CN112310379A - Preparation method and application of carbon nano tube loaded ferrous sulfide micron electrode material - Google Patents

Preparation method and application of carbon nano tube loaded ferrous sulfide micron electrode material Download PDF

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CN112310379A
CN112310379A CN202011308661.2A CN202011308661A CN112310379A CN 112310379 A CN112310379 A CN 112310379A CN 202011308661 A CN202011308661 A CN 202011308661A CN 112310379 A CN112310379 A CN 112310379A
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ferrous sulfide
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张天旭
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Chengde Petroleum College
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • C01B32/00—Carbon; Compounds thereof
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    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H—ELECTRICITY
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    • 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
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    • H—ELECTRICITY
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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method and application of a carbon nano tube loaded ferrous sulfide micron electrode material, wherein the preparation method comprises the following steps: (1) adding ferric salt and deionized water into a reaction bottle to prepare a salt solution, placing the solution in an ice-water bath under the protection of nitrogen, and stirring to obtain a solution A; (2) adding sodium borohydride and sodium hydroxide into deionized water, uniformly mixing, slowly adding the mixture into the solution A, stirring, aging and standing to obtain a standing solution B; (3) to a standing solutionAdding sublimed sulfur, urea and multi-wall carbon nano tube slurry into the solution B, uniformly stirring to obtain a solution C, and preserving heat at 140-180 ℃; (4) and centrifuging the product, washing the product with distilled water and absolute ethyl alcohol, and drying the product in vacuum. The carbon nano tube supported ferrous sulfide micron electrode material FeS prepared by the invention2The continuous CNTs network from the surface to the inside shortens the transport path of ions and electrons, and can still keep stable under huge volume change, thereby enhancing the diffusion performance of lithium ions.

Description

Preparation method and application of carbon nano tube loaded ferrous sulfide micron electrode material
Technical Field
The invention relates to the technical field of energy storage and conversion materials, in particular to a preparation method and application of a carbon nano tube loaded ferrous sulfide micron electrode material.
Background
Transition metal sulfides have attracted increasing attention as potential positive electrode materials for Lithium Ion Batteries (LIBs) due to high capacity, low cost, and environmental friendliness. In the past decade, simple compounds Fe-based conversion of positive electrode materials (e.g., FeF)3And FeS2) The lithium ion battery has the advantages of high energy density and low cost, and is expected to be applied to the positive electrode of the lithium metal battery.
FeS2Has the characteristics of high theoretical capacity (894mAh/g), environmental protection, rich resources, low price and the like, and becomes one of the best candidates of the electrode material of the lithium ion battery. However, FeS2Compared with the traditional electrode material, the electrode material has obvious gap in the aspects of cycle stability and short service life, and the practical application of the electrode material is hindered. FeS2The main reason for the poor cycling stability of metal sulfides is that, first, FeS2The conversion reaction occurs during deep discharge, the volume change is serious, the pulverization is easy, and the reaction reversibility is rapidly deteriorated after the separation from the current collector. Second, the intermediate product, long-chain lithium sulfide (LiS)nN is more than or equal to 2) is easy to dissolve in the electrolyte and diffuse to the cathode for deposition, so that the shuttle effect is generated, and the active substances are continuously reduced. Third, FeS2The electrode material has low electronic conductivity and the final product Li of lithium-storing reaction2S is also an electronic insulator, and therefore the electronic conductivity accompanying the recycled material is further reduced.
To solve the above problems, FeS is currently used2The methods of nano-processing of the electrode material, compounding with carbon material and the like improve the electronic conductivity and ionic conductivity of the system and improve the electrochemical performance. But despite FeS2The design of the nano wire, the nano sheet and the nano tube and the composition of the nano wire, the nano sheet and the nano tube with porous carbon, graphene, the carbon nano tube and carbon fiber obviously improve the actual release capacity of the material and improve the cycling stability of the material to a certain extent, but the nano process causes serious mismatch of surface chemical states, aggravates side reactions, and still cannot effectively inhibit shuttle effect, thereby influencing the structural stability and the chemical stability of the material under long-term working conditions. Furthermore, the nano-formation and the compounding of the electrode material particlesThe problem of low active material content in the material causes low volume energy density of the system, and the system cannot meet the design requirements of modern lithium ion batteries.
In contrast, FeS of micron size2The particles are more practical as active materials for lithium ion batteries. However, since the volume expansion is severe, the proportion of the reaction substance is small, Li+Low diffusion coefficient, insufficient electron conductivity, and limitation of micron-sized FeS2Use of particles as electrode material.
Disclosure of Invention
The invention aims to provide a preparation method and application of a carbon nano tube loaded ferrous sulfide micron electrode material, and the prepared carbon nano tube loaded ferrous sulfide micron electrode material FeS2The continuous CNTs network from the surface to the inside shortens the transport path of ions and electrons, and can still keep stable under huge volume change, thereby enhancing the diffusion performance of lithium ions.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a carbon nanotube-loaded ferrous sulfide micron electrode material comprises the following steps:
(1) adding 10-20g of iron salt and 500ml of deionized water into a reaction bottle to prepare a salt solution, placing the solution in an ice water bath at the temperature of 5-5 ℃ under the protection of nitrogen, and mechanically and violently stirring the solution for 0.5-1 hour to obtain a solution A;
(2) adding 3-5g of sodium borohydride and 0.5-2g of sodium hydroxide into 100ml of deionized water, uniformly mixing the solution, slowly adding the solution into the solution A, stirring for 1.5-3 hours until the solution is completely mixed to obtain a turbid solution B, and aging and standing for 12-24 hours to obtain a standing solution B;
(3) adding 5-10g of sublimed sulfur, 1-2g of urea and 2-5g of multi-walled carbon nanotube slurry into the standing solution B, fully and uniformly stirring to obtain a solution C, transferring the solution C into a polytetrafluoroethylene lining stainless steel autoclave, and preserving heat for 12-24 hours at the temperature of 140-;
(4) centrifuging the product obtained in the step (3), washing the product with distilled water and absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain carbonNano-tube loaded ferrous sulfide micron electrode material FeS2@CNTs。
Preferably, the preparation method of the multi-walled carbon nanotube slurry comprises the following steps: fully grinding and uniformly mixing 10g of multi-walled carbon nano-tube and 0.1g of cobaltosic oxide, and preserving heat for 5-10 hours at 750 ℃ under the protection of nitrogen to obtain a mixture; then the mixture is purified and acidified, and then is dissolved in N-methyl pyrrolidone according to the mass percent of 1-4 percent, and the mixture is obtained by 500-1000r/min vacuum grinding for 48 hours.
Preferably, the specific steps of the purification and acidification treatment are: soaking the mixture in 0.1mol/L HCl solution for 2 hr, filtering, vacuum drying, and adding HNO with concentration of 1mol/L3And 1mol/L of H2SO4And continuing acidification in the mixed solution to oxidize the surface of the mixed solution to generate carboxyl and hydroxyl groups.
Preferably, HNO3And H2SO4The volume of (2) is 1: 3.
The carbon nano tube loaded ferrous sulfide micron electrode material prepared by the preparation method is applied to a normal-temperature lithium ion battery.
Preferably, the lithium ion battery assembling process is as follows: mixing and grinding a carbon nano tube loaded ferrous sulfide micron electrode material, polyvinylidene fluoride and acetylene black according to a mass ratio, uniformly coating the mixture on a current collector to form an electrode, wherein the counter electrode is metal lithium, and the electrolyte is a diethylene glycol dimethyl ether solution of bis (trifluoromethyl) sulfonyl imide lithium LiTFSI.
Preferably, the mass ratio of the ferrous sulfide micron electrode material loaded on the carbon nano tube, the polyvinylidene fluoride and the acetylene black is 90:7.5: 2.5.
Preferably, the concentration of the electrolyte is 1 mol/L.
Preferably, the mass to electrolyte mass ratio of the carbon nanotube-supported ferrous sulfide micron electrode material is 5: 1.
Preferably, the voltage range is 0.8-3V.
The invention has the beneficial effects that:
(1) the invention firstly constructs the product with large specific surface area through the normal temperature reduction reaction of ferric salt and sodium borohydrideThe two-dimensional material has rich chemical adsorption sites, can be rapidly combined with sulfur simple substance, and generates FeS in hydrothermal reaction2And agglomerating in the process to construct the micron-sized material. Meanwhile, the multi-walled carbon nanotube with good mechanical property is used as an excellent external introduced carbon source, the surface environment of the carbon nanotube is enriched by utilizing the catalytic action of cobalt through the high-temperature reaction of the carbon nanotube and cobaltosic oxide, the surface functional groups of the carbon nanotube are enriched through purification and acidification treatment, finally, the carbon nanotube is in-situ combined with an iron-based two-dimensional material through simple stirring and hydrothermal reaction, the combination of ferrous sulfide and the carbon nanotube is constructed through a C-S bond, and the chemical anchoring introduction mode can ensure the stability of the combination.
(2) In the invention, the multi-wall carbon nano-tube with good mechanical property is used as an excellent external introduced carbon source, FeS2And the CNT are bonded by C-S bonds, and the bonding stability can be ensured by the introduction mode of the chemical anchoring. The cage-shaped shell formed by winding and interweaving the carbon nano tubes and the two-dimensional carbon source can be used as a strong mechanical buffer layer to inhibit adverse effects caused by volume change, and meanwhile, the protective shell becomes a good polysulfide adsorber through rich functional groups, so that the electrochemical activity of the electrode material in an overlong cycle period is ensured.
(3) The lithium ion diffusion performance is very important during the conversion reaction. FeS in the invention2The continuous CNTs network from the surface to the inside shortens the transport path of ions and electrons, can still keep stable under huge volume change, enhances the diffusion performance of lithium ions, and enables the diffusion coefficient of the lithium ions to reach 10-5cm2At the/s level, with FeS2The @ CNTs are used as electrode materials and have higher tap density (not less than 3.0 g/cm)3) And high active substance loading capacity (not less than 2.5 mg/cm)2) The composite material has high energy density, high coulombic efficiency, high multiplying power performance, long cycle life and other advantages, and micron FeS level2@ CNTs can retain electrochemical activity over long cycles.
(4) FeS of the invention2@ CNTs electrode Material TableThe invention shows higher reversible capacity, and provides a technical scheme for realizing multi-electron reaction and long cycle life for the transition metal sulfide electrode material which can not avoid conversion reaction by the design and preparation idea of the invention.
Drawings
FIG. 1 shows (a) FeS2And FeS2XRD patterns of @ CNTs samples, (b) FeS2@ CNTs Raman spectrum.
FIG. 2 shows FeS2(upper) and FeS2XPS spectra of sample C1s @ B-CNTs (bottom).
Fig. 3 is a Scanning Electron Microscope (SEM) image of the synthesized carbon nanotube-supported ferrous sulfide micro-electrode material.
Fig. 4 is a Scanning Electron Microscope (SEM) image of a conventional ferrous sulfide micro-electrode material in a comparative example.
Fig. 5 is a graph of the electrical cycle performance of the micron cobalt disulfide composite material with surface functional group modification as an electrode of a metal lithium battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples described below, multi-walled carbon nanotubes were purchased from Cnano technologies, ltd, china, and other drugs were purchased from Sigma-Aldrich without any post-treatment.
Example 1:
a preparation method of a carbon nanotube-loaded ferrous sulfide micron electrode material comprises the following steps:
(1) adding 10g of iron salt and 500ml of deionized water into a 1000ml three-necked bottle to prepare a salt solution, placing the salt solution in a water bath at 5 ℃ under the protection of nitrogen, and mechanically and violently stirring for 0.5 hour to obtain a solution A;
(2) adding 3g of sodium borohydride and 0.5g of sodium hydroxide into 100ml of deionized water, uniformly mixing the solution, slowly adding the solution into the solution A, stirring for 1.5 hours until the solution is completely mixed to obtain a turbid solution B, aging and standing for 12 hours to obtain a standing solution B;
(3) adding 5g of sublimed sulfur, 1g of urea and 2g of multi-walled carbon nanotube slurry into the standing solution B, fully and uniformly stirring to obtain a solution C, transferring the solution C into a polytetrafluoroethylene-lined stainless steel autoclave, and preserving heat for 12 hours at 140 ℃;
(4) centrifuging the product obtained in the step (3), washing the product by distilled water and absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain the carbon nano tube loaded ferrous sulfide micron electrode material FeS2@CNTs。
The multi-walled carbon nanotube slurry is prepared by purifying, acidifying and grinding, and the preparation method comprises the following steps: fully grinding and uniformly mixing 10g of multi-walled carbon nano tube and 0.1g of cobaltosic oxide, and preserving heat for 5 hours at 750 ℃ under the protection of nitrogen to obtain a mixture; then the mixture is purified and acidified, and is dissolved in N-methyl pyrrolidone according to the mass percent of 2 percent, and the mixture is obtained after vacuum grinding for 48 hours at the speed of 500 r/min.
The purification and acidification treatment comprises the following specific steps: soaking the mixture in 0.1mol/L HCl solution for 2 hr, filtering, vacuum drying, and adding HNO with concentration of 1mol/L3And 1mol/L of H2SO4Continuing acidification in the mixed solution, HNO3And H2SO4Is 1:3, the surface is oxidized to produce carboxyl and hydroxyl groups.
Example 2:
a preparation method of a carbon nano tube loaded ferrous sulfide micron electrode material comprises the following steps
(1) Adding 15g of iron salt and 500ml of deionized water into a 1000ml three-necked bottle to prepare a salt solution, placing the salt solution in an ice water bath at 0 ℃ under the protection of nitrogen, and mechanically and violently stirring for 0.5 hour to obtain a solution A;
(2) adding 4g of sodium borohydride and 1g of sodium hydroxide into 100ml of deionized water, uniformly mixing the solution, slowly adding the solution into the solution A, stirring for 2 hours until the solution is completely mixed to obtain a turbid solution B, aging and standing for 16 hours to obtain a standing solution B;
(3) adding 8g of sublimed sulfur, 1.5g of urea and 3g of multi-walled carbon nanotube slurry into the standing solution B, fully and uniformly stirring to obtain a solution C, transferring the solution C into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 16 hours at 160 ℃;
(4) centrifuging the product obtained in the step (3), washing the product by distilled water and absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain the carbon nano tube loaded ferrous sulfide micron electrode material FeS2@CNTs。
The multi-walled carbon nanotube slurry is prepared by purifying, acidifying and grinding, and the preparation method comprises the following steps: fully grinding and uniformly mixing 10g of multi-walled carbon nano tube and 0.1g of cobaltosic oxide, and preserving heat for 8 hours at 750 ℃ under the protection of nitrogen to obtain a mixture; then the mixture is purified and acidified, and is dissolved in N-methyl pyrrolidone according to the mass percent of 3 percent, and the mixture is obtained by vacuum grinding for 48 hours at the speed of 800 r/min.
The purification and acidification treatment comprises the following specific steps: soaking the mixture in 0.1mol/L HCl solution for 2 hr, filtering, vacuum drying, and adding HNO with concentration of 1mol/L3And 1mol/L of H2SO4Continuing acidification in the mixed solution, HNO3And H2SO4Is 1:3, the surface is oxidized to produce carboxyl and hydroxyl groups.
Example 3:
a preparation method of a carbon nano tube loaded ferrous sulfide micron electrode material comprises the following steps
(1) Adding 20g of iron salt and 500ml of deionized water into a 1000ml three-necked bottle to prepare a salt solution, placing the salt solution in an ice water bath at the temperature of minus 5 ℃ under the protection of nitrogen, and mechanically and violently stirring for 0.5 hour to obtain a solution A;
(2) adding 5g of sodium borohydride and 2g of sodium hydroxide into 100ml of deionized water, uniformly mixing the solution, slowly adding the solution into the solution A, stirring for 3 hours until the solution is completely mixed to obtain a turbid solution B, aging and standing for 24 hours to obtain a standing solution B;
(3) adding 10g of sublimed sulfur, 2g of urea and 5g of multi-walled carbon nanotube slurry into the standing solution B, fully and uniformly stirring to obtain a solution C, transferring the solution C into a polytetrafluoroethylene-lined stainless steel autoclave, and preserving heat for 24 hours at 180 ℃;
(4) centrifuging the product obtained in the step (3), washing the product by distilled water and absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain the carbon nano tube loaded ferrous sulfide micron electrode material FeS2@CNTs。
The multi-walled carbon nanotube slurry is prepared by purifying, acidifying and grinding, and the preparation method comprises the following steps: fully grinding and uniformly mixing 10g of multi-walled carbon nano tube and 0.1g of cobaltosic oxide, and preserving heat at 750 ℃ for 10 hours under the protection of nitrogen to obtain a mixture; then the mixture is purified and acidified, and is dissolved in N-methyl pyrrolidone in a mass percent of 4 percent, and the mixture is obtained after vacuum grinding for 48 hours at a speed of 1000 r/min.
The purification and acidification treatment comprises the following specific steps: soaking the mixture in 0.1mol/L HCl solution for 2 hr, filtering, vacuum drying, and adding HNO with concentration of 1mol/L3And 1mol/L of H2SO4Continuing acidification in the mixed solution, HNO3And H2SO4Is 1:3, the surface is oxidized to produce carboxyl and hydroxyl groups.
In examples 1 to 3 of the present invention, the ice-water bath was carried out by a cold trap.
In examples 1 to 3 of the present invention, in order to increase the active groups on the surface of the carbon nanotubes and oxidize the surface thereof, carboxyl groups and hydroxyl groups were generated, and specific properties are shown in table 1.
TABLE 1 Performance of carbon nanotubes after Oxidation treatment
Figure BDA0002789072510000081
Example 4:
the carbon nano tube loaded ferrous sulfide micron electrode material prepared in the embodiment 1-3 of the invention is used for a normal temperature lithium ion battery; the assembling process of the lithium ion battery comprises the following steps: loading a ferrous sulfide micron composite material on a carbon nano tube according to the mass ratio: polyvinylidene fluoride: acetylene black 75:10:15, uniformly coated on a current collector to form an electrode, the counter electrode is metal lithium, the electrolyte is 1M diethylene glycol dimethyl ether solution of lithium bis (trifluoromethyl) sulfonyl imide LiTFSI, and the voltage range is 0.8-3V.
Comparative example:
FeS2a method of preparing a powder comprising the steps of:
(1) 4mmol of FeSO4·7H2O, 20mmol of sublimed sulphur were dissolved in 70mL of a mixture of dimethylformamide and ethylene glycol.
(2) The suspension was transferred to a 100ml teflon lined stainless steel autoclave and incubated at 180 ℃ for 12 hours.
(3) Centrifuging the product, washing with distilled water and absolute ethyl alcohol, and drying in a vacuum drying oven at 80 ℃ for 6h to obtain FeS2And (3) powder.
To determine the crystal structure of the synthesized material, FeS, the product prepared in example 1, was added2@ CNTs powder was subjected to powder X-ray diffraction (XRD) and Raman spectroscopy (Raman) tests. FeS2And FeS2The powder X-ray diffraction pattern of @ CNTs is shown in FIG. 1(a), and the main peak position corresponds to FeS2The carbon nanotube shows a very small diffraction peak (2 θ ═ 26 °). The raman spectroscopy test shows that the overall conductivity of the material is better, as shown in fig. 1 (b).
To determine the bonding environment of the synthetic materials, FeS, the product prepared in example 2, was used2The @ CNTs powder was subjected to X-ray photoelectron spectroscopy (XPS) analysis, and the C element was analyzed by XPS, and the upper graph in FIG. 2 is FeS2Control sample, FeS2@ CNTs sample at FeS2A peak of 285.8eV was observed in the @ CNTs sample, corresponding to carbon and FeS2Bonding of the S element. The presence of a C-S bond makes FeS2Is fixed on the carbon nano tube in a chemical bonding mode, and simultaneously ensures the stability and the conductivity of the structure in the circulating process.
FeS2Scanning Electron Microscope (SEM) microtopography of @ CNTsThe particle is cage-shaped as shown in fig. 3, and some carbon nanotubes are observed to exist on the surface of the particle, and it can be seen that the size of the material is in the micrometer scale. The SEM image of the comparative example is shown in fig. 4.
And (3) electrochemical performance testing:
the lithium ion battery is a complex system, the electrode material, especially the novel electrode material, is required to realize the electrochemical performance, the improvement is not only the electrode material itself, and the electrolyte, the diaphragm, the counter electrode and even the charging and discharging system matched with the electrode material need to be adjusted. To reliably realize FeS2The electrochemical performance of the @ CNTs material cannot use the traditional electrolyte, and the main reasons are as follows:
(1) rechargeable Li/FeS2The electrochemical reaction of the cell is a switching reaction, during the first cycle of discharge, FeS2Reaction with Li produces a lithium sulfur polymer, which undergoes a side reaction with an ester group in a conventional electrolyte.
Figure BDA0002789072510000101
To avoid such adverse effects, the present invention uses an ether-based electrolyte instead of an ester-based electrolyte for rechargeable Li/FeS2The electrochemical performance of the battery was investigated. It is worth noting that ether-based electrolytes are advantageous for Li-S/Li-O2And (4) realizing the electrochemical performance of the battery.
(2) In the electrochemical measurement temperature range, the ionic association degree, viscosity and anion size all influence the conductivity, and the factors interact with each other, so that the conductivity of the finally obtained lithium salt has the following rule: LiFSI>LiPF6>LiTFSI>LiClO4>LiBF4. LiPF is used as the conventional electrolyte6For LiPF6PF which is unfavorable for reaction is generated after dissolution6 -The anion pair has a strong activity even against weak nucleophiles, and a slight amount of water (or alcohol) reacts therewith to form HF or the like, which adversely affects the stability of the ether-based electrode solution. Further, LiPF is shown by the formula (1-1)6Enough heat of solutionPromoting the local decomposition of the phosphorus pentafluoride and releasing a small amount of phosphorus pentafluoride. PF (particle Filter)5Is a strong lewis acid and initiates strong polymerization reactions.
Figure BDA0002789072510000102
The chemical mechanism can be summarized as LiPF6Is a cation-initiated ether group polymerization of a particular initiator.
Based on the research results, the electrolyte is adjusted, and the LiTFSI is used as a lithium salt and the diethylene glycol dimethyl ether is used as a solvent to prepare the 1mol/L LiTFSI ether-based electrolyte.
For FeS2The lithium ion button cell with @ B-CNTs as the electrode is subjected to cycle performance test, the test current is 1000mA/g (1.12C,1C ═ 890mA/g), the voltage range is 0.8-3.0V, and in the voltage range, the lithium storage amount of the carbon nano tube can be ignored. The test results are shown in fig. 5, with an initial coulombic efficiency of 91.3%. After 90 cycles, the reversible capacity of the electrode is 784 mAh/g.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the carbon nano tube loaded ferrous sulfide micron electrode material is characterized by comprising the following steps of:
(1) adding 10-20g of iron salt and 500ml of deionized water into a reaction bottle to prepare a salt solution, placing the solution in an ice water bath at the temperature of 5-5 ℃ under the protection of nitrogen, and mechanically and violently stirring the solution for 0.5-1 hour to obtain a solution A;
(2) adding 3-5g of sodium borohydride and 0.5-2g of sodium hydroxide into 100ml of deionized water, uniformly mixing the solution, slowly adding the solution into the solution A, stirring for 1.5-3 hours until the solution is completely mixed to obtain a turbid solution B, and aging and standing for 12-24 hours to obtain a standing solution B;
(3) adding 5-10g of sublimed sulfur, 1-2g of urea and 2-5g of multi-walled carbon nanotube slurry into the standing solution B, fully and uniformly stirring to obtain a solution C, transferring the solution C into a polytetrafluoroethylene lining stainless steel autoclave, and preserving heat for 12-24 hours at the temperature of 140-;
(4) centrifuging the product obtained in the step (3), washing the product by distilled water and absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain the carbon nano tube loaded ferrous sulfide micron electrode material FeS2@CNTs。
2. The method for preparing the carbon nanotube-supported ferrous sulfide micron electrode material as claimed in claim 1, wherein the method for preparing the multi-wall carbon nanotube slurry comprises the following steps: fully grinding and uniformly mixing 10g of multi-walled carbon nano-tube and 0.1g of cobaltosic oxide, and preserving heat for 5-10 hours at 750 ℃ under the protection of nitrogen to obtain a mixture; then the mixture is purified and acidified, and then is dissolved in N-methyl pyrrolidone according to the mass percent of 1-4 percent, and the mixture is obtained by 500-1000r/min vacuum grinding for 48 hours.
3. The method for preparing the carbon nanotube supported ferrous sulfide micron electrode material as claimed in claim 2, wherein the specific steps of purification and acidification treatment are as follows: soaking the mixture in 0.1mol/L HCl solution for 2 hr, filtering, vacuum drying, and adding HNO with concentration of 1mol/L3And 1mol/L of H2SO4And continuing acidification in the mixed solution to oxidize the surface of the mixed solution to generate carboxyl and hydroxyl groups.
4. The method for preparing the carbon nanotube-supported ferrous sulfide micro-electrode material according to claim 3, wherein HNO3And H2SO4The volume of (2) is 1: 3.
5. The application of the carbon nanotube-supported ferrous sulfide micron electrode material prepared by the preparation method according to any one of claims 1 to 4, wherein the carbon nanotube-supported ferrous sulfide micron electrode material is applied to a normal-temperature lithium ion battery.
6. The use of claim 5, wherein the lithium ion battery assembly process is: mixing and grinding a carbon nano tube loaded ferrous sulfide micron electrode material, polyvinylidene fluoride and acetylene black according to a mass ratio, uniformly coating the mixture on a current collector to form an electrode, wherein the counter electrode is metal lithium, and the electrolyte is a diethylene glycol dimethyl ether solution of bis (trifluoromethyl) sulfonyl imide lithium LiTFSI.
7. The application of claim 6, wherein the mass ratio of the ferrous sulfide micron electrode material loaded on the carbon nano tube to the polyvinylidene fluoride to the acetylene black is 90:7.5: 2.5.
8. Use according to claim 6, wherein the electrolyte has a concentration of 1 mol/L.
9. The use of claim 6, wherein the mass to electrolyte mass ratio of the carbon nanotube-supported ferrous sulfide microelectrode material is 5: 1.
10. Use according to claim 6, wherein the voltage is in the range of 0.8-3V.
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