WO2016075916A1 - 硫黄-カーボン複合体、硫黄―カーボン複合体を含む電極を備えた非水電解質電池、及び硫黄-カーボン複合体の製造方法 - Google Patents
硫黄-カーボン複合体、硫黄―カーボン複合体を含む電極を備えた非水電解質電池、及び硫黄-カーボン複合体の製造方法 Download PDFInfo
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- H01M4/139—Processes of manufacture
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- Y02T10/60—Other road transportation technologies with climate change mitigation effect
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Definitions
- the present invention relates to a sulfur-carbon composite, a nonaqueous electrolyte battery equipped with an electrode containing the sulfur-carbon composite, and a method for producing the sulfur-carbon composite.
- a lithium secondary battery which is a nonaqueous electrolyte battery, is a device having a high energy density and a high output density.
- lithium transition metals such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 are used as positive electrode materials for lithium secondary batteries.
- Composite oxides have been put into practical use. Their capacity per mass is about 150 mAhg ⁇ 1 .
- Sulfur has a high theoretical capacity per mass of 1675 mAhg ⁇ 1 and has been studied as a positive electrode material that provides a capacity that is 10 times or more that of the prior art. However, it has not yet been put into practical use because of its high reactivity with the electrolyte and high resistance.
- Non-Patent Document 1 discloses a sulfur-carbon composite electrode material in which porous carbon into which lithium ions can be inserted and sulfur are mixed and heat-treated at 400 ° C. for 6 hours to carry sulfur on porous carbon. It is described that it was manufactured, and a lithium-sulfur secondary battery using the same, and that after 100 cycles of charge and discharge, the capacity based on sulfur mass was 720 mAhg- 1 .
- Patent Document 1 a porous carbon matrix having nanopores and nanochannels having an average diameter of 1 to 999 nm, a pore volume of 10 to 99% by volume, and sulfur are mixed and heat-treated at 120 to 180 ° C.
- a porous matrix in which sulfur is adsorbed in a part of the nanopores and nanochannels is described, and it is described that 70% by mass of the material is sulfur.
- Patent Document 2 discloses a mesoporous carbon composite material used for an electrode of a non-aqueous electrolyte type secondary battery, wherein 5% or more of the total weight is contained in mesoporous carbon mesopores having an average pore diameter of 1 to 40 nm. A composite material containing sulfur is described.
- the present invention provides a sulfur-carbon composite having a high sulfur utilization rate, a nonaqueous electrolyte battery equipped with an electrode containing the sulfur-carbon composite, and a method for producing a sulfur-carbon composite having a high sulfur utilization rate. With the goal.
- one aspect of the present invention has the following configuration.
- (1) It is composed of a sulfur-carbon composite in which sulfur is combined with porous carbon, and a mass reduction rate X from room temperature to 500 ° C. in thermal mass spectrometry and sulfur / quantity in SEM-EDS quantitative analysis in a 1000 times observation field.
- the mass ratio Y of (sulfur + carbon) is A sulfur-carbon composite satisfying a relationship of
- a method for producing a sulfur-carbon composite wherein the specific surface area is 2000 m 2 g ⁇ 1 or more and 3000 m 2 g ⁇ 1 or less, and the half width of the peak of the log differential pore volume distribution is 1.0 to 2
- a mixture of porous carbon and sulfur having a thickness of 5 nm is heated in a sealed container to form a sulfur-carbon composite, and the heating step is performed for 5 hours at a temperature at which sulfur is melted.
- a method for producing a sulfur-carbon composite comprising: a first step of heating as described above; and a second step of heating at a temperature at which sulfur is vaporized after the first step.
- a method for producing a sulfur-carbon composite wherein the specific surface area is 2000 m 2 g ⁇ 1 or more and 3000 m 2 g ⁇ 1 or less, and the half width of the peak of the log differential pore volume distribution is 1.0 to 2
- a mixture of porous carbon having a thickness of 5 nm and sulfur is heated in a closed container to form a sulfur-carbon composite, and the heating step passes through a temperature at which sulfur melts.
- a method for producing a sulfur-carbon composite which is a step of raising the temperature to a vaporizing temperature at a rate of 0.5 ° C / min or less.
- a non-aqueous electrolyte battery including a sulfur-carbon composite having a high sulfur utilization rate and an electrode containing the sulfur-carbon composite can be obtained.
- the graph which shows log pore volume distribution of the porous carbon which concerns on the Example of this embodiment, and the ketjen black which concerns on the comparative example 3 The graph showing the heat processing process of the sulfur-carbon composite_body
- the photograph showing the EDS quantitative analysis of the sulfur-carbon composite of Example 1 according to this embodiment The perspective view of the nonaqueous electrolyte battery concerning this embodiment Schematic of the power storage device according to this embodiment
- the sulfur content in the sulfur-carbon composite is preferably 50% by mass or more. Since the theoretical capacity of sulfur is 1675 mAhg ⁇ 1 , the discharge capacity per mass of the sulfur-carbon composite is set to 800 mAhg ⁇ 1 or more by setting the sulfur content in the sulfur-carbon composite to 50 mass% or more. can do.
- the porous carbon in the present embodiment preferably has a specific surface area of 2000 m 2 g ⁇ 1 or more and 3000 m 2 g ⁇ 1 or less.
- the specific surface area of the porous carbon is within this range, the carbon and sulfur are in good contact with each other and the conductivity is increased, so that an electrode having a high sulfur utilization rate can be obtained.
- porous carbon having pores with an average pore diameter of 1 to 6 nm.
- the particle size of the supported sulfur can be in the range of 6 nm or less, so that ion conductivity and electronic conductivity are excellent, and the sulfur utilization rate can be increased.
- the average pore diameter By setting the average pore diameter to 1 nm or more, the permeability of the electrolytic solution can be sufficiently increased.
- the porous carbon of the present embodiment preferably has a half width of a peak in the log differential pore volume distribution in the range of 1.0 nm to 2.5 nm.
- the particle size of sulfur particles in the sulfur-carbon composite is uniform, so that the utilization rate of sulfur can be increased.
- the porous carbon preferably has a single peak in the log differential pore volume distribution. By having a single peak, the particle size of the sulfur particles in the pores becomes uniform, so that the utilization rate of sulfur can be improved.
- Porous carbon having a specific surface area of 2000 m 2 g -1 or more and 3000 m 2 g -1 or less, an average pore diameter of 1 to 6 nm, and a peak half-value width in a log differential pore volume distribution of 1.0 to 2.5 nm is a layered clay.
- a template method in which mineral, porous glass, silica gel, silica sol, zeolite, and mesoporous silica are synthesized as a template may be used (see carbon No. 199 (200) 176-186), or a surfactant micelle and carbon source.
- the polymer complex may be heated to simultaneously remove the surfactant and carbonize the polymer (see Chem. Commun. (2005) 2125-2127).
- carbon may be isolated by extracting MgO from carbon-coated MgO produced by heating magnesium citrate.
- magnesium citrate anhydride as a raw material because porous carbon having a small average pore diameter can be obtained.
- the temperature for heating the magnesium citrate is preferably lower than 1000 ° C., more preferably 950 ° C. or lower, and further preferably 900 ° C. or lower in order to reduce the pore diameter and make the pore distribution monodisperse.
- the temperature for heating the magnesium citrate is preferably equal to or higher than the temperature at which the magnesium citrate used is carbonized.
- the present inventor paid attention to the heat treatment in the compositing step when compositing a mixture in which sulfur is mixed with porous carbon satisfying the above conditions. Then, in the step of heating the above mixture in a sealed container, sulfur utilization is performed by performing a first step of heating at a temperature at which sulfur is melted and a second step of heating at a temperature at which sulfur is vaporized. As a result of increasing the rate, it has been found that a discharge capacity closer to the theoretical capacity can be obtained.
- the sulfur utilization rate is calculated by the ratio of the discharge capacity to the theoretical capacity, and indicates the ratio of sulfur that contributes to the electrode reaction with respect to sulfur in the electrode.
- the first step the surface of the porous carbon is uniformly coated with sulfur.
- sulfur uniformly supported on the carbon surface by the first step can be vaporized in the vicinity of the carbon pores.
- the sulfur utilization rate increases, and a discharge capacity closer to the theoretical capacity can be obtained. Inferred.
- the first step is to raise the temperature of the mixture from room temperature to 112 to 159 ° C.
- the second step it is preferable to raise the temperature to 250 ° C. or higher and hold it.
- the rate of temperature increase in the first step and the second step is not limited, but is preferably 1 to 5 ° C./min in terms of work efficiency.
- the reason for heating at a temperature at which sulfur is melted for 5 hours or more is to uniformly support sulfur on the carbon surface.
- the present inventor can realize the same high sulfur utilization rate as described above by increasing the temperature at a moderate rate to the temperature at which sulfur is vaporized in the step of heating the above mixture in a closed container. I found it. In this case, due to the gradual rise to the temperature at which sulfur melts, the loading of sulfur on the carbon surface occurs uniformly, and thereafter the temperature rises gradually to the temperature at which sulfur vaporizes. It is assumed that vaporization occurs uniformly and sufficiently, sulfur is highly dispersed in the pores as well as the carbon surface, and the sulfur utilization rate is increased as in the above case.
- the heating rate at which uniform loading occurs is preferably 0.5 ° C./min or less, and 0.1 to 0.5 ° C./min is preferable in consideration of work efficiency.
- the present inventor analyzed the sulfur-carbon composite produced by the above heat treatment step, and found that the mass reduction rate X at 500 ° C. in the thermal mass spectrometry and the SEM-EDS quantitative analysis in the 1000 ⁇ observation field of view.
- the mass ratio Y of sulfur / (sulfur + carbon) is
- the mass reduction rate X at 500 ° C. in the thermal mass analysis shown in FIG. 6 corresponds to the sulfur content in the sulfur-carbon composite
- sulfur (S) / in the SEM-EDS quantitative analysis shown in FIG.
- the mass ratio Y of sulfur (S) + carbon (C)) corresponds to the sulfur content present in the vicinity of the surface of the sulfur-carbon composite. Therefore, the above formula shows that the sulfur content of the entire composite and the sulfur content in the vicinity of the composite surface are substantially the same, that is, sulfur is also present in the carbon pores as much as in the vicinity of the carbon surface of the composite. Represents high dispersion.
- An electrode material having a high sulfur utilization rate is provided by the heat-treated sulfur-carbon composite that achieves such a highly dispersed state.
- a conductive material, a binder, a thickener, a filler, and the like are added to the electrode material as necessary, mixed with a solvent to form a slurry, and the slurry is applied to a current collector to form a nonaqueous electrolyte.
- An electrode for a battery is produced.
- polyethyleneimine (PEI), polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene butylene rubber (SBR), polyacrylonitrile (PAN), polyacrylic acid (PAA) Etc. can be used.
- PEI polyethyleneimine
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- SBR styrene butylene rubber
- PAN polyacrylonitrile
- PAA polyacrylic acid
- a lithium secondary battery is manufactured by combining an electrode containing the above electrode material as a positive electrode and a negative electrode containing lithium.
- Any negative electrode containing lithium can be used as long as it is a lithium metal, a lithium alloy, or a material in which lithium is inserted.
- a lithium salt generally used as an electrolyte in a conventional nonaqueous electrolyte secondary battery can be used.
- LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (F 2 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiAsF 6 , lithium difluoro (oxalato) borate can be used, or two or more may be used in combination.
- LiN (F 2 SO 2 ) 2 or LiN (CF 3 SO 2 ) 2 is preferably used in combination with an electrode containing sulfur.
- non-aqueous electrolyte solvents examples include cyclic carbonates, chain carbonates, esters, cyclic ethers, chain ethers, nitriles or amides that are usually used as nonaqueous solvents for batteries. At least one selected from these can be used.
- cyclic carbonates include ethylene carbonate, propylene carbonate, butylene carbonate, and the like, and trifluoropropylene carbonate or fluoroethyl carbonate in which some or all of these hydrogen groups are fluorinated.
- chain carbonic acid esters examples include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, and the like, and some or all of these hydrogens are fluorinated. Also mentioned.
- esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate or ⁇ -butyrolactone.
- cyclic ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,4-dioxane, 1,3 , 5-trioxane, furan, 2-methylfuran, 1,8-cineole or crown ether.
- 1,3-dioxolane is preferably used in combination with an electrode containing sulfur.
- chain ethers examples include 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, Pentylphenyl ether, methoxytoluene, benzylethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1 , 1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether or Tiger ethylene glycol dimethyl ether and the like.
- nitriles include acetonitrile
- amides include dimethylformamide
- the nonaqueous electrolyte may be a solid system using a polymer electrolyte such as polyethylene oxide. Further, a gel electrolyte in which a nonaqueous electrolyte is held in a polymer may be used, or an inorganic compound electrolyte may be used.
- the separator may be a porous film or non-woven fabric exhibiting high rate discharge performance, which may be used alone or in combination.
- the material is represented by a polyolefin resin typified by polyethylene, polypropylene, etc., polyethylene terephthalate, polybutylene terephthalate, etc.
- Polyester resin polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-perfluorovinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer
- Polymer vinylidene fluoride-fluoroethylene copolymer, vinylidene fluoride-hexafluoroacetone copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-propylene copolymer, vinylidene fluoride-trifluoro B propylene copolymer, vinylidene fluoride - tetrafluoroethylene - hexafluoropropylene copolymer, vinylidene fluoride - can be exemplified tetrafluoroethylene copolymer - ethylene.
- the shape of the nonaqueous electrolyte battery according to the present embodiment is not particularly limited, and examples thereof include a cylindrical battery, a square battery (rectangular battery), a flat battery, and the like.
- FIG. 8 shows a perspective view of the inside of the container when the nonaqueous electrolyte battery according to the present invention has a rectangular shape.
- the electrode group 2 is housed in a battery container 3.
- the electrode group 2 is formed by winding a positive electrode including a positive electrode active material and a negative electrode including a negative electrode active material via a separator.
- the positive electrode is electrically connected to the positive electrode terminal 4 via the positive electrode lead 4 ′, and the negative electrode is electrically connected to the negative electrode terminal 5 via the negative electrode lead 5 ′.
- the present embodiment can also be realized as a power storage device in which a plurality of the above nonaqueous electrolyte batteries are assembled.
- a power storage device is shown in FIG.
- the power storage device 30 includes a plurality of power storage units 20.
- Each power storage unit 20 includes a plurality of nonaqueous electrolyte batteries 1.
- the power storage device 30 can be mounted as a power source for vehicles such as an electric vehicle (EV), a hybrid vehicle (HEV), and a plug-in hybrid vehicle (PHEV).
- EV electric vehicle
- HEV hybrid vehicle
- PHEV plug-in hybrid vehicle
- Measuring device High-performance fully automatic gas adsorption measuring device Autosorb-1-MP-9 (manufactured by Quantachrome) Degassing conditions: Samples are at room temperature (under vacuum) for 12 hours or more Degassing cell size: 1.8 cc (stem outline 6 mm)
- Adsorption gas Nitrogen gas Measurement item: Adsorption / desorption isotherm analysis at arbitrary measurement points: Specific surface area, total pore volume, average pore diameter by BET other store method, pore size distribution by BJH method (mesopore region) Pore size distribution by DFT method (micropore to mesopore region) The average pore diameter was calculated from the values of total pore volume and specific surface area assuming that the pore structure was cylindrical.
- this porous carbon was found to have an average pore diameter of 3 nm, a pore volume of 2 cm 3 g ⁇ 1 , and a specific surface area of 2500 m 2 g ⁇ 1 .
- FIG. 1 shows the measurement result of log pore volume distribution. The full width at half maximum of the peak of the log differential pore volume distribution was 1.8 nm.
- Example 1 Sulfur produced by the above process and porous carbon were mixed at a mass ratio of 70:30. The mixture is sealed in an airtight container under an argon atmosphere, and as shown in FIG. 2, the temperature is raised to 150 ° C. at a rate of temperature rise of 5 ° C./min, and held for 5 hours. The mixture was allowed to cool to 0 ° C., and then heated again to 300 ° C. at a rate of temperature increase of 5 ° C./min, and heat treatment was performed for 2 hours.
- Example 2 A mixture similar to that in Example 1 was sealed in a sealed container under an argon atmosphere, and as shown in FIG. 3, the temperature was raised to 300 ° C. at a rate of temperature increase of 0.5 ° C./min. Heat treatment for hours was performed.
- Comparative Example 1 The same mixture as in Example 1 was sealed in a sealed container under an argon atmosphere, and as shown in FIG. 4, the temperature was raised to 300 ° C. at a temperature raising rate of 5 ° C./min, and heat treatment was held for 2 hours.
- Comparative Example 2 A mixture similar to that in Example 1 was sealed in a sealed container under an argon atmosphere, and as shown in FIG. 5, the temperature was raised to 150 ° C. at a rate of temperature rise of 5 ° C./min, and heat treatment was held for 5 hours.
- Comparative Example 3 A mixture obtained by mixing sulfur and ketjen black having an average pore diameter of 7 nm and a specific surface area of 1000 m @ 2 g-1 at a mass ratio of 70:30 was sealed in a sealed container under an argon atmosphere, and the same as in Example 1 shown in FIG. Heat treatment was performed.
- SEM-EDS quantitative analysis was performed under the following measurement conditions.
- SEM Scanning electron microscope JSM-6060LA (manufactured by JEOL Ltd.)
- EDS Energy dispersive X-ray analyzer
- EX-23000BU manufactured by JEOL Ltd.
- Detector Mini cup type EDS detector
- EX-54175JMU manufactured by JEOL Ltd.
- Acceleration voltage 15 kV Spot size: 60 WD (distance between samples): 10 mm
- FIG. 7 shows the result of Example 1 in the SEM-EDS quantitative analysis with 1000 ⁇ field observation. Since the SEM-EDS quantitative analysis represents the surface state of the sample, the mass ratio Y (S / (S + C)) of sulfur / (sulfur + carbon) corresponds to the sulfur mass ratio in the vicinity of the composite surface.
- a battery was produced using the produced electrode as a working electrode, metal Li as a counter electrode, and a solvent of tetraethylene glycol dimethyl ether (TEGDME) in which 1M lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was dissolved as a non-aqueous electrolyte. .
- TEGDME tetraethylene glycol dimethyl ether
- LiTFSI lithium bis (trifluoromethanesulfonyl) imide
- the temperature at which sulfur vaporizes after a mixture of sulfur and porous carbon is heated and held at a temperature at which sulfur melts for 5 hours or more. It can be seen that it is sufficient to disperse sulfur also in the pores of the porous carbon by reheating to a low temperature. At that time, it is preferable that the temperature is once cooled from the melting temperature to a temperature at which sulfur is present in a solid state, since the fixation of sulfur coated on the surface is promoted.
- Example 2 the sulfur and porous carbon mixture was raised to the vaporization temperature of sulfur at a moderate temperature increase rate, so that the sulfur supported on the surface was uniformly vaporized and the carbon pores were Sulfur may be dispersed in
- Example 3 is a battery including an electrode using polyethyleneimine as a binder to the sulfur-carbon composite obtained in Example 1, and showed a higher discharge capacity than that using polyvinylidene fluoride. .
- the sulfur-carbon composite subjected to the heat treatment step of Comparative Example 2 also had a low sulfur utilization rate. This is presumably because the surface-coated sulfur hardly moves into the pores because the vaporization step by raising the temperature to the vaporization temperature is not included.
- the active material of Comparative Example 3 does not use porous carbon, and is a mixture of ketjen black and sulfur having an average pore diameter of 7 nm, a specific surface area of 1000 m 2 g ⁇ 1 and a log differential pore volume distribution shown in FIG. A heat treatment was performed under the same conditions as in Example 1. In this case, since sulfur is only distributed on the surface of carbon, the sulfur utilization rate is low.
- an electrode material having a high sulfur utilization rate and a discharge capacity closer to the theoretical capacity can be obtained by the sulfur-carbon composite having a sulfur distribution of
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Abstract
Description
硫黄は、質量あたりの理論容量が1675mAhg-1と大きく、従来の10倍以上の容量をもたらす正極材料として検討されてきた。しかし、電解液との反応性が高く、また、高抵抗であるため、未だ実用化には至っていない。
非特許文献1には、リチウムイオンを挿入可能な多孔性カーボンと硫黄とを混合し、400℃6時間の熱処理を行って、多孔性カーボンに硫黄を担持した硫黄-カーボン複合体の電極材料を作製したこと、及び、これを用いたリチウム-硫黄二次電池が記載され、100サイクルの充放電後、硫黄質量基準の容量が720mAhg-1であったことが記載されている。
本発明は、硫黄利用率が高い硫黄-カーボン複合体、その硫黄-カーボン複合体を含む電極を備えた非水電解質電池、及び硫黄利用率の高い硫黄-カーボン複合体の製造方法を提供することを目的とする。
(1)多孔性カーボンに硫黄を複合した硫黄-カーボン複合体からなり、熱質量分析における室温から500℃までの質量減少率Xと、1000倍の観察視野でのSEM-EDS定量分析における硫黄/(硫黄+炭素)の質量比率Yとが、
|X/Y-1|≦0.12の関係を満たす、硫黄-カーボン複合体。
(2)硫黄-カーボン複合体の製造方法であって、比表面積が2000m2g-1以上3000m2g-1以下であり、log微分細孔容積分布のピークの半値幅が1.0から2.5nmである多孔性カーボンと硫黄とを混合した混合体を、密閉容器内で加熱して硫黄-カーボン複合体を形成する工程を含み、前記加熱する工程が、硫黄が溶融する温度で5時間以上加熱する第一の工程と、第一の工程の後に、その硫黄が気化する温度で加熱する第二の工程とを含む、硫黄-カーボン複合体の製造方法。
(3)硫黄-カーボン複合体の製造方法であって、比表面積が2000m2g-1以上3000m2g-1以下であり、log微分細孔容積分布のピークの半値幅が1.0から2.5nmである多孔性カーボンと硫黄とを混合した混合体を、密閉容器内で加熱して硫黄-カーボン複合体を形成する工程を含み、前記加熱する工程が、硫黄が溶融する温度を経由し気化する温度まで0.5℃/分以下の速度で昇温する工程である、硫黄-カーボン複合体の製造方法。
(1)第一の工程で、多孔性カーボンの表面に硫黄が均一にコートされる。
(2)第二の工程で、第一の工程により均一にカーボン表面に担持した硫黄を、カーボンの細孔の近傍で気化できる。
以上の作用が好適に起こり、多孔性カーボンの表面ばかりでなく、細孔内にも硫黄粒子が高分散に担持されるために、硫黄利用率が高まり、理論容量により近い放電容量が得られると推察される。
ここで、硫黄の溶融温度、気化温度はそれぞれ、112~159℃、250℃以上であるから、第一の工程は混合体を室温から112~159℃の範囲まで昇温したのちに、その範囲内の温度で保持すること、第二の工程は、250℃以上まで昇温し保持することが好ましい。第一の工程及び第二の工程における昇温速度は、限定されないが、作業効率上1~5℃/分が好ましい。
第一の工程において、硫黄が溶融する温度で5時間以上加熱するのは、硫黄をカーボン表面に均一に担持させるためである。第一の工程と第二の工程の間には、カーボン表面にコートされた硫黄の固定化を促進するため、95℃以下まで放冷する工程を有してもよい。
この場合、硫黄が溶融する温度までの緩やかな上昇により、カーボン表面への硫黄の担持が均一に起こり、その後も硫黄が気化する温度まで緩やかに温度が上昇するから、カーボンの細孔近傍での気化が均一かつ十分に起こり、カーボンの表面と同様に細孔内にも硫黄が高分散化され、上記の場合と同様に、硫黄利用率が高まると推察される。
均一な担持が起こる昇温速度としては、0.5℃/分以下が好ましく、作業効率を考慮すると、0.1~0.5℃/分が好適である。
|X/Y-1|≦0.12の関係式を満たす、すなわち、X/Yが1±0.12の範囲内である場合に、硫黄利用率が高いリチウム二次電池用正極材料が得られることを知見した。
リチウムを含む負極は、リチウム金属、リチウム合金、又はリチウムがインサートされた材料であれば、いずれも使用できる。
無水ジクエン酸トリマグネシウム(小松屋株式会社製)を昇温速度5℃/分で昇温し、900℃、窒素雰囲気下で、1時間保持することにより炭化処理した後、1MのH2SO4水溶液中に浸漬して、MgOを抽出し、洗浄及び乾燥して多孔性カーボンを得た。以下の条件にて、この多孔性カーボンの窒素ガス吸着法による細孔径分布測定をおこなった。
測定装置:高性能全自動ガス吸着量測定装置 オートソーブ-1-MP-9 (Quantachrome社製)
脱気条件:試料を室温(真空下)12時間以上脱気
セルサイズ:1.8 cc (ステム外形 6 mm)
吸着ガス:窒素ガス
測定項目:任意測定点の吸着/脱着等温線
解析項目: BET他店法による比表面積,全細孔容積,平均細孔直径
BJH法による細孔径分布(メソポア領域)
DFT法による細孔径分布(ミクロポア~メソポア領域)
なお、平均細孔直径は、細孔構造が円筒形と仮定して全細孔容積と比表面積の値から算出した。全細孔容積は、細孔が液体窒素により充填されていると仮定して,P/P0(相対圧)=0.99の吸着ガス量から計算した。
その結果、この多孔性カーボンは、平均細孔径3nm、細孔体積2cm3g-1、比表面積2500m2g-1であることが分かった。図1にlog細孔容積分布の測定結果を示す。
log微分細孔容積分布のピークの半値幅は1.8nmであった。
実施例1
上記の工程により作成された硫黄と多孔性カーボンとを質量比70:30で混合した。
この混合物を、アルゴン雰囲気下で密閉容器に封入し、図2に示すように、昇温速度5℃/分で150℃まで昇温し、5時間保持した後、硫黄が固化する温度である80℃まで放冷し、その後、再び昇温速度5℃/分で300℃まで昇温し、2時間保持する熱処理を行った。
実施例1と同様の混合物を、アルゴン雰囲気下で密閉容器に封入し、図3に示すように、昇温度速度0.5℃/分で300℃まで昇温し、300℃を保ったまま2時間の熱処理を行った。
実施例1と同様の混合物を、アルゴン雰囲気下で密閉容器に封入し、図4に示すように昇温速度5℃/分で300℃まで昇温し、2時間保持する熱処理を行った。
実施例1と同様の混合物を、アルゴン雰囲気下で密閉容器に封入し、図5に示すように、昇温速度5℃/分で150℃まで昇温し、5時間保持する熱処理を行った。
硫黄と、平均孔径7nm、比表面積1000m2g-1のケッチェンブラックとを、質量比70:30で混合した混合物を、アルゴン雰囲気下で密閉容器に封入し、図2に示す実施例1と同様の熱処理を行った。
上記の実施例、及び比較例の熱処理を受けた混合物を、以下の条件で熱質量分析したところ、図6に示すように200℃から300℃を超える範囲の温度で質量減少が見られ、400℃手前から500℃の温度にかけての質量の変化はなかった。硫黄は200℃を超える温度で気化を開始し、400℃程度で気化を終了するから、熱質量分析における500℃の質量減少率Xは、複合体全体の硫黄質量比に相当する。
(熱質量分析条件)
昇温速度:10℃/分
雰囲気:ヘリウム
試料質量:10mg
SEM-EDS定量分析は、以下の測定条件で行った。
SEM:走査電子顕微鏡 JSM-6060LA(日本電子社製)
EDS:エネルギー分散型X線分析装置 EX-23000BU(日本電子社製)
検出器:ミニカップ型EDS検出器 EX-54175JMU(日本電子社製)
加速電圧:15kV
スポットサイズ:60
WD(試料間距離):10mm
1000倍の視野観察でのSEM-EDS定量分析における実施例1の結果を図7に示す。SEM-EDS定量分析は、試料の表面状態を表すことから、硫黄/(硫黄+炭素)の質量比率Y(S/(S+C))は、複合体表面近傍の硫黄質量比に相当する。
N-メチルピロリドン(NMP)を分散媒とし、上記の実施例1,2、及び比較例1~3で得られた硫黄-カーボン複合体、導電材としてのアセチレンブラック、及び結着材としてのポリフッ化ビニリデン(PVdF)を85:5:10の質量比で含有するスラリーを集電体に塗布し、乾燥して電極を作製した。作製した電極を作用極とし、金属Liを対極とし、1Mのリチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)を溶解したテトラエチレングリコールジメチルエーテル(TEGDME)の溶媒を非水電解液として備える電池を作製した。
水を分散媒とし、実施例1で得られた硫黄-カーボン複合体を用い、結着剤としてポリエチレンイミン(PEI)とを用いたこと以外は、上記と同様の電池を製作した。
作製した電池の充放電試験を以下の条件で行った。
放電(リチエーション):電流0.1CA、終止電圧1.0Vの定電流放電
充電(デリチエーション):電流0.1CA、終止電圧3.0Vの定電流充電、終止電圧に達しない場合は10時間規制(1CAはSの理論容量1675mAhg-1を基準とした。)
以下の表1に、実施例、比較例の結果を示す。
また、硫黄-カーボン複合体の製造方法において、溶融温度と気化温度の2工程の熱処理を行う、又は0.5℃/分以下の昇温速度で気化温度まで熱処理を行うことにより、硫黄利用率が高く、より理論容量に近い放電容量を有する電極材料を得ることができる。
1 非水電解質電池
2 電極群
3 電池容器
4 正極端子
4’ 正極リード
5 負極端子
5’ 負極リード
20 蓄電ユニット
30 蓄電装置
Claims (9)
- 多孔性カーボンに硫黄を複合した硫黄-カーボン複合体からなり、
熱質量分析における室温から500℃までの質量減少率Xと、1000倍の観察視野でのSEM-EDS定量分析における硫黄/(硫黄+炭素)の質量比率Yとが、
|X/Y-1|≦0.12の関係を満たすことを特徴とする、硫黄-カーボン複合体。 - 前記多孔性カーボンの平均細孔径が1~6nmである、請求項1に記載の硫黄-カーボン複合体。
- 前記多孔性カーボンの比表面積が2000m2g-1以上3000m2g-1以下である、請求項1又は2に記載の硫黄-カーボン複合体。
- 前記硫黄-カーボン複合体中の硫黄の含有率が50質量%以上である請求項1から3のいずれかに記載の硫黄-カーボン複合体。
- 請求項1から4のいずれかに記載の硫黄-カーボン複合体を含む電極。
- さらにポリエチレンイミンを含有する請求項5に記載の電極。
- 請求項5又は6に記載の電極を備えた非水電解質電池。
- 硫黄-カーボン複合体の製造方法であって、
比表面積が2000m2g-1以上3000m2g-1以下であり、log細孔容積分布のピークの半値幅が1.0nmから2.5nmである多孔性カーボンと硫黄とを混合した混合体を、密閉容器内で加熱して硫黄-カーボン複合体を形成する工程を含み、
前記加熱する工程が、
硫黄が溶融する温度で5時間以上加熱する第一の工程と、
第一の工程の後に、その硫黄が気化する温度で加熱する第二の工程とを含むことを特徴とする、硫黄-カーボン複合体の製造方法。 - 硫黄-カーボン複合体の製造方法であって、
比表面積が2000m2g-1以上3000m2g-1以下であり、log細孔容積分布のピークの半値幅が1.0nmから2.5nmである多孔性カーボンと硫黄とを混合した混合体を、密閉容器内で加熱して硫黄-カーボン複合体を形成する工程を含み、
前記加熱する工程が、硫黄が溶融する温度を経由し気化する温度まで0.5℃/分以下の速度で昇温する工程であることを特徴とする、硫黄-カーボン複合体の製造方法。
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US15/526,206 US10164247B2 (en) | 2014-11-13 | 2015-11-06 | Sulfur-carbon composite, nonaqueous electrolyte battery including electrode containing sulfur-carbon composite, and method for producing sulfur-carbon composite |
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KR102229453B1 (ko) * | 2017-11-24 | 2021-03-17 | 주식회사 엘지화학 | 황-탄소 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지 |
FR3080222B1 (fr) * | 2018-04-11 | 2020-03-20 | Saft | Element electrochimique lithium/soufre |
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US20230317918A1 (en) * | 2022-03-15 | 2023-10-05 | Ii-Vi Delaware, Inc. | Electrically Conductive Substrate for an Electrochemical Device |
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WO2023090445A1 (ja) * | 2021-11-22 | 2023-05-25 | 学校法人 関西大学 | 非水電解質蓄電素子、機器及び非水電解質蓄電素子の製造方法 |
KR102682579B1 (ko) | 2021-12-29 | 2024-07-09 | 한국기초과학지원연구원 | 한지로부터 유래한 다공성 탄소를 포함하는 탄소-황 복합체의 제조방법 및 이에 의해 제조된 탄소-황 복합체를 포함하는 리튬-황 전지 |
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JP6796254B2 (ja) | 2020-12-09 |
DE112015005161T5 (de) | 2017-08-17 |
US10164247B2 (en) | 2018-12-25 |
US20170317340A1 (en) | 2017-11-02 |
CN107108214A (zh) | 2017-08-29 |
JPWO2016075916A1 (ja) | 2017-09-28 |
US20190058188A1 (en) | 2019-02-21 |
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