CN108394937B - Preparation method of manganese iron sulfide solid solution and application of manganese iron sulfide solid solution as negative electrode material of lithium ion battery - Google Patents
Preparation method of manganese iron sulfide solid solution and application of manganese iron sulfide solid solution as negative electrode material of lithium ion battery Download PDFInfo
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Abstract
VulcanizationThe invention discloses a preparation method of a ferromanganese solid solution and application of the ferromanganese solid solution in a lithium ion battery cathode material. The method has the advantages of low required temperature, short time, low energy consumption, simple operation, low requirements on instruments, low cost and the like. A solid solution of manganese sulfide and iron sulfide is used as a negative electrode material of a lithium ion battery, the lithium ion battery is assembled into a simulated battery, and the lithium battery performance of the simulated battery is tested. The research finds that 1Ag is added‑1Under high current density, the capacity after 1000 times of circulation is still maintained at 500mAhg‑1And exhibits excellent cycle stability.
Description
Technical Field
The invention relates to preparation of inorganic energy materials, in particular to a preparation method of a manganese iron sulfide solid solution and application of the manganese iron sulfide solid solution as a lithium ion battery cathode material.
Background
With the unprecedented development of modern society, the demand of various countries for energy sources is increasing. Traditional fossil energy and resources have not been able to meet the needs of modern human society. The use of new clean energy sources such as wind, solar, geothermal and tidal energy is greatly restricted by conditions, so it is an important topic to develop certain energy storage devices to store these energy sources. The basis for the use and development of new energy sources is therefore the development of high performance energy storage and conversion devices, i.e. chemical power sources. Lithium ion batteries have received wide attention from all societies as a new type of portable batteries due to their advantages of high energy density, long life, rapid charge and discharge, and the like. However, with the continuous popularization of the application range, the performance requirements of the lithium battery are increasingly raised and explored. Therefore, the development direction in this field is mainly to search and develop high-performance electrode materials. Since the properties of the electrode material determine the performance of the overall battery.
Solid solutions are uniformly mixed solid solutions formed by dissolving atoms of other constituents (solute atoms) in a crystal lattice of a certain constituent as a solvent, and the crystal structure type of the solvent is maintained. The formation of the solid solution can form a large number of defects in the substrate material, and the existence of the defects in the material can obviously influence the transport, storage and reaction properties of electrons and ions in the solid, interface and surface, so that the specific capacity of the substrate material is improved; meanwhile, the existence of the defects can provide more ion transport channels, and the conductivity of the material is improved; the presence of the defect structure may also provide additional lithium storage sites, which may also increase the specific capacity of the substrate material. The transition metal sulfide has the advantages of good conductivity, higher theoretical specific capacity, low price, environmental friendliness and the like. The current methods for synthesizing transition metal sulfide solid solutions include: high temperature solid phase method, electrochemical deposition method, chemical vapor deposition method (CVD), and the like. Without exception, the synthesis methods have the defects of long synthesis time, high energy consumption, high requirements on operation and instruments, high synthesis cost and the like.
Disclosure of Invention
In view of the above, there is a need to provide a preparation method and application of a solid solution of manganese sulfide and iron sulfide, which has the advantages of low temperature, short time, low energy consumption, simple operation, low requirements on instruments, and low cost.
A process for preparing solid solution of ferromanganese sulfide from the iron hexacyanoferrate (Mn) as the prussian blue coordination compound3[Fe(CN)6]2) And vulcanizing under the protection of inert gas to obtain the manganese sulfide iron solid solution as a precursor.
Preferably, the preparation method of the solid solution of the manganese sulfide iron comprises the following steps:
mixing: grinding and uniformly mixing the precursor manganese hexacyanoferrate and excessive sulfur powder to obtain a mixture;
and (3) calcining: and (3) placing the mixture in a sealed tube furnace, and calcining under the protection of inert gas to obtain the manganese sulfide iron solid solution.
Preferably, the calcining step specifically comprises: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, wherein the temperature rise process comprises the steps of firstly raising the temperature from room temperature to 250-280 ℃, keeping the temperature at 250-280 ℃ for calcining for 1-2 hours, then raising the temperature from 250-280 ℃ to 550-600 ℃, keeping the temperature at 550-600 ℃ for calcining for 6-7 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Preferably, the calcining step specifically comprises: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, wherein in the heating process, the temperature is increased from room temperature to 250-280 ℃ at the heating rate of 5-7 ℃/min, the temperature is maintained at 250-280 ℃ for calcining for 1-2 hours, then the temperature is increased from 250-280 ℃ to 550-600 ℃ at the heating rate of 3-5 ℃/min, the temperature is maintained at 550-600 ℃ for calcining for 6-7 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Preferably, the calcining step specifically comprises: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, heating from room temperature to 280 ℃ at a heating rate of 6 ℃/min, keeping the temperature of 280 ℃ for calcining for 1 hour, heating from 280 ℃ to 600 ℃ at a heating rate of 4 ℃/min, keeping the temperature of 600 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Preferably, in the mixing step, 1 molar part of precursor manganese hexacyanoferrate and at least 5 molar parts of sulfur powder are ground and uniformly mixed to obtain a mixture.
Preferably, the preparation method of the solid solution of the manganese sulfide iron further comprises the following steps:
preparing a precursor: respectively preparing soluble solid potassium hexacyanoferrate and anhydrous manganese sulfate into solutions, mixing the two solutions, wherein the ratio of the molar weight of iron atoms to the molar weight of manganese atoms in the mixed solution is 2:3, magnetically stirring for 1-2 hours to obtain brown precipitates, repeatedly centrifuging the brown precipitates for a plurality of times by using distilled water to obtain solid precipitates, separating the solid precipitates, and drying for 8-10 hours to obtain brown powdery precursor manganese hexacyanoferrate.
Preferably, the preparation method of the precursor comprises the specific steps of mixing 0.1 mol/L soluble solid potassium hexacyanoferrate solution with the thickness of 20-30 m L and 0.1 mol/L anhydrous manganese sulfate solution with the thickness of 20-30 m L, magnetically stirring for 1-2 hours to obtain brown precipitate, repeatedly centrifuging the brown precipitate for a plurality of times by using distilled water to obtain solid precipitate, separating the solid precipitate, and drying at 50-90 ℃ for at least 2 hours to obtain brown powdery precursor manganese hexacyanoferrate.
Preferably, the preparation method of the precursor comprises the specific steps of mixing 0.1 mol/L soluble solid potassium hexacyanoferrate solution with the concentration of 20m L and 0.1 mol/L anhydrous manganese sulfate solution with the concentration of 30m L, carrying out magnetic stirring for 2 hours to obtain brown precipitate, repeatedly centrifuging the brown precipitate for a plurality of times by using distilled water to obtain solid precipitate, separating the solid precipitate, and drying at the temperature of 60 ℃ for 10 hours to obtain brown powdery precursor manganese hexacyanoferrate.
The application of the manganese iron sulfide solid solution as the negative electrode material of the lithium ion battery.
The invention relates to a preparation method and application of a manganese iron sulfide solid solution, wherein a Prussian blue-like coordination compound manganese hexacyanoferrate is selected as a precursor, and Cyanide (CN) in the coordination compound is utilized-) And hexacyanoferrate ([ Fe (CN))6]3-) Easy to be regulated and controlled, and sulfurizing in inert gas to obtain solid solution of manganese sulfide and iron sulfide. The method has the advantages of low required temperature, short time, low energy consumption, simple operation, low requirements on instruments, low cost and the like. The solid solution is used as an electrode material of a lithium ion battery and assembled into a simulated battery, and the lithium battery performance of the simulated battery is tested. The research finds that 1Ag is added-1Under high current density, the capacity after 1000 times of circulation is still maintained at 500mAhg-1And exhibits excellent cycle stability.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a solid solution of ferromanganese sulfide.
FIG. 2 is an enlarged partial view of the X-ray powder diffraction pattern of a solid solution of ferromanganese sulfide.
FIG. 3 is an X-ray photoelectron spectroscopy analysis chart of a solid solution of ferromanganese sulfide.
FIG. 4 is an EDS elemental analysis chart of a solid solution of ferromanganese sulfide.
FIG. 5 is a graph of cycle life performance of lithium ion batteries using solid solutions of manganese iron sulfide.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
a preparation method of a manganese sulfide iron solid solution comprises the following steps of using a Prussian blue-like coordination compound manganese hexacyanoferrate as a precursor, and vulcanizing under the protection of nitrogen gas to obtain the manganese sulfide iron solid solution:
mixing: 1 molar part of precursor manganese hexacyanoferrate and 5 molar parts of sulfur powder are mixed and ground uniformly by an agate mortar to obtain a mixture.
And (3) calcining: and placing the mixture in a sealed tube furnace, calcining under the protection of nitrogen gas, heating from room temperature to 280 ℃ at a heating rate of 6 ℃/min, keeping the temperature of 280 ℃ for calcining for 1 hour, heating from 280 ℃ to 600 ℃ at a heating rate of 4 ℃/min, keeping the temperature of 600 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Example 2:
a preparation method of a manganese sulfide iron solid solution uses a Prussian blue-like coordination compound manganese hexacyanoferrate as a precursor, and under the protection of argon gas, the manganese sulfide iron solid solution is obtained by vulcanization, and comprises the following steps:
the preparation of the precursor comprises the steps of adding 1mmol of soluble solid potassium hexacyanoferrate into a beaker containing 20m L of distilled water, stirring and dissolving, adding 2mmol of anhydrous manganese sulfate into a beaker containing 20m L of distilled water, stirring and dissolving, mixing the two, magnetically stirring for 2 hours to obtain brown precipitate, repeatedly centrifuging the brown precipitate for a plurality of times by using distilled water to obtain solid precipitate, separating the solid precipitate, and drying at 60 ℃ for 8 hours to obtain brown powdery precursor manganese hexacyanoferrate.
Mixing: 1 molar part of precursor manganese hexacyanoferrate and 5 molar parts of sulfur powder are mixed and ground uniformly by an agate mortar to obtain a mixture.
And (3) calcining: and placing the mixture in a sealed tube furnace, calcining under the protection of argon gas, heating from room temperature to 280 ℃ at a heating rate of 6 ℃/min, keeping the temperature of 280 ℃ for calcining for 1 hour, heating from 280 ℃ to 600 ℃ at a heating rate of 4 ℃/min, keeping the temperature of 600 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Example 3:
a preparation method of a manganese sulfide iron solid solution comprises the following steps of using a Prussian blue-like coordination compound manganese hexacyanoferrate as a precursor, and vulcanizing under the protection of nitrogen gas to obtain the manganese sulfide iron solid solution:
the preparation of the precursor comprises the steps of mixing 0.1 mol/L soluble solid potassium hexacyanoferrate solution with the concentration of 20m L and 0.1 mol/L anhydrous manganese sulfate solution with the concentration of 30m L, magnetically stirring for 2 hours to obtain brown precipitate, repeatedly centrifuging the brown precipitate for a plurality of times by using distilled water to obtain solid precipitate, separating the solid precipitate, and drying at the temperature of 60 ℃ for 10 hours to obtain brown powdery precursor manganese hexacyanoferrate.
Mixing: 1 molar part of precursor manganese hexacyanoferrate and 10 molar parts of sulfur powder are mixed and ground uniformly by an agate mortar to obtain a mixture.
And (3) calcining: and placing the mixture in a sealed tube furnace, calcining under the protection of nitrogen gas, heating from room temperature to 250 ℃ at a heating rate of 5 ℃/min, keeping the temperature at 250 ℃ for calcining for 1 hour, heating from 250 ℃ to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature at 550 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
Example 4:
a preparation method of a manganese sulfide iron solid solution uses a Prussian blue-like coordination compound manganese hexacyanoferrate as a precursor, and under the protection of argon gas, the manganese sulfide iron solid solution is obtained by vulcanization, and comprises the following steps:
the preparation of the precursor comprises the steps of mixing 0.1 mol/L soluble solid potassium hexacyanoferrate solution with the concentration of 30m L and 0.1 mol/L anhydrous manganese sulfate solution with the concentration of 40m L, magnetically stirring for 2 hours to obtain brown precipitate, repeatedly centrifuging the brown precipitate for a plurality of times by using distilled water to obtain solid precipitate, separating the solid precipitate, and drying at the temperature of 60 ℃ for 10 hours to obtain brown powdery precursor manganese hexacyanoferrate.
Mixing: 1 molar part of precursor manganese hexacyanoferrate and 10 molar parts of sulfur powder are mixed and ground uniformly by an agate mortar to obtain a mixture.
And (3) calcining: and placing the mixture in a sealed tube furnace, calcining under the protection of argon gas, heating from room temperature to 280 ℃ at a heating rate of 7 ℃/min, keeping the temperature of 280 ℃ for calcining for 1 hour, heating from 280 ℃ to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature of 600 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
We carried out the following experimental analysis of the obtained product:
first, the ferromanganese sulfide solid solution is subjected to X-ray diffraction analysis, as shown in an X-ray powder diffraction diagram of the ferromanganese sulfide solid solution in FIG. 1, which shows that the product only has a set of XRD diffraction peaks corresponding to MnS. In the case of a simple mixture of MnS and FeS, there should be two sets of XRD diffraction peaks, one corresponding to FeS and one corresponding to MnS.
As shown in the enlarged partial X-ray powder diffraction pattern of the solid solution of ferromanganese sulfide of fig. 2, when one element is substituted for another in the crystal lattice after the solid solution is formed, the unit cell parameters change and the peak position (i.e., 2 θ angle) of XRD shifts.
Thus indicating that the sample was not a simple mixture of manganese sulfide and iron sulfide.
Then, performing X-ray photoelectron spectroscopy analysis on the ferromanganese sulfide solid solution, wherein as shown in FIG. 3, the X-ray photoelectron spectroscopy analysis on the ferromanganese sulfide solid solution shows that the peak at 642eV is assigned to Mn2p 3/2, and the peak at 653eV is assigned to Mn2p 1/2, which indicates that manganese exists in the material; the peak at 711eV is assigned to Fe2p 3/2, and the peak at 724eV is assigned to Fe2p 1/2, indicating that the iron element exists in the material; the peak at 642eV is assigned to Mn2p 3/2, and the peak at 653eV is assigned to Mn2p 1/2, indicating that manganese is present in the material; the peak at 162eV is assigned to S2 p 3/2 and the peak at 164eV is assigned to S2 p 1/2, indicating the presence of elemental sulfur in the material; we can find that the Fe element is indeed present in the sample.
FIG. 4 is an EDS elemental analysis chart of a solid solution of ferromanganese sulfide, which shows that the solid solution contains three elements of sulfur, iron and manganese.
According to the analysis of fig. 1, fig. 2, fig. 3 and fig. 4, the manganese iron sulfide solid solution is determined to be successfully synthesized.
And then, carrying out an experiment on the battery performance of the obtained product, wherein the assembly process is carried out in a glove box filled with high-purity argon, the water content and the oxygen content are both lower than 0.1ppm, the copper foil coated with manganese iron sulfide is used as a positive electrode, a high-purity lithium sheet is used as a negative electrode, the electrolyte is 1M L iPF6 (EC: DMC =1:1, volume), the battery is assembled, a sealing machine is used for packaging in the glove box, and the battery performance is tested after standing for 6 hours at room temperature.
As shown in the cycle life performance chart of the lithium ion battery of FIG. 5, 1Ag is used-1Under high current density, the capacity after 1000 times of circulation is still maintained at 500mAhg-1The coulombic efficiency reaches more than 98 percent, and the excellent cycle stability performance is shown.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of a manganese sulfide iron solid solution is characterized by comprising the following steps: using a prussian blue-like coordination compound manganese hexacyanoferrate as a precursor, and vulcanizing under the protection of inert gas to obtain a manganese iron sulfide solid solution; the method comprises the following steps:
mixing: grinding and uniformly mixing the precursor manganese hexacyanoferrate and excessive sulfur powder to obtain a mixture;
and (3) calcining: placing the mixture in a sealed tube furnace, and calcining under the protection of inert gas to obtain a manganese iron sulfide solid solution;
the calcining step specifically comprises: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, wherein in the heating process, the temperature is increased from room temperature to 250-280 ℃ at the heating rate of 5-7 ℃/min, the temperature is maintained at 250-280 ℃ for calcining for 1-2 hours, then the temperature is increased from 250-280 ℃ to 550-600 ℃ at the heating rate of 3-5 ℃/min, the temperature is maintained at 550-600 ℃ for calcining for 6-7 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
2. The method for producing a solid solution of ferromanganese sulfide according to claim 1, characterized in that: the calcining step specifically comprises: and placing the mixture in a sealed tube furnace, calcining under the protection of inert gas, heating from room temperature to 280 ℃ at a heating rate of 6 ℃/min, keeping the temperature of 280 ℃ for calcining for 1 hour, heating from 280 ℃ to 600 ℃ at a heating rate of 4 ℃/min, keeping the temperature of 600 ℃ for calcining for 6 hours, and cooling to room temperature to obtain the manganese sulfide iron solid solution.
3. The method for producing a solid solution of ferromanganese sulfide according to any one of claims 1 to 2, characterized in that: in the mixing step, 1 molar part of precursor manganese hexacyanoferrate and at least 5 molar parts of sulfur powder are ground and uniformly mixed to obtain a mixture.
4. The method for producing a solid solution of ferromanganese sulfide according to claim 3, characterized in that: further comprising the steps of:
preparing a precursor: respectively preparing soluble solid potassium hexacyanoferrate and anhydrous manganese sulfate into solutions, mixing the two solutions, wherein the ratio of the molar weight of iron atoms to the molar weight of manganese atoms in the mixed solution is 2:3, magnetically stirring for 1-2 hours to obtain brown precipitates, repeatedly centrifuging the brown precipitates for a plurality of times by using distilled water to obtain solid precipitates, separating the solid precipitates, and drying for 8-10 hours to obtain brown powdery precursor manganese hexacyanoferrate.
5. The preparation method of the manganese ferric sulfide solid solution according to claim 4, wherein the preparation step of the precursor comprises the steps of mixing a 0.1 mol/L soluble solid potassium hexacyanoferrate solution with a volume of 20-30 m L with a 0.1 mol/L anhydrous manganese sulfate solution with a volume of 20-30 m L, magnetically stirring for 1-2 hours to obtain a brown precipitate, repeatedly centrifuging the brown precipitate with distilled water for several times to obtain a solid precipitate, separating the solid precipitate, and drying at 50-90 ℃ for at least 2 hours to obtain a brown powdery precursor manganese hexacyanoferrate.
6. The method for preparing the manganese ferric sulfide solid solution according to claim 5, wherein the step of preparing the precursor comprises the steps of mixing a 0.1 mol/L soluble solid potassium hexacyanoferrate solution with the concentration of 20m L with a 0.1 mol/L anhydrous manganese sulfate solution with the concentration of 30m L, magnetically stirring for 2 hours to obtain a brown precipitate, repeatedly centrifuging the brown precipitate for several times by using distilled water to obtain a solid precipitate, separating the solid precipitate, and drying at the temperature of 60 ℃ for 10 hours to obtain a brown powdery precursor manganese hexacyanoferrate.
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| CN105084393A (en) * | 2014-05-05 | 2015-11-25 | 吴学文 | Manganese hexacyanoferrate crystalline nanoparticles and preparation method for nuclear magnetic resonance contrast agent using same |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
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| CN105084393A (en) * | 2014-05-05 | 2015-11-25 | 吴学文 | Manganese hexacyanoferrate crystalline nanoparticles and preparation method for nuclear magnetic resonance contrast agent using same |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
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