WO2021210525A1 - Matériau d'électrode positive pour batteries secondaires au lithium-soufre, batteries secondaires au lithium-soufre l'utilisant et procédé de production de matériau d'électrode positive pour batteries secondaires au lithium-soufre - Google Patents

Matériau d'électrode positive pour batteries secondaires au lithium-soufre, batteries secondaires au lithium-soufre l'utilisant et procédé de production de matériau d'électrode positive pour batteries secondaires au lithium-soufre Download PDF

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WO2021210525A1
WO2021210525A1 PCT/JP2021/015144 JP2021015144W WO2021210525A1 WO 2021210525 A1 WO2021210525 A1 WO 2021210525A1 JP 2021015144 W JP2021015144 W JP 2021015144W WO 2021210525 A1 WO2021210525 A1 WO 2021210525A1
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sulfur
activated carbon
lithium
weight
positive electrode
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Japanese (ja)
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石川　正司
由紀子 松井
剛 殿納屋
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学校法人 関西大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a positive electrode material for a lithium-sulfur secondary battery, a lithium-sulfur secondary battery using the same, and a method for manufacturing a positive electrode material for a lithium-sulfur secondary battery.
  • lithium-ion batteries are widely used as secondary batteries used in mobile phones, personal computers, digital cameras, etc., but further improvement in energy density and cost reduction are required.
  • a lithium sulfur secondary battery is a secondary battery that uses sulfur as a positive electrode active material and lithium metal as a negative electrode active material, and charges and discharges by moving lithium ions (Li + ) between the positive electrode and the negative electrode. ..
  • the lithium-sulfur secondary battery Li + ions are eluted from the negative electrode during discharge, reacts with sulfur in the positive electrode, to generate a Li 2 S, a current flows to an external circuit.
  • Sulfur atoms have a large number of electrons related to the redox reaction per weight, and are expected to have a theoretically five times higher energy density than conventional lithium-ion batteries. Moreover, since sulfur is inexpensive and easy to secure, it is possible to reduce the cost of the material. For this reason, lithium-sulfur secondary batteries are being actively researched as next-generation secondary batteries.
  • the positive electrode includes a first positive electrode layer and a second positive electrode layer, and the first positive electrode layer contains sulfur particles coated with a polymer, sulfur particles, and carbon.
  • a lithium-sulfur battery in which the positive electrode layer of No. 2 contains carbon and does not contain sulfur is disclosed.
  • Patent Document 2 carbon aggregates having a hierarchical pore structure composed of aligned pores which are three-dimensionally connected to each other; and at least a part of the outer surface and the inside of the carbon aggregates.
  • a carbon-sulfur complex containing introduced sulfur is disclosed.
  • Patent Document 3 describes a material containing carbon and sulfur so that the carbon is in the form of a porous matrix having nanoporous properties and has a free volume available within the nanoporous properties.
  • a material in which the sulfur is adsorbed in a part of the nanoporous of the carbon matrix is disclosed.
  • the lithium-sulfur secondary battery has a high energy density, it has a problem that polysulfide ions generated at the positive electrode during discharge are eluted into the electrolytic solution. Specifically, eluted polysulfide ions produces a sulfide reacts with lithium ion in the electrolyte (e.g., polysulfide, such as Li 2 S), a 1.8 times the volume of sulfur. For this reason, when the lithium-sulfur secondary battery is repeatedly charged and discharged, the positive electrode is crushed or cracked due to the volume change, which leads to a problem that the discharge capacity is lowered.
  • the electrolyte e.g., polysulfide, such as Li 2 S
  • the first positive electrode layer close to the positive electrode current collector contains sulfur particles coated with a polymer to suppress the amount of sulfur eluted during discharge, and the second positive electrode layer close to the electrolytic solution layer.
  • the amount of lithium sulfide precipitated at the interface between the electrolytic solution layer and the positive electrode is reduced, and instead, lithium sulfide is precipitated inside the positive electrode. It is stated that it can be done.
  • the positive electrode described in Patent Document 1 is indispensable to include a first positive electrode layer and a second positive electrode layer, and the functions are shared between the first positive electrode layer and the second positive electrode layer. , It is necessary to bother to prepare two positive electrode layers. Therefore, it can be said that the invention described in Patent Document 1 has room for improvement from the viewpoint of preventing the elution of sulfur by a simple structure.
  • Patent Document 2 states that a carbon-sulfur complex in which sulfur is introduced into at least a part of the outer surface and the inside of a carbon aggregate having a hierarchical pore structure reduces the outflow of sulfur to an electrolyte. (Patent Document 2 [0018]).
  • the carbon aggregate obtained by heat-treating the template particle-carbon composite obtained by spray-drying a mixed dispersion of the template particles and the cylindrical carbon material is impregnated with sulfur. Manufactured by letting. As described above, the carbon-sulfur complex disclosed in Patent Document 2 needs to be obtained through a complicated process.
  • Patent Document 3 describes that the cycle life and the like can be improved by using a carbon material having nanoporous as a matrix and adsorbing sulfur in the nanoporous. However, there is no mention of elution of sulfur into the electrolyte.
  • One aspect of the present invention can be obtained by a simple method, and can maintain conductivity and suppress elution of polysulfide ions into an electrolytic solution by a configuration completely different from that of the prior art.
  • An object of the present invention is to provide a positive electrode material for a sulfur secondary battery.
  • the present inventor uses a composite activated carbon obtained by mixing (a) sulfur-supported activated carbon and (b) sulfur-free activated carbon as a positive electrode material. As a result, it was found that the amount of sulfur carried on the positive electrode can be kept high and the battery characteristics such as discharge capacity can be made excellent.
  • the present invention includes the following configurations.
  • a positive electrode material for a lithium-sulfur secondary battery which comprises a composite activated carbon obtained by mixing (a) a sulfur-supported activated carbon and (b) a sulfur-free activated carbon.
  • the composite activated carbon contains 50% by weight or more and 98% by weight or less of the above (a) and 2% by weight or more and 50% by weight or less of the (b) with respect to the weight of the composite activated carbon.
  • the composite activated carbon contains 60% by weight or more and 80% by weight or less of the above (a) and 10% by weight or more and 30% by weight or less of the (b) with respect to the weight of the composite activated carbon.
  • the composite activated carbon is contained in an amount of 90% by weight or more and 95% by weight or less.
  • ⁇ 5> The positive electrode material for a lithium-sulfur secondary battery according to any one of ⁇ 1> to ⁇ 4>, wherein the (a) carries 60% by weight or more of sulfur with respect to the weight of the (a).
  • ⁇ 6> The positive carbon material for a lithium-sulfur secondary battery according to any one of ⁇ 1> to ⁇ 5>, wherein the activated carbon carrying (a) sulfur and the activated carbon not supporting (b) sulfur are the same type of activated carbon.
  • the specific surface area of the activated carbon supporting (a) sulfur and the activated carbon not supporting sulfur (b) is 1500 m 2 g -1 or more and 2900 m 2 g -1 or less.
  • a lithium-sulfur secondary battery comprising the positive electrode material for the lithium-sulfur secondary battery according to any one of ⁇ 1> to ⁇ 8>.
  • a method for producing a positive electrode material for a lithium-sulfur secondary battery comprising the steps of (a) a sulfur-supporting activated carbon, (b) a sulfur-free activated carbon, a conductive auxiliary agent, and an aqueous binder. .. ⁇ 12>
  • a positive electrode for a lithium-sulfur secondary battery containing a composite activated carbon obtained by mixing (a) an activated carbon carrying sulfur and (b') an activated carbon supporting a smaller proportion of sulfur than the above (a). material.
  • the (a) carries 60% by weight or more of sulfur with respect to the weight of the (a), and the (b') is more than 0% by weight and 10% by weight or less with respect to the weight of the (b').
  • the present invention it is possible to provide a lithium-sulfur secondary battery in which the amount of sulfur carried in the positive electrode is kept high and the battery characteristics such as discharge capacity are excellent.
  • the positive electrode material for a lithium-sulfur secondary battery includes (a) sulfur-supporting activated carbon (hereinafter, may be abbreviated as “(a)”) and (b) sulfur-supporting activated carbon. It contains a composite activated carbon obtained by mixing with activated carbon that has not been used (hereinafter, may be abbreviated as “(b)”).
  • the activated carbon supporting (a) sulfur is an activated carbon in which sulfur is supported in the pores of the activated carbon.
  • Support of sulfur in the pores can be performed, for example, by mixing activated carbon and sulfur using a mortar or the like, and then heating the obtained mixture in a muffle furnace or the like.
  • sulfur commercially available sulfur flower or the like can be used.
  • the "sulfur-supporting activated carbon” is an activated carbon in which the molten sulfur is diffused into the pores of the activated carbon to adsorb the sulfur in the pores.
  • the adsorption may be physical adsorption or chemical adsorption.
  • the activated carbon supporting (a) sulfur carries 60% by weight or more of sulfur with respect to the weight of (a).
  • a method for setting the weight of sulfur carried by (a) to a desired value for example, the ratio of the weight of sulfur to the weight of (a) is increased by 1 to 4% by weight from the desired value.
  • a method of mixing activated charcoal and sulfur using a mortar or the like, putting the obtained mixture into a muffle furnace, and treating under the conditions shown in Example 1 described later can be mentioned.
  • the form of sulfur is not particularly limited.
  • one or more sulfur selected from the group consisting of ⁇ -sulfur (oblique sulfur), ⁇ -sulfur (monoclinic sulfur), ⁇ -sulfur (monoclinic sulfur), rubbery sulfur, and plastic sulfur can be used.
  • the activated carbon that supports sulfur is not particularly limited, but since it has a large specific surface area and pore volume and has a structure suitable for supporting a large amount of sulfur, after carbonizing a resin, fossil resource material, etc., potassium hydroxide is used.
  • Activated carbon or the like obtained by activating with an alkali such as the above can be preferably used.
  • the specific surface area of the (a) and (b), from the viewpoint of increasing carrying sulfur is preferably 1500m 2 g -1 ⁇ 2900m 2 g -1, with 2200m 2 g -1 ⁇ 2900m 2 g -1 More preferably.
  • the specific surface area is a value measured by the BET method.
  • the specific surface area can be measured, for example, by using AUTOSORB iQ manufactured by Quantachrome.
  • the volume of the pores (a) and (b) is preferably 0.6 cc ⁇ g -1 to 1.2 cc ⁇ g -1 from the viewpoint of supporting a large amount of sulfur, preferably 0.9 cc ⁇ g -1. It is more preferably g -1 to 1.2 cc ⁇ g -1.
  • the volume of the pores can be measured using, for example, AUTOSORB iQ manufactured by Quantachrome.
  • the particle size of (a) is preferably 1.7 ⁇ m or more and 6.0 ⁇ m or less in D50 from the viewpoint of the cumulative frequency% diameter. From the viewpoint of the cumulative frequency% diameter, the particle size of (b) is preferably smaller than that of (a) and preferably 1.7 ⁇ m or more and 6.0 ⁇ m or less, and 1.7 ⁇ m or more and 3.1 ⁇ m or less. Is more preferable. It is considered that this is because the smaller the particle size of (b), the larger the surface area and the more polysulfide can be adsorbed.
  • the preferred range of the particle size of (b'), which will be described later, is the same as that of (b).
  • the cumulative frequency% diameter can be measured by a wet batch type measuring method using a scattering type particle size distribution measuring device (LASER SCATTERING PARTICLE SIZE DISTRIBUTION ANALYZER LA-950 (manufactured by HORIBA)).
  • LASER SCATTERING PARTICLE SIZE DISTRIBUTION ANALYZER LA-950 manufactured by HORIBA
  • the wet batch type measurement method can be performed by the following method.
  • the sample After dispersing the dispersion, the sample is irradiated with a semiconductor laser beam to measure the transmittance of the sample, and the particle size of the (a) and / or the (b) is calculated from the transmittance. do.
  • the above-mentioned (a) and (b) used for the measurement are small, and the amount of sewage generated after the measurement is sufficient. Is a small amount, so the measurement can be easily performed.
  • the activated carbon (b) that does not support sulfur is an activated carbon that does not support sulfur in its pores. Since sulfur itself is an insulator, the above (a) supports sulfur on activated carbon for the purpose of ensuring conductivity. However, in a lithium-sulfur secondary battery, expansion and contraction of the positive electrode may occur due to charging and discharging. At that time, the larger the amount of sulfur supported in (a), the greater the expansion / contraction of the positive electrode material.
  • the supported sulfur may be eluted as polysulfide in the electrolytic solution due to the expansion / contraction.
  • problems such as a decrease in the discharge capacity of the lithium-sulfur secondary battery occur.
  • the present inventor has attempted to use the composite activated carbon obtained by mixing the above (a) and the above (b) as the positive electrode material for the purpose of preventing the expansion and contraction of the positive electrode material. Then, surprisingly, it became clear that the cycle characteristics of the lithium-sulfur secondary battery were significantly improved. Therefore, as a result of measuring the cross section of the positive electrode material for the lithium sulfur secondary battery after charging and discharging by the Auger electron spectroscopic analysis method using an electric field radiation type Auger electron spectroscopic analyzer (manufactured by AES PHI), the above (b) Sulfur was also detected at the site. From this result, it was clarified that the (b) adsorbs the polysulfide eluted from the (a).
  • the positive electrode material for a lithium-sulfur secondary battery is a composite composed of (a) a sulfur-supporting activated charcoal and (b) a sulfur-non-supporting activated charcoal.
  • the activated charcoal By containing the activated charcoal, even when the polysulfide is eluted from the (a) to the electrolytic solution by charging / discharging of the lithium-sulfur secondary battery, the polysulfide can be adsorbed by the (b).
  • Activated carbon that does not support sulfur is activated carbon that does not support sulfur in the pores of the activated carbon. Therefore, the step (b) does not need to go through the step of combining activated carbon and sulfur as in the step (a).
  • the step (b) for example, commercially available activated carbon can be used as it is.
  • the activated carbon (b) may be the same type of activated carbon as the activated carbon used in the above (a) before carrying sulfur, or may be a different type of activated carbon, but the polysulfide eluted from the above (a) may be used. From the viewpoint of adsorption, it is preferable that the activated carbon is of the same type.
  • activated carbon obtained by carbonizing the above-mentioned resin, fossil resource material, or the like and then activating with alkali can be preferably used.
  • the "composite activated carbon” means a mixture of a sulfur-supported activated carbon and a sulfur-non-supporting activated carbon.
  • the mixing of the (a) and the (b) is performed so that the (a) and the (b) are uniformly mixed.
  • a method of homogeneously mixing the above (a) and the above (b) for example, the above (a), the above (b), and other components (conductive aid, water-based binder, etc.) described later are used using a mortar or pestle or the like. ), And the obtained mixture is further stirred using a rotation / revolution mixer.
  • the (a) preferably carries 60% by weight or more of sulfur with respect to the weight of the (a). That is, it is preferable that the ratio of the weight of sulfur to the total of the weight of sulfur constituting the activated carbon carrying sulfur and the weight of activated carbon is 60% by weight or more.
  • the ratio is more preferably 70% by weight or more, and more preferably higher, but the upper limit is about 60 to 66% by weight in view of the carrying capacity of activated carbon and the like.
  • the amount of sulfur supported can be confirmed by the method described later in Example 1.
  • the pores (a) may be mesopores or micropores.
  • the pores are micropores means that the diameter of the pores is 2 nm or more.
  • the pores are micropores by measuring the specific surface area by the BET method and measuring the pore distribution and the volume of the pores by the quenching solid phase density function method (QSDFT) using AUTOSORB iQ manufactured by Quantachrome. , Can be confirmed.
  • QSDFT quenching solid phase density function method
  • the specific surface area, pore distribution, and pore volume can be measured by measuring the adsorption isotherm of nitrogen at the temperature of liquid nitrogen for a sample that has been vacuum degassed at 200 ° C. for 3 hours.
  • the electrolytic solution does not easily penetrate into the pores, so that the elution of polysulfide into the electrolytic solution that has penetrated the pores is small. Therefore, a high discharge capacity can be obtained even if an arbitrary electrolytic solution is used.
  • the activated carbon with further developed micropores is an activated carbon obtained by carbonizing the above-mentioned raw materials such as resin and fossil resource material and then activating them with alkali from the viewpoint of facilitating the support of a large amount of sulfur. Is preferable.
  • the pores are mesopores means that the diameter of the pores is more than 2 nm and 50 nm or less.
  • Activated carbon with mesopores has a large pore diameter, so that it is easier to support sulfur than activated carbon with micropores.
  • the electrolytic solution is more likely to penetrate into the pores than activated carbon having micropores.
  • activated carbon having mesopores in the pores is more likely to elute polysulfide into the electrolytic solution than activated carbon having micropores in the pores.
  • any electrolytic solution can be used, but the pores (a) may be mesopores or micropores.
  • the positive electrode material for a lithium-sulfur secondary battery for example, fluoroethylene carbonate is used as a solvent for the electrolytic solution
  • the SEI film formed by the reduced decomposition product of the electrolytic solution in the initial discharge is formed.
  • the pores are formed in the pores of activated carbon, which are mesopores.
  • a suitable solvent for forming such an SEI film include vinylene carbonate, lithium bis (fluorosulfonyl) imide, and the like, in addition to fluoroethylene carbonate.
  • the pores of (a) are micropores, elution of polysulfide is unlikely to occur, so any electrolytic solution can be used.
  • the pores of (a) are mesopores, the energy density increases because the pores of (a) can carry a large amount of sulfur. Therefore, the pores of (a) may be mesopores or micropores.
  • the pores of (b) are used to adsorb the polysulfide eluted from (a) due to expansion of the positive electrode material or the like. Therefore, the pores of (b) are preferably micropores.
  • the composite activated carbon contains 50% by weight or more and 98% by weight or less of the above (a) with respect to the weight of the composite activated carbon.
  • b) is preferably contained in an amount of 2% by weight or more and 50% by weight or less.
  • the sulfur supported on (a) is eluted as polysulfide due to expansion of the positive electrode or the like, the polysulfide can be efficiently adsorbed by (b). As a result, it is possible to more easily provide a lithium-sulfur secondary battery exhibiting excellent cycle characteristics and the like.
  • the composite activated carbon contains 60% by weight or more and 90% by weight or less of the above (a) with respect to the weight of the composite activated carbon. It is more preferable to contain b) in an amount of 10% by weight or more and 40% by weight or less.
  • the composite activated carbon contains the (a) in an amount of 60% by weight or more and 80% by weight or less, and contains the (b) in an amount of 10% by weight or more and 30% by weight or more. It is more preferable to contain% or less.
  • the positive electrode material for a lithium-sulfur secondary battery according to an embodiment of the present invention contains 90% by weight or more and 95% by weight or less of the composite activated carbon with respect to the weight of the positive electrode material for a lithium-sulfur secondary battery, and other components. Is preferably contained in an amount of 5% by weight or more and 10% by weight or less.
  • the content of the composite activated carbon in the positive electrode material for the lithium-sulfur secondary battery and the content of other components are in an appropriate balance. Therefore, even when the sulfur supported on (a) is eluted as polysulfide due to expansion of the positive electrode or the like, the polysulfide can be efficiently adsorbed by (b).
  • Examples of the other components include a conductive auxiliary agent, an aqueous binder, and the like.
  • a conductive auxiliary agent any electronically conductive material that does not adversely affect the battery performance can be used.
  • carbon black such as acetylene black and ketjen black is used, but natural graphite (scaly graphite, scaly graphite, earthy graphite, etc.), artificial graphite, carbon whisker, carbon fiber powder, metal (copper, nickel, etc.) (Aluminum, silver, gold, etc.)
  • a conductive material such as powder, metal fiber, or conductive ceramic material may be used. These may be used alone or as a mixture of two or more kinds.
  • the conductive auxiliary agent is preferably made of a material different from that of the composite activated carbon.
  • all of the above-exemplified conductive materials such as natural graphite are different materials from the activated carbon obtained by carbonizing the above-mentioned resin, fossil resource material and the like and then alkali-activating them.
  • the water-based binder is not particularly limited as long as it can bind the composite activated carbon and the conductive auxiliary agent or the like.
  • the composite activated carbon and the conductive auxiliary agent or the like For example, one or more kinds of styrene-butadiene rubber (SBR) aqueous dispersion, carboxymethyl cellulose (CMC), alginate and the like can be used.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the other components are homogeneously mixed with the above (a) and the above (b).
  • the other components are put into a mortar or the like together with the above (a) and the above (b) and mixed, and the obtained mixture is further used with a rotation / revolution mixer.
  • a method of stirring can be mentioned.
  • the positive electrode material for the lithium-sulfur secondary battery according to the embodiment of the present invention includes (a) activated carbon supporting sulfur and (b') activated carbon supporting a smaller proportion of sulfur than the above (a). , May contain a composite activated carbon in which is mixed.
  • the (a) preferably carries 60% by weight or more of sulfur with respect to the weight of the (a). Further, the (b') preferably carries sulfur of more than 0% by weight and 10% by weight or less with respect to the weight of the above (b'), and more than 0% by weight and 5% by weight or less of sulfur. It is more preferable to carry it.
  • the composite activated carbon is a mixture of the above (a) and the above (b')
  • there is a difference in the amount of sulfur supported so that the above (a) is different from the case where only the above (a) is used.
  • the polysulfide eluted from () can be adsorbed by the above (b').
  • the amount of sulfur supported in (b') is preferably as small as possible from the viewpoint of efficiently adsorbing the polysulfide eluted from (a).
  • the efficiency with which the activated carbon (b') carrying sulfur of more than 0% by weight and 10% by weight or less adsorbs polysulfide is slightly inferior to the case of using the activated carbon not supporting sulfur as described in (b) above. However, it is possible to solve the problems of the present invention.
  • the positive electrode material for a lithium-sulfur secondary battery includes a composite activated carbon obtained by mixing (a) a sulfur-supported activated carbon and (b) a sulfur-free activated carbon. It may contain a conductive auxiliary agent made of a material different from that of the composite activated carbon. The other conditions in this case are the same as those of the positive electrode material for the lithium-sulfur secondary battery described above.
  • the method for producing a positive electrode material for a lithium-sulfur secondary battery according to an embodiment of the present invention is a step of (a) obtaining activated carbon carrying sulfur by mixing activated carbon and sulfur and heating the obtained mixture.
  • a step of mixing (a) a sulfur-supported activated carbon, (b) a sulfur-free activated carbon, a conductive auxiliary agent, and an aqueous binder is provided.
  • the above (a), the above (b), the conductive auxiliary agent, the water-based binder, the mixing ratio, etc. [1. Lithium-sulfur secondary battery positive electrode material].
  • the activated carbon supporting (a) sulfur is, for example, [1. It can be produced by the method described in [Positive Material for Lithium-Sulfur Secondary Battery].
  • the method of mixing each substance is not particularly limited, and may be mixed by an agate mortar or the like, may be mixed by stirring, or a plurality of methods may be used in combination.
  • the method of stirring is not particularly limited, but for example, as in the examples described later, stirring may be performed using a rotation / revolution mixer.
  • the stirring conditions are not particularly limited, but may be, for example, 1000 to 3000 rpm.
  • the stirring time is also not particularly limited, but may be, for example, 20 to 40 minutes.
  • the lithium-sulfur secondary battery according to the embodiment of the present invention includes a positive electrode material for the lithium-sulfur secondary battery according to the embodiment of the present invention. According to this configuration, even when the positive electrode material expands and contracts due to charging and discharging and the polysulfide is eluted from the above (a), the polysulfide can be adsorbed by the above (b). As shown in the example, excellent cycle characteristics and the like can be shown.
  • the positive electrode can be prepared by applying or filling the positive electrode material for a lithium-sulfur secondary battery according to an embodiment of the present invention to a current collector, drying it, pressure-molding it, and then vacuum-drying it. can.
  • an electronic conductor that does not adversely affect the configured battery can be used.
  • aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer, conductive glass and the like can be mentioned.
  • a current collector whose surface is treated with carbon, nickel, titanium, silver or the like may be used for the purpose of improving adhesiveness, conductivity, oxidation resistance and the like.
  • the shape of the current collector may be any of foil, film, sheet, net and the like. Among them, a current collector having a three-dimensional structure such as a honeycomb shape is preferable because more positive electrode materials for the lithium-sulfur secondary battery can be filled and the capacity can be increased.
  • the negative electrode can be obtained by subjecting a negative electrode material for a lithium-sulfur secondary battery containing metallic lithium as an active material, the above-mentioned conductive auxiliary agent, an aqueous binder and the like to, for example, the same method as the above-mentioned method for obtaining a positive electrode. can.
  • the lithium sulfur secondary battery according to the embodiment of the present invention includes an electrolyte containing lithium, carbonates, ethers, sulfur compounds, halogenated hydrocarbons, phosphate ester compounds, sulfolane hydrocarbons, and the like. It is preferable to provide an electrolytic solution containing one or more solvents selected from the group consisting of ionic liquids.
  • lithium-containing electrolyte examples include LiPF 6 , LiBF 4 , lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), and lithium bis (fluorosulfonyl) imide (LiFSI). Of these, LiPF 6 , LiFSI, and LiTFSI are preferable, and LiTFSI is even more preferable. Only one type of the lithium-containing electrolyte may be used, or two or more types may be used in combination.
  • the solvent contains one or more solvents selected from the group consisting of carbonates and ethers.
  • carbonates examples include cyclic carbonates such as ethylene carbonate (EC), fluoroethylene carbonate (FEC), and vinylene carbonate (VC); dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and the like. It is preferably chain carbonates.
  • cyclic carbonates such as ethylene carbonate (EC), fluoroethylene carbonate (FEC), and vinylene carbonate (VC); dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and the like. It is preferably chain carbonates.
  • ethers examples include cyclic ethers such as dioxolane (DOL) and tetrahydrofuran; dimethoxyethane (DME), triglime (G3), tetraglime (G4), 1,1,2,2-tetrafluoro-3- (1). , 1,2,2-Tetrafluoroethoxy) -Propane (HFE) and other chain ethers are preferred.
  • DOL dioxolane
  • DME dimethoxyethane
  • DME dimethoxyethane
  • G3 dimethoxyethane
  • G4 triglime
  • G4 tetraglime
  • 1,1,2,2-tetrafluoro-3- (1) 1,2,2-Tetrafluoro-3- (1).
  • HFE 1,2,2-Tetrafluoroethoxy) -Propane
  • the solvent is more preferably a solvent containing the carbonates.
  • the solvents containing the carbonates are FEC and HFE from the viewpoint that an SEI film can be formed on the activated carbon having micropores and mesopores at the time of initial discharge of the lithium-sulfur secondary battery. It is particularly preferable that it is a mixture with.
  • the lithium-sulfur secondary battery according to the embodiment of the present invention can be manufactured by assembling by a conventionally known method using a positive electrode, a negative electrode, an electrolytic solution, a separator, a housing and the like.
  • the AC impedance of the lithium-sulfur secondary batteries produced in Examples and Comparative Examples was measured using an electrochemical measurement system S1 1280B (manufactured by Solartron). Specifically, the lithium-sulfur secondary battery is operated for 10 cycles in a voltage range of 1 to 3 V to charge and discharge, relaxed for 24 hours, and then the AC impedance is adjusted under the conditions of an amplitude width of 10 mV and a frequency range of 500 kHz to 10 MHz. It was measured.
  • Cyclic voltammetry of the lithium-sulfur secondary batteries prepared in Examples and Comparative Examples was measured using an electrochemical measurement system S1 1280B (manufactured by Solartron). Specifically, using the above equipment, the lithium-sulfur secondary battery was operated for two cycles at a scanning speed of 0.03 mV ⁇ s -1 and a voltage range of 1 to 3 V, and a cyclic voltammogram was prepared for the second cycle.
  • ⁇ Charge / discharge test> A constant current charge / discharge test was performed using a positive electrode material for a lithium-sulfur secondary battery prepared in Examples and Comparative Examples as a working electrode and BTS2400W (manufactured by Nagano). Set the charging mode to C.I. C. The method (“CC” is an abbreviation for consistent currant) is used, and the mode at the time of discharge is changed to C.I. C. It was set to the mode.
  • the set current density was 167.2 mA / g (current density 1672 mA / g is defined as 1C. Hereinafter, 167.2 mA / g is referred to as 0.1C).
  • the cutoff voltage has a lower limit of 1.0 V and an upper limit of 3.0 V. The test was conducted in an environment of 25 ° C.
  • the charge capacity and discharge capacity are defined as mA ⁇ h (g sulfur) -1 based on the weight of sulfur.
  • ⁇ Cycle property test> The charge / discharge rate was set to 0.1 / 0.1C, and 1-100 cycles of charge / discharge were performed. The higher the discharge capacity at each cycle, the better the lithium-sulfur secondary battery.
  • the initial discharge capacity retention rate and energy density were calculated by the following formulas.
  • the volume of the pores of the activated carbon was 1.202 cc / g, and the specific surface area was 2863 m 2 / g.
  • the pore distribution of the activated carbon was such that pores of 2 nm or less accounted for 93% or more, and in particular, pores of around 0.8 nm were most developed.
  • the temperature inside the furnace was raised to 155 ° C., and this temperature was maintained for 5 hours to melt sulfur. Then, the temperature was raised to 300 ° C. at a rate of 5 ° C./min, and this temperature was maintained for 2 hours. Then, the inside of the furnace was sufficiently air-cooled, and the metal container was taken out from the inside of the furnace to obtain (a) sulfur-supported activated carbon.
  • the amount of sulfur supported in (a) above was measured by the following method. That is, the above (a) was placed in an alumina cell, and thermogravimetric analysis (TGA) was performed using DTG-60AH manufactured by Shimadzu Corporation. The measurement was performed under the conditions of the measurement gas Ar, the gas flow rate of 50 ml / min, the heating rate of 5 ° C./min, and the upper limit temperature of 600 ° C. The amount of sulfur supported was 61 to 63% by weight based on the total weight of (a).
  • the measured material was mixed using an agate mortar, and the obtained mixture was transferred to an ointment case. Next, the mixture was stirred at a rotation speed of 2000 rpm for a total of 25 minutes using a rotation / revolution mixer to obtain a positive electrode material for a lithium-sulfur secondary battery.
  • the positive electrode material for the lithium-sulfur secondary battery was filled in a 3D aluminum current collector (manufactured by Sumitomo Electric Industries, Ltd.) and dried at 40 ° C. for 1 hour using a hot plate. After rolling the dried current collector using a roll press machine, it is cut into a size of 2.4 cm ⁇ 2.4 cm using scissors to obtain a molded body, and then using a bell jar at 50 ° C., 12 more. It was dried for an hour to prepare a positive electrode.
  • a 3D aluminum current collector manufactured by Sumitomo Electric Industries, Ltd.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • non-aqueous solvents fluoroethylene carbonate (hereinafter referred to as FEC) and 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane (hereinafter referred to as HFE).
  • FEC fluoroethylene carbonate
  • HFE 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane
  • the method for preparing the electrolytic solution will be described more specifically.
  • FEC and HFE were mixed so as to have a volume ratio of 1: 1 to obtain a mixed solvent.
  • LiTFSI was dissolved in the mixed solvent so as to have LiTFSI / FEC: HFE of 1.0 mol / L, and vinylene carbonate (VC) was added in an amount of 10 Volume% to 90 Volume% of LiTFSI / FEC: HFE. It was used as the electrolyte for the lithium-sulfur secondary battery.
  • VC vinylene carbonate
  • the cell shape includes a cylindrical metal can type, a coin type, a laminated type, and the like, and a laminated type cell was used in this test.
  • a lithium sulfur battery was prepared by the following procedure in an air atmosphere having a dew point of ⁇ 40 ° C. or lower.
  • the laminate assembled so that the positive electrode, the separator, and the negative electrode were laminated in this order was housed in an aluminum laminate film formed into a bag shape by thermocompression bonding. Further, after injecting the electrolytic solution into the laminated film, thermocompression bonding was performed while evacuating the laminated film to prepare a lithium-sulfur secondary battery.
  • Example 2 For lithium-sulfur secondary batteries by the same method as in Example 1 except that the weight ratios of (a), (b), acetylene black, and the aqueous binder were changed to 80:10: 5: 5. A positive electrode material and a lithium-sulfur secondary battery were produced.
  • Example 3 Lithium-sulfur secondary battery by the same method as in Example 1 except that the weight ratio of (a), (b), acetylene black, and water-based binder was changed to 60:30: 5: 5. A positive electrode material for use and a lithium-sulfur secondary battery were manufactured.
  • FIG. 1 shows the results of measuring the AC impedance of the lithium-sulfur secondary batteries produced in Example 1 and Comparative Example 1.
  • the positive electrode for a lithium-sulfur secondary battery of Example 1 which contains a composite activated carbon obtained by mixing (a) a sulfur-supporting activated carbon and (b) a sulfur-free activated carbon, from the above (a). It is suggested that the eluted polysulfide is adsorbed to the above (b) as it is before causing a side reaction, so that the irreversible reaction on the surface of the activated carbon is suppressed and the resistance is lowered.
  • FIG. 2 is a cyclic voltammogram of the second cycle in the lithium-sulfur secondary battery produced in Example 1 and Comparative Example 1.
  • the positive electrode material for the lithium-sulfur secondary battery contains the composite activated carbon obtained by mixing the above (a) and the above (b), so that the capacity of sulfur supported on the positive electrode material for the lithium-sulfur secondary battery is increased. It turned out that can be used efficiently.
  • Example 1 the reaction potentials of Example 1 and Comparative Example 1 were different. That is, it was shown that the polysulfide reaction of Example 1 was different from that of Comparative Example 1 because the positive electrode material for the lithium-sulfur secondary battery contained the composite activated carbon.
  • FIG. 3 shows the charge / discharge curves of the first cycle and the 100th cycle in Examples 1 to 3 and Comparative Example 1.
  • FIG. 4 is an enlarged view of the circled portion in FIG.
  • Example 1 had a larger discharge capacity per sulfur weight than Comparative Example 1. That is, it was found that the discharge capacity is improved by containing the composite activated carbon obtained by mixing the above (a) and the above (b) in the positive electrode material for the lithium-sulfur secondary battery.
  • Example 1 had a larger initial discharge capacity than Comparative Example 1. That is, it was found that the initial discharge capacity is improved by containing the composite activated carbon obtained by mixing the above (a) and the above (b) in the positive electrode material for the lithium-sulfur secondary battery. Furthermore, it was found that the initial discharge capacity was further improved as the content of (b) was increased.
  • FIG. 5 shows the results of cycle characteristic tests of 1 to 100 cycles in Examples 1 to 3 and Comparative Example 1.
  • the vertical axis on the left represents the discharge capacity, and the vertical axis on the right represents the cycle efficiency.
  • Table 1 shows the results of the cycle characteristic test and the initial discharge capacity retention rate.
  • “(a): (b)” refers to (a) sulfur-supporting activated carbon and (b) sulfur in the positive electrode material for a lithium-sulfur secondary battery produced in Examples 1 to 3 and Comparative Example 1. It is a weight ratio with activated carbon that is not supported.
  • Example 2 the decrease in discharge capacity up to about the 20th cycle was improved as compared with Comparative Example 1. Further, it can be seen that in Example 1 in which the content of (b) was increased as compared with Example 2, the decrease in the discharge capacity was dramatically improved. Furthermore, it was clarified that in Example 3 in which the content of (b) was increased as compared with Example 1, the decrease in the initial discharge capacity was further improved as compared with Example 1.
  • Example 1 showed a higher initial discharge capacity retention rate than Comparative Example 1, and Example 3 showed a higher initial discharge capacity retention rate.
  • Table 2 shows the energy densities of the positive electrodes used in Examples 1 to 3 and Comparative Example 1 in the second cycle obtained from the results of the cycle characteristic test.
  • the meaning of "(a): (b)" is the same as that in Table 1.
  • Examples 1 to 3 had a higher energy density than Comparative Example 1. That is, it was found that the energy density of the positive electrode can be improved by containing the composite activated carbon obtained by mixing the above (a) and the above (b) in the positive electrode material for the lithium-sulfur secondary battery.
  • the positive electrode material for a lithium-sulfur secondary battery according to an embodiment of the present invention contains the above (a) sulfur-supporting activated carbon as high as 60% by weight or more based on the weight of the above (a). It was revealed that even when sulfur was supported at a rate, it exhibited excellent properties. That is, it was shown that the positive electrode material for a lithium-sulfur secondary battery exhibits high conductivity, can suppress a decrease in discharge capacity due to elution of polysulfide into an electrolytic solution, and can achieve a high energy density. ..
  • the positive electrode material for a lithium-sulfur secondary battery can be manufactured at low cost by a simple process, and a lithium-sulfur secondary battery having both a high sulfur content and a high discharge capacity can be produced. Can be provided.
  • the lithium-sulfur secondary battery exhibits high energy density and can exhibit stable charge / discharge characteristics, it is considered that it can greatly contribute to the practical use of the lithium-sulfur secondary battery in the future.
  • Example 4 Comparative Example 2: Polysulfide adsorption test
  • a polysulfide adsorption test was conducted to investigate whether activated carbon adsorbs polysulfide.
  • the method for manufacturing a positive electrode material for a lithium sulfur secondary battery according to the present invention, a lithium sulfur secondary battery using the same, and a positive electrode material for a lithium sulfur secondary battery according to the present invention is a portable device such as a mobile phone or a mobile information terminal (PDA).

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Abstract

La présente invention aborde le problème de la fourniture d'un matériau d'électrode positive pour des batteries secondaires au lithium-soufre, qui conserve la conductivité et peut supprimer l'élution d'ions polysulfure dans la solution d'électrolyte. Afin de résoudre ce problème, un matériau d'électrode positive pour batteries secondaires au lithium-soufre selon un mode de réalisation de la présente invention contient un carbone actif composite fourni par mélange (a) de charbon actif porteur de soufre avec (b) du charbon actif ne portant pas de soufre.
PCT/JP2021/015144 2020-04-14 2021-04-12 Matériau d'électrode positive pour batteries secondaires au lithium-soufre, batteries secondaires au lithium-soufre l'utilisant et procédé de production de matériau d'électrode positive pour batteries secondaires au lithium-soufre WO2021210525A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013219152A (ja) * 2012-04-06 2013-10-24 Asahi Kasei Corp 正極材料及びその製造方法並びに蓄電素子
CN103490027A (zh) * 2013-08-12 2014-01-01 中国科学院化学研究所 锂-硫电池用隔膜及其制备方法
KR20160078821A (ko) * 2014-12-24 2016-07-05 주식회사 포스코 리튬 설퍼 전지용 양극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 설퍼 전지

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013219152A (ja) * 2012-04-06 2013-10-24 Asahi Kasei Corp 正極材料及びその製造方法並びに蓄電素子
CN103490027A (zh) * 2013-08-12 2014-01-01 中国科学院化学研究所 锂-硫电池用隔膜及其制备方法
KR20160078821A (ko) * 2014-12-24 2016-07-05 주식회사 포스코 리튬 설퍼 전지용 양극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 설퍼 전지

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