CN108183227B - Manganese dioxide-doped sulfur-carbon anode composite material, preparation method thereof and battery - Google Patents

Manganese dioxide-doped sulfur-carbon anode composite material, preparation method thereof and battery Download PDF

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CN108183227B
CN108183227B CN201711493157.2A CN201711493157A CN108183227B CN 108183227 B CN108183227 B CN 108183227B CN 201711493157 A CN201711493157 A CN 201711493157A CN 108183227 B CN108183227 B CN 108183227B
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sulfur
manganese dioxide
graphene
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CN108183227A (en
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苗力孝
池子翔
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Soundon New Energy Technology Co Ltd
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Sander New Energy Technology Development Co ltd
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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
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
    • H01M4/38—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
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    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
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Abstract

The invention relates to a manganese dioxide doped graphene sulfur-carbon anode composite material and a preparation method thereof. According to the preparation method, the preparation of graphene, manganese dioxide doping and sulfur compounding are realized in one step in the graphene oxide preparation process, and the preparation by-product of graphene is utilized to obtain the uniformly doped graphene oxide/manganese dioxide/nano sulfur ternary mixed composite material. The method has the advantages of simple and convenient process, low cost and suitability for mass production, the prepared composite anode material has good conductivity and high cycle stability, the polysulfide dissolution and shuttle effect is effectively inhibited, the secondary utilization of waste liquid in the graphene production process is realized, and the resource waste and the environmental pollution are avoided.

Description

Manganese dioxide-doped sulfur-carbon anode composite material, preparation method thereof and battery
Technical Field
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, in particular to a manganese dioxide doped graphene sulfur-carbon positive electrode composite material and a preparation method thereof.
Background
With the increasing demand for energy and the associated pollution problems, lithium ion batteries with high energy density have attracted much attention and have been successfully used in the sustainable renewable energy industry, the transportation industry, and particularly the consumer electronics industry. However, the development of a new electrochemical energy storage system is imperative due to the limitation of the theoretical specific capacity of the conventional lithium ion battery cathode material. The theoretical energy density of a lithium-sulfur battery (Li-S battery) can reach 2600Wh/kg at most, and the introduction of sulfur elements is cheap, abundant in resources and environment-friendly, so that the lithium-sulfur battery is expected to become the first choice of a secondary battery with the advantages of high energy density and long cycle life in the future.
However, the lithium-sulfur battery has some disadvantages that restrict the commercialization process, such as low electronic conductivity and low electrochemical activity of the positive active material sulfur, low charge-discharge efficiency and low active material utilization rate due to the fact that lithium polysulfide, which is an intermediate product of charge and discharge, is easily dissolved in the electrolyte, and poor mechanical properties due to the volume expansion of the material during the charge and discharge process, which affect the cycle performance.
In order to solve the above problems, it is necessary to improve cycle performance and charge-discharge efficiency of the lithium-sulfur battery. Researchers have employed methods of co-compounding graphene and metal oxides with sulfur to increase the conductivity of the positive active material and to limit the dissolution of polysulfides. The graphene has the advantages of high specific surface area, ultrahigh conductivity, light weight, high structural strength and the like, can effectively coat sulfur particles to form a conductive network, reduces interface impedance, greatly improves the electrochemical activity of sulfur, and contains O in metal oxide2-The anionic functional groups also provide abundant polar active sites for polysulfide uptake. However, although the above method improves the conductivity of sulfur to a certain extent, limits the dissolution of polysulfide, and inhibits shuttle effect, graphene and metal oxide need to be added or prepared respectively in the process of preparing the sulfur/graphene/metal oxide composite positive electrode material, the process is complicated and high in cost, which is not beneficial to industrial mass production, and the treatment cost of waste liquid generated in graphene production is not very high.
Therefore, there is still a need to find a new metal oxide doped sulfur-carbon cathode composite material with good conductivity, good battery performance and high cycling stability, and to find a preparation process of the material with the advantages of simple process, low cost and secondary utilization of waste liquid.
Disclosure of Invention
Technical problem to be solved
In order to overcome the defects of the prior art, the invention aims to provide a manganese dioxide doped graphene sulfur-carbon cathode composite material and a preparation method thereof.
The manganese dioxide doped graphene sulfur-carbon anode composite material provided by the invention has the advantages of good conductivity, good battery performance and high cycle stability, and can effectively inhibit polysulfide dissolution and shuttle effect. The preparation method has the advantages of simple process, low cost and environmental protection. Therefore, the invention has wide application prospect in the fields of lithium-sulfur batteries and batteries using the batteries.
(II) technical scheme
The invention provides a manganese dioxide doped graphene sulfur-carbon anode composite material which is prepared by compounding and doping a graphene oxide/manganese dioxide/sulfur ternary nano material.
In a preferred embodiment of the present invention, the positive electrode composite material contains 40 to 90 mass% of sulfur and MnO2The mass percent of the graphene is 5-30%, and the mass percent of the graphene is 5-30%. More preferably, the mass percent of sulfur in the positive electrode composite material is 50% -80%, and MnO is2The mass percent of the graphene is 10-25%, and the mass percent of the graphene is 10-25%.
In a preferred mode of the invention, the positive electrode composite material is prepared by compounding and doping graphene oxide, manganese dioxide and nano sulfur in one step in the graphene oxide preparation process.
The invention also provides a preparation method of the manganese dioxide doped graphene sulfur-carbon anode composite material, which comprises the following steps:
a) preparing graphene oxide by using a Hummers method;
b) mixing a sulfur source with the reaction mixture obtained in the step a) to prepare the manganese dioxide doped graphene sulfur-carbon anode composite material.
The sulfur source in the step b) can be organic solution or inorganic solution of elemental sulfurOne or more of sulfide, organic sulfide, thiosulfate and polysulfide. The organic solution of elemental sulfur is obtained by dissolving elemental sulfur in one or more solvents such as toluene, carbon disulfide, mercaptan, C2-C11 dialkyl disulfide, dimethylformamide and the like, wherein the solvent is preferably carbon disulfide, and the elemental sulfur can be sublimed sulfur; the inorganic sulfide may be a sulfide such as sodium sulfide, potassium sulfide, magnesium sulfide, ammonium sulfide, or the like; the organic sulfide can be mercaptan, thioether, etc.; the thiosulfate can be sodium thiosulfate, potassium thiosulfate, magnesium thiosulfate and the like; the polysulfide can be an organic polysulfide or an inorganic polysulfide, for example sodium polysulfide (Na)2Sx) Potassium polysulfide (K)2Sx) Wherein x is preferably 2 to 12, and more preferably 2 to 8.
According to the method, according to the graphene oxide/manganese dioxide/sulfur ratio of the graphene sulfur-carbon anode composite material doped with manganese dioxide, potassium permanganate can be further supplemented and/or the pH condition can be changed in the step b) to adjust the content of manganese dioxide in the product anode composite material if necessary. Before the reducing sulfur source in the step b) is mixed with the reaction mixture obtained in the step a), a reducing agent such as hydrogen peroxide, sodium sulfite and the like can be used for reducing potassium permanganate so as to reduce the consumption of the reducing sulfur source and/or ensure the smooth generation of elemental sulfur.
The preferable preparation method is characterized in that the raw materials in the step a) are graphite raw materials, potassium permanganate, sodium nitrate and concentrated sulfuric acid.
The preferable production method of the present invention is characterized by further comprising a method of producing polysulfide as a sulfur source.
As a preferred preparation method of the invention, the method comprises the following steps:
1) preparation of graphene oxide by Hummers method
Mixing a graphite raw material, potassium permanganate and sodium nitrate in a molar ratio of 30-50: 2-5: 0.2-1 in 98% concentrated sulfuric acid, wherein the total mass of the graphite raw material, the potassium permanganate and the sodium nitrate accounts for 3-20% of the mass of the concentrated sulfuric acid, preferably 5-18%, further preferably 8-15%, further preferably 8.5%, 9%, 10%, 12%, 13% and 14%, uniformly stirring at-5-15 ℃, removing an ice bath after reacting for 30-180 min, and stirring at room temperature for 6-120 h. Preferably, the stirring temperature is 0 to 10 ℃ in an ice bath.
2) Preparation of polysulfide ion solution
Mixing elemental sulfur and sodium sulfide according to the weight ratio of 0.3-4: 1 is added into deionized water, the molar ratio of elemental sulfur to sodium sulfide is preferably 2:1, the mixture is heated to 50-80 ℃, and the mixture is stirred for 0.5-2 hours.
3) Adding the polysulfide ion solution prepared in the step 2) into the reaction mixture in the step 1), stirring and reacting for 1-8 hours, washing the product with deionized water for 3-5 times, collecting the precipitate, and drying at 40-80 ℃ for 1-72 hours.
The invention also provides a battery, and the positive electrode material of the battery is the manganese dioxide doped graphene sulfur-carbon positive electrode composite material.
(III) advantageous effects
The preparation method disclosed by the invention realizes the preparation of graphene, manganese dioxide doping and one-step compounding of sulfur, and utilizes the preparation by-product of graphene to obtain the uniformly doped graphene oxide/manganese dioxide/nano sulfur ternary mixed composite material. The method overcomes the defect that excessive acid, manganese dioxide and manganese sulfate need to be removed by washing a large amount of water after graphene is prepared by the existing method, makes full use of by-product waste acid and excessive potassium permanganate in the preparation process of graphene oxide, adds a sulfur source, and utilizes the strong reducibility of the sulfur source to react with the excessive potassium permanganate to generate MnO2And nano elemental sulfur and nano MnO generated by oxidation at the same time2Coprecipitation is formed on the surface of graphene, the coprecipitation is uniformly dispersed on the surface of the graphene, and meanwhile, excessive polysulfide ions and oxygen-containing functional groups on the surface of graphene oxide are subjected to redox reaction, so that nano sulfur is better adsorbed and fixed on the surface of the graphene, and the sulfur, the graphene and manganese dioxide are simultaneously, uniformly compounded and doped at one time.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the method has the advantages of simple and convenient process, low cost and suitability for mass production, and the prepared composite anode material has good conductivity, good performance and high cycling stability.
(2) The waste liquid in the graphene production process is recycled, and resource waste and environmental pollution are avoided.
(3) By one-step composite doping with MnO2The mixed graphene carbon-sulfur composite material has good conductivity and MnO2And rich oxygen functional groups in the graphene oxide can form a bonding effect with polysulfide ions, so that the dissolution and shuttle effects of polysulfide serving as a charge-discharge intermediate product are effectively inhibited.
Drawings
Fig. 1 is an SEM image of a sample of manganese dioxide doped graphene sulfur carbon positive electrode composite obtained in example 1;
FIG. 2 is a charge and discharge curve of the batteries fabricated by the samples of example 1 and comparative example 1;
FIG. 3 is a graph of the ambient temperature cycle for the samples of example 1 and comparative example 1.
Detailed Description
The following detailed description of the present invention is provided to further illustrate the invention, and it is to be understood that the examples provided herein are for the purpose of illustration and explanation and are not to be construed as limiting the scope of the invention.
Example 1
(1) Preparing a graphene oxide mother solution: weighing 1g of graphite raw material, mixing the graphite raw material with KMnO4And NaNO3In a molar ratio of 14: 4.4: 1 in a proportion of 8.5 percent, the total mass of the graphite raw material, the potassium permanganate and the sodium nitrate accounts for 8.5 percent of the mass of the concentrated sulfuric acid, and the mixture is stirred for 2 hours on an ice bath at 4 ℃ and then stirred for 48 hours at room temperature.
(2) Preparation of polysulfide ion solution: 9.6g of elemental sulfur and 36g of Na were weighed out2S∙9H2O was slowly added to 1000mL of deionized water, heated to 60 ℃ and stirred for 1 hour to give a clear aqueous polysulfide ion solution (Na)2S3An aqueous solution).
(3) Adding all the polysulfide ion solution obtained in the step (2) into the graphene oxide obtained in the step (1)The mother liquor was stirred for 4 hours. And filtering and collecting a precipitate, washing with deionized water for 5 times, and drying at 60 ℃ for 12 hours to obtain the manganese dioxide doped graphene sulfur-carbon anode composite material. Through TGA test, the sulfur content in the positive electrode composite material is 71.3%, the powder after the TGA test is subjected to chemical titration analysis, and MnO in the positive electrode composite material is obtained through conversion2The content of the manganese dioxide doped graphene sulfur-carbon anode composite material is 10.4%, so that the mass ratio of graphene oxide/manganese dioxide/nano sulfur in the manganese dioxide doped graphene sulfur-carbon anode composite material is 1.76:1: 6.86. The SEM image of the manganese dioxide doped graphene sulfur carbon cathode composite material obtained in example 1 is shown in fig. 1.
Comparative example 1
(1) Preparing graphene oxide: weighing 1g of graphite raw material, 0.5g of sodium nitrate and 3g of potassium permanganate, adding 20ml of concentrated sulfuric acid, stirring for 2 hours on an ice bath at 4 ℃, and then stirring for 48 hours at room temperature; after the reaction is finished, adding a proper amount of hydrogen peroxide to reduce the residual oxidant to make the solution become bright yellow, centrifuging, filtering, collecting precipitate, washing with water for 4 times, and drying the solid at 60 ℃.
(2) Preparing nano manganese dioxide: stirring at room temperature at a certain speed to obtain a certain amount of 1mol/L MnCl2The solution is added to a given volume of a mixed solution of NaOH and NaOCl (molar ratio, NaOH: MnCl)2＝2.5；NaOCl：MnCl2Stirring for 2h, standing for 24h, repeatedly washing with deionized water until the washing liquid is colorless, then performing suction filtration, drying at 100 ℃, and grinding in an agate mortar to obtain the nano manganese dioxide.
(3) Preparing nano sulfur: adding the fully ground sulfur powder into 0.25mol/L sodium sulfide solution for sulfur dissolving reaction (molar ratio, S: Na)2S ═ 3), and stirred at room temperature until the sulfur powder was completely dissolved, to obtain a sodium polysulfide solution. Adding 10mL of sodium polysulfide solution into 100mL of deionized water containing PEG-400, and adjusting the pH to be more than 8 by using 0.1mol/L of sodium hydroxide solution to obtain a clear light yellow reaction solution A; and adding a proper amount of PEG-400 into 100mL of 2mol/L formic acid solution to obtain reaction solution B. Slowly dripping the reaction solution A into the reaction solution B under stirring at room temperature, continuously stirring for 30min after dripping, wherein the solution is milky sol, and the solution is separated at 5000r/minAnd (4) after the heart is kept for 20min, washing the precipitate for 3 times by using a proper amount of hexane, and naturally drying the precipitate for 48h at room temperature to obtain a light yellow powder.
(4) Preparing a manganese dioxide doped graphene sulfur-carbon anode composite material: weighing the raw materials according to the mass ratio of graphene oxide to manganese dioxide to nano sulfur of 1.76:1:6.86, putting the raw materials into a high-speed mixer for fully mixing, putting the mixture into a vacuum drying oven, heating to 155 ℃, vacuumizing, and heating for 10 hours to ensure that the graphene oxide and the manganese dioxide are coated with the sulfur through melting and sublimation, thus preparing the manganese dioxide doped graphene sulfur-carbon anode composite material.
Example 2
(1) Preparing a graphene oxide mother solution: weighing 1g of graphite raw material, mixing the graphite raw material with KMnO4And NaNO3In a molar ratio of 14: 4.4: 1 in a proportion of 8.5 percent, the total mass of the graphite raw material, the potassium permanganate and the sodium nitrate accounts for 8.5 percent of the mass of the concentrated sulfuric acid, and the mixture is stirred for 2 hours on an ice bath and then stirred for 48 hours at room temperature.
(2) Adding hydrogen peroxide into the oxidized graphene mother liquor obtained in the step (1) until oxidizing substances are removed, and then adding a 0.1mol/L sodium thiosulfate solution prepared from sodium thiosulfate pentahydrate to enable the molar ratio of the sodium thiosulfate pentahydrate to the graphite added in the step (1) to be 2.5: 1, stirring for 4 hours. And filtering and collecting a precipitate, washing with deionized water for 5 times, and drying at 40 ℃ for 70h to obtain the manganese dioxide doped graphene sulfur-carbon anode composite material.
Effect example 1
Cell performance testing of the samples:
respectively mixing the samples of example 1 or comparative example 1 with conductive carbon black super P and a binder PVDF according to a ratio of 8:1:1, dissolving the mixture in N-methylpyrrolidone (NMP), uniformly stirring the mixture, coating the mixture on an aluminum foil to prepare a positive plate, drying the positive plate in a vacuum oven at 60 ℃ for 12 hours, and drying the dried positive plate, a negative electrode prepared from a metal lithium plate, a polypropylene diaphragm and an electrolyte (a LiTFSI/(DME + DOL) solution with the composition of 1M and containing 0.2M LiNO3Additive, wherein DOL is dioxolane and DME is 1, 2-dimethoxyethane) under the condition of filling high-purity argonWas assembled in a glove box to obtain a CR2025 type button cell.
Cycling experimental conditions: the battery test temperature is 25 ℃, the voltage window is 1.7-2.7V, and the battery is charged and discharged at 0.2C.
As can be seen from FIGS. 2 and 3, the initial capacity of the battery prepared from the material of example 1 was 1238.2mAh/g, and the capacity retention rate of the battery after 300 cycles was 62.3%. The initial capacity of the battery prepared from the material of comparative example 1 was 887.1mAh/g, and the capacity retention rate of the battery after 300 cycles was 25.1%. The initial capacity of the battery prepared from the material of example 2 measured in the same manner is 1211.5mAh/g, and the capacity retention rate of the battery after 300 cycles is 61.8%.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. It will be appreciated by those skilled in the art that changes may be made in this embodiment or equivalents may be substituted for elements thereof without departing from the scope of the invention.

Claims (2)

1. The preparation method of the manganese dioxide doped graphene sulfur-carbon anode composite material is characterized by comprising the following steps of:
(1) preparing a graphene oxide mother solution: weighing 1g of graphite raw material, mixing the graphite raw material with KMnO4And NaNO3In a molar ratio of 14: 4.4: 1 in a proportion of 8.5 percent by mass of the total mass of graphite raw materials, potassium permanganate and sodium nitrate accounting for 8.5 percent by mass of the concentrated sulfuric acid, stirring for 2 hours on an ice bath at 4 ℃, and then stirring for 48 hours at room temperature;
(2) preparation of polysulfide ion solution: 9.6g of elemental sulfur and 36g of Na were weighed out2S∙9H2Slowly adding O into 1000mL of deionized water, heating to 60 ℃, and stirring for 1 hour to obtain a clear polysulfide ion aqueous solution;
(3) and (3) completely adding the polysulfide ion solution obtained in the step (2) into the graphene oxide mother liquor obtained in the step (1), stirring for 4 hours, filtering and collecting precipitate, washing with deionized water for 5 times, and drying at 60 ℃ for 12 hours to obtain the manganese dioxide doped graphene sulfur-carbon cathode composite material.
2. The preparation method of the manganese dioxide doped graphene sulfur-carbon anode composite material is characterized by comprising the following steps of:
(1) preparing a graphene oxide mother solution: weighing 1g of graphite raw material, mixing the graphite raw material with KMnO4And NaNO3In a molar ratio of 14: 4.4: 1 in a proportion of 8.5 percent by mass of the total mass of graphite raw materials, potassium permanganate and sodium nitrate in the concentrated sulfuric acid of 98 percent, stirring for 2 hours on an ice bath, and then stirring for 48 hours at room temperature;
(2) adding hydrogen peroxide into the oxidized graphene mother liquor obtained in the step (1) until oxidizing substances are removed, and then adding a 0.1mol/L sodium thiosulfate solution prepared from sodium thiosulfate pentahydrate to enable the molar ratio of the sodium thiosulfate pentahydrate to the graphite added in the step (1) to be 2.5: 1, stirring for 4 hours; and filtering and collecting a precipitate, washing with deionized water for 5 times, and drying at 40 ℃ for 70h to obtain the manganese dioxide doped graphene sulfur-carbon anode composite material.
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CN109301254B (en) * 2018-11-12 2020-07-07 中南大学 Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof
CN112670496A (en) * 2019-10-16 2021-04-16 中国科学院大连化学物理研究所 Iron-doped manganese dioxide composite reduced graphene oxide material, and preparation and application thereof
CN113937278B (en) * 2021-10-15 2023-03-24 北京化工大学 Sulfur anion doped manganese dioxide material, preparation and application thereof, and zinc ion battery comprising sulfur anion doped manganese dioxide material
CN115000395A (en) * 2022-05-11 2022-09-02 中南大学 K-doped alpha-manganese dioxide nanorod, direct-writing forming ink, zinc ion battery anode and preparation methods thereof

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