CN112607792B - Sodium-ion battery negative electrode material, and preparation method and application thereof - Google Patents

Sodium-ion battery negative electrode material, and preparation method and application thereof Download PDF

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CN112607792B
CN112607792B CN202011492700.9A CN202011492700A CN112607792B CN 112607792 B CN112607792 B CN 112607792B CN 202011492700 A CN202011492700 A CN 202011492700A CN 112607792 B CN112607792 B CN 112607792B
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containing compound
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CN112607792A (en
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章根强
李�杰
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University of Science and Technology of China USTC
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Abstract

The invention relates to the technical field of sodium-ion batteries, in particular to a sodium-ion battery cathode material, and a preparation method and application thereof. The preparation method comprises the following steps: A) mixing 2-mercaptopyridine and a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on 2-mercaptopyridine and a metal compound, and drying an obtained product to obtain precursor powder; the metal compound comprises one or more of a cobalt-containing compound, a nickel-containing compound, a manganese-containing compound, an iron-containing compound, a copper-containing compound, a tin-containing compound, a molybdenum-containing compound, a tungsten-containing compound and a zinc-containing compound; B) and calcining the precursor powder to obtain the sodium-ion battery negative electrode material. The sodium ion battery cathode material is synthesized by a simple solid phase method or a hydrothermal method, and the prepared sodium ion battery cathode material has the advantages of high sodium storage capacity, long cycle life, excellent rate capability and low cost, and is an ideal cathode material of a sodium ion battery.

Description

Sodium ion battery negative electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery cathode material, and a preparation method and application thereof.
Background
In recent years, the rapid development of portable electronic devices and electric vehicles has greatly pushed research into the development of energy storage systems with high efficiency and low cost. Sodium ion batteries are receiving more and more attention due to abundant metal sodium reserves, wide distribution, low cost and similar electrochemical performance as lithium ion batteries. Among these, the search for suitable sodium ion battery negative electrode materials is one of the hot spots. Therefore, it is very important to find a simple, fast and efficient preparation method and research the electrochemical performance of the preparation method.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a sodium ion battery negative electrode material, a preparation method and an application thereof, wherein the sodium ion battery negative electrode material prepared by the present invention has high sodium storage capacity and long cycle life.
The invention provides a preparation method of a sodium ion battery cathode material, which comprises the following steps:
A) mixing 2-mercaptopyridine with a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on 2-mercaptopyridine and a metal compound, and drying the obtained product to obtain precursor powder;
the metal compound comprises one or more of a cobalt-containing compound, a nickel-containing compound, a manganese-containing compound, an iron-containing compound, a copper-containing compound, a tin-containing compound, a molybdenum-containing compound, a tungsten-containing compound and a zinc-containing compound;
B) and calcining the precursor powder to obtain the sodium-ion battery negative electrode material.
Preferably, the cobalt-containing compound comprises one or more of cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt sulfate and cobalt chloride;
the nickel-containing compound comprises one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride;
the manganese-containing compound comprises one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride;
the iron-containing compound comprises one or more of ferric acetate, ferric nitrate, ferric sulfate, ferric trichloride and ferrous chloride;
the copper-containing compound comprises one or more of copper acetate, copper nitrate, copper oxalate, copper sulfate and copper chloride;
the stanniferous compound comprises one or more of stannic chloride, potassium stannate, stannous oxalate, stannous sulfate and stannous chloride;
the molybdenum-containing compound comprises one or more of ammonium molybdate, sodium molybdate, molybdenum acetylacetonate and molybdenum chloride;
the tungsten-containing compound comprises one or more of ammonium metatungstate, sodium tungstate and tungsten chloride;
the zinc-containing compound comprises one or more of zinc acetate, zinc nitrate, zinc oxalate, zinc sulfate and zinc chloride.
Preferably, the molar ratio of the 2-mercaptopyridine to the metal compound is 1: 1 to 10.
Preferably, the temperature of the hydrothermal synthesis is 180 ℃, and the time of the hydrothermal synthesis is 2-10 h.
Preferably, the calcining temperature is 400-600 ℃, and the calcining time is 1-6 h;
the calcination is carried out in a nitrogen atmosphere or a reducing atmosphere.
Preferably, before the calcining, the method further comprises the following steps: heating the precursor powder to a calcination temperature;
the rate of temperature rise is 1-10 ℃/min.
The invention also provides the sodium-ion battery cathode material prepared by the preparation method.
The invention also provides a sodium ion battery negative plate which is prepared from the raw materials comprising a negative material, a conductive additive, a binder and a solvent;
the negative electrode material is the sodium ion battery negative electrode material.
The invention also provides a sodium ion battery, which consists of a positive electrode, a negative electrode, a diaphragm, organic electrolyte and a counter electrode;
the negative electrode is the sodium-ion battery negative electrode piece.
The sodium ion battery is applied to solar power generation, wind power generation, smart grid peak regulation, distributed power stations or communication base energy storage devices.
The invention provides a preparation method of a sodium ion battery cathode material, which comprises the following steps: A) mixing 2-mercaptopyridine and a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on 2-mercaptopyridine and a metal compound, and drying the obtained product to obtain precursor powder; the metal compound includes cobalt-containing compound, nickel-containing compound, manganese-containing compound, iron-containing compound, copper-containing compound, tin-containing compound, molybdenum-containing compoundOne or more of a tungsten-containing compound and a zinc-containing compound; B) and calcining the precursor powder to obtain the sodium-ion battery negative electrode material. The invention synthesizes the cathode material M of the sodium-ion battery by a simple solid-phase method or a hydrothermal methodxSyand/C, wherein M is selected from Co, Ni, Mn, Fe, Cu, Sn, Mo, W or Zn, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2. The prepared negative electrode material of the sodium ion battery has high sodium storage capacity, long cycle life, excellent rate capability and low cost, and is an ideal negative electrode material of the sodium ion battery.
Drawings
FIG. 1 is an XRD pattern of a target product CoS/C obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a target product CoS/C obtained in example 1 of the present invention;
FIG. 3 is a TEM image of a target product CoS/C obtained in example 1 of the present invention;
FIG. 4 shows that the target product CoS/C obtained in example 1 of the present invention is 0.1A g-1A first loop charge-discharge curve under current density;
FIG. 5 shows that the target product CoS/C obtained in example 1 of the present invention is 2A g-1A cycle curve at current density;
FIG. 6 is a rate performance curve of a target product CoS/C obtained in example 1 of the present invention;
FIG. 7 shows that the target product CoS/C obtained in example 2 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 8 shows that the target product CoS/C obtained in example 2 of the present invention is at 1A g-1A cycle curve at current density;
FIG. 9 shows that the target product CoS/C obtained in example 3 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 10 shows that the target product CoS/C obtained in example 3 of the present invention is 2A g-1A cycle curve at current density;
FIG. 11 is an XRD pattern of a NiS/C target product obtained in example 4 of the present invention;
FIG. 12 is an SEM photograph of a target product NiS/C obtained in example 4 of the present invention;
FIG. 13 is a TEM image of the target product NiS/C obtained in example 4 of the present invention;
FIG. 14 shows that the NiS/C ratio of the target product obtained in example 4 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 15 shows that the NiS/C ratio of the target product obtained in example 4 of the present invention is 2A g-1A cycle curve at current density;
FIG. 16 is an XRD pattern of MnS/C which is a target product obtained in example 5 of the present invention;
FIG. 17 is an SEM picture of MnS/C which is a target product obtained in example 5 of the invention;
FIG. 18 is a TEM image of MnS/C which is a target product obtained in example 5 of the present invention;
FIG. 19 shows that the MnS/C ratio of the target product obtained in example 5 of the invention is 0.1A g-1A first loop charge-discharge curve under current density;
FIG. 20 shows that the MnS/C target product obtained in example 5 of the invention is 2A g-1A cycle curve at current density;
FIG. 21 is an XRD pattern of FeS/C as a target product obtained in example 6 of the present invention;
FIG. 22 is an SEM photograph of a target product FeS/C obtained in example 6 of the present invention;
FIG. 23 is a TEM image of FeS/C as a target product obtained in example 6 of the present invention;
FIG. 24 shows that the FeS/C ratio of the target product obtained in example 6 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 25 shows that the FeS/C ratio of the target product obtained in example 6 of the present invention is 1A g-1A cycle curve at current density;
FIG. 26 shows the objective product Cu obtained in example 7 of the present invention2XRD pattern of S/C;
FIG. 27 shows the objective product Cu obtained in example 7 of the present invention2SEM picture of S/C;
FIG. 28 shows the target product Cu obtained in example 7 of the present invention2TEM image of S/C;
FIG. 29 shows the objective product Cu obtained in example 7 of the present invention2S/C at 1A g-1Head at current densityA loop charge-discharge curve;
FIG. 30 shows the objective product Cu obtained in example 7 of the present invention2S/C at 2A g-1A cycle curve at current density;
FIG. 31 is an XRD pattern of SnS/C, a target product obtained in example 8 of the present invention;
FIG. 32 is an SEM picture of a target product SnS/C obtained in example 8 of the present invention;
FIG. 33 is a TEM image of the objective product SnS/C obtained in example 8 of the present invention;
FIG. 34 shows that the SnS/C ratio of the target product obtained in example 8 of the present invention is 1A g-1A cycle curve at current density;
FIG. 35 shows the target product MoS obtained in example 9 of the present invention2XRD pattern of/C;
FIG. 36 shows a MoS target product obtained in example 9 of the present invention2SEM picture of/C;
FIG. 37 shows the MoS as the target product obtained in example 9 of the present invention2TEM image of/C;
FIG. 38 shows a MoS target product obtained in example 9 of the present invention2C is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 39 shows the target product MoS obtained in example 9 of the present invention2C is 2A g-1A cycle curve at current density;
FIG. 40 shows WS as a target product obtained in example 10 of the present invention2XRD pattern of/C;
FIG. 41 is WS as the target product obtained in example 10 of the present invention2SEM picture of/C;
FIG. 42 is a diagram of WS as a target product obtained in example 10 of the present invention2TEM image of/C;
FIG. 43 shows the target product WS obtained in example 10 of the present invention2C is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 44 shows WS as a target product obtained in example 10 of the present invention2C at 2A g-1A cycle curve at current density;
FIG. 45 is an XRD pattern of the target product CoS/C obtained in example 11 of the present invention;
FIG. 46 is an SEM photograph of a target product CoS/C obtained in example 11 of the present invention;
FIG. 47 shows that the target product CoS/C obtained in example 11 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 48 shows that the target product CoS/C obtained in example 11 of the present invention is at 2A g-1A cycle curve at current density;
FIG. 49 is a graph showing the rate capability of the target product CoS/C obtained in example 11 according to the present invention;
FIG. 50 is an XRD pattern of NiS/C, a target product obtained in example 12 of the present invention;
FIG. 51 is an SEM photograph of a target product NiS/C obtained in example 12 of the present invention;
FIG. 52 shows that the NiS/C ratio of the target product obtained in example 12 of the present invention is 0.1A g-1A first-turn charge-discharge curve under current density;
FIG. 53 shows that the NiS/C ratio of the target product obtained in example 12 of the present invention is 2A g-1Cycling profile at current density.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a sodium ion battery cathode material, which comprises the following steps:
A) mixing 2-mercaptopyridine with a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on 2-mercaptopyridine and a metal compound, and drying an obtained product to obtain precursor powder;
the metal compound comprises one or more of a cobalt-containing compound, a nickel-containing compound, a manganese-containing compound, an iron-containing compound, a copper-containing compound, a tin-containing compound, a molybdenum-containing compound, a tungsten-containing compound and a zinc-containing compound;
B) and calcining the precursor powder to obtain the sodium-ion battery negative electrode material.
In certain embodiments of the present invention, the metal compound comprises one or more of a cobalt-containing compound, a nickel-containing compound, a manganese-containing compound, an iron-containing compound, a copper-containing compound, a tin-containing compound, a molybdenum-containing compound, a tungsten-containing compound, and a zinc-containing compound.
In certain embodiments of the invention, the cobalt-containing compound comprises one or more of cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt sulfate, and cobalt chloride.
In certain embodiments of the present invention, the nickel-containing compound comprises one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate, and nickel chloride.
In certain embodiments of the invention, the manganese-containing compound comprises one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride.
In certain embodiments of the invention, the iron-containing compound comprises one or more of ferric acetate, ferric nitrate, ferric sulfate, ferric trichloride, and ferrous chloride.
In certain embodiments of the invention, the copper-containing compound comprises one or more of copper acetate, copper nitrate, copper oxalate, copper sulfate, and copper chloride.
In certain embodiments of the present invention, the tin-containing compound comprises one or more of tin tetrachloride, potassium stannate, stannous oxalate, stannous sulfate, and stannous chloride.
In certain embodiments of the invention, the molybdenum-containing compound comprises one or more of ammonium molybdate, sodium molybdate, molybdenum acetylacetonate, and molybdenum chloride.
In certain embodiments of the present invention, the tungsten-containing compound comprises one or more of ammonium metatungstate, sodium tungstate, and tungsten chloride.
In certain embodiments of the invention, the zinc-containing compound comprises one or more of zinc acetate, zinc nitrate, zinc oxalate, zinc sulfate, and zinc chloride.
Mixing 2-mercaptopyridine and a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on the 2-mercaptopyridine and the metal compound, and drying the obtained product to obtain precursor powder.
In the present invention, 2-mercaptopyridine is the sulfur source. In certain embodiments of the present invention, the molar ratio of the 2-mercaptopyridine to the metal compound is 1: 1 to 10. In certain embodiments, the molar ratio of 2-mercaptopyridine to metal compound is 1: 10.
in certain embodiments of the invention, the milling is performed at room temperature. In certain embodiments of the invention, the grinding is uniform.
In some embodiments of the invention, the temperature of the hydrothermal synthesis is 180 ℃, and the time of the hydrothermal synthesis is 2-10 h. In some embodiments, the hydrothermal synthesis time is 5-7 hours or 6 hours.
In some embodiments of the present invention, after the hydrothermal synthesis is completed, the method further comprises: and cooling the product after the hydrothermal synthesis to room temperature, and sequentially washing with deionized water and absolute ethyl alcohol for three times respectively.
The drying method and parameters are not particularly limited in the present invention, and those known to those skilled in the art can be used.
And after precursor powder is obtained, calcining the precursor powder to obtain the sodium-ion battery cathode material.
In some embodiments of the invention, the temperature of the calcination is 400-600 ℃, and the time of the calcination is 1-6 h. In certain embodiments, the temperature of the calcination is from 500 to 600 ℃. In certain embodiments, the calcination time is 2 hours.
In certain embodiments of the invention, the calcining is performed in a nitrogen atmosphere or a reducing atmosphere.
In certain embodiments of the present invention, prior to the calcining, further comprising: and heating the precursor powder to the calcining temperature.
In some embodiments of the invention, the temperature increasing rate is 1-10 ℃/min. In some embodiments, the temperature rise rate is 2-5 ℃/min. In certain embodiments, the rate of temperature increase is 2 ℃/min.
The invention also provides the sodium-ion battery cathode material prepared by the preparation method. The chemical formula of the cathode material of the sodium ion battery provided by the invention is MxSyand/C, wherein M is selected from Co, Ni, Mn, Fe, Cu, Sn, Mo, W or Zn, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2.
The anode material provided by the invention comprises:
a carbon substrate;
and metal sulfide particles uniformly distributed on the carbon substrate.
In some embodiments of the present invention, the metal sulfide particles have a particle size of 10 to 50nm, 20 to 50nm, or 50 to 200 nm.
In certain embodiments of the present invention, the anode material provided by the present invention is a spherical particle. In certain embodiments of the present invention, the anode material has a particle size of no greater than 4 μm. In some embodiments, the negative electrode material has a particle size of 0.1 to 0.5 μm (100 to 500nm), 0.2 to 0.8 μm (200 to 800nm), 1 to 2 μm, or 2 to 4 μm.
In some embodiments of the present invention, the anode material provided by the present invention has a micron-scale bulk morphology. In certain embodiments of the present invention, the anode material provided by the present invention is a sheet-like structure. In some embodiments of the invention, the negative electrode material provided by the invention is a mixture of a sheet structure and a tubular structure, wherein the size of the sheet structure is not more than 0.5 μm, and the size of the tubular structure is 1-5 μm. In some embodiments of the invention, the negative electrode material provided by the invention is in a flower-shaped structure, and the size of the negative electrode material is 0.2-1 μm.
In some embodiments of the invention, the negative electrode material has better crystallinity. In certain embodiments of the invention, the anode material is of the hexagonal system P63/mmc, the hexagonal system P63mc, the cubic system Fm-3m, the tetragonal system P43212, or the orthorhombic system Pbnm.
The invention also provides a sodium ion battery negative plate which is prepared from the raw materials comprising a negative material, a conductive additive, a binder and a solvent;
the negative electrode material is the sodium ion battery negative electrode material.
In certain embodiments of the present invention, the conductive additive is selected from one or more of Super-P, carbon black, and Ketjen black.
In certain embodiments of the present invention, the binder is selected from one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, and sodium alginate.
In some embodiments of the invention, the mass ratio of the negative electrode material, the conductive additive and the binder is 7-8: 1-2: 1. in certain embodiments, the mass ratio of the anode material, the conductive additive, and the binder is 7: 2: 1 or 8: 1: 1.
in certain embodiments of the present invention, the solvent is selected from N-methylpyrrolidone or deionized water. The amount of the solvent used in the present invention is not particularly limited, and any amount of the solvent known to those skilled in the art may be used.
In some embodiments of the invention, the sodium-ion battery negative electrode sheet is prepared according to the following method:
mixing the negative electrode material, the conductive additive, the binder and the solvent, and then pulping, smearing and drying to obtain the sodium-ion battery negative electrode plate.
In the preparation method of the sodium-ion battery cathode piece, the adopted raw material components and the proportion are the same as above, and are not described again here.
The method of smearing and drying is not particularly limited in the present invention, and a method of smearing and drying known to those skilled in the art may be used. In some embodiments of the invention, the loading capacity of the anode material after smearing is 1-2 mg-cm-3. In certain embodiments, the method of drying is oven drying.
The invention also provides a sodium ion battery, which consists of a positive electrode, a negative electrode, a diaphragm, organic electrolyte and a counter electrode;
the negative electrode is the sodium-ion battery negative electrode piece.
In some embodiments of the present invention, the organic electrolyte is an ether electrolyte. In some embodiments, the concentration of the organic electrolyte is 0.1-2 mol/L; preferably 1 mol/L. In certain embodiments of the present invention, the solute of the organic electrolyte comprises sodium hexafluorophosphate (NaPF)6) Sodium perchlorate and sodium triflate (NaCF)3SO3) At least one of (a); sodium hexafluorophosphate or sodium trifluoromethanesulfonate is preferred. In certain embodiments of the present invention, the solvent of the organic electrolyte comprises one of diglyme (diglyme), glyme (DME), diglyme and tetraglyme; preferably diethylene glycol dimethyl ether or ethylene glycol dimethyl ether.
In certain embodiments of the invention, the separator is fiberglass.
In certain embodiments of the invention, the counter electrode is a sodium metal counter electrode.
In some embodiments of the invention, the voltage range of the sodium ion battery is 0.01-3.0V or 0.4-3.0V.
The preparation method of the sodium ion battery is not particularly limited, and the preparation method of the sodium ion battery known to those skilled in the art can be adopted.
The invention also provides application of the sodium ion battery in solar power generation, wind power generation, smart grid peak regulation, distributed power stations or communication base energy storage devices.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
The invention has the following advantages and beneficial effects:
(1) transition metal sulfide/carbon composite material M synthesized by using sulfur source 2-mercaptopyridinexSythe/C, wherein M is selected from Co, Ni, Mn, Fe, Cu, Sn, Mo, W or Zn, x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 1 and less than or equal to 2, and the material can be used as a negative electrode material of a sodium ion battery, so that a material system of the sodium ion battery is enriched.
(2) The transition metal sulfide/carbon composite material M prepared by the inventionxSyHigh sodium storage capacity of/CThe lithium ion battery cathode material has the advantages of long cycle life, excellent rate capability and low cost, and is an ideal cathode material of a sodium ion battery.
(3) The transition metal sulfide/carbon composite material M prepared by the inventionxSythe/C has high capacity, long cycle life and high rate capability. E.g., CoS/C, at 0.1A g-1Has high sodium storage capacity at high current density of 2A g-1Next, the capacity retention rate reached 76.6% after 6000 weeks of cycling.
(4) The synthesis can be carried out by a simple solid phase method or a hydrothermal method, the process is simple and easy to control, and the mass production is easy.
In order to further illustrate the present invention, the following will describe the negative electrode material of sodium ion battery, its preparation method and application in detail with reference to the examples, but it should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
1. The target product of the transition metal sulfide/carbon composite material prepared by the solid phase method is a CoS/C compound, and the raw materials comprise 2-mercaptopyridine and a metal source compound cobalt acetate:
at room temperature, putting raw materials 2-mercaptopyridine and cobalt acetate in a mortar according to a certain molar ratio of 1: 10, fully grinding the raw materials to uniformly mix the raw materials to obtain precursor powder. And then, placing the precursor powder in a tube furnace, heating at the rate of 2 ℃/min, and calcining at the temperature of 600 ℃ for 2h in the nitrogen atmosphere to obtain the target product CoS/C.
2. Preparing a transition metal sulfide/carbon composite material electrode plate:
mixing the prepared target product, Super P and polyvinylidene fluoride serving as a binder according to the mass ratio of 7: 2: 1, adding N-methylpyrrolidone serving as a solvent, pulping, and smearing (the load of the anode material after smearing is 1.5 mg-cm)-3) And drying to obtain the electrode plate containing the target product metal sulfide/carbon composite material.
3. Assembling a sodium-ion battery taking the target product CoS/C as a negative electrode:
the above preparation is carried outThe target product of the sodium ion battery is assembled by a negative electrode plate and a counter electrode metal sodium, GF/F is a battery diaphragm, and the electrolyte is an ether electrolyte (1 mol/LNaCF)3SO3The diglyme solution) with a voltage range of 0.4-3.0V.
FIG. 1 is an XRD pattern of a target product CoS/C obtained in example 1 of the present invention. As can be seen from figure 1, the synthesized target product CoS/C has better crystallinity, and the obtained target product belongs to a hexagonal system P63/mmc.
FIG. 2 is an SEM photograph of a target product CoS/C obtained in example 1 of the present invention. The SEM image shows that the obtained composite material is spherical particles with the particle size of 100-500 nm.
FIG. 3 is a TEM image of a target product CoS/C obtained in example 1 of the present invention. According to TEM images, small CoS particles with the particle size of 10-50 nm are uniformly distributed on the carbon substrate.
FIG. 4 shows that the target product CoS/C obtained in example 1 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 4, the material has higher initial specific capacity 707.9/551.1mAh g when being applied to a sodium-ion battery-1。
FIG. 5 shows that the target product CoS/C obtained in example 1 of the present invention is at 2A g-1Cycling profile at current density. As can be seen from FIG. 5, the initial capacity is 385.0mAh g-1The capacity retention rate after 6000 weeks of cycling was 76.6%, showing excellent cycling stability.
FIG. 6 is a graph showing the rate capability of the target product CoS/C obtained in example 1 of the present invention, and it can be seen from FIG. 6 that the current density is 0.1A g-1，0.2A g-1，0.5A g-1，1A g-1，2A g-1，5A g-1And 10A g-1The specific discharge capacity is 487.6mAh g-1，480.0mAh g-1，458.3mAh g-1，442.3mAh g-1，417.5mAh g-1，370.6mAh g-1And 315.6mAh g-1. When the current density returns to 0.1A g-1And the specific discharge capacity is 95.7% of the initial capacity, and the excellent structural stability is shown.
Example 2
The preparation method was the same as in example 1 except that the calcination temperature was changed to 400 ℃ to obtain the objective product CoS/C.
FIG. 7 shows that the target product CoS/C obtained in example 2 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 7, the material has higher initial specific capacity 664.3/526.1mAh g when being applied to a sodium-ion battery-1。
FIG. 8 shows that the target product CoS/C obtained in example 2 of the present invention is at 1A g-1Cycling profile at current density. As can be seen in FIG. 8, the specific capacity after 700 cycles was stabilized at about 460mAh g-1And exhibits excellent cycle stability.
Example 3
The preparation method was the same as in example 1 except that the calcination temperature was changed to 500 ℃ to obtain the objective product CoS/C.
FIG. 9 shows that the target product CoS/C obtained in example 3 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 9, the material has higher initial specific capacity 736.3/534.7mAh g when being applied to a sodium-ion battery-1。
FIG. 10 shows that the target product CoS/C obtained in example 3 of the present invention is 2A g-1Cycling profile at current density. As can be seen in FIG. 10, the specific capacity stabilized at about 350.0mAh g after 350 cycles-1。
Example 4
The preparation method is the same as that of the example 1, except that the metal compound is changed into nickel acetate to obtain a product NiS/C, and the electrolyte is NaPF with 1mol/L6The DME solution has a battery test voltage interval of 0.4-3.0V.
FIG. 11 is an XRD pattern of a target product NiS/C obtained in example 4 of the present invention, and as can be seen from FIG. 11, the synthesized material has better crystallinity, and the obtained target product belongs to a hexagonal system P63 mc.
FIG. 12 is an SEM photograph of the NiS/C target product obtained in example 4 of the invention. As seen from the SEM image, the obtained NiS/C composite material is spherical particles with the particle size of 1-2 μm.
FIG. 13 is a TEM image of the target product NiS/C obtained in example 4 of the present invention. As can be seen from FIG. 13, small particles of 10-50 nm NiS are distributed on the carbon substrate.
FIG. 14 shows that the NiS/C ratio of the target product obtained in example 4 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 14, the material has higher initial specific capacity 632.8/466.7mAh g when being applied to a sodium-ion battery-1。
FIG. 15 shows that the NiS/C ratio of the target product obtained in example 4 of the present invention is 2A g-1Cycling profile at current density. As can be seen from FIG. 15, after 1000 cycles, the specific capacity still remained 323.0mAh g-1And exhibits excellent structural stability.
Example 5
The preparation method is the same as that of example 1, except that the metal compound is changed into manganese acetate to obtain a product MnS/C, and the electrolyte is NaPF with 1mol/L6The DME solution has a battery test voltage interval of 0.01-3.0V.
FIG. 16 is an XRD pattern of MnS/C which is a target product obtained in example 5 of the present invention. As can be seen from FIG. 16, the synthesized material has better crystallinity, and the obtained target product belongs to a cubic system Fm-3 m.
FIG. 17 is an SEM picture of MnS/C which is a target product obtained in example 5 of the present invention. As can be seen from FIG. 17, the obtained MnS/C composite material is spherical particles, and the particle size of the spherical particles is 200-800 nm.
FIG. 18 is a TEM image of MnS/C which is a target product obtained in example 5 of the present invention. As seen in a TEM image, the MnS particles with the particle size of 20-50 nm are uniformly distributed on the carbon substrate.
FIG. 19 shows that the MnS/C ratio of the target product obtained in example 5 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 19, the material has higher initial specific capacity 863.2/550.2mAh g when being applied to a sodium-ion battery-1。
FIG. 20 shows that the MnS/C target product obtained in example 5 of the invention is 2A g-1Cycling profile at current density. As can be seen from FIG. 20, the initial capacity was 376.4mAh g-1The capacity retention rate after 600 weeks of cycling was 92.5%, showing excellent cycling stability.
Example 6
The preparation method is the same as example 1, except thatThe metal compound is changed into ferric nitrate to obtain a product FeS/C, and the electrolyte is NaPF with 1mol/L6The DME solution has a battery test voltage interval of 0.01-3.0V.
FIG. 21 is an XRD pattern of FeS/C, a target product obtained in example 6 of the present invention. As can be seen from FIG. 21, the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 22 is an SEM photograph of a target product FeS/C obtained in example 6 of the present invention. The obtained FeS/C composite material is in a flaky shape as seen from the SEM image.
FIG. 23 is a TEM image of FeS/C as a target product obtained in example 6 of the present invention. According to a TEM image, the FeS small particles with the particle size of 20-50 nm are uniformly distributed on the carbon substrate.
FIG. 24 shows that the FeS/C ratio of the target product obtained in example 6 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from FIG. 24, the material has higher initial specific capacity of 864.2/563.8mAh g when being applied to a sodium-ion battery-1。
FIG. 25 shows that the target product FeS/C obtained in example 6 of the present invention is 1Ag-1Cycling profile at current density. As can be seen from FIG. 25, the initial capacity is 406.0mAh g-1The capacity retention rate after 400 weeks of cycling was 87.6%, showing excellent cycling stability.
Example 7
The preparation method was the same as example 1 except that the metal source compound was changed to copper nitrate to obtain Cu as a product2S/C, electrolyte is 1mol/L NaPF6The DME solution has a battery test voltage interval of 0.01-3.0V.
FIG. 26 shows the objective product Cu obtained in example 7 of the present invention2XRD pattern of S/C. As can be seen from FIG. 26, the synthesized material has better crystallinity, and the obtained target product belongs to a tetragonal system P43212.
FIG. 27 shows the target product Cu obtained in example 7 of the present invention2SEM image of S/C. As seen from the SEM photograph, the resulting Cu2The S/C composite material is in a micron-sized block shape.
FIG. 28 shows the target product Cu obtained in example 7 of the present invention2TEM image of S/C. From TEM imageVisible, nanoscale Cu2The small S particles are uniformly distributed on the carbon substrate.
FIG. 29 shows the objective product Cu obtained in example 7 of the present invention2S/C at 1A g-1First loop charge and discharge curve under current density. As can be seen from figure 29, the material has higher initial specific capacity 729.7/408.4mAh g when being applied to a sodium-ion battery-1。
FIG. 30 shows the objective product Cu obtained in example 7 of the present invention2S/C at 2A g-1Cycling profile at current density. As can be seen from FIG. 30, the initial capacity was 338.0mAh g-1The capacity retention rate after 1000 weeks of cycling was 91.7%, showing excellent cycling stability.
Example 8
The preparation method is the same as that of the example 1, except that the metal compound is changed into stannous oxalate to obtain a product SnS/C, and the electrolyte is 1mol/L NaCF3SO3The voltage interval of the diglyme solution is 0.4-3.0V.
FIG. 31 is an XRD pattern of SnS/C, a target product obtained in example 8 of the present invention. As can be seen from FIG. 31, the synthesized material has better crystallinity, and the obtained target product belongs to an orthorhombic Pbnm system.
FIG. 32 is an SEM picture of a target product SnS/C obtained in example 8 of the present invention. As seen from the SEM image, the obtained SnS/C composite material particles have a sheet-like structure.
FIG. 33 is a TEM image of the objective product SnS/C obtained in example 8 of the present invention. As can be seen from the TEM image, the small SnS particles of 20-50 nm are uniformly distributed on the carbon substrate.
FIG. 34 shows that the SnS/C ratio of the target product obtained in example 8 of the present invention is 1A g-1Cycling profile at current density. As can be seen from FIG. 34, after 400 cycles, the specific capacity was still 211.7mAh g-1And exhibits excellent cycle stability.
Example 9
The preparation method was the same as example 1 except that the metal compound was changed to ammonium molybdate to obtain a product MoS2C, electrolyte is 1mol/L NaPF6The DME solution has a battery test voltage interval of 0.01-3.0V.
FIG. 35 is the bookTarget product MoS obtained in invention example 92XRD pattern of/C. As can be seen in FIG. 35, the phase is MoS2。
FIG. 36 shows a MoS target product obtained in example 9 of the present invention2SEM image of/C. As can be seen from the SEM image, the MoS obtained2the/C composite material is in a micron-sized blocky shape.
FIG. 37 shows the desired product, MoS, obtained in example 9 of the present invention2TEM image of/C. As can be seen from the TEM image, 50-200 nm MoS2The small particles are uniformly distributed on the carbon substrate.
FIG. 38 shows a MoS target product obtained in example 9 of the present invention2C is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from figure 38, the material has higher initial specific capacity 726.7/446.0mAh g when being applied to a sodium-ion battery-1。
FIG. 39 shows the target product MoS obtained in example 9 of the present invention2C is 2A g-1Cycling profile at current density. As can be seen from FIG. 39, the initial capacity was 282.2mAh g-1The capacity retention rate after 1500 weeks of cycling was 98.5%, showing excellent cycling stability.
Example 10
The preparation method is the same as that of example 1, except that the metal compound is changed into ammonium metatungstate to obtain the product WS2C, electrolyte is 1mol/L NaPF6The DME solution has a battery test voltage interval of 0.01-3.0V.
FIG. 40 shows the target product WS obtained in example 10 of the present invention2XRD pattern of/C. As can be seen from FIG. 40, the phase is WS2The target product obtained belongs to the hexagonal system P63/mmc.
FIG. 41 is WS as the target product obtained in example 10 of the present invention2SEM image of/C. FIG. 42 is a diagram of WS as a target product obtained in example 10 of the present invention2TEM image of/C. As can be seen from FIGS. 41 and 42, the resulting WS2the/C composite material is a mixture of a sheet structure and a tubular structure, the size of the sheet structure is not more than 0.5 mu m, and the size of the tubular structure is 1-5 mu m.
FIG. 43 shows the target product WS obtained in example 10 of the present invention2C is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from FIG. 43, the material has higher initial specific capacity of 629.1/432.1mAh g when being applied to a sodium-ion battery-1。
FIG. 44 shows WS as a target product obtained in example 10 of the present invention2C at 2A g-1Cycling profile at current density. As can be seen from FIG. 44, the initial capacity is 351.5mAh g-1The capacity retention rate after 2000 weeks of cycling was 98.8%, showing excellent cycling stability.
Example 11
1. Preparing a transition metal sulfide/carbon composite material by a hydrothermal method:
the target product is a CoS/C compound, the raw materials comprise 2-mercaptopyridine and a metal compound, and the solvent is deionized water.
Mixing raw material 2-mercaptopyridine and metal compound according to a molar ratio of 1: 10 was dissolved in 30mL of deionized water and stirred well. And then, transferring the mixed solution into a 50mL reaction kettle, preserving the heat at 180 ℃ for 6h, cooling to room temperature, sequentially washing with deionized water and absolute ethyl alcohol for three times respectively, and then placing the product in an oven for drying to obtain a powder precursor. And placing the precursor powder in a tube furnace, heating at the rate of 2 ℃/min, and calcining at 600 ℃ for 2h in a nitrogen atmosphere to obtain the target product CoS/C.
2. The procedure for preparing the metal sulfide/carbon composite electrode sheet was the same as in example 1. The electrolyte is ether electrolyte (1mol/L NaCF)3SO3The diglyme solution) with a voltage range of 0.4-3.0V.
FIG. 45 is an XRD pattern of the target product CoS/C obtained in example 11 of the present invention. As can be seen from FIG. 45, the synthesized material has better crystallinity, and the obtained target product belongs to the hexagonal system P63/mmc.
FIG. 46 is an SEM picture of a target product CoS/C obtained in example 11 of the present invention. As seen in the SEM image, the obtained CoS/C material is in a flower shape with the size of 0.2-1 μm.
FIG. 47 shows that the target product CoS/C obtained in example 11 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from FIG. 47, the material has a higher initial value when applied to a sodium ion batteryInitial specific capacity 717.2/567.0mAh g-1。
FIG. 48 shows that the target product CoS/C obtained in example 11 of the present invention is 2A g-1The initial capacity of the current density, as seen in FIG. 48, is 538.0mAh g-1The capacity retention rate after 1000 weeks of cycling was 85.2%, showing excellent cycling stability.
FIG. 49 is a graph showing the rate capability of the target product CoS/C obtained in example 11 of the present invention. As can be seen from FIG. 49, at a current density of 0.1A g-1，0.2A g-1，0.5A g-1，1A g-1，2A g-1，5A g-1And 10A g-1The specific discharge capacity is 530.6mAh g-1，525.3mAh g-1，519.3mAh g-1，509.6mAh g-1，497.3mAh g-1，467.3mAh g-1And 405.6mAh g-1. When the current density returns to 0.1A g-1The discharge specific capacity is almost 100% of the initial capacity, and excellent structural stability is shown.
Example 12
The preparation method is the same as that of example 11, except that the metal compound is changed into nickel acetate to obtain a product NiS/C, and the electrolyte is 1mol/L NaPF6The DME solution has a cell test voltage range of 0.4-2.5V.
FIG. 50 is an XRD pattern of NiS/C, a target product obtained in example 12 of the present invention. As can be seen from FIG. 50, the synthesized material has better crystallinity, and the obtained target product belongs to a hexagonal system P63 mc.
FIG. 51 is an SEM picture of the NiS/C target product obtained in example 12 of the invention. As seen from the SEM image, the obtained NiS/C is a sphere with the shape of 2-4 μm.
FIG. 52 shows that the NiS/C ratio of the target product obtained in example 12 of the present invention is 0.1A g-1First loop charge and discharge curve under current density. As can be seen from FIG. 52, the material has higher initial specific capacity 656.3/561.4mAh g when being applied to a sodium-ion battery-1。
FIG. 53 shows that the NiS/C ratio of the target product obtained in example 12 of the present invention is 2A g-1Cycling profile at current density. As can be seen from FIG. 53, the initial capacity was 366.0mAh g-1The capacity retention rate after 2000 weeks of cycling was 94.4%, showing excellent cycling stability.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a sodium ion battery negative electrode material comprises the following steps:
A) mixing 2-mercaptopyridine with a metal compound, and grinding to obtain precursor powder; or carrying out hydro-thermal synthesis on 2-mercaptopyridine and a metal compound, and drying the obtained product to obtain precursor powder;
the metal compound comprises one or more of a cobalt-containing compound, a nickel-containing compound, a manganese-containing compound, an iron-containing compound, a copper-containing compound, a tin-containing compound, a molybdenum-containing compound, a tungsten-containing compound and a zinc-containing compound;
B) calcining the precursor powder to obtain a sodium ion battery cathode material;
the calcination is carried out in a nitrogen atmosphere or a reducing atmosphere;
the chemical formula of the negative electrode material of the sodium ion battery is MxSyand/C, wherein M is selected from Co, Ni, Mn, Fe, Cu, Sn, Mo, W or Zn, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2.
2. The preparation method according to claim 1, wherein the cobalt-containing compound comprises one or more of cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt sulfate and cobalt chloride;
the nickel-containing compound comprises one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride;
the manganese-containing compound comprises one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride;
the iron-containing compound comprises one or more of ferric acetate, ferric nitrate, ferric sulfate, ferric trichloride and ferrous chloride;
the copper-containing compound comprises one or more of copper acetate, copper nitrate, copper oxalate, copper sulfate and copper chloride;
the stanniferous compound comprises one or more of stannic chloride, potassium stannate, stannous oxalate, stannous sulfate and stannous chloride;
the molybdenum-containing compound comprises one or more of ammonium molybdate, sodium molybdate, molybdenum acetylacetonate and molybdenum chloride;
the tungsten-containing compound comprises one or more of ammonium metatungstate, sodium tungstate and tungsten chloride;
the zinc-containing compound comprises one or more of zinc acetate, zinc nitrate, zinc oxalate, zinc sulfate and zinc chloride.
3. The method according to claim 1, wherein the molar ratio of the 2-mercaptopyridine to the metal compound is 1: 1 to 10.
4. The preparation method according to claim 1, wherein the temperature of the hydrothermal synthesis is 180 ℃ and the time of the hydrothermal synthesis is 2-10 h.
5. The preparation method according to claim 1, wherein the calcination temperature is 400-600 ℃, and the calcination time is 1-6 h.
6. The method of claim 1, further comprising, prior to the calcining: heating the precursor powder to a calcination temperature;
the temperature rise rate is 1-10 ℃/min.
7. The negative electrode material of the sodium-ion battery prepared by the preparation method of any one of claims 1 to 6.
8. A sodium ion battery negative plate is prepared from raw materials including a negative electrode material, a conductive additive, a binder and a solvent;
the negative electrode material is the sodium-ion battery negative electrode material in claim 7.
9. A sodium ion battery consists of a positive electrode, a negative electrode, a diaphragm, an organic electrolyte and a counter electrode;
the negative electrode is the negative electrode sheet of the sodium-ion battery of claim 8.
10. Use of the sodium ion battery of claim 9 in solar power generation, wind power generation, smart grid peak shaving, distributed power stations or communication base energy storage devices.
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