CN108598417B - Conductive carbon black modified silica aerogel sulfur-loaded composite cathode material and preparation method thereof - Google Patents

Conductive carbon black modified silica aerogel sulfur-loaded composite cathode material and preparation method thereof Download PDF

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CN108598417B
CN108598417B CN201810373134.6A CN201810373134A CN108598417B CN 108598417 B CN108598417 B CN 108598417B CN 201810373134 A CN201810373134 A CN 201810373134A CN 108598417 B CN108598417 B CN 108598417B
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carbon black
conductive carbon
silica aerogel
sulfur
modified silica
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CN108598417A (en
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李健
张凡
刘圆圆
叶冉冉
刘韬
张丽娟
李文静
刘斌
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Aerospace Research Institute of Materials and Processing Technology
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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
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite cathode material and a preparation method thereof. The composite positive electrode material comprises conductive carbon black modified silica aerogel and elemental sulfur loaded in the conductive carbon black modified silica aerogel; the conductive carbon black modified silica aerogel comprises silica aerogel and conductive carbon black doped in the silica aerogel. The method comprises the steps of uniformly mixing conductive carbon black modified silica aerogel with elemental sulfur to obtain a mixture; and under the conditions of sealing and inert gas protection, carrying out heat treatment on the obtained mixture at the temperature of 115-160 ℃ to obtain the conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite positive electrode material. The composite cathode material disclosed by the invention has the advantages of excellent capacity performance, excellent cycling stability, high coulombic efficiency and the like in a lithium-sulfur battery. The method is simple and convenient, has low cost and is easy to realize batch production.

Description

Conductive carbon black modified silica aerogel sulfur-loaded composite cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material for a lithium-sulfur battery and a preparation method thereof.
Background
The development of an efficient and safe electrochemical energy storage device is one of the key links for the development of a novel clean energy industry. Secondary battery systems represented by lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and lithium ion batteries have been widely used in the fields of portable electronic devices, electric bicycles, and aerospace. At present, the most excellent comprehensive performance common positive electrode material of the commercial lithium ion battery is mainly lithium iron phosphate, lithium cobaltate, layered ternary metal oxide and the like, the actual energy density of the lithium ion battery is only about 200Wh/kg, and the lithium ion battery is far difficult to meet the relevant requirements of industries such as new energy electric automobiles and the like on high-energy density secondary batteries (>300 Wh/kg). Since the first report in the 60's of the 20 th century, lithium sulfur battery systems have attracted considerable attention from researchers. Lithium sulfur batteries using elemental sulfur as the positive electrode and lithium metal as the negative electrode can produce theoretical energy densities of up to 2600Wh/kg by multi-electron reactions. The actual energy density of the current soft package lithium-sulfur battery reaches 300-. Lithium-sulfur batteries are therefore considered to be one of the most promising lithium secondary battery systems currently in research and application.
Although the lithium-sulfur battery has great attraction in the aspects of energy density, use cost, environmental friendliness and the like, the lithium-sulfur battery has the problems of low utilization rate of active materials (poor capacity performance), serious capacity attenuation (poor cycle stability), low coulombic efficiency, poor rate performance and the like in the operation process, which restrict the practical application of the lithium-sulfur battery. The reasons for the above problems are as follows: firstly, the high electrochemical inertia of elemental sulfur and its charge and discharge products; elemental sulfur and its final discharge products are typical electronic and ionic insulators. The great electrochemical inertness makes it difficult for electrode materials prepared from pure elemental sulfur to exert an effective capacity. Second, the "shuttling effect" of polysulfides; the intermediate discharge product of the sulfur electrode is a liquid polysulfide (Li)2SnAnd n-3-8) which is very soluble in the organic liquid electrolyte and then crosses the separator. The repeated oxidation-reduction process of polysulfide between positive and negative electrodes results in loss of active material and corrosion of the metallic lithium negative electrode, thereby reducing the cycle life and coulombic efficiency of the battery. Third, lithium dendrites and volume expansion; in the lithium-sulfur battery, metal lithium is used as a negative electrode, lithium dendrites can be formed by uneven deposition of lithium ions on the metal lithium under the conditions of long cycle or high-rate charge and discharge, and the lithium dendrites can continuously grow and pass through a diaphragm to cause short circuit, so that safety problems such as combustion, explosion and the like are caused. In addition, since the starting material (S) is reacted with the end product (Li)2S), a large density difference between them, causes a volume shrinkage/expansion of approximately 80% during charge and discharge, resulting in destruction of the electrode and battery structure.
Because the porous carbon material has the characteristics of large specific surface area, high conductivity and the like, the performance improvement work of the lithium-sulfur battery at present mainly focuses on utilizing the carbon material with a porous structure as a carrier of elemental sulfur and inhibiting the loss of liquid polysulfide in the electrochemical reaction process through the capillary adsorption force of pores. Although porous carbon materials with various structures play an obvious role in improving the electrical conduction and the cycling stability of the sulfur electrode, the slow loss problem of polysulfide in the cycling process is difficult to fundamentally inhibit only by weak physical adsorption force. For example, chinese patent CN103107318B discloses a method for preparing a composite cathode material for a lithium-sulfur battery, wherein the first discharge specific capacity of the composite cathode material for a lithium-sulfur battery prepared by the method when used as an electrode reaches 1328mAh/g, and the discharge specific capacity is reduced to about 550mAh/g after 50 cycles; chinese patent application CN106532043A discloses a preparation method of a carbon gel sulfur-lithium sulfur battery anode material, the initial discharge specific capacity of the carbon gel sulfur-lithium sulfur battery anode material prepared by the method can reach 1100mAh/g when being used as an electrode, and the discharge specific capacity is reduced to below 460mAh/g after 50 times of circulation; chinese patent application CN103996830A discloses a preparation method of a graphene aerogel sulfur-loaded composite material, wherein the initial discharge specific capacity of the graphene aerogel sulfur-loaded composite material prepared by the method is about 900mAh/g when the graphene aerogel sulfur-loaded composite material is used as an electrode, the discharge specific capacity is kept about 660mAh/g after 50 times of circulation, and the specific capacity is lower; the positive electrode materials for the lithium-sulfur battery prepared by the methods have the problems of poor capacity performance, serious capacity attenuation and the like when being used in the lithium-sulfur battery.
In view of the above problems, it is very necessary to develop a highly conductive carrier material having both strong physical and chemical adsorption capacity to active sulfur species, so as to simultaneously improve the capacity performance and cycle stability of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a conductive carbon black modified silica aerogel sulfur-loaded composite cathode material and a preparation method thereof, and aims to solve the problems of poor capacity performance and cycle stability, low coulombic efficiency and the like of a lithium-sulfur battery in the prior art. The sulfur-loaded composite positive electrode material of the conductive carbon black modified silica aerogel takes the conductive carbon black modified silica aerogel which is light in weight, high in porosity, high in conductivity and strong in adsorption capacity as a simple substance sulfur carrier, and the composite positive electrode material is used as an electrode to assemble a lithium sulfur battery, so that the lithium sulfur battery has the advantages of excellent capacity performance, excellent cycling stability, high coulombic efficiency and the like. The method is simple and convenient, has low raw material preparation cost, is easy to realize batch production, and has high market application potential.
In order to achieve the above object, the present invention provides, in a first aspect, a conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material comprising a conductive carbon black modified silica aerogel and elemental sulfur loaded in the conductive carbon black modified silica aerogel; the conductive carbon black modified silica aerogel comprises silica aerogel and conductive carbon black doped in the silica aerogel.
Preferably, the mass percentage of elemental sulfur in the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material is 40-80%; the particle size of the conductive carbon black is 30-200 nm; and/or the mass percentage of the conductive carbon black in the conductive carbon black modified silica aerogel is 5-35%.
The invention provides a preparation method of a conductive carbon black modified silica aerogel sulfur-loaded composite cathode material, which comprises the following steps:
(1) uniformly mixing conductive carbon black modified silica aerogel with elemental sulfur to obtain a mixture; and
(2) and (2) under the conditions of sealing and inert gas protection, carrying out heat treatment on the mixture obtained in the step (1) at 115-160 ℃ to obtain the conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite positive electrode material.
Preferably, the temperature of the heat treatment is 145-160 ℃, and the time of the heat treatment is 12-24 h.
Preferably, the mass ratio of the conductive carbon black modified silica aerogel to the elemental sulfur is 1: (0.66-4).
Preferably, the method further comprises a step of preparing a conductive carbon black-modified silica aerogel before the step (1), the step of preparing comprising the substeps of:
(a) uniformly mixing organosilicate, an organic solvent, water and an anionic surfactant to obtain a mixed solution;
(b) adding conductive carbon black into the mixed solution obtained in the step (a) and uniformly stirring to obtain a mixed material;
(c) adding a catalyst into the mixture obtained in the step (b) and stirring the mixture to a gel state to obtain wet gel; and
(d) and (c) sequentially carrying out solvent exchange and aging steps and normal pressure sectional drying steps at more than two different temperature stages on the wet gel obtained in the step (c) to obtain the conductive carbon black modified silica aerogel.
Preferably, the mass ratio of the usage amount of the organosilicone to the usage amount of the water is (3-4): 2, the organic silicon ester accounts for 25 to 50 percent of the mixed solution by mass; the concentration of the anionic surfactant in the mixed solution is 0.004-0.006 mol/L; the particle size of the conductive carbon black is 30-200 nm; and/or the dosage of the catalyst is 3wt% -5 wt% of the dosage of the mixture.
Preferably, the organosilicate is methyl orthosilicate or ethyl orthosilicate; the organic solvent is selected from the group consisting of methanol, ethanol, acetone and acetonitrile, preferably ethanol; the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; and/or the catalyst is selected from one or more of oxalic acid solution, hydrochloric acid solution, ammonia water solution and ammonium fluoride solution.
Preferably, the rotation speed of the stirring in the step (b) is 200-300 rpm; the rotating speed of the stirring in the step (c) is 100-200 rpm; and/or the solvent exchange and aging steps in step (d) are: and (c) sequentially placing the wet gel obtained in the step (c) into ethanol, organic silicon ester and normal hexane to be soaked for 1-2 days respectively.
Preferably, the atmospheric pressure staged drying of the two or more different temperature stages in the step (d) comprises first temperature stage drying, second temperature stage drying, third temperature stage drying and fourth temperature stage drying; the drying temperature of the first temperature stage is 45-55 ℃, and the drying time of the first temperature stage is 18-30 h; the drying temperature of the second temperature stage is 75-85 ℃, and the drying time of the second temperature stage is 10-15 h; the drying temperature of the third temperature stage is 95-105 ℃, and the drying time of the third temperature stage is 5-8 h; the drying temperature of the fourth temperature stage is 115-150 ℃, and the drying time of the fourth temperature stage is 3-5 h.
Compared with the prior art, the method of the invention at least has the following beneficial effects:
(1) the invention provides a high-performance conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite cathode material and a preparation method thereof. Conductive carbon black modified silica aerogel (SiO)2Aerogel) has the following advantages as a carrier for elemental sulphur: the highly conductive carbon black particles are uniformly dispersed in the porous structure of the silica aerogel and can formA good electronic transmission network; light SiO2The aerogel has extremely high porosity and specific surface area, so that the unit mass of SiO2The aerogel carrier can realize uniform loading of a large amount of elemental sulfur, and the specific energy density of the integral composite anode material as an electrode is improved; SiO 22The surface of the aerogel has a large number of hydroxyl functional groups, and can form strong chemical adsorption on polysulfide which is easily dissolved in electrolyte in the charging and discharging process, so that the cycling stability of the lithium-sulfur battery electrode is improved. The invention uniformly disperses elemental sulfur to SiO modified by conductive carbon black through co-heat treatment2Preparing composite anode material in the inner pores of the aerogel carrier due to the SiO modified by the conductive carbon black2The composite anode material prepared by the method has excellent capacity performance and cycling stability when used as an electrode.
(2) The positive electrode material provided by the invention can fix liquid polysulfide formed in the lithium-sulfur battery in the charging and discharging process on the SiO modified by the conductive carbon black through the physical and chemical adsorption effects2On the aerogel carrier, the capacity performance and the cycling stability of the lithium-sulfur battery are effectively improved. In addition, compared with the complicated preparation process of the commonly used porous carbon material carrier in the current composite sulfur electrode material, the conductive carbon black used in the invention modifies SiO2The aerogel carrier is easy to prepare and low in cost, so that the conductive carbon black modified silicon dioxide aerogel loaded sulfur composite positive electrode material provided by the invention has high market application potential as a positive electrode material for a lithium sulfur battery.
(3) The sulfur-loaded composite material of the conductive carbon black modified silica aerogel (conductive carbon black doped silica aerogel) has the advantages of excellent capacity performance, excellent cycling stability, high coulombic efficiency and the like in a lithium-sulfur battery by taking the conductive carbon black modified silica aerogel which is light in weight, high in porosity, high in conductivity and strong in adsorption capacity as a simple substance sulfur carrier; the positive electrode material has higher initial charge and discharge specific capacity in the lithium-sulfur battery, keeps extremely high coulombic efficiency in the circulating process, and keeps the charge and discharge specific capacity at about 983mAh/g after circulating for 50 times.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the conductive carbon black-modified silica aerogel in example 1 of the present invention.
Fig. 2 is a graph of electrochemical cycle performance and coulombic efficiency of the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material in a lithium-sulfur battery in example 1 of the present invention.
Fig. 3 is a graph showing a relationship between the first charge-discharge specific capacity and the voltage of the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material in the lithium sulfur battery in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a sulfur-loaded conductive carbon black modified silica aerogel composite positive electrode material in a first aspect, which comprises conductive carbon black modified silica aerogel and elemental sulfur loaded in the conductive carbon black modified silica aerogel; the conductive carbon black modified silica aerogel comprises silica aerogel and conductive carbon black doped in the silica aerogel. In particular, in the present invention, the elemental sulphur is selected from the group consisting of orthorhombic sulphur, amorphous sulphur and sublimed sulphur, preferably sublimed sulphur; the silica aerogel (SiO)2Aerogel) is rich in hydroxyl functional groups.
According to some preferred embodiments, the conductive carbon black-modified silica aerogel sulfur-loaded composite positive electrode material consists of a conductive carbon black-modified silica aerogel and elemental sulfur loaded in the conductive carbon black-modified silica aerogel; the conductive carbon black modified silica aerogel consists of silica aerogel and conductive carbon black doped in the silica aerogel.
According to some preferred embodiments, the conductive carbon black modified silica aerogel supported sulfur composite positive electrode material contains 40% to 80% (e.g., 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%) of elemental sulfur by mass.
According to some preferred embodiments, the conductive carbon black has a particle size of 30 to 200nm (e.g., 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 nm); and/or the conductive carbon black in the conductive carbon black modified silica aerogel is 5-35% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, or 35%) by mass.
The sulfur-loaded composite cathode material of the conductive carbon black modified silica aerogel in the invention takes the conductive carbon black modified silica aerogel which is light in weight, high in porosity, high in conductivity and strong in adsorption capacity as a simple substance sulfur carrier, and has the advantages of excellent capacity performance, excellent cycling stability, high coulombic efficiency and the like when being used as an electrode of a lithium-sulfur battery.
The invention provides a preparation method of a conductive carbon black modified silica aerogel sulfur-loaded composite cathode material, which comprises the following steps:
(1) uniformly mixing conductive carbon black modified silica aerogel with elemental sulfur to obtain a mixture; and
(2) and (2) under the conditions of sealing and inert gas protection, carrying out heat treatment on the mixture obtained in the step (1) at 115-160 ℃ (for example, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃) to obtain the conductive carbon black modified silica aerogel supported sulfur composite cathode material.
In the present invention, the inert gas may be, for example, nitrogen gas, argon gas, or helium gas, preferably nitrogen gas; such as in a closed container (e.g. a closed tank) filled with nitrogen,elemental sulfur enters conductive carbon black to modify SiO in a liquid form through heating treatment2Obtaining the conductive carbon black modified silica aerogel loaded sulfur composite cathode material for the lithium-sulfur battery through the internal pores of the aerogel. In the invention, when the temperature of the heat treatment is more than 115 ℃, the elemental sulfur can be melted into a liquid form and enters the conductive carbon black modified SiO2In the internal pores of the aerogel.
According to some more specific embodiments, the preparation process of the conductive carbon black modified silica aerogel supported sulfur composite cathode material is as follows: uniformly mixing conductive carbon black modified silica aerogel (conductive carbon black doped silica aerogel) with elemental sulfur according to a certain proportion to obtain a mixture; then placing the mixture in a metal container, introducing enough nitrogen to replace the original air in the container, and sealing the metal container; then placing the metal container in a high-temperature environment (such as a heat treatment furnace) for uniform heat treatment, so that elemental sulfur enters the internal pores of the conductive carbon black modified silica aerogel in a liquid state with lower viscosity; and finally, taking out the mixture in the metal container after the heat treatment is finished, thereby obtaining the conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite positive electrode material. In order to further obtain the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material with more uniform particle size, the composite cathode material can be properly ground.
According to some preferred embodiments, the temperature of the heat treatment is 145 ℃ to 160 ℃ (e.g., 145 ℃, 150 ℃, 155 ℃ or 160 ℃), and the time of the heat treatment is 12 to 24 hours (e.g., 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours). In the invention, when the temperature of the heat treatment is 145-160 ℃, the viscosity of the elemental sulfur in a liquid state is most suitable and relatively small, which is beneficial to the uniform loading of a large amount of elemental sulfur by the conductive carbon black silicon dioxide aerogel carrier, thereby improving the specific energy density of the composite cathode material as an electrode. In the invention, the heat treatment time is preferably 12-24 h, and if the heat treatment time is insufficient, elemental sulfur cannot be uniformly dispersed in the conductive carbon black modified silica aerogel carrier, so that the electrochemical performance of the composite cathode material is poor.
According to some preferred embodiments, the mass ratio of the amount of the conductive carbon black modified silica aerogel to the amount of the elemental sulfur is 1: (0.66-4).
In the invention, the high-conductivity conductive carbon black particles are uniformly dispersed in the porous structure of the silica aerogel, so that a good electron transmission network (conductive network) can be formed; light SiO2The aerogel has extremely high porosity and specific surface area, so that the unit mass of SiO2The aerogel carrier can realize uniform loading of a large amount of elemental sulfur, and the specific energy density of the integral composite anode material as an electrode is improved; SiO 22The surface of the aerogel has a large number of hydroxyl functional groups, so that strong chemical adsorption can be formed on polysulfide which is easily dissolved in electrolyte in the charging and discharging processes, and stable load on elemental sulfur is realized, thereby improving the capacity performance and the cycling stability of the anode of the lithium-sulfur battery.
In order to combine the characteristics of large specific surface area and high conductivity, a carbon material (such as carbon aerogel) with a porous structure is usually used as a carrier of elemental sulfur, and the conductive carbon black modified silica aerogel is directly used as the carrier of the elemental sulfur, so that on the basis of overcoming the defect of insufficient conductivity of the silica aerogel, the conductive carbon black modified silica aerogel loaded sulfur composite positive electrode material can have strong physical and chemical adsorption capacity on an active sulfur substance, and the conductive carbon black modified silica aerogel loaded sulfur composite positive electrode material has more excellent capacity performance and cycle stability than other porous carbon material loaded sulfur composite positive electrode materials when being used as the positive electrode of a lithium sulfur battery. In addition, as the conductive carbon black modified silica aerogel has strong physical and chemical adsorption effects, uniform loading of a large amount of elemental sulfur can be easily realized under simple and convenient heat treatment operation, so that the preparation process of the invention is simplified to a great extent, the method of the invention is easy to realize batch production, and has high market application potential.
According to some preferred embodiments, the method further comprises, before step (1), a step of preparing a conductive carbon black-modified silica aerogel, the preparation step comprising the sub-steps of:
(a) uniformly mixing organosilicate, an organic solvent, water (such as deionized water) and an anionic surfactant to obtain a mixed solution;
(b) adding conductive carbon black into the mixed solution obtained in the step (a) and uniformly stirring to obtain a mixed material;
(c) adding a catalyst into the mixture obtained in the step (b) and stirring the mixture to a gel state to obtain wet gel; and
(d) and (c) sequentially carrying out solvent exchange and aging steps and normal pressure sectional drying steps at more than two different temperature stages on the wet gel obtained in the step (c) to obtain the conductive carbon black modified silica aerogel.
In the invention, the addition of the anionic surfactant is beneficial to obtaining stable wet gel and also beneficial to uniform dispersion of the conductive carbon black in the silica aerogel structure, so that subsequent elemental sulfur is also beneficial to being uniformly loaded in the conductive carbon black modified silica aerogel, and the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material for the lithium sulfur battery, which has more excellent capacity performance and cycle stability, is obtained. According to the invention, the specific surface area and porosity of the final conductive carbon black modified silica aerogel are improved by normal-pressure sectional drying, so that the physical and chemical adsorption capacities of the conductive carbon black modified silica aerogel are improved. In the invention, the conductive carbon black modified silica aerogel doped with the conductive carbon black before the gelation process is preferably prepared, and the conductive carbon black modified silica aerogel prepared by the method has a better loading effect on elemental sulfur, so that the capacity performance and the cycling stability of the prepared conductive carbon black modified silica aerogel sulfur-loaded composite cathode material in the lithium-sulfur battery are more excellent.
According to some preferred embodiments, the mass ratio of the usage amount of the organosilicate to the usage amount of the water is (3-4): 2 (e.g., 3:2, 3.5:2, or 4:2), preferably 3:2, and the silicone ester accounts for 25% to 50% by mass (e.g., 25%, 30%, 35%, 40%, 45%, or 50%) of the mixed solution; the concentration of the anionic surfactant in the mixed solution is 0.004-0.006 mol/L (such as 0.004, 0.005 or 0.006mol/L), preferably 0.005 mol/L; the particle size of the conductive carbon black is 30-200 nm; and/or the catalyst is present in an amount of 3wt% to 5wt% (e.g., 3wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%) of the amount of the mix. In particular, the concentration of the anionic surfactant in the mixed solution is the concentration of the added anionic surfactant in the whole mixed solution system when the silicone ester, the organic solvent, water (for example, deionized water) and the anionic surfactant are uniformly mixed.
In the invention, the particle size of the conductive carbon black is preferably 30-200 nm, and when the particle size of the conductive carbon black is 30-200 nm, the particle size is close to the size of a silica aerogel skeleton, so that the conductive carbon black can be uniformly dispersed in the silica aerogel skeleton structure, and the subsequent conductive carbon black modified silica aerogel can be uniformly loaded with active elemental sulfur. In the invention, the conductive carbon black modified silica aerogel with the mass percentage of 5-35% of conductive carbon black is preferably prepared, when the content is lower than 5%, the conductivity of the conductive carbon black modified silica aerogel is poor, and when the content is higher than 35%, the chemical adsorption performance of the conductive carbon black modified silica aerogel on elemental sulfur is reduced, so that the capacity performance and the cycle stability of the prepared conductive carbon black modified silica aerogel loaded sulfur composite cathode material as an electrode are influenced, and the coulombic efficiency of the prepared conductive carbon black modified silica aerogel loaded sulfur composite cathode material is reduced. In the present invention, the coulombic efficiency, also called discharge efficiency, refers to the ratio of the battery discharge capacity to the charge capacity in the same cycle process, i.e. the percentage of the discharge capacity to the charge capacity.
According to some preferred embodiments, the organosilicate is methyl orthosilicate or ethyl orthosilicate; the organic solvent is selected from the group consisting of methanol, ethanol, acetone and acetonitrile, preferably ethanol; the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; and/or the catalyst is selected from one or two of oxalic acid solution, hydrochloric acid solution, ammonia water solution and ammonium fluoride solution. In particular, when two catalysts are used, it is necessary to add the second catalyst after the addition of the former catalyst is completed.
According to some preferred embodiments, when the organic silicon ester is methyl orthosilicate, the mass ratio of the conductive carbon black to the amount of the methyl orthosilicate is 1: (4.7-48.1), so that the mass percentage of the conductive carbon black in the prepared conductive carbon black modified silica aerogel is 5% -35%; when the organic silicon ester is tetraethoxysilane, the mass ratio of the conductive carbon black to the tetraethoxysilane is 1: (6.4-65.9), so that the mass percentage of the conductive carbon black in the prepared conductive carbon black modified silica aerogel is 5% -35%.
According to some preferred embodiments, the rotation speed of the stirring in step (b) is 200 to 300rpm (e.g. 200, 250 or 300 rpm); the stirring speed in the step (c) is 100-200 rpm (for example 100, 150 or 200 rpm); wherein the unit "rpm" represents the unit "rpm" of the rotation speed.
According to some preferred embodiments, the solvent exchange and aging step in step (d) is: and (c) sequentially placing the wet gel obtained in the step (c) into ethanol, organic silicon ester and normal hexane to be soaked for 1-2 days respectively. Soaking the wet gel obtained in the step (c) in ethanol for 1-2 days to exchange solvents, gradually replacing water in the wet gel with ethanol by using a diffusion effect, and preliminarily removing the water to obtain alcogel; then sequentially placing the alcogel in the organic silicon ester for soaking for 1-2 days, and further depositing a monomer on the aerogel framework to enhance the framework strength besides aging; and finally, soaking the mixture in n-hexane for 1-2 days, and finally filling the pores with a solvent with low surface activity so as to facilitate subsequent normal-pressure sectional drying.
According to some preferred embodiments, the atmospheric staged drying of the two or more different temperature stages in step (d) comprises first temperature stage drying, second temperature stage drying, third temperature stage drying and fourth temperature stage drying; the temperature of the first temperature stage drying is 45-55 ℃ (such as 45 ℃, 50 ℃ or 55 ℃), preferably 50 ℃, and the time of the first temperature stage drying is 18-30 h (such as 18, 24 or 30 h); the temperature of the second temperature stage drying is 75-85 ℃ (for example, 75 ℃, 80 ℃ or 85 ℃), preferably 80 ℃, and the time of the second temperature stage drying is 10-15 h (for example, 10, 12 or 15 h); the temperature of the third temperature stage drying is 95-105 ℃ (such as 95 ℃, 100 ℃ or 105 ℃), preferably 100 ℃, and the time of the third temperature stage drying is 5-8 h (such as 5, 6, 7 or 8 h); the temperature of the fourth temperature stage drying is 115 ℃ to 150 ℃ (for example 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃), preferably 120 ℃, and the time of the fourth temperature stage drying is 3 h to 5h (for example 3, 4 or 5 h).
According to some more specific embodiments, the process for preparing the conductive carbon black modified silica aerogel is as follows: preparing a uniform mixed solution from tetraethoxysilane, ethanol, deionized water and an anionic surfactant according to a certain ratio; wherein the mass ratio of the ethyl orthosilicate to the deionized water is 3:2, and the addition amount of the ethanol is adjusted to ensure that the mass ratio of the ethyl orthosilicate in the mixed liquid system is 25-50%; then adding conductive carbon black into the mixed solution, and stirring at the rotating speed of 200-300 rpm for 1-2 hours to obtain a mixture; dripping a catalyst for gel into the mixture, stirring at the rotating speed of 100-200 rpm for 10-15 min, and standing to obtain wet gel, wherein the addition amount of the catalyst is 3-5 wt% of the amount of the mixture; respectively soaking the obtained wet gel in ethanol, ethyl orthosilicate and n-hexane solution for 24 hours respectively to perform solvent exchange and aging steps to obtain gel; finally, carrying out normal-pressure segmented drying treatment on the obtained gel at more than two different temperature stages within the temperature range of 50-150 ℃ to obtain the conductive carbon black modified SiO2An aerogel.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
Firstly, ethyl orthosilicate and ethanolDeionized water and sodium dodecyl sulfate are prepared into uniform mixed solution, wherein the mass ratio of the ethyl orthosilicate to the ethanol to the deionized water is 3:5:2, and the concentration of the sodium dodecyl sulfate in the mixed solution is 5 multiplied by 10- 3mol/L; then adding conductive carbon black with the particle size of 50nm into the mixed solution, and stirring at the rotating speed of 200rpm for 1h to obtain a mixed material, wherein the mass ratio of the addition amount of the conductive carbon black to the tetraethoxysilane in the mixed solution is 1: 19.7; adding a hydrochloric acid solution with the concentration of 1mol/L into the mixture, wherein the addition amount is 4% of the mass of the mixture, stirring at the rotating speed of 150rpm for 10min, and standing to obtain wet gel; respectively soaking the obtained wet gel in ethanol, ethyl orthosilicate and n-hexane for 24 hours respectively to perform solvent exchange and aging steps to obtain gel; finally, the obtained gel is placed in an oven to be dried for 24 hours at 50 ℃, 12 hours at 80 ℃, 6 hours at 100 ℃ and 4 hours at 120 ℃ in sequence to obtain the conductive carbon black modified silica aerogel (conductive carbon black modified SiO) with the conductive carbon black doping amount of 15 percent2Aerogel).
② modifying SiO by sublimed sulfur powder and conductive carbon black2Uniformly mixing aerogel according to the mass ratio of 7:3 to obtain a solid mixture; then placing the obtained solid mixture in a metal container, introducing enough nitrogen to replace the original air in the container, and sealing the metal container; and finally, placing the metal container in an environment at 155 ℃ for heat treatment for 12 hours, taking out a solid mixture (solid) in the metal container after the heat treatment is finished, and properly grinding the solid mixture to obtain the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material with the elemental sulfur content of 70% by mass.
A Scanning Electron Microscope (SEM) image of the conductive carbon black-modified silica aerogel prepared in this example is shown in fig. 1. From the results of fig. 1, it can be seen that the conductive carbon black is uniformly dispersed in the silica aerogel, the particle size of the conductive carbon black is also close to the size of the aerogel skeleton, no agglomerated conductive carbon black particles are seen in fig. 1, and the conductive carbon black modifies the silica aerogel material to have a highly porous structure, which is helpful for uniformly loading active elemental sulfur.
This example also addresses the preparation of electrical conductorsThe carbon black modified silica aerogel sulfur-loaded composite cathode material is subjected to electrochemical performance test. The test method comprises the following steps: uniformly mixing the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material powder with the elemental sulfur content of 70% by mass, acetylene black and polyvinylidene fluoride in a proper amount of N-methyl pyrrolidone according to the mass ratio of 7:2:1 to obtain slurry; and coating the obtained slurry on an aluminum foil current collector to obtain an electrode plate, and stamping the electrode plate into the electrode plate with the diameter of 10mm after drying. The button cell (lithium sulfur battery) is assembled in a glove box by taking a metal lithium sheet as a negative electrode, the result of constant current charge-discharge circulation at the rate of 0.2C (current density of 335mA/g) is shown in figure 2, and the relation curve of the first charge-discharge specific capacity and the voltage is shown in figure 3. The results of fig. 2 and fig. 3 show that the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material has high initial charge and discharge specific capacity when used as an electrode, maintains extremely high coulombic efficiency (the coulombic efficiency is over 98%) in the cycle process, and has charge and discharge specific capacities of about 983mAh/g after 50 cycles (weeks) of charge and discharge; wherein the unit "mAh/g" is also referred to as "mAhg-1", indicates the specific mass capacity unit, i.e., the amount of electricity that can be discharged per unit weight of the battery or active material.
Example 2
Example 2 is essentially the same as example 1, except that:
in (1): the mass ratio of the ethyl orthosilicate to the ethanol to the deionized water is 3:2: 2; the particle size of the conductive carbon black is 30nm, and the mass ratio of the addition amount of the conductive carbon black to the tetraethoxysilane in the mixed solution is 1: 66; the addition amount of the hydrochloric acid solution is 5 percent of the mass of the mixture; and obtaining the conductive carbon black modified silica aerogel with the conductive carbon black doping amount of 5%.
In step two: sublimed sulfur powder and conductive carbon black modified SiO2The mass ratio of the aerogel is 1: 1; the heat treatment temperature is 150 ℃; the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material contains 50% of elemental sulfur by mass.
Example 3
Example 3 is essentially the same as example 1, except that:
in (1): sodium dodecyl sulfate is used as an anionic surfactant instead of sodium dodecyl sulfate; the particle size of the conductive carbon black is 100nm, and the mass ratio of the addition amount of the conductive carbon black to the tetraethoxysilane in the mixed solution is 1: 8.1; sequentially adding 1mol/L oxalic acid solution and 2mol/L ammonium fluoride solution into the mixture, wherein the adding amount is 2.5% of the mass of the mixture respectively; and obtaining the conductive carbon black modified silica aerogel with the conductive carbon black doping amount of 30%.
In step two: sublimed sulfur powder and conductive carbon black modified SiO2The mass ratio of the aerogel is 8: 2; the heat treatment temperature is 160 ℃, and the heat treatment time is 18 h; the sulfur-loaded composite anode material of the conductive carbon black modified silica aerogel contains 80 mass percent of elemental sulfur.
Example 4
Example 4 is essentially the same as example 1, except that:
in (1): by changing the mass ratio of the addition amount of the conductive carbon black to the tetraethoxysilane in the mixed solution (the mass ratio of the addition amount of the conductive carbon black to the tetraethoxysilane in the mixed solution is 1:4.2), the conductive carbon black modified silica aerogel (conductive carbon black modified SiO) with the conductive carbon black doping amount of 45% is obtained2Aerogel).
Example 5
Example 5 is essentially the same as example 1, except that:
in (1): adding conductive carbon black with the particle size of 15nm into the mixed solution.
Example 6
Example 6 is essentially the same as example 1, except that:
in (1): the gel obtained after the solvent exchange and aging steps was dried in an oven at 70 ℃ for 46 h.
Example 7
Example 7 is essentially the same as example 1, except that:
in the first step, sodium lauryl sulfate is not mixed, and the prepared mixed solution does not contain an anionic surfactant.
Example 8
Example 8 is substantially the same as example 1, except that the conductive carbon black-modified silica aerogel in (i) is prepared by: fully and uniformly mixing 82% of silicon dioxide aerogel particles, 15% of conductive carbon black (the particle size is 50nm) and 3% of polyvinylidene fluoride binder in percentage by mass to obtain the conductive carbon black modified silicon dioxide aerogel (conductive carbon black modified SiO) with the conductive carbon black doping amount of 15%2Aerogel).
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
in step two: and (2) placing the metal container in an environment at 150 ℃ for heat treatment for 6h, taking out a solid mixture (solid) in the metal container after the heat treatment is finished, and properly grinding the solid mixture to obtain the conductive carbon black modified silica aerogel sulfur-loaded composite cathode material with the elemental sulfur content of 70% by mass.
Comparative example 2
Adding 4g of potassium hydroxide and 2g of melamine into 1g of carbon aerogel, uniformly mixing, pouring into a nickel crucible, placing in a muffle furnace under the inert atmosphere of argon or nitrogen, heating to 800 ℃, and preserving heat for 2 hours. Washing the obtained solid with a dilute sulfuric acid solution, then washing the solid with distilled water or ethanol to be neutral, and drying the solid at 120 ℃ to obtain the carbon aerogel material modified by the activation and nitrogen doping synchronous process, wherein the nitrogen doping amount reaches 15.8 at%; wherein the unit "at%" represents the unit of "atomic percent".
② under the condition of room temperature, 2g of elemental sulfur is dissolved in 40g of carbon disulfide organic solvent to form organic sulfur solution with 5 percent of sulfur content, 0.37g of modified carbon aerogel material is slowly added, and ultrasonic oscillation is carried out for 1 hour at room temperature. And then putting the solution into an extraction kettle, extracting by using supercritical ethane fluid as an extracting agent at the extraction temperature of 40 ℃ and the pressure of 30MPa for 40 minutes, wherein the flow rate of the supercritical fluid is 1000 ml/minute, performing reduced pressure separation at the separation pressure of 7MPa and the separation temperature of 50 ℃, and then leaching by using ethanol eluent. Vacuum drying at 60 ℃ to obtain the modified carbon aerogel-sulfur composite cathode material with the sulfur content of 79.2%.
The composite positive electrode materials prepared in examples 2 to 8 and comparative examples 1 to 2 were assembled into a button cell (lithium sulfur battery) in the same manner as in example 1, and were subjected to constant current charge-discharge cycle electrochemical performance test under the same conditions as in example 1, with the results shown in table 1.
Table 1: the electrochemical performance test results of the composite positive electrode materials prepared in examples 1 to 8 and comparative examples 1 to 2 in a lithium sulfur battery.
Figure BDA0001639098790000171
Finally, it should be noted that: 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 (9)

1. The conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite cathode material is characterized in that:
the sulfur-loaded conductive carbon black modified silica aerogel composite positive electrode material comprises conductive carbon black modified silica aerogel and elemental sulfur loaded in the conductive carbon black modified silica aerogel;
the conductive carbon black modified silica aerogel comprises silica aerogel and conductive carbon black doped in the silica aerogel; the particle size of the conductive carbon black is 30-200 nm; the mass percentage of the conductive carbon black in the conductive carbon black modified silica aerogel is 5-35%; the mass percentage of elemental sulfur in the conductive carbon black modified silicon dioxide aerogel sulfur-loaded composite positive electrode material is 40-80%.
2. The preparation method of the conductive carbon black modified silica aerogel loaded sulfur composite cathode material is characterized by comprising the following steps of:
(1) uniformly mixing conductive carbon black modified silica aerogel with elemental sulfur to obtain a mixture; the particle size of the conductive carbon black is 30-200 nm; the mass percentage of the conductive carbon black in the conductive carbon black modified silica aerogel is 5-35%; and
(2) under the conditions of sealing and inert gas protection, performing heat treatment on the mixture obtained in the step (1) at 115-160 ℃ to obtain the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material, wherein the mass percentage of elemental sulfur in the conductive carbon black modified silica aerogel sulfur-loaded composite positive electrode material is 40-80%.
3. The method of claim 2, wherein:
the temperature of the heat treatment is 145-160 ℃, and the time of the heat treatment is 12-24 h.
4. The method of claim 2, wherein:
the mass ratio of the conductive carbon black modified silica aerogel to the elemental sulfur is 1: (0.66-4).
5. The method of claim 2, further comprising a step of preparing a conductive carbon black-modified silica aerogel before the step (1), the step of preparing comprising the substeps of:
(a) uniformly mixing organosilicate, an organic solvent, water and an anionic surfactant to obtain a mixed solution;
(b) adding conductive carbon black into the mixed solution obtained in the step (a) and uniformly stirring to obtain a mixed material;
(c) adding a catalyst into the mixture obtained in the step (b) and stirring the mixture to a gel state to obtain wet gel; and
(d) and (c) sequentially carrying out solvent exchange and aging steps and normal pressure sectional drying steps at more than two different temperature stages on the wet gel obtained in the step (c) to obtain the conductive carbon black modified silica aerogel.
6. The method of claim 5, wherein:
the mass ratio of the usage amount of the organosilicone to the usage amount of the water is (3-4): 2, the organic silicon ester accounts for 25-50% of the mixed solution by mass percent;
the concentration of the anionic surfactant in the mixed solution is 0.004-0.006 mol/L;
the dosage of the catalyst is 3-5 wt% of that of the mixture.
7. The method of claim 5, wherein:
the organic silicon ester is methyl orthosilicate or ethyl orthosilicate;
the organic solvent is selected from the group consisting of methanol, ethanol, acetone, and acetonitrile;
the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate;
the catalyst is selected from one or more of oxalic acid solution, hydrochloric acid solution, ammonia water solution and ammonium fluoride solution.
8. The method of claim 5, wherein:
the rotating speed of the stirring in the step (b) is 200-300 rpm;
the rotating speed of the stirring in the step (c) is 100-200 rpm;
the solvent exchange and aging step in the step (d) is as follows: and (c) sequentially placing the wet gel obtained in the step (c) into ethanol, organic silicon ester and normal hexane to be soaked for 1-2 days respectively.
9. The method of claim 5, wherein:
the atmospheric pressure sectional drying of more than two different temperature stages in the step (d) comprises first temperature stage drying, second temperature stage drying, third temperature stage drying and fourth temperature stage drying;
the drying temperature of the first temperature stage is 45-55 ℃, and the drying time of the first temperature stage is 18-30 h;
the drying temperature of the second temperature stage is 75-85 ℃, and the drying time of the second temperature stage is 10-15 h;
the drying temperature of the third temperature stage is 95-105 ℃, and the drying time of the third temperature stage is 5-8 h;
the drying temperature of the fourth temperature stage is 115-150 ℃, and the drying time of the fourth temperature stage is 3-5 h.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865136A (en) * 2005-05-19 2006-11-22 同济大学 Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method
CN102992333A (en) * 2013-01-04 2013-03-27 同济大学 Low-cost method for preparing aerosil
CN105047893A (en) * 2015-08-10 2015-11-11 哈尔滨工业大学 Preparation method of graphene nanoscroll/sulfur composite material and application of graphene nanoscroll/sulfur composite material
WO2016076636A1 (en) * 2014-11-12 2016-05-19 한국기술교육대학교 산학협력단 Lithium-sulfur battery
CN105742587A (en) * 2016-02-25 2016-07-06 南京师范大学 Preparation method of sulfur/silica gel three-dimensional composite material for positive electrode of lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865136A (en) * 2005-05-19 2006-11-22 同济大学 Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method
CN102992333A (en) * 2013-01-04 2013-03-27 同济大学 Low-cost method for preparing aerosil
WO2016076636A1 (en) * 2014-11-12 2016-05-19 한국기술교육대학교 산학협력단 Lithium-sulfur battery
CN105047893A (en) * 2015-08-10 2015-11-11 哈尔滨工业大学 Preparation method of graphene nanoscroll/sulfur composite material and application of graphene nanoscroll/sulfur composite material
CN105742587A (en) * 2016-02-25 2016-07-06 南京师范大学 Preparation method of sulfur/silica gel three-dimensional composite material for positive electrode of lithium-sulfur battery

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