CN115557537A - MnS nanodot material, ternary sodium electric precursor, anode material and preparation method - Google Patents

MnS nanodot material, ternary sodium electric precursor, anode material and preparation method Download PDF

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CN115557537A
CN115557537A CN202211044870.XA CN202211044870A CN115557537A CN 115557537 A CN115557537 A CN 115557537A CN 202211044870 A CN202211044870 A CN 202211044870A CN 115557537 A CN115557537 A CN 115557537A
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李骕
范鑫铭
林杭
李国钦
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Hunan Zhongda Zilong Technology Co ltd
Central South University
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Central South University
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Abstract

The invention discloses a MnS nano-dot material, a ternary sodium electric precursor, preparation methods of the MnS nano-dot material and the ternary sodium electric precursor, and a ternary sodium electric anode material, wherein the preparation method of the MnS nano-dot material comprises the following steps: s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, a manganese salt and a sulfur-containing additive in a solvent to obtain a solution B; s2, dropwise adding the solution B into the solution A; s3, transferring the nano-dots into polytetrafluoroethylene to perform a hydrothermal reaction to obtain a nano-dot precursor; and (4) performing high-temperature sintering and etching to obtain the MnS nanodot material. The nano-dots in the material are uniformly distributed, the material structure is complete, the conductivity and the ion transmission rate of the electrode material can be effectively improved, the preparation process is simple, the flow is short, the raw materials are easy to obtain, no toxic or harmful substances are generated, and the large-scale production is easy to realize; the ternary sodium electro-precursor is modified by adopting the nano-dot material, so that surface byproducts are not generated, and the electrochemical performance of the material can be greatly improved.

Description

MnS nanodot material, ternary sodium electric precursor, anode material and preparation method
Technical Field
The invention relates to the technical field of sodium ion battery manufacturing, in particular to a MnS nanodot material, a ternary sodium electric precursor, preparation methods of the MnS nanodot material and the ternary sodium electric precursor, and a ternary sodium electric anode material.
Background
Sodium ion batteries have been increasingly studied in recent years, and the types of electrode materials have been increasing. Similar to lithium ion batteries, sodiumcomponents have received many studies due to their advantages of high specific capacity and good stability. Unlike lithium ion batteries, the ion radius of sodium ions is much larger than that of lithium ions, and therefore, the structural stability of ternary sodium electric materials in the ion transmission process is much worse than that of ternary materials in lithium ion batteries, and therefore, the ternary sodium electric materials still have larger intrinsic defects in the practical application of future sodium ion batteries. In order to overcome the above problems, researchers often adopt a surface coating modification method. The typical surface coating is mainly divided into a conductive layer and an inert protective layer, both of which exhibit different modification effects.
It is known that the smaller the particles of the coating layer, the better the coating effect, but when the particle size is as small as nanometer, the particles are easy to agglomerate and have uneven distribution, which seriously affects the performance of the material. The nano-dots change the mode of the traditional battery, have super-strong storage capacity and can greatly improve the charging speed. To mitigate agglomeration of the nanodots, the nanodots typically need to be confined by the template so that the nanodot material is uniformly supported on the template. Usually, the supported nanodots are mainly of metal particles, metal oxides, metal sulfides, and the like. The formation of the metal sulfide nano-dots is usually accompanied with the doping of corresponding heteroatoms (S atoms) of the substrate carbon material, and the carbon material of the substrate is modified, so that the modified heteroatom-modified porous carbon material is formed, the structural stability of the material main body is improved, and more stable ion diffusion channels are provided. The metal sulfide nanodots prepared by the existing method have the following defects: 1. due to element selection, the metal bond bonding capability between the nano-dots and the electrode material is poor, so that the composite effect between the nano-dots and the electrode material is influenced; 2. the existing metal sulfide nanodot has poor structural stability, and the application of the metal sulfide nanodot in an electrode material is influenced.
Disclosure of Invention
The invention provides a MnS nanodot material, a ternary sodium electric precursor, a positive electrode material and a preparation method, which are used for solving the technical problems in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a MnS nanodot material comprises the following steps:
s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, manganese salt and a sulfur-containing additive in a solvent, and adjusting the pH value to 5-7 to obtain a solution B;
s2, dropwise adding the solution B into the solution A, and adjusting the pH value to 8-10 to obtain a mixed solution;
s3, transferring the mixed solution into polytetrafluoroethylene to perform a hydrothermal reaction, and obtaining a nanodot precursor after the reaction is completed; and sintering the nanodot precursor at high temperature, and etching by using an acid solution to obtain the MnS nanodot material.
The technical scheme includes that the design idea is that a specific solution A and a specific solution B are subjected to coprecipitation reaction to generate a graphene-coated ZnAlMn-based layered hydroxide, the completion of the coprecipitation reaction and the complete formation of metal sulfides are further promoted through hydrothermal reaction, the morphology and the structure of the hydroxide are adjusted, and finally the nano-dot material with the specific morphology is formed through high-temperature sintering. In the coprecipitation reaction process, zinc ions of the laminates are partially replaced by aluminum ions, main laminates show positive charges, anions between layers are needed to offset the positive charges, so that charge balance is achieved, and in the reaction process, anions and sulfur-containing anions in the chelating agent play a role in balancing charges between layers. The nanodot material prepared by the method of the technical scheme has a hydrotalcite structure, the cations and the anions between the main layer plates of the material are adjustable, and the nanodot material has topology transformation property and can maintain the inherent property of invariable orientability of spatial configuration in a continuously changing space; manganese sulfide has metal elements similar to ternary materials, metal bond combining capacity is better, a composite effect is better, and meanwhile, manganese plays a main structural supporting role in a main body and a composite layer, so that the structural stability of the materials can be improved more effectively.
As a further preferable mode of the above technical solution, the zinc salt in S1 includes at least one of zinc nitrate, zinc acetate, and zinc oxalate, the aluminum salt includes at least one of aluminum nitrate, aluminum acetate, and aluminum oxalate, and a molar ratio of the zinc salt, the aluminum salt, and graphene oxide is (2 to 4): 1: (0.01-0.05).
As a further preferable mode of the above technical solution, in S1, the chelating agent is disodium EDTA, the manganese salt includes at least one of manganese nitrate, manganese acetate, and manganese oxalate, and the sulfur-containing additive is SDS or SDBS; the molar ratio of the chelating agent to the manganese salt to the sulfur-containing additive is 1: (0.1 to 0.5); the molar ratio of the chelating agent, manganese salt and sulphur-containing additive is further preferably 1: (0.1-0.2). The proportions of the above components ensure the solubility of the sulfur-containing additive and avoid substantial foaming during agitation.
As a further optimization of the technical scheme, the temperature of the hydrothermal reaction in S3 is 140-180 ℃, and the reaction time is 10-14 h; the hydrothermal reaction temperature is more preferably 140 to 160 ℃. The temperature range of the hydrothermal reaction can ensure that the hydrothermal reaction is carried out smoothly and the MnS nanodot precursor has a better precursor appearance.
In a further preferred embodiment of the above method, the temperature for the high-temperature sintering in S3 is 300 to 600 ℃ and the sintering time is 2 to 10 hours.
Based on the same technical concept, the invention also provides a MnS nano-dot material which is prepared by adopting the preparation method and has a hydrotalcite-like structure, and comprises a carbon material substrate and MnS nano-dots loaded on the carbon material substrate.
Based on the same technical concept, the invention also provides a ternary sodium electric precursor material, which comprises a ternary precursor matrix and MnS nano-dot materials coated on the surface of the ternary precursor matrix, wherein the MnS nano-dot materials are the MnS nano-dot materials or the MnS nano-dot materials prepared by the preparation method; the mass ratio of the MnS point material to the ternary precursor is (0.1-10): 100.
as a further optimization of the technical scheme, the molecular formula of the ternary precursor matrix is NaMn (1-m) N m C 6 H 5 O 7 Wherein N comprises at least two of Fe, ni, co and Cu, and x is more than or equal to 0.1 and less than or equal to 0.5.
Based on the same technical concept, the invention also provides a preparation method of the ternary sodium electric precursor material, which comprises the following steps:
s1, dissolving manganese salt, sodium salt and doped metal salt in a solvent according to a stoichiometric ratio, adding citric acid, and fully reacting to form a mixture; the doped metal salt is a salt substance of N, wherein the N comprises at least two of Fe, ni, co and Cu;
and S2, adding the MnS nanodot material into the mixture, uniformly stirring, and drying to obtain the ternary sodium electric precursor material.
As a further preferable mode of the above technical solution, a ratio of a sum of molar amounts of the manganese salt, the sodium salt and the doping metal salt in S1 to a molar amount of citric acid is (1 to 2): 1.
in a more preferable embodiment of the above method, the reaction temperature in S1 is 60 to 100 ℃.
Based on the same technical concept, the invention also provides a ternary sodium electric anode material which is prepared by sintering the ternary sodium electric precursor material at high temperature.
In the technical scheme, the high-temperature sintering temperature is preferably 700-1000 ℃, and the sintering time is preferably 2-12 h.
Compared with the prior art, the invention has the advantages that:
(1) The method comprises the steps of using hydrotalcite as a template, combining a carbon material, sintering and carrying out acid etching to prepare the carbon material-loaded MnS nano-dot material with the hydrotalcite layered structure. The nano-dots in the coating material are uniformly distributed, and the structure of the material is complete. The carbon material can effectively improve the conductivity of the electrode material, and the MnS nano-dots can promote the ion transmission rate of the material;
(2) The preparation method has the advantages of simple preparation process, short flow, easily obtained raw materials and no generation of toxic and harmful substances in the preparation process. The large-scale production is easy to realize;
(3) The ternary sodium electric anode material is subjected to coating modification based on the ternary sodium electric precursor, and the nanodot-coated modified ternary sodium electric anode material is synthesized by sintering, so that surface byproducts are not generated, and the electrochemical performance of the material can be greatly improved.
Drawings
Fig. 1 is an SEM image of the ternary sodium positive electrode material of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The MnS nanodot material of the embodiment is prepared by the following method:
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide is dispersed in 100ml of deionized water to obtain a solution A; 2mmol of EDTA-2Na and 2mmol of Mn (NO) 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water and 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) And transferring the mixed solution into polytetrafluoroethylene, carrying out hydrothermal reaction for 12h at 160 ℃, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nanodot precursor. Sintering the nanodot precursor at high temperature, cooling, and adding 2mol L of the cooled nanodot precursor -1 And etching the hydrotalcite-based carbon composite MnS nano-dot material for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based carbon composite MnS nano-dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and a MnS nano-dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano-dot material is the MnS nano-dot material of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 Dissolving O in 100ml of deionized water, adding 0.1mol of citric acid, and fully stirring at 80 ℃ for reaction until a gel-like mixture is formed; citric acid as complexing agent can complex effective metal ions to form NaMn (1-m) N m C 6 H 5 O 7 Microgels;
(2) Adding the MnS nanodot material into the gel-like mixture, continuously stirring and reacting for 1h, and drying at 120 ℃ for 12h to obtain the ternary sodium electro-precursor material.
The ternary sodium cathode material of the embodiment is prepared by the following method: the ternary sodium electrode of the present example was chargedThe precursor material is placed in a muffle furnace for high-temperature sintering, preburning at 300 ℃ for 2h, and further high-temperature sintering at 900 ℃ for 10h to obtain the ternary sodium electric anode material (represented as MnS @ C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 ). The SEM results are shown in FIG. 1.
Na complexed with MnS @ C 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The metallic sodium is rolled into thin sheets and punched into 14mm round sodium sheets serving as the negative electrode, and 1mol/L of NaClO is added 4 The solution is used as electrolyte, and a glass fiber membrane with the diameter of 16mm is used as a diaphragm.
And after the battery is assembled and aged for 12 hours, carrying out charge and discharge tests of different potentials. The specific discharge capacity of the calcined sample is 123.7mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention ratio was 86.6%.
Comparative example 1
Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml of deionized water, 0.1mol of citric acid is added and the reaction is stirred well at 80 ℃ until a gel-like mixture is formed. After gel is formed, drying the gel at 120 ℃ for 12h, then placing the gel in a muffle furnace for high-temperature sintering, presintering the gel at 300 ℃ for 2h, and further sintering the gel at 900 ℃ for 10h to obtain the final Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 And (3) obtaining the product. The conductive material is mixed with Acetylene Black (AB) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the mass ratio of 8 to 1, N-methylpyrrolidone (NMP) serving as a solvent is placed in a small beaker, and the mixture is stirred and mixed for 2 hours at the rotating speed of 800r/min, so that slurry is obtained. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. Metallic sodium was rolled into a sheet and punched into 14mm round sodium pieces serving as negative electrodes with 1mol/L of NaClO 4 The solution is used as electrolyte, and the type with the diameter of 16mm is a glass fiber membrane which is a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The specific discharge capacity of the calcined sample is 65.8mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention rate was 52.2%.
Comparative example 2
(1) Adding 5mmol of Zn (NO) 3 ) 2 And 2mmol Al (NO) 3 ) 3 Dispersed in 100ml of deionized water to obtain solution A. Then 2mmol of EDTA-2Na and 2mmol of Mn (NO) are added 3 ) 2 And 0.2mmol SDS dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B, dropwise adding the solution B into the solution A under the protection of nitrogen atmosphere, further adjusting the pH value to 9-10, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction at 160 ℃ for 12h, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based precursor. Sintering the precursor at high temperature, cooling and using 2mol L -1 And etching the hydrotalcite-based MnS nanodots for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based MnS nanodots.
(2) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml of deionized water, 0.1mol of citric acid is added and the reaction is stirred well at 80 ℃ until a gel-like mixture is formed. After gel is formed, adding the MnS nanodots in the step (1) into the gel-like mixture, continuously stirring for reaction for 1h, drying the gel at 120 ℃ for 12h, placing the gel in a muffle furnace for high-temperature sintering, presintering at 300 ℃ for 2h, and further sintering at 900 ℃ for 10h to obtain the final MnS nanodot compounded Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 。
Na composited with MnS nanodots 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The metallic sodium is rolled into thin sheets and punched into 14mm round sodium sheets serving as the negative electrode, and 1mol/L of NaClO is added 4 The solution is used as electrolyte, and the type with the diameter of 16mm is a glass fiber membrane which is a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The specific discharge capacity of the calcined sample is 89.6mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention ratio was 76.3%.
Comparative example 3
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide was dispersed in 100ml of deionized water to obtain solution A. Then 2mmol of EDTA-2Na and 2mmol of Mn (NO) are added 3 ) 2 Dissolved in 50ml of deionized water and further 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B, dropwise adding the solution B into the solution A under the protection of nitrogen atmosphere, further adjusting the pH value to 9-10, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction at 160 ℃ for 12h, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based precursor. Sintering the precursor at high temperature, cooling and using 2mol L -1 And etching the nano dots by using a hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnO nano dots.
(2) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml of deionized water, 0.1mol of citric acid is added and the reaction is stirred well at 80 ℃ until a gel-like mixture is formed. After gel is formed, adding MnO nanodots in the step (1) into the gel-like mixture, continuously stirring for reaction for 1h, drying the gel at 120 ℃ for 12h, placing the gel in a muffle furnace for high-temperature sintering, presintering at 300 ℃ for 2h, and further sintering at 900 ℃ for 10h to obtain the final MnO @ C composite Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 。
Na coated with MnO @ C 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing the conductive agent Acetylene Black (AB) and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. Metallic sodium was rolled into a sheet and punched into 14mm round sodium pieces serving as negative electrodes with 1mol/L of NaClO 4 The solution is used as electrolyte, and a glass fiber membrane with the diameter of 16mm is used as a diaphragm.
And after the battery is assembled and aged for 12 hours, carrying out charge and discharge tests of different potentials. The specific discharge capacity of the calcined sample is 118.3mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention ratio was 84.9%.
Example 2
The MnS nanodot material is prepared by the following method:
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 10mg of graphene oxide is dispersed in 100ml of deionized water to obtain a solution A; 2mmol of EDTA-2Na and 2mmol of Mn (NO) 3 ) 2 And 0.2mmol SDS dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) And transferring the mixed solution into polytetrafluoroethylene, carrying out hydrothermal reaction for 12h at 160 ℃, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nanodot precursor. Sintering the nanodot precursor at high temperature, cooling, and adding 2mol L of the cooled nanodot precursor -1 And etching the hydrotalcite-based carbon composite MnS nanodot material for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based carbon composite MnS nanodot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and a MnS nano-dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano-dot material is the MnS nano-dot material of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml of deionized water, 0.1mol of citric acid is added and the reaction is stirred well at 80 ℃ until a gel-like mixture is formed.
(2) Adding the MnS nanodot material into the gel-like mixture, continuously stirring and reacting for 1h, and drying at 120 ℃ for 12h to obtain the ternary sodium electro-precursor material.
The ternary sodium cathode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace for high-temperature sintering, presintering is carried out for 2 hours at 300 ℃, and then high-temperature sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric anode material (expressed as MnS @ C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na complexed with MnS @ C 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and assembling the pole piece into a CR2032 type button cell in the glove box. The metallic sodium is rolled into thin sheets and punched into 14mm round sodium sheets serving as the negative electrode, and 1mol/L of NaClO is added 4 The solution is used as electrolyte, and a glass fiber membrane with the diameter of 16mm is used as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The discharge specific capacity of the calcined sample is 106.8mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention rate was 82.7%.
Example 3
The MnS nanodot material of the embodiment is prepared by the following method:
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 30mg of graphene oxide dispersed in 100ml of deionized water,obtaining a solution A; 2mmol of EDTA-2Na and 2mmol of Mn (NO) 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water and 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) And transferring the mixed solution into polytetrafluoroethylene, carrying out hydrothermal reaction for 12h at 160 ℃, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nanodot precursor. Sintering the nanodot precursor at high temperature, cooling, and adding 2mol L -1 And etching the hydrotalcite-based carbon composite MnS nano-dot material for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based carbon composite MnS nano-dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and a MnS nano-dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano-dot material is the MnS nano-dot material of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 Dissolving O in 100ml of deionized water, adding 0.1mol of citric acid, and fully stirring at 80 ℃ for reaction until a gel-like mixture is formed;
(2) Adding the MnS nanodot material into the gel-like mixture, continuously stirring and reacting for 1h, and drying at 120 ℃ for 12h to obtain the ternary sodium electro-precursor material.
The ternary sodium cathode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace for high-temperature sintering, presintering is carried out for 2h at 300 ℃, and then high-temperature sintering is further carried out for 10h at 900 ℃ to obtain the ternary sodium electric anode material (represented as MnS @ C compounded Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na complexed with MnS @ C 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. Metallic sodium was rolled into a sheet and punched into 14mm round sodium pieces serving as negative electrodes with 1mol/L of NaClO 4 The solution is used as electrolyte, and a glass fiber membrane with the diameter of 16mm is used as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The discharge specific capacity of the calcined sample is 120.4mA h g after circulating for 100 circles under the current density of 1C under the voltage of 2-4V -1 The capacity retention rate was 85.8%.
Example 4
The MnS nanodot material of the embodiment is prepared by the following method:
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide is dispersed in 100ml of deionized water to obtain a solution A; 2mmol of EDTA-2Na and 2mmol of Mn (NO) 3 ) 2 And 0.2mmol SDS dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) And transferring the mixed solution into polytetrafluoroethylene, carrying out hydrothermal reaction for 12h at 160 ℃, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nanodot precursor. Subjecting the nanodot precursor toSintering at high temperature, cooling, and then using 2mol L -1 And etching the hydrotalcite-based carbon composite MnS nanodot material for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based carbon composite MnS nanodot material.
The ternary sodium electric precursor material comprises a ternary precursor matrix and MnS nanodot materials coated on the surface of the ternary precursor matrix, wherein the MnS nanodot materials are the MnS nanodot materials in the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) Adding 0.035mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Cu(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml of deionized water, 0.1mol of citric acid is added and the reaction is stirred well at 80 ℃ until a gel-like mixture is formed.
(2) Adding the MnS nanodot material into the gel-like mixture, continuously stirring and reacting for 1h, and drying at 120 ℃ for 12h to obtain the ternary sodium electro-precursor material.
The ternary sodium cathode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace for high-temperature sintering, presintering is carried out for 2 hours at 300 ℃, and then high-temperature sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric anode material (expressed as MnS @ C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na complexed with MnS @ C 0.67 Mn 0.7 Cu 0.2 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing on toughened glass, transferring to a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm from the punching sheet, and drying in the vacuum drying oven at 105 DEG CDrying for 4h, placing in a glove box with water content and oxygen content lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transfer process, and assembling into a CR2032 button cell in the glove box. Metallic sodium was rolled into a sheet and punched into 14mm round sodium pieces serving as negative electrodes with 1mol/L of NaClO 4 The solution is used as electrolyte, and a glass fiber membrane with the diameter of 16mm is used as a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The specific discharge capacity of the calcined sample is 103.7mA h g after the sample is circulated for 100 circles under the voltage of 2-4V and the current density of 1C -1 The capacity retention rate was 82.1%.
Example 5
The MnS nanodot material of the embodiment is prepared by the following method:
(1) Adding 5mmol of Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide is dispersed in 100ml of deionized water to obtain a solution A; 2mmol of EDTA-2Na and 2mmol of Mn (NO) 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water and 2mol L -1 Adjusting the pH value of NaOH solution to 5.5-6 to obtain solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) And transferring the mixed solution into polytetrafluoroethylene, carrying out hydrothermal reaction for 12h at 160 ℃, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nanodot precursor. Sintering the nanodot precursor at high temperature, cooling, and adding 2mol L -1 And etching the hydrotalcite-based carbon composite MnS nanodot material for 5 hours by using a hydrochloric acid solution to obtain the hydrotalcite-based carbon composite MnS nanodot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and a MnS nano-dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano-dot material is the MnS nano-dot material of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.025mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.02mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 Dissolving O in 100ml of deionized water, adding 0.1mol of citric acid, and fully stirring at 80 ℃ for reaction until a gel-like mixture is formed;
(2) Adding the MnS nanodot material into the gel-like mixture, continuously stirring and reacting for 1h, and drying at 120 ℃ for 12h to obtain the ternary sodium electro-precursor material.
The ternary sodium cathode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace for high-temperature sintering, presintering is carried out for 2 hours at 300 ℃, and then high-temperature sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric anode material (expressed as MnS @ C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na complexed with MnS @ C 0.67 Mn 0.5 Ni 0.4 Fe 0.1 O 2 Mixing the conductive agent with Acetylene Black (AB) and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, flatly placing the current collector aluminum foil on toughened glass, transferring the current collector aluminum foil to a vacuum drying oven at 85 ℃ for drying for 4h, preparing a pole piece with the diameter of 12mm by punching, drying for 4h at 105 ℃ in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content both lower than 0.1ppm and filled with argon atmosphere for 4h to reduce the water absorbed by the pole piece in the transferring process, and then assembling the pole piece into a CR2032 type button cell in the glove box. Metallic sodium was rolled into a sheet and punched into 14mm round sodium pieces serving as negative electrodes with 1mol/L of NaClO 4 The solution is used as electrolyte, and the type with the diameter of 16mm is a glass fiber membrane which is a diaphragm.
After the battery is assembled and aged for 12 hours, the charging and discharging tests of different potentials are carried out. The calcined sample is cycled for 100 circles under the voltage of 2-4V and the current density of 1CThe specific discharge capacity of the lithium secondary battery is 126.3mA h g -1 The capacity retention ratio was 84.9%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (13)

1. A preparation method of a MnS nanodot material is characterized by comprising the following steps:
s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, manganese salt and a sulfur-containing additive in a solvent, and adjusting the pH value to 5-7 to obtain a solution B;
s2, dropwise adding the solution B into the solution A, and adjusting the pH value to 8-10 to obtain a mixed solution;
s3, transferring the mixed solution into polytetrafluoroethylene to carry out hydrothermal reaction, and obtaining a nanodot precursor after the reaction is finished; and sintering the nanodot precursor at a high temperature, and etching with an acid solution to obtain the MnS nanodot material.
2. The method for preparing a MnS nanodot material as claimed in claim 1, wherein the zinc salt in S1 comprises at least one of zinc nitrate, zinc acetate and zinc oxalate, the aluminum salt comprises at least one of aluminum nitrate, aluminum acetate and aluminum oxalate, and the molar ratio of the zinc salt, the aluminum salt and the graphene oxide is (2-4): 1: (0.01-0.05).
3. The method for preparing a MnS nanodot material as claimed in claim 1, wherein the chelating agent in S1 is disodium EDTA, the manganese salt comprises at least one of manganese nitrate, manganese acetate and manganese oxalate, and the sulfur-containing additive is SDS or SDBS; the molar ratio of the chelating agent to the manganese salt to the sulfur-containing additive is 1: (0.1-0.5).
4. The method for preparing MnS nanodot material as claimed in claim 1, wherein the hydrothermal reaction temperature in S3 is 140-180 ℃ and the reaction time is 10-14 hours.
5. The method for preparing MnS nanodot material as claimed in any one of claims 1 to 4, wherein the sintering temperature at the high temperature of S3 is 300 to 600 ℃ and the sintering time is 2 to 10 hours.
6. The MnS nanodot material, which is produced by the production method according to any one of claims 1 to 5, has a hydrotalcite-like structure, and comprises a carbon material substrate and MnS nanodots supported on the carbon material substrate.
7. A ternary sodium electric precursor material is characterized by comprising a ternary precursor matrix and a MnS nanodot material coated on the surface of the ternary precursor matrix, wherein the MnS nanodot material is the MnS nanodot material disclosed in claim 6 or prepared by the preparation method disclosed in any one of claims 1-5; the mass ratio of the MnS point material to the ternary precursor is (0.1-10): 100.
8. the ternary sodium electro-precursor material of claim 7, wherein the ternary precursor matrix has the formula NaMn (1-m) N m C 6 H 5 O 7 Wherein, N comprises at least two of Fe, ni, co and Cu, and x is more than or equal to 0.1 and less than or equal to 0.5.
9. A method for preparing the ternary sodium electro-precursor material according to claim 7 or 8, characterized in that it comprises the following steps:
s1, dissolving manganese salt, sodium salt and doped metal salt in a stoichiometric ratio in a solvent, adding citric acid, and fully reacting to form a mixture; the doped metal salt is a salt substance of N, wherein the N comprises at least two of Fe, ni, co and Cu;
and S2, adding the MnS nano-dot material into the mixture, uniformly stirring, and drying to obtain the ternary sodium electric precursor material.
10. The method for preparing the ternary sodium electro-precursor material according to claim 9, wherein the ratio of the sum of the molar amounts of the manganese salt, the sodium salt and the doping metal salt to the molar amount of the citric acid in S1 is (1-2): 1.
11. the method for preparing a ternary sodium electro-precursor material according to claim 9, wherein the reaction temperature in S1 is 60-100 ℃.
12. The ternary sodium electric cathode material is characterized by being prepared by sintering the ternary sodium electric precursor material of claim 7 or 8 at a high temperature.
13. The ternary sodium electric cathode material according to claim 12, wherein the high-temperature sintering temperature is 700-1000 ℃, and the sintering time is 2-12 h.
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