CN112366298B - Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof - Google Patents
Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material, wherein a three-dimensional frame structure with holes is assembled by carbon in the zinc sulfide cobalt sulfide hollow nano polyhedral. The invention also discloses a preparation method of the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material, which comprises the steps of firstly synthesizing a zinc-cobalt mixed metal organic frame material, then assembling the zinc-cobalt mixed metal organic frame material into a three-dimensional frame structure by a polyvinylpyrrolidone boiling method, and then obtaining a final product by a one-step gas phase vulcanization and carbonization method. The invention can improve the conductivity, structural stability and cycling stability of the zinc sulfide cobalt sulfide, so that the zinc sulfide cobalt sulfide has high specific capacity and stable cycling performance. The carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material has important application value as a sodium ion battery electrode material.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material and preparation and application thereof.
Background
Although lithium ion batteries have been widely used in the fields of portable electronic devices and new energy vehicles, the high cost and low reserves of the relevant raw materials have prompted further research on alternative batteries. Sodium element is abundant in earth, accounts for about 2.36% of earth crust and is more than 1000 times of lithium, so that the sodium ion battery is an ideal energy storage system for replacing a lithium ion battery. Transition metal sulfide as sodium ion battery negative electrode materialIt is considered to be a promising candidate anode material due to its high theoretical specific capacity. Wherein, the theoretical capacity of zinc sulfide is 963mAh g-1Theoretical capacity of cobalt sulfide 590mAh g-1And are sodium ion battery cathode materials with great application value, but the rapid capacity fading and poor rate performance seriously hinder the practical application of the cathode materials, which are due to the large volume change and low conductivity of zinc sulfide and cobalt sulfide in charge-discharge cycles.
In order to improve the performance of sodium ion batteries of zinc sulfide and cobalt sulfide, people mainly adopt two strategies, namely nanocrystallization and composite high-conductivity materials. Patent CN109638243A discloses a zinc sulfide/multi-walled carbon nanotube composite material, in which although the three-dimensional network structure formed by multi-walled carbon nanotubes significantly improves the conductivity of the material, the volume change of zinc sulfide cannot be effectively inhibited, and the cycle stability of the zinc sulfide is improved. Patent CN110492090A discloses a biomass carbon-coated cobalt sulfide-cobalt octasulfide composite material, the spherical particle size of which is close to 200nm, and such a large particle size and a compact spherical structure are not beneficial to embedding sodium ions into the material. Therefore, a new breakthrough is urgently needed for the application of sodium ion batteries of zinc sulfide and cobalt sulfide, by how to improve the conductivity of the material, inhibit the volume change of the material and improve the cycle stability of the material through a smart structural design.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material, and a large number of holes are formed in a frame structure.
A carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material is characterized in that a three-dimensional frame structure with holes is assembled by the zinc sulfide cobalt sulfide hollow nano polyhedral through carbon.
Preferably, the particle size of the zinc sulfide cobalt sulfide hollow nano polyhedron is 10-200nm, and the shell thickness is 2-100 nm;
the diameter of the holes is 10-100 nm.
Preferably, in the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material, the mass percentage of the zinc sulfide cobalt sulfide hollow nano polyhedral is 5-95%.
Preferably, the carbon is amorphous carbon and is formed by carbonizing polyvinylpyrrolidone (PVP).
The invention also provides a preparation method of the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material, which comprises the following steps:
(1) adding Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Pouring the methanol solution of O into the methanol solution of dimethyl imidazole, continuously stirring for 24h at 0-40 ℃, centrifugally separating the product, washing with methanol, and drying at 60 ℃ to obtain a zinc-cobalt mixed Metal Organic Framework (MOF);
(2) dispersing the zinc-cobalt mixed metal organic framework prepared in the step (1) in ethanol to obtain an ethanol solution of the zinc-cobalt mixed metal organic framework, then pouring the ethanol solution into an ethanol solution of polyvinylpyrrolidone, uniformly stirring, heating the solution to boiling, and keeping the boiling to be completely dry; placing the obtained product at the downstream of the gas in the tubular furnace, placing sublimed sulfur at the upstream of the gas in the tubular furnace, introducing argon, and heating at 1-5 deg.C for min-1Heating to 600-800 ℃ at the speed and keeping the temperature for 0.5-3h to obtain the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material.
The preparation method comprises the following steps: firstly synthesizing a zinc-cobalt mixed MOF material, slightly pushing away zinc-cobalt mixed MOF nanoparticles by utilizing bubbles generated by solution boiling through a PVP boiling method, forming a large number of holes after solidification, assembling the zinc-cobalt mixed MOF into a three-dimensional framework structure with the holes, finally vulcanizing the zinc-cobalt mixed MOF into a zinc sulfide cobalt sulfide hollow nano polyhedron through a one-step gas-phase vulcanization and carbonization method, and carbonizing PVP into amorphous carbon to obtain a final product.
Preferably, in step (1), Zn (NO)3)2·6H2O、Co(NO3)2·6H2The mass ratio of O to dimethyl imidazole is 1.13:0.54:3.7, Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Zn (NO) in methanol solution of O3)2·6H2O、Co(NO3)2·6H2The ratio of O to methanol was 1.13g:0.54g:80mL, and the ratio of dimethylimidazole to methanol in a solution of dimethylimidazole in methanol was 3.7g:80 mL.
Preferably, in the step (2), the mass ratio of the zinc-cobalt mixed metal organic framework, the polyvinylpyrrolidone and the sublimed sulfur is 0.2:0.1-0.6:0.24, the ratio of the zinc-cobalt mixed metal organic framework to the ethanol in the ethanol solution of the zinc-cobalt mixed metal organic framework is 0.2g:40mL, and the ratio of the polyvinylpyrrolidone to the ethanol in the ethanol solution of the polyvinylpyrrolidone is 0.1-0.6g:12 mL.
A preferred method of preparation, comprising the steps of:
(1) 1.13g of Zn (NO)3)2·6H2O and 0.54g Co (NO)3)2·6H2Dissolving O in 80mL of methanol, dissolving 3.7g of dimethylimidazole in 80mL of methanol, and dissolving Zn (NO)3)2And Co (NO)3)2Pouring the methanol solution into dimethyl imidazole methanol solution, continuously stirring for 24h at 0-40 ℃, centrifugally separating the product, cleaning for 3 times by using methanol, and drying at 60 ℃ to obtain a zinc-cobalt mixed Metal Organic Framework (MOF);
(2) dispersing 0.2g of zinc-cobalt mixed MOF prepared in the step (1) in 40mL of ethanol; dissolving 0.1-0.6g of PVP in 12mL of ethanol, pouring an ethanol solution of zinc-cobalt mixed MOF, and uniformly stirring; the solution was heated to boiling and kept boiling to complete dryness. Placing the product at downstream of gas in quartz tube furnace, placing 0.24g of sublimed sulfur at upstream of gas in quartz tube furnace, introducing argon gas, and heating at 1-5 deg.C for min-1Heating to 600-800 ℃ at the speed and keeping the temperature for 0.5-3h to obtain the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material.
The invention also provides application of the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material in a sodium ion battery electrode (such as a negative electrode) material.
The carbon assembled zinc sulfide cobalt sulfide hollow nanometer polyhedral frame material is adopted to manufacture the sodium ion battery electrode: respectively weighing the composite material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 8:1:1, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground composite material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
And assembling the prepared electrode slice, a sodium sheet and a diaphragm into the CR2025 button type sodium ion battery in a glove box filled with high-purity argon. The electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycling stability of the sodium ion battery. Charge-discharge current density 500mA g-1The voltage range is 0.01-3.0V.
The invention can improve the conductivity, structural stability and cycling stability of the zinc sulfide cobalt sulfide, and improve the specific capacity and cycling performance of the zinc sulfide cobalt sulfide.
Compared with the prior art, the invention has the main advantages that:
(1) the nano particles of the zinc-cobalt mixed MOF are adhered together through PVP, and carbon formed after carbonization is coated on the surface of the zinc sulfide-cobalt sulfide hollow nano polyhedron, so that the volume change of the hollow polyhedron can be effectively inhibited, and the structural stability and the circulation stability of the hollow polyhedron are improved. The formed frame carbon shell forms a good conductive network, improves the conductivity of the zinc sulfide and cobalt sulfide hollow nano polyhedron, and promotes the electrochemical reaction of zinc sulfide and cobalt sulfide, especially the rate reaction.
(2) The hollow nano polyhedral honeycomb structure formed by the conventional PVP solution evaporation drying method is tightly filled with carbon and is compact and non-porous, and the structure is not beneficial to rapid penetration of electrolyte. According to the invention, the zinc-cobalt mixed MOF nanoparticles are slightly pushed away by bubbles generated by boiling of the solution, and a large number of holes are formed after solidification, so that the electrolyte can conveniently permeate into the frame material, which is particularly important for a sodium ion battery, because the sodium ions have large sizes and are not easy to diffuse and penetrate through a carbon material.
(3) In the hollow nano polyhedron formed by the vulcanization of the zinc-cobalt mixed MOF, the zinc sulfide and the cobalt sulfide are mixed together, so that the zinc-cobalt mixed MOF has a unique composite effect, can promote the intercalation/deintercalation of sodium ions, and shows a better sodium storage performance.
(4) The solid zinc-cobalt mixed MOF is firstly assembled by PVP, and then vulcanized into the zinc sulfide-cobalt sulfide hollow nano polyhedron by a one-step gas-phase vulcanization and carbonization method, so that the forming capability and the structural integrity of the hollow nano polyhedron can be improved, and the defect that the hollow nano polyhedron is easy to break in the process of firstly preparing the hollow nano polyhedron and then assembling the PVP is thoroughly solved.
(5) The zinc sulfide cobalt sulfide has a hollow nano polyhedral structure, so that the specific surface area is large, and the number of electrochemical active sites of the zinc sulfide cobalt sulfide is increased; the wall thickness (shell thickness) of the hollow polyhedron is nano-scale, so that the diffusion path of sodium ions is shortened, and the diffusion dynamics of the sodium ions in zinc sulfide and cobalt sulfide are accelerated; the hollow structure enables the zinc sulfide and cobalt sulfide to better adapt to volume expansion and contraction in the charge-discharge cycle process, and the structural stability is improved; the hollow structure can also store electrolyte, and the requirement of the electrochemical reaction of zinc sulfide and cobalt sulfide is met; therefore, the zinc sulfide and cobalt sulfide hollow nano polyhedron has good electrochemical sodium storage performance.
(6) The gas-phase vulcanization and carbonization method of one-step calcination enables the zinc-cobalt mixed MOF to be vulcanized into the zinc sulfide-cobalt sulfide hollow nano polyhedron, and simultaneously enables PVP to be carbonized into amorphous carbon.
Drawings
FIG. 1 is an SEM photograph of a zinc cobalt mixed MOF prepared in example 1;
FIG. 2 is an SEM photograph of the carbon assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material prepared in example 1;
FIG. 3 shows the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material prepared in example 1 at a current density of 500mA g-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) 1.13g of Zn (NO)3)2·6H2O and 0.54g Co (NO)3)2·6H2Dissolving O in 80mL of methanol, dissolving 3.7g of dimethylimidazole in 80mL of methanol, and dissolving Zn (NO)3)2And Co (NO)3)2And pouring the methanol solution into a methanol solution of dimethyl imidazole, continuously stirring for 24 hours at the temperature of 20 ℃, centrifugally separating the product, washing for 3 times by using methanol, and drying at the temperature of 60 ℃ to obtain the zinc-cobalt mixed MOF.
(2) Dispersing 0.2g of zinc-cobalt mixed MOF prepared in the step (1) in 40mL of ethanol; dissolving 0.24g of PVP in 12mL of ethanol, pouring the ethanol solution of zinc-cobalt mixed MOF, and uniformly stirring; the solution was heated to boiling and kept boiling to complete dryness. Placing the product at the downstream of gas in quartz tube furnace, placing 0.24g of sublimed sulfur at the upstream of gas in quartz tube furnace, introducing argon gas, and heating at 2 deg.C for min-1Heating to 700 ℃ at the speed of the temperature and preserving heat for 2 hours to obtain the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material.
FIG. 1 is an SEM photograph of the prepared zinc-cobalt mixed MOF, which is similar to that of ZIF-8 in structure and is a crystal having a dodecahedral structure, smooth surface, uniform size and a particle size of about 50 nm. Fig. 2 is an SEM photograph of a carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material, and it can be seen that polyhedral particles are assembled into a framework structure by carbon connection, and individual broken particles show an inner hollow, indicating that the polyhedron has formed a hollow structure. The particle size of the zinc sulfide and cobalt sulfide hollow nanometer polyhedron is basically kept unchanged, and the wall thickness is about 10 nm. A large number of holes are formed among the polyhedral particles, the diameter of each hole is 10-100nm, and the holes are generated as a result of boiling evaporation. FIG. 2 shows that a three-dimensional framework structure with hollow nano-polyhedra as constituent units and rich in a large number of holes has been successfully prepared. The energy spectrum analysis shows that the mass content of the zinc sulfide and the cobalt sulfide is 65.7 percent.
The carbon-assembled zinc sulfide cobalt sulfide hollow nanometer polyhedral frame material of the embodiment is adopted to manufacture the sodium ion battery electrode: respectively weighing the composite material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 8:1:1, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground composite material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
And assembling the prepared electrode slice, a sodium sheet and a diaphragm into the CR2025 button type sodium ion battery in a glove box filled with high-purity argon. The electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycling stability of the sodium ion battery. Charge-discharge current density 500mA g-1The voltage range is 0.01-3.0V.
FIG. 3 shows the carbon assembled zinc sulfide cobalt sulfide hollow nanometer polyhedron frame material at current density of 500mA g-1Cycle performance map of (c). The specific discharge capacity of the 1 st cycle was 923mAh g-1After 7 cycles, the discharge specific capacity is reduced to 645mAh g-1And remained stable, the specific discharge capacity to the 200 th cycle was 566mAh g-1. The average specific discharge capacity of 200 cycles was 594mAh g-1. The specific discharge capacity and the cycle performance of the carbon-assembled zinc sulfide cobalt sulfide Hollow nano polyhedral framework material exceed the technology of CN104868102A and CN109133191A, and the work of Jingyao Ma (Hollow ZnS subspheres encapsulated in carbon shells with enhanced lithium and sodium storage properties, Journal of Alloys and composites, 735(2018)51-61) and the like.
Example 2
(1) 1.13g of Zn (NO)3)2·6H2O and 0.54g Co (NO)3)2·6H2Dissolving O in 80mL of methanol, dissolving 3.7g of dimethylimidazole in 80mL of methanol, and dissolving Zn (NO)3)2And Co (NO)3)2The methanol solution is poured into the methanol solution of the dimethyl imidazole, the mixture is continuously stirred for 24 hours at the temperature of 20 ℃,and (3) centrifugally separating the product, washing the product for 3 times by using methanol, and drying the product at the temperature of 60 ℃ to obtain the zinc-cobalt mixed MOF.
(2) Dispersing 0.2g of zinc-cobalt mixed MOF prepared in the step (1) in 40mL of ethanol; dissolving 0.30g of PVP in 12mL of ethanol, pouring the ethanol solution of zinc-cobalt mixed MOF, and uniformly stirring; the solution was heated to boiling and kept boiling to complete dryness. Placing the product at the downstream of gas in quartz tube furnace, placing 0.24g of sublimed sulfur at the upstream of gas in quartz tube furnace, introducing argon gas, and heating at 2 deg.C for min-1Heating to 700 ℃ at the speed of the temperature and preserving heat for 2 hours to obtain the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material.
The structure of the product carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material is similar to that of the embodiment 1, and the main difference is that the mass content of the zinc sulfide cobalt sulfide is reduced to 58.1%.
The same procedure as in example 1 was used to fabricate an electrode for a sodium ion battery, which was assembled into a sodium ion battery at a current density of 500mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The specific discharge capacity of the 1 st cycle was 839mAh g-1After 7 cycles, the discharge specific capacity is reduced to 584mAh g-1And the specific discharge capacity is kept stable until the 200 th cycle is 512mAh g-1. The average specific discharge capacity of 200 cycles was 537mAh g-1。
Example 3
(1) 1.13g of Zn (NO)3)2·6H2O and 0.54g Co (NO)3)2·6H2Dissolving O in 80mL of methanol, dissolving 3.7g of dimethylimidazole in 80mL of methanol, and dissolving Zn (NO)3)2And Co (NO)3)2And pouring the methanol solution into a methanol solution of dimethyl imidazole, continuously stirring for 24 hours at the temperature of 2 ℃, centrifugally separating the product, washing for 3 times by using methanol, and drying at the temperature of 60 ℃ to obtain the zinc-cobalt mixed MOF.
The subsequent process was the same as in example 1.
The structure of the product carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material is similar to that of the embodiment 1, and the main difference is that the zinc sulfide cobalt sulfide hollow nano polyhedral becomes small, the particle size is about 39nm, and the wall thickness is about 7 nm.
The same procedure as in example 1 was used to fabricate an electrode for a sodium ion battery, which was assembled into a sodium ion battery at a current density of 500mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The specific discharge capacity at the 1 st cycle was 1029mAh g-1After 10 cycles, the discharge specific capacity is reduced to 712mAh g-1And the specific discharge capacity is 627mAh g till 200 th cycle-1. The average specific discharge capacity of 200 cycles was 655mAh g-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a carbon-assembled zinc sulfide cobalt sulfide hollow nanometer polyhedral frame material is characterized by comprising the following steps:
(1) adding Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Pouring the methanol solution of O into the methanol solution of dimethyl imidazole, continuously stirring for 24h at 0-40 ℃, centrifugally separating the product, washing with methanol, and drying at 60 ℃ to obtain a zinc-cobalt mixed metal organic frame;
(2) dispersing the zinc-cobalt mixed metal organic framework prepared in the step (1) in ethanol to obtain an ethanol solution of the zinc-cobalt mixed metal organic framework, then pouring the ethanol solution into an ethanol solution of polyvinylpyrrolidone, uniformly stirring, heating the solution to boiling, and keeping the boiling to be completely dry; placing the obtained product at the downstream of the gas in the tubular furnace, placing sublimed sulfur at the upstream of the gas in the tubular furnace, introducing argon, and heating at 1-5 deg.C for min-1Heating to 600-800 ℃ at the speed and keeping the temperature for 0.5-3h to obtain the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material;
the carbon-assembled zinc sulfide cobalt sulfide hollow nanometer polyhedron frame material is characterized in that a three-dimensional frame structure with holes is assembled by the carbon-assembled zinc sulfide cobalt sulfide hollow nanometer polyhedron.
2. The method for preparing the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral frame material according to claim 1, wherein the particle size of the zinc sulfide cobalt sulfide hollow nano polyhedral is 10-200nm, and the shell thickness is 2-100 nm;
the diameter of the holes is 10-100 nm.
3. The method for preparing the carbon-assembled zinc sulfide cobalt hollow nano polyhedral frame material according to claim 1, wherein the mass percentage of the zinc sulfide cobalt sulfide hollow nano polyhedral is 5-95%.
4. The method for preparing the carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material according to claim 1, wherein the carbon is amorphous carbon and is formed by carbonizing polyvinylpyrrolidone.
5. The method according to claim 1, wherein in the step (1), Zn (NO)3)2·6H2O、Co(NO3)2·6H2The mass ratio of O to dimethyl imidazole is 1.13:0.54:3.7, Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Zn (NO) in methanol solution of O3)2·6H2O、Co(NO3)2·6H2The ratio of O to methanol was 1.13g:0.54g:80mL, and the ratio of dimethylimidazole to methanol in a solution of dimethylimidazole in methanol was 3.7g:80 mL.
6. The production method according to claim 1 or 5, wherein in step (2), the mass ratio of the zinc-cobalt mixed metal organic framework, polyvinylpyrrolidone and sublimed sulfur is 0.2:0.1 to 0.6:0.24, the ratio of the zinc-cobalt mixed metal organic framework to ethanol in the ethanol solution of the zinc-cobalt mixed metal organic framework is 0.2g:40mL, and the ratio of polyvinylpyrrolidone to ethanol in the ethanol solution of polyvinylpyrrolidone is 0.1 to 0.6g:12 mL.
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