CN114709392A - Metal sulfide/metal simple substance-carbon composite material with carbon point regulated and control, preparation method thereof and application thereof in lithium/sodium ion battery - Google Patents

Metal sulfide/metal simple substance-carbon composite material with carbon point regulated and control, preparation method thereof and application thereof in lithium/sodium ion battery Download PDF

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CN114709392A
CN114709392A CN202210361216.5A CN202210361216A CN114709392A CN 114709392 A CN114709392 A CN 114709392A CN 202210361216 A CN202210361216 A CN 202210361216A CN 114709392 A CN114709392 A CN 114709392A
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carbon
metal
sulfide
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metal sulfide
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CN114709392B (en
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纪效波
侯红帅
邹国强
邓文韬
项赢尔
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention provides a metal sulfide/metal simple substance-carbon composite material with carbon points regulated and controlled, a preparation method thereof and application thereof in a lithium/sodium ion battery. By adjusting the mass ratio of the carbon dots to the metal sulfide, the adjustment of different metal simple substances and carbon contents can be realized so as to meet the requirements of high coulomb efficiency, good stability, excellent rate capability and the like. The preparation method is simple, the raw materials are rich, and a universal and efficient method is provided for optimizing the material structure.

Description

Metal sulfide/metal simple substance-carbon composite material with carbon point regulated and control, preparation method thereof and application thereof in lithium/sodium ion battery
Technical Field
The invention relates to the technical field of preparation of metal sulfide cathode materials, in particular to a carbon point regulated metal sulfide/metal simple substance-carbon composite material, a preparation method thereof and application thereof in a lithium/sodium ion battery, and also relates to a method for improving the first coulomb efficiency of the metal sulfide.
Background
Nowadays, energy crisis and environmental issues are the hot spots for the development of the times. Due to the intermittency and diversity of clean energy sources, the realization of large-scale energy storage systems depends on electric energy storage devices with high energy, high power density and low cost, and alkali metal ion batteries become the main choice of the next-generation energy technology due to the advantages of portability, energy conservation, environmental protection and the like. The metal sulfide material is used as a high-capacity alkali metal ion battery cathode material, the working voltage is moderate, and the application potential is very large.
Antimony sulfide (Sb)2S3) The theoretical specific capacity of the alloy reaches 946mAh/g, and the energy storage mechanism of the alloy comprises intercalation reaction, conversion reaction and alloying reaction. Sb is, in contrast to other antimony-based materials2S3The cathode material has significant energy storage advantages. Sb based on alloy reaction and Sb based on transformation-alloy reaction2S3Compared with the prior art, the alloy has lower theoretical specific capacity (660mAh/g), and Sb has serious volume expansion in the alloying reaction process, thereby greatly influencing the cycle life of the material. Sb2S3Li is formed during the conversion reaction2S, it can buffer certain volume expansion, and further improve electrochemical performance. Sb2S3The sulfur atom of the seed can improve the flexibility of the material and also has the function of buffering volume expansion. Albeit Sb2O3Has a higher theoretical specific capacity (1109mAh/g), but Sb2O3Bond energy of Sb-O in the composition is larger than that of Sb2S3The bond energy of Sb-S in (A) is stronger, which lowers Sb2O3With Li+Kinetics of the conversion reaction of (a). Compared with the reversible intercalation/deintercalation process of metal ions in sulfide, the reversibility of the reaction of oxide and metal ions is poor, and the capacity fading is fast.
Stibium (II) as a main componentOre as Sb2S3The natural mineral material is directly obtained from nature, has low cost and simple crushing process, and can be used for replacing chemically synthesized Sb2S3The material is developed into an environment-friendly advanced battery cathode material. However, the natural stibnite particles have the defects of large particle size, slow electron transfer rate, serious volume expansion in the charging and discharging process, shuttle effect of polysulfide and the like, so that the energy storage value of stibnite products can be realized by further treatment, the aim of maximizing strategic resource utilization rate is achieved, and the large-scale popularization of environment-friendly new energy materials is realized.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to provide a method for preparing a metal sulfide-metal simple substance-carbon composite material with carbon dots regulated, wherein the method uses a metal sulfide as a precursor, uses the carbon dots as an oxidant, a reducing agent and a small molecule-based template, and the metal sulfide-metal simple substance-carbon composite material is obtained by reacting the metal sulfide and the small molecule-based template in a protective atmosphere.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a metal sulfide/metal simple substance-carbon composite material with carbon points regulated comprises the following steps:
and mixing the metal sulfide with the carbon dots, then placing the mixture in an inert atmosphere, calcining the mixture at the temperature of 300-1200 ℃, and cooling the calcined mixture to obtain the metal sulfide/metal simple substance-carbon composite material.
In some embodiments, the metal sulfide is at least one of antimony sulfide, tin sulfide, bismuth sulfide.
In some embodiments, the mass ratio of the metal sulfide to the carbon dots is 1: 0 to 1; the mass of carbon dots is more than 0. Preferably, the mass ratio of the metal sulfide to the carbon dots is 1: 0.1 to 0.5.
In some embodiments, the calcination temperature is 700 to 1000 ℃.
In some embodiments, the calcination time is 3 to 5 hours.
It is another object of the present invention to provide a metal sulfide/elemental metal-carbon composite material produced by the production method according to any one of the above embodiments.
The invention also aims to provide an electrode plate, which comprises the metal sulfide/metal simple substance-carbon composite material.
The fourth objective of the present invention is to provide a battery, which comprises the above electrode plate.
In some embodiments, the battery is an alkali metal ion battery, including but not limited to a lithium ion battery and/or a sodium ion battery.
The fifth purpose of the invention is to provide a method for improving the first coulombic efficiency of a metal sulfide negative electrode material, which comprises the following steps: and mixing carbon points with the metal sulfide, and calcining at 300-1200 ℃ under the protection of inert atmosphere to obtain the metal sulfide/metal simple substance-carbon composite material.
Preferably, the mass ratio of the metal sulfide to the carbon dots is 1: 0 to 1. More preferably, the mass ratio of the metal sulfide to the carbon dots is 1: 0.1 to 0.5.
The "metal sulfide/metal element" in the "metal sulfide/metal element-carbon composite material" in the invention means that the metal sulfide and the metal element are included at the same time, or the metal element is included.
Compared with the prior art, the invention has the following beneficial effects:
the method takes a metal sulfide as a precursor, carbon dots as an oxidant, a reducing agent and a micromolecular carbon-based material, in the process of heating, oxygen-containing functional groups in the carbon dots oxidize the metal sulfide into corresponding metal oxides, and then the metal oxides are reduced into metal simple substances in the stage of natural cooling and cooling to form the segmented action of local oxidation-partial reduction-deep coupling, wherein in the oxidation stage, sulfur and oxygen exchange occurs, so that sulfur doping of the carbon-based material can be realized, a C-S bond is formed, and the C-S bond in the carbon-based material is influenced by the oxygen-rich environment of the carbon dots, so that the bond length is shortened, the bond energy is enlarged, and the carbon-based material is not easy to damage. In the reaction process of the application, on one hand, the carbon dots partially reduce the metal sulfide to convert metal ions into a metal simple substance, meanwhile, the carbon dots are self-assembled in the reaction process to form a small molecular carbon-based material and anchor the metal simple substance, and on the other hand, a stable X-O-C (X is antimony, bismuth or tin) heterogeneous interface is constructed with the metal element to realize the formation of the metal sulfide/metal simple substance-carbon composite material.
In the composite material, the C-S bond in the carbon-based material is not easily damaged, and S is not easily converted into the sulfite with poor reversibility during the first charging and discharging, so that the first coulombic efficiency of the alkali metal ion battery is improved. In addition, an X-O-C bond (X is antimony, bismuth or tin) formed between the metal element and the carbon group effectively reduces an ion transfer energy barrier and improves the conductivity of the material. In addition, the carbon-based material formed by self-assembling carbon dots has various effects of alleviating volume expansion, providing an ion transport channel, inhibiting dissolution of polysulfide, and the like, and can also improve the conductivity of the material.
The preparation method can also realize the preparation of composite materials with different carbon contents by adjusting the mass ratio of the carbon points to the metal sulfide, and can meet the requirements of high coulombic efficiency, good stability, excellent rate capability and the like.
The composite material prepared by the method is applied to a battery as a negative electrode, the first coulombic efficiency and the rate capability are high, and the rate capability is obviously improved compared with other reported metal sulfide/carbon composite materials.
In addition, the preparation method is simple, the raw materials are rich, and a universal and efficient method is provided for optimizing the material structure.
Drawings
FIG. 1 is an in situ high temperature XRD pattern of reaction of carbon dots with stibnite powder in an inert atmosphere;
FIG. 2 is a scanning electron micrograph of samples obtained in comparative example 1 and examples 1, 2 and 3, wherein a is the sample of comparative example 1 and b is the sample of example 1 (Sb)2S3@0.1CDs，Sb2S3The mass ratio to the carbon dots is 1: 0.1), c is the sample of example 2 (Sb)2S3@0.3CDs，Sb2S3The mass ratio to the carbon dots is 1: 0.3), d is the sample of example 3 (Sb)2S3@0.5CDs，Sb2S3The mass ratio to the carbon dots is 1: 0.5).
FIG. 3 shows the stibnite powder (Sb) of comparative example 12S3) XPS spectrum of middle S element;
FIG. 4 shows the stibnite powder (Sb) of comparative example 12S3) The multiplying power performance diagram of the lithium ion battery;
FIG. 5 shows a sample (Sb) of example 12S3@0.1CDs) XPS spectrum of S element;
FIG. 6 shows a sample (Sb) of example 12S3@0.1CDs) rate performance graph of a lithium ion battery;
FIG. 7 shows a sample (Sb) of example 22S3@0.3CDs) XPS spectrum of S element;
FIG. 8 shows a sample (Sb) of example 22S3@0.3CDs) rate performance graph of the lithium ion battery;
FIG. 9 shows a sample (Sb) of example 32S3@0.5CDs) XPS spectrum of S element;
FIG. 10 shows a sample (Sb) of example 32S3@0.5CDs) rate performance graph of the lithium ion battery;
fig. 11 is a plot of the first coulombic efficiency of the lithium ion batteries of the samples of examples 1, 2, 3 and comparative example 1.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The inert atmosphere used in the following examples was high purity argon gas with a purity of 99.999%; the precursor is commercially purchased stibnite (Sb)2S399.9%), the raw materials or chemical agents used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified.
Comparative example 1
The preparation method of the stibnite powder comprises the following steps:
s1, placing 5g of stibnite particles into an agate ball milling tank, adding a proper amount of absolute ethyl alcohol to submerge the stibnite particles, adjusting the rotating speed to 400r/min, and continuously ball milling for 4 hours;
s2, carrying out suction filtration on the mixture, removing a large amount of ethanol, placing the mixture in a blast drying oven, and drying the mixture for 10 hours at 70 ℃; and grinding the dried stibnite powder to obtain a comparison sample, and using the comparison sample as a precursor of the experimental sample.
The obtained stibnite powder was subjected to XPS test, and the test results are shown in fig. 3. As shown in FIG. 3, the S element is present only in Sb2S3In the form of Sb-S bonds.
Example 1
1. Preparation of carbon dots
Magnetically stirring 8g of sodium hydroxide and 40mL of acetaldehyde (40% aqueous solution) for 1h to mix uniformly, and then standing at normal temperature and pressure for 72 h; and then adding 1M hydrochloric acid to adjust the mixture to be neutral, centrifugally washing the mixture for 3 times by using deionized water, and drying the mixture by air blowing to obtain orange-yellow carbon dots with the particle size of 3-5 nm.
2. A preparation method of an antimony sulfide-antimony-carbon composite material with regulated carbon points comprises the following steps:
s1, grinding 1g of stibnite powder of the comparative example 1 and 0.1g of carbon dot powder for 30min to obtain a uniform mixture;
s2, transferring the mixture obtained in the step S1 to a tube furnace, continuously heating to 700 ℃ at a heating rate of 10 ℃/min under the atmosphere of high-purity argon, then preserving heat for 5h, and naturally cooling at room temperature. The obtained sample was named Sb2S3@0.1CDs。
The reaction process of the carbon dots and the stibnite powder is carried out in situThe results of the monitoring are shown in FIG. 1. As can be seen from FIG. 1, Sb is present as the temperature gradually increases2S3Is oxidized into Sb by oxygen-containing groups in the carbon dots2O4And then reduced into Sb simple substance by carbon in the carbon dots in the temperature reduction process.
The obtained sample was subjected to XPS test, and the test results are shown in fig. 5. Sb is clearly shown in FIG. 52S3The S moiety in (1) is transferred to the carbon layer to form a C-S bond, in which case the C-S bond and the Sb-S bond coexist.
Example 2
The specific preparation method and steps of the carbon dots in this example are the same as those in example 1, and the precursor is stibnite powder prepared in comparative example 1, except that:
s1, mixing 1g of stibnite powder of the comparative example 1 and 0.3g of carbon dot powder, and grinding for 30min to obtain a uniform mixture;
s2, transferring the sample to a tube furnace, continuously heating to 700 ℃ at a heating rate of 10 ℃/min under the atmosphere of high-purity argon, then preserving heat for 5h, and naturally cooling at room temperature. The obtained sample was named Sb2S3@0.3CDs。
The obtained sample was subjected to XPS test, and the test results are shown in fig. 7. It is apparent from FIG. 7 that Sb is increased with the number of carbon dots2S3The S transfer in (2) is increased and the C-S bond is significantly enhanced, and at this time, the C-S bond and the Sb-S bond coexist.
Example 3
The specific preparation method and steps of the carbon dots in this example are the same as those in example 1, and the precursor is stibnite powder prepared in comparative example 1, except that:
s1, mixing 1g of stibnite powder of the comparative example 1 with 0.5g of carbon dot powder, and grinding for 30min to obtain a uniform mixture;
and S2, transferring the mixture into a tube furnace, continuously heating to 700 ℃ at a heating rate of 10 ℃/min under the atmosphere of high-purity argon, then preserving heat for 5h, and naturally cooling at room temperature. The obtained sample was named Sb2S3@0.5CDs。
The obtained sample was subjected to XPS test, and the test results are shown in fig. 9. From FIG. 9As is evident, Sb2S3Is completely reduced to Sb. The presence of C-S bonds in the material instead of Sb-S bonds may prove that S enters C in doped form.
The samples obtained in comparative example 1 and examples 1 to 3 were examined by scanning electron microscopy, and the results are shown in FIG. 2. As can be seen from FIG. 2, after the carbon dots are added, a significant carbon sheet appears on the surface of the sample; as the content of carbon dots increases, the carbon sheets are connected to form a large carbon layer.
The samples prepared in examples 1-3 and comparative example 1 were subjected to electrochemical performance tests as follows:
taking 70mg of Sb2S3@0.1CDs、Sb2S3@0.3CDs、Sb2S3@0.5CDs composite material, 15mg of Super P (conductive agent) and 15mg of sodium carboxymethylcellulose (CMC, binder), uniformly mixing, adding a proper amount of deionized water to prepare uniform slurry, coating the uniform slurry on a current collector copper foil by using a coating method, transferring the current collector copper foil to a vacuum drying oven, and drying the current collector copper foil for 12 hours at 80 ℃; the copper foil to which the active material was attached was cut into a circular pole piece having a diameter of 14mm, pressed into a sheet by applying a pressure of 15MPA, and then transferred into an Ar atmosphere glove box.
In an Ar atmosphere glove box, metal lithium is used as a counter electrode, a Celgard 2400 membrane is used as a diaphragm, and LiPF6DMC, DEC 1:1:1 as electrolyte, assembling CR2016 type button cell. Electrochemical performance tests were then performed, and the test results are shown in fig. 4, 6, 8, 10, and 11.
Wherein, fig. 4 is a rate performance graph of the sample of comparative example 1 used as the negative electrode material of the lithium ion battery. As shown in FIG. 4, at 0.1, 0.2, 0.5, 1, 2, 5Ag-1Has a reversible specific capacity of 718.8, 718.5, 669.7, 608.2, 511.4 and 304.1mAh g respectively-1。
FIG. 6 is a graph of rate capability of the sample of example 1 as a negative electrode material for a lithium ion battery. As shown in fig. 6, at 0.1, 0.2, 0.5, 1, 2, 5A g-1Has a reversible specific capacity of 920.2, 860.3, 813.7, 771.1, 724.8 and 660.0mAh g respectively-1。
FIG. 8 shows the negative electrode of the lithium ion battery of example 2The rate performance of the material. As shown in fig. 8, at 0.1, 0.2, 0.5, 1, 2, 5A g-1Has a reversible specific capacity of 816.4, 774.6, 720.5, 681.5, 638.0 and 570.4mAh g-1。
Fig. 10 is a graph of rate performance of the sample of example 1 as a negative electrode material for a lithium ion battery. As shown in fig. 10, at 0.1, 0.2, 0.5, 1, 2, 5A g-1Has a reversible specific capacity of 811.2, 788.0, 747.0, 713.0, 684.9 and 645.2mAh g-1。
Fig. 11 is a plot of the initial coulombic efficiency of the lithium ion batteries of comparative example 1 and examples 1, 2, and 3. As shown in fig. 11, the first coulombic efficiency of comparative example 1 was 66.7%, and the first coulombic efficiencies of example 1, example 2, and example 3 were 85.2%, 81.7%, and 80.8%, respectively. Therefore, the composite material obtained by the method can obviously improve the first coulombic efficiency of antimony sulfide.
The invention utilizes carbon dots as an oxidant, a reducing agent and a small-molecular carbon-based material, and natural stibnite as a raw material to prepare the antimony sulfide-antimony-carbon composite material, thereby realizing the partial or complete reduction of the stibnite and the doping of the carbon-based material. By adjusting the mass ratio of the carbon dots to the stibnite, the composite materials with different antimony and carbon contents are realized, and the requirements of high coulombic efficiency, good stability, excellent rate capability and the like can be met. The preparation method is simple, the raw materials are rich, and a universal and efficient method is provided for optimizing the material structure.
In conclusion, the method provided by the invention has the advantages that the carbon dots are used as the oxidant, the reducing agent and the small-molecule carbon-based material, the natural stibnite is processed, a stable heterogeneous interface can be induced to form, the doping of the carbon-based material by sulfur is realized, and the electrochemical performance is obviously improved. Compared with the prior art, the antimony sulfide/antimony-carbon composite material prepared by the method has the advantages that the conductivity is remarkably improved, and the rate capability is excellent.
It should be noted that the method of the present invention is also applicable to the preparation of tin sulfide/tin-carbon composite materials and bismuth sulfide/bismuth-carbon composite materials, the preparation methods of the two are basically the same as those in the above examples, and the adjustment of appropriate reaction conditions including temperature and reaction time for obtaining composite materials with optimal structures is not excluded.
The metal sulfide-metal simple substance-carbon composite material regulated and controlled by the carbon points can also be used as a negative pole piece active material of a sodium ion battery so as to improve the rate capability and the cycling stability of the sodium ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a metal sulfide/metal simple substance-carbon composite material with regulated carbon points is characterized by comprising the following steps:
and mixing the metal sulfide with the carbon dots, then placing the mixture in an inert atmosphere, calcining the mixture at the temperature of 300-1200 ℃, and cooling the calcined mixture to obtain the metal sulfide/metal simple substance-carbon composite material.
2. The method for preparing a carbon point-controlled metal sulfide/elemental metal-carbon composite material according to claim 1, wherein the metal sulfide is at least one of antimony sulfide, tin sulfide and bismuth sulfide.
3. The method for preparing a carbon-point-controlled metal sulfide/elemental metal-carbon composite material according to claim 1, wherein the mass ratio of the metal sulfide to the carbon point is 1: 0 to 1.
4. The method for preparing a carbon point-controlled metal sulfide/metal simple substance-carbon composite material according to claim 1, wherein the calcination temperature is 700 to 1000 ℃.
5. The preparation method of the carbon point-regulated metal sulfide/metal simple substance-carbon composite material according to claim 1, wherein the calcination time is 3-5 hours.
6. A metal sulfide/elemental metal-carbon composite material produced by the production method according to any one of claims 1 to 5.
7. An electrode sheet comprising the metal sulfide/elemental metal-carbon composite material according to claim 6.
8. A battery comprising the electrode sheet of claim 7.
9. The battery according to claim 8, wherein the battery is a lithium ion battery and/or a sodium ion battery.
10. The method for improving the first coulombic efficiency of the metal sulfide negative electrode material is characterized in that after carbon dots are mixed with the metal sulfide, the mixture is calcined at 300-1200 ℃ under the protection of inert atmosphere to obtain a sulfide/metal simple substance-carbon composite material.
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