN111933893 A CN 111933893A CN 202010734786 A CN202010734786 A CN 202010734786A CN 111933893 A CN111933893 A CN 111933893A
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graphene oxide
sodium
reduced graphene
tin
tin phosphide
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CN111933893B (en
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马越
白苗
汤晓宇
刘瑜婕
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Northwestern Polytechnical University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and a preparation method thereof, and reduced graphene oxide and tin phosphide. The reduced graphene oxide substrate with the three-dimensional structure effectively reduces the current density of the electrode and inhibits the generation of dendritic crystals; the contact area of the metal sodium is increased, the deposited metal sodium can be attached to the surface of the metal sodium and in front of the sheet layer, the deposition of the sodium can be accommodated, the generation of dead sodium is reduced, and the volume change of the sodium metal cathode in the charge-discharge cycle process is slowed down; the tin phosphide as a sodium-philic material can be used as a sodium deposition site, so that sodium ions are effectively dispersed, ion accumulation is reduced, and the possibility of forming sodium dendrites is reduced; compared with a pure metal lithium/sodium metal cathode, the lithium/sodium metal cathode has better circulation stability and more stable voltage distribution curve; the battery can be applied to flexible energy storage devices, and the safety performance of the battery is high after the battery is applied to a sodium metal battery; the preparation method of the silicon flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode is simple and easy to implement.

Description

Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochemical energy materials, and relates to a flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and a preparation method thereof.
Background
The traditional fossil fuel produces a large amount of harmful gas and smoke dust in the combustion, which not only seriously affects the natural environment and social environment, but also poses great threat to the living environment of human beings. Therefore, it is urgent to develop renewable clean energy. The sodium metal cathode has higher specific capacity (1166mA h g)-1) And a lower redox potential (-2.714V), is a high energy density battery (e.g.: Na-O2Na — S cell). However, in the battery cycling process, because of uneven deposition, dendritic crystal is easily formed at an interface position, and along with the growth of the dendritic crystal, a diaphragm can be punctured, and then short circuit is caused to cause explosion hazard, on the other hand, a solid electrolyte interface film (SEI film) on the surface of a negative electrode can be damaged, so that exposed metal sodium reacts with an electrolyte, so that the utilization rate of the electrode is reduced, and due to the characteristic of a skeleton-free structure of the metal sodium, in the charging and discharging processes, the volume expansion is large, the stability of the electrode is seriously damaged, the SEI film is broken, the coulomb efficiency is reduced, the overpotential is increased, meanwhile, because of the poor chemical stability of the sodium metal, the binding energy is low, so that the processing difficulty is caused, and the problems provide great challenges for commercialization of the.
In order to solve the dendrite problem of metallic sodium, researchers have proposed various solutions. For example, sodium tablets coated with a chemically inert protective layer (e.g., Al)2O3) (ii) a Modifying the electrolyte (e.g., by using a new electrolyte salt, or by using a solid/gel polymer electrolyte, or by introducing electrolyte additives, etc.). Although performance may be improved to some extent by the above methods, the inherent dendrite formation resulting from non-uniform nucleation of sodium metal is still inherent, the suppression of dendrites during long-term cycling is still not adequately addressed, and needlesThe problem of volume expansion caused by the no-framework structure of the sodium metal cathode is not effectively solved. Another scholars proposed that metallic sodium be encapsulated with hard carbon for suppressing the volume expansion during sodium metal cycling, but hard carbon does not have excellent flexibility and thus the effect is not significant. Therefore, if the dendritic growth of the negative electrode of the sodium metal battery is inhibited, the problem of volume expansion is solved, and the method has very important significance for the development of the sodium metal battery.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides the flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and the preparation method thereof, and the flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode can effectively inhibit the generation of sodium dendrite and improve the cycle stability; the preparation method is simple and easy to implement.
Technical scheme
A flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode is characterized by comprising reduced graphene oxide and tin phosphide, wherein the reduced graphene oxide is used as a flexible substrate, and the tin phosphide is embedded on the graphene oxide; wherein the mass ratio of the reduced graphene oxide to the tin phosphide is 1.7: 1-1: 1.
The granularity of the tin phosphide is 20 nm-50 nm.
A preparation method of the cathode of the flexible reduced graphene oxide coated tin phosphide film sodium metal battery is characterized by comprising the following steps:
step 1: carrying out ultrasonic treatment on graphene oxide by using ethanol to obtain a graphene oxide solution;
step 2: dissolving stannous chloride dihydrate in ethanol and stirring to obtain a transparent stannous chloride ethanol solution;
and step 3: adding the graphene oxide solution into a stannous chloride solution, stirring, and transferring to a high-pressure hydrothermal kettle for hydrothermal reaction; the hydrothermal reaction condition is 120-140 ℃, and the hydrothermal time is 8-12 h;
the ratio of the stannous chloride to the graphene oxide is 3: 1-5: 1;
and 4, step 4: freeze-drying the product of the hydrothermal reaction to obtain graphene oxide coated tin oxide;
and 5: respectively placing the tin oxide coated with the graphene oxide and sodium hypophosphite at two ends in a closed ceramic crucible, placing the ceramic crucible in a tubular furnace for phosphorization and sintering, washing and performing suction filtration after sintering to finally obtain tin phosphide-coated reduced graphene oxide;
the ratio of the graphene oxide-coated tin oxide to the sodium hypophosphite is 1: 4-1: 5;
the phosphorization sintering conditions are as follows: the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h.
The concentration of the graphene oxide ethanol solution is 60-80%.
The concentration of the stannous chloride ethanol solution is 60-90%.
The washing conditions are as follows: 0.1mol/L diluted hydrochloric acid, water and ethanol are respectively washed for three times.
Advantageous effects
The invention provides a flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and a preparation method thereof, wherein the battery cathode comprises reduced graphene oxide and tin phosphide; the method comprises the following steps of taking reduced graphene oxide as a flexible substrate, and inlaying tin phosphide on the graphene oxide, wherein the mass ratio of the reduced graphene oxide to the tin phosphide is 1.7: 1-1: 1.
The invention has the beneficial effects that:
1. according to the invention, the tin phosphide film sodium metal battery cathode is coated by the flexible reduced graphene oxide, and the reduced graphene oxide substrate with a three-dimensional structure can effectively reduce the current density of the electrode and inhibit the generation of dendritic crystals; the three-dimensional graphene oxide structure increases the contact area of the metal sodium, and the deposited metal sodium can be attached to the surface of the three-dimensional graphene oxide structure and in front of the sheet layer, so that the deposition of the sodium can be accommodated, the generation of 'dead sodium' is reduced, and the volume change of a sodium metal cathode in the charge-discharge cycle process is slowed down; the tin phosphide as a sodium-philic material can be used as a sodium deposition site, so that sodium ions are effectively dispersed, ion accumulation is reduced, and the possibility of forming sodium dendrites is reduced; compared with a pure metal lithium/sodium metal cathode, the lithium/sodium metal cathode has better circulation stability and more stable voltage distribution curve; the battery can be applied to flexible energy storage devices, and the safety performance of the battery is high after the battery is applied to a sodium metal battery;
2. the preparation method of the cathode of the flexible reduced graphene oxide coated tin phosphide film sodium metal battery is simple and easy to implement.
Drawings
Fig. 1 is an SEM result of the graphene oxide-coated tin oxide prepared in step 4 in example 1 of the present invention;
fig. 2 is a TEM result of the graphene oxide-coated tin oxide prepared in step 4 in example 1 of the present invention;
FIG. 3 is a SEM result of the tin phosphide-coated reduced graphene oxide prepared in step 5 in example 1 of the present invention;
FIG. 4 is a TEM result of the tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention;
fig. 5 is XRD results of the tin phosphide-coated reduced graphene oxide prepared in example 1, example 2 and example 3 of the present invention;
fig. 6 is a photograph showing a bent state of tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention;
FIG. 7 shows the BET test result of the tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention;
FIG. 8 shows that the tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention is deposited at 5mA h cm-2SEM results for sodium metal;
FIG. 9 shows the reduced graphene oxide coated with tin phosphide prepared in examples 1, 2 and 3, and the reduced graphene oxide and copper electrode at 0.5mA cm-2Sodium nucleation overpotential curve under current density;
fig. 10 shows the coulombic efficiency of the tin phosphide-coated reduced graphene oxide electrode obtained in example 1 of the present invention at different current densities;
FIG. 11 shows the tin phosphide-coated reduced graphene oxide prepared in examples 1, 2 and 3 of the present invention, and copper foil and sodium foil electrodesSymmetric cell at 0.5mA cm-2A voltage-time curve;
fig. 12 is a capacity retention rate curve of a full cell prepared by matching the cathode of the flexible reduced graphene oxide coated tin phosphide film sodium metal battery provided in embodiment 1 of the present invention with a commercial sodium vanadium fluorophosphate cathode material at a rate of 0.5C.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
Step 1, carrying out ultrasonic treatment on 60mg of graphene oxide by using 30mL of ethanol to obtain a graphene oxide solution;
step 2, dissolving 0.22g of stannous chloride dihydrate in 30mL of ethanol and stirring to obtain a transparent stannic chloride solution;
step 3, adding the graphene oxide solution obtained in the step 1 into the tin chloride solution obtained in the step 2, uniformly stirring, transferring to a high-pressure hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 140 ℃, and the hydrothermal time is 10 hours;
step 4, freeze-drying the product of the hydrothermal reaction obtained in the step 3 to obtain graphene oxide coated tin oxide;
step 5, preparing the tin phosphide-coated reduced graphene oxide: weighing the graphene oxide coated tin oxide and sodium hypophosphite obtained in the step 4, wherein the ratio of the graphene oxide coated tin oxide to the sodium hypophosphite is 1:5, placing the two ends of the graphene oxide coated tin oxide to the sodium hypophosphite in a sealed ceramic crucible respectively, placing the two ends of the sealed ceramic crucible in a tubular furnace for sintering, wherein the conditions of phosphorization and sintering are that the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h. And then washing with 0.1mol/L dilute hydrochloric acid, water and ethanol for three times respectively, and carrying out suction filtration to finally obtain the tin phosphide-coated reduced graphene oxide.
And (4) SEM characterization:
SEM and TEM characterization of the graphene oxide coated tin oxide prepared in step 4 in example 1 shows that tin oxide particles are uniformly distributed on graphene oxide sheets, the grain size is not more than 5nm, and the size is uniform, as shown in FIG. 1 and FIG. 2.
SEM and TEM characterization of the tin phosphide-coated reduced graphene oxide prepared in step 5 of example 1 shows that tin phosphide particles are uniformly distributed, the grain size is about 20nm, and the size is uniform, as shown in FIG. 3 and FIG. 4.
The XRD test results of fig. 5 show that the synthesized tin phosphide of example 1 is a pure phase.
Fig. 6 is a photograph of a bent state of the tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention, which shows that the synthesized tin phosphide-coated reduced graphene oxide has a certain flexibility.
FIG. 7 shows the BET test result of the tin phosphide-coated reduced graphene oxide obtained in example 1 of the present invention, and the result shows that the specific surface area is 53.29m2And the larger specific surface area is derived from the overlapping and interlacing of the lamellar graphene structure, so that the current density is effectively dispersed, and the formation of sodium dendrites is inhibited.
Example 2
Step 1, carrying out ultrasonic treatment on 60mg of graphene oxide by using 20mL of ethanol to obtain a graphene oxide solution;
step 2, dissolving 0.18g of stannous chloride dihydrate in 25mL of ethanol and stirring to obtain a transparent stannic chloride solution;
step 3, adding the graphene oxide solution obtained in the step 1 into the tin chloride solution obtained in the step 2, uniformly stirring, transferring to a high-pressure hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 130 ℃, and the hydrothermal time is 8 hours;
step 4, freeze-drying the product of the hydrothermal reaction obtained in the step 3 to obtain graphene oxide coated tin oxide;
step 5, preparing the tin phosphide-coated reduced graphene oxide: weighing the graphene oxide coated tin oxide and sodium hypophosphite obtained in the step 4, wherein the ratio of the graphene oxide coated tin oxide to the sodium hypophosphite is 1:4, placing the two ends of the graphene oxide coated tin oxide to the sodium hypophosphite in a sealed ceramic crucible respectively, placing the two ends of the sealed ceramic crucible in a tubular furnace for sintering, wherein the conditions of phosphorization and sintering are that the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h. And then washing with 0.1mol/L dilute hydrochloric acid, water and ethanol for three times respectively, and carrying out suction filtration to finally obtain the tin phosphide-coated reduced graphene oxide.
Example 3
Step 1, carrying out ultrasonic treatment on 60mg of graphene oxide by using 15mL of ethanol to obtain a graphene oxide solution;
step 2, dissolving 0.3g of stannous chloride dihydrate in 25mL of ethanol and stirring to obtain a transparent stannic chloride solution;
step 3, adding the graphene oxide solution obtained in the step 1 into the tin chloride solution obtained in the step 2, uniformly stirring, transferring to a high-pressure hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 120 ℃, and the hydrothermal time is 12 hours;
step 4, freeze-drying the product of the hydrothermal reaction obtained in the step 3 to obtain graphene oxide coated tin oxide;
step 5, preparing the tin phosphide-coated reduced graphene oxide: weighing the graphene oxide coated tin oxide and sodium hypophosphite obtained in the step 4, wherein the ratio of the graphene oxide coated tin oxide to the sodium hypophosphite is 1:4.5, placing the two ends of the graphene oxide coated tin oxide to the sodium hypophosphite in a sealed ceramic crucible respectively, and placing the two ends of the sealed ceramic crucible in a tubular furnace for sintering, wherein the conditions of phosphorization and sintering are that the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h. And then washing with 0.1mol/L dilute hydrochloric acid, water and ethanol for three times respectively, and carrying out suction filtration to finally obtain the tin phosphide-coated reduced graphene oxide.
Example 4
Step 1, carrying out ultrasonic treatment on 60mg of graphene oxide by using 25mL of ethanol to obtain a graphene oxide solution;
step 2, dissolving 0.2g of stannous chloride dihydrate in 30mL of ethanol and stirring to obtain a transparent stannic chloride solution;
step 3, adding the graphene oxide solution obtained in the step 1 into the tin chloride solution obtained in the step 2, uniformly stirring, transferring to a high-pressure hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction condition is 130 ℃, and the hydrothermal time is 12 hours;
step 4, freeze-drying the product of the hydrothermal reaction obtained in the step 3 to obtain graphene oxide coated tin oxide;
step 5, preparing the tin phosphide-coated reduced graphene oxide: weighing the graphene oxide coated tin oxide and sodium hypophosphite obtained in the step 4, wherein the ratio of the graphene oxide coated tin oxide to the sodium hypophosphite is 1:5, placing the two ends of the graphene oxide coated tin oxide to the sodium hypophosphite in a sealed ceramic crucible respectively, placing the two ends of the sealed ceramic crucible in a tubular furnace for sintering, wherein the conditions of phosphorization and sintering are that the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h. And then washing with 0.1mol/L dilute hydrochloric acid, water and ethanol for three times respectively, and carrying out suction filtration to finally obtain the tin phosphide-coated reduced graphene oxide.
And (3) testing the charge and discharge performance:
the flexible reduced graphene oxide coated tin phosphide film obtained in the embodiments 1 to 3 of the invention is rolled into a flexible self-supporting pole piece, the flexible self-supporting pole piece is dried in vacuum for 12 hours, the flexible self-supporting pole piece is sliced into a round piece with the diameter of 12mm, the round piece and sodium metal are used as counter electrodes, and the electrolyte is NaPF6(1M) in diglyme. Meanwhile, reduced graphene oxide, copper foil and sodium foil were used as comparative samples. The 2032 button cell was assembled in a glove box filled with high purity argon, water and oxygen both less than 0.1 ppm. After 12h of standing, the charge limit voltage of the battery was 1.0V in the constant current mode. And (4) carrying out charge and discharge performance tests under different current densities. As shown in FIG. 8, the flexible tin phosphide-coated graphene prepared in example 1 was deposited at 5mA cm-2The SEM image shows that sodium metal is deposited on the surface of the pole piece and in the holes to form a dense and smooth continuous conductor.
The current density is 0.5mAcm-2The following test results are shown in fig. 9, and it can be seen that: the minimum nucleation overpotential of the battery adopting the electrode in the embodiment 1 is about 4mV, the nucleation overpotentials of the battery adopting the electrode in the embodiments 2 and 3 are respectively 13mV and 9mV, and the nucleation overpotentials of the reduced graphene oxide and the copper foil in the comparison sample are respectively 22mV and 20mV, which shows that the tin phosphide-coated reduced graphene oxide prepared in the embodiment 1 effectively reduces the nucleation overpotential and is beneficial to inhibiting the generation of sodium dendrite. And under different current densities, the tin phosphide-coated reduced graphene oxide prepared in example 1 is subjected to different electric potentialsCoulombic efficiency at current density, it can be seen that when the current density is raised to 5mA cm-2The hourly coulombic efficiency was 99.4%.
Testing of symmetric cells: firstly depositing 10mA h cm-2Sodium metal is added to the working pole piece, and constant current charging and discharging are carried out, as shown in fig. 11, during the stripping/deposition process of sodium, the overvoltage of example 1 is obviously less than that of other electrodes (20mV), the cycling stability is better, and the voltage distribution curve is more stable.
And (3) full battery test: as shown in FIG. 12, deposit 10mA h cm-2Sodium metal is added to the working pole piece and matched with the sodium vanadium fluorophosphate positive electrode, the retention rate of 150 circles at 0.5C multiplying power is 95.6%, and the circulation stability is good.
Therefore, the tin phosphide-coated reduced graphene oxide cathode prepared by the technical scheme of the invention has the advantages of high coulombic efficiency, good cycle stability, effective inhibition of sodium dendrite and the like in electrical properties.
According to the invention, the flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode, the reduced graphene oxide substrate with the three-dimensional structure can effectively reduce the current density of the electrode and inhibit the generation of dendritic crystals; the three-dimensional graphene oxide structure increases the contact area of the metal sodium, and the deposited metal sodium can be attached to the surface of the three-dimensional graphene oxide structure and in front of the sheet layer, so that the deposition of the sodium can be accommodated, the generation of 'dead sodium' is reduced, and the volume change of a sodium metal cathode in the charge-discharge cycle process is slowed down; the tin phosphide as a sodium-philic material can be used as a sodium deposition site, so that sodium ions are effectively dispersed, ion accumulation is reduced, and the possibility of forming sodium dendrites is reduced; compared with a pure metal lithium/sodium metal cathode, the lithium/sodium metal cathode has better circulation stability and more stable voltage distribution curve; the battery can be applied to flexible energy storage devices, and the safety performance of the battery is high after the battery is applied to a sodium metal battery; the preparation method of the cathode of the flexible reduced graphene oxide coated tin phosphide film sodium metal battery is simple and easy to implement.

Claims (6)

1. A flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode is characterized by comprising reduced graphene oxide and tin phosphide, wherein the reduced graphene oxide is used as a flexible substrate, and the tin phosphide is embedded on the graphene oxide; wherein the mass ratio of the reduced graphene oxide to the tin phosphide is 1.7: 1-1: 1.
2. The flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode as claimed in claim 1, wherein: the granularity of the tin phosphide is 20 nm-50 nm.
3. The preparation method of the cathode of the flexible reduced graphene oxide coated tin phosphide film sodium metal battery as claimed in claim 1 or 2, which is characterized by comprising the following steps:
step 1: carrying out ultrasonic treatment on graphene oxide by using ethanol to obtain a graphene oxide solution;
step 2: dissolving stannous chloride dihydrate in ethanol and stirring to obtain a transparent stannous chloride ethanol solution;
and step 3: adding the graphene oxide solution into a stannous chloride solution, stirring, and transferring to a high-pressure hydrothermal kettle for hydrothermal reaction; the hydrothermal reaction condition is 120-140 ℃, and the hydrothermal time is 8-12 h;
the ratio of the stannous chloride to the graphene oxide is 3: 1-5: 1;
and 4, step 4: freeze-drying the product of the hydrothermal reaction to obtain graphene oxide coated tin oxide;
and 5: respectively placing the tin oxide coated with the graphene oxide and sodium hypophosphite at two ends in a closed ceramic crucible, placing the ceramic crucible in a tubular furnace for phosphorization and sintering, washing and performing suction filtration after sintering to finally obtain tin phosphide-coated reduced graphene oxide;
the ratio of the graphene oxide-coated tin oxide to the sodium hypophosphite is 1: 4-1: 5;
the phosphorization sintering conditions are as follows: the sintering temperature is 250-300 ℃, the atmosphere is argon, the sintering speed is 2-5 ℃/min, and the sintering time is 3-5 h.
4. The method of claim 3, wherein: the concentration of the graphene oxide ethanol solution is 60-80%.
5. The method of claim 3, wherein: the concentration of the stannous chloride ethanol solution is 60-90%.
6. The method of claim 3, wherein: the washing conditions are as follows: 0.1mol/L diluted hydrochloric acid, water and ethanol are respectively washed for three times.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006551A (en) * 2015-06-03 2015-10-28 中南大学 Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof
CN106876670A (en) * 2016-12-28 2017-06-20 广东工业大学 The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application
JP2017152351A (en) * 2016-02-26 2017-08-31 住友電気工業株式会社 Sodium ion secondary battery
CN108123141A (en) * 2017-12-07 2018-06-05 北京理工大学 A kind of three-dimensional porous foams grapheme material and its application
CN108336301A (en) * 2018-02-06 2018-07-27 哈尔滨工业大学 A kind of high-performance sodium-ion battery cathode and preparation method thereof
CN108461732A (en) * 2018-03-16 2018-08-28 北京理工大学 A kind of flexibility sodium metal battery negative material and preparation method thereof
CN108630918A (en) * 2018-04-04 2018-10-09 广东工业大学 A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application
CN110993913A (en) * 2019-12-06 2020-04-10 湘潭大学 Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105006551A (en) * 2015-06-03 2015-10-28 中南大学 Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof
JP2017152351A (en) * 2016-02-26 2017-08-31 住友電気工業株式会社 Sodium ion secondary battery
CN106876670A (en) * 2016-12-28 2017-06-20 广东工业大学 The metal oxide of a kind of flexible self-supporting/graphene nano composite membrane and its preparation method and application
CN108123141A (en) * 2017-12-07 2018-06-05 北京理工大学 A kind of three-dimensional porous foams grapheme material and its application
CN108336301A (en) * 2018-02-06 2018-07-27 哈尔滨工业大学 A kind of high-performance sodium-ion battery cathode and preparation method thereof
CN108461732A (en) * 2018-03-16 2018-08-28 北京理工大学 A kind of flexibility sodium metal battery negative material and preparation method thereof
CN108630918A (en) * 2018-04-04 2018-10-09 广东工业大学 A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application
CN110993913A (en) * 2019-12-06 2020-04-10 湘潭大学 Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王娟: ""锡基纳米复合材料的制备及其储锂性能研究"", 《中国优秀硕士学位论文全文数据库-工程科技Ⅰ辑》 *

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