WO2013001693A1 - Matériau actif d'électrode positive contenant du soufre et procédé pour sa production, et électrode positive pour batterie rechargeable lithium-ion - Google Patents

Matériau actif d'électrode positive contenant du soufre et procédé pour sa production, et électrode positive pour batterie rechargeable lithium-ion Download PDF

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WO2013001693A1
WO2013001693A1 PCT/JP2012/002613 JP2012002613W WO2013001693A1 WO 2013001693 A1 WO2013001693 A1 WO 2013001693A1 JP 2012002613 W JP2012002613 W JP 2012002613W WO 2013001693 A1 WO2013001693 A1 WO 2013001693A1
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sulfur
positive electrode
electrode active
active material
ion secondary
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PCT/JP2012/002613
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English (en)
Japanese (ja)
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中川　敏
加藤　崇行
一仁 川澄
淳一 丹羽
修 大森
正孝 仲西
晶 小島
琢寛 幸
敏勝 小島
境　哲男
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株式会社豊田自動織機
独立行政法人産業技術総合研究所
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Publication of WO2013001693A1 publication Critical patent/WO2013001693A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • 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
    • 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
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Definitions

  • the present invention relates to a sulfur-based positive electrode active material containing sulfur, a method for producing the same, and a positive electrode for a lithium ion secondary battery including the sulfur-based positive electrode active material.
  • a lithium ion secondary battery which is a type of non-aqueous electrolyte secondary battery, is a battery with a large charge / discharge capacity, and is mainly used as a battery for portable electronic devices. Lithium ion secondary batteries are also expected as batteries for electric vehicles.
  • a positive electrode active material of a lithium ion secondary battery As a positive electrode active material of a lithium ion secondary battery, a material containing a rare metal such as cobalt or nickel is generally used. However, since these metals have a small circulation amount and are expensive, in recent years, a positive electrode active material using a material replacing these rare metals has been demanded.
  • a technique using sulfur as a positive electrode active material of a lithium ion secondary battery is known.
  • sulfur as the positive electrode active material
  • the charge / discharge capacity of the lithium ion secondary battery can be increased.
  • the charge / discharge capacity of a lithium ion secondary battery using sulfur as a positive electrode active material is approximately six times the charge / discharge capacity of a lithium ion secondary battery using a lithium cobaltate positive electrode material, which is a common positive electrode material. is there.
  • a compound of sulfur and lithium is generated during discharge.
  • This compound of sulfur and lithium is soluble in a non-aqueous electrolyte solution (for example, ethylene carbonate, dimethyl carbonate, etc.) of a lithium ion secondary battery.
  • a non-aqueous electrolyte solution for example, ethylene carbonate, dimethyl carbonate, etc.
  • the lithium ion secondary battery using sulfur as the positive electrode active material has a problem that, when charging and discharging are repeated, it gradually deteriorates due to elution of the sulfur compound into the electrolytic solution, and the battery capacity is reduced.
  • Patent Document 1 a positive electrode active material containing sulfur (hereinafter referred to as a sulfur-based positive electrode active material) is blended with a material other than sulfur, such as a carbon material.
  • Patent Document 1 introduces a technique using polysulfide carbon containing carbon and sulfur as main constituent elements as a sulfur-based positive electrode active material.
  • This polysulfide carbon is obtained by adding sulfur to a linear unsaturated polymer.
  • This sulfur-based positive electrode active material is said to be able to suppress a decrease in charge / discharge capacity of a lithium ion secondary battery due to repeated charge / discharge.
  • cycle characteristic the characteristic of the lithium ion secondary battery in which the charge / discharge capacity decreases with repeated charge / discharge.
  • a lithium ion secondary battery with a small degree of decrease in charge / discharge capacity is a lithium ion secondary battery with excellent cycle characteristics, and a lithium ion secondary battery with a large degree of decrease in charge / discharge capacity is a lithium ion secondary battery with inferior cycle characteristics. is there.
  • Patent Document 2 a sulfur-based positive electrode active material obtained by heat-treating a mixture of polyacrylonitrile and sulfur.
  • Patent Document 2 The charge / discharge capacity of a lithium ion secondary battery using this positive electrode active material for the positive electrode is large, and the lithium ion secondary battery using this positive electrode active material for the positive electrode is excellent in cycle characteristics.
  • JP 2002-154815 A International Publication No. 2010/044437
  • the larger the amount of sulfur in the positive electrode active material the better.
  • the amount of sulfur varies greatly depending on the production lot, and even if the amount of sulfur is increased, the battery characteristics are not necessarily improved.
  • the amount of sulfur becomes too large, there arises a problem that excess sulfur is precipitated in the electrolyte solution to deteriorate the battery characteristics.
  • the present invention has been made in view of the above circumstances, and has a large charge / discharge capacity when it is used as a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, and has excellent cycle characteristics. It aims at providing the sulfur type positive electrode active material which can be expressed, the manufacturing method of this sulfur type positive electrode active material, and the positive electrode for lithium ion secondary batteries using this sulfur type positive electrode active material.
  • a feature of the sulfur-based positive electrode active material of the present invention that solves the above problems is that it comprises a polyacrylonitrile-derived carbon skeleton and sulfur (S) contained in the carbon skeleton, and the sulfur content is 30 to 70% by mass. There is to be.
  • the sulfur content is particularly preferably 45 to 55% by mass.
  • the positive electrode for a lithium ion secondary battery of the present invention is characterized by including the sulfur-based positive electrode active material of the present invention.
  • the feature of the manufacturing method of the sulfur type positive electrode active material of the present invention which can manufacture the sulfur type positive electrode active material of the present invention is the mixing step of mixing the raw material powder containing the sulfur powder and the polyacrylonitrile powder, and preventing the outflow of sulfur vapor
  • the specific surface area of the polyacrylonitrile powder is 30 m 2 / g or more.
  • the sulfur-based positive electrode active material and the positive electrode for a lithium ion secondary battery of the present invention can improve the charge / discharge capacity and cycle characteristics of the lithium ion secondary battery.
  • a sulfur-based positive electrode active material of the present invention capable of improving the charge / discharge capacity and cycle characteristics of a lithium ion secondary battery can be reliably and stably produced.
  • the production method of the present invention includes a mixing step of mixing raw powder containing sulfur powder and polyacrylonitrile powder, and a heat treatment step of heating in a non-oxidizing atmosphere while preventing the outflow of sulfur vapor.
  • a mixing step sulfur powder and polyacrylonitrile powder are mixed.
  • a mixer, various mills, etc. can be used for a mixing means.
  • the particle size of the sulfur powder is not particularly limited, but when it is classified using a sieve, it is preferably in the range of about 150 ⁇ m to 40 ⁇ m, more preferably in the range of about 100 ⁇ m to 40 ⁇ m. preferable.
  • the polyacrylonitrile powder preferably has a weight average molecular weight in the range of about 10,000 to 300,000.
  • the particle size of polyacrylonitrile is preferably in the range of about 0.5 to 50 ⁇ m, more preferably in the range of about 1 to 10 ⁇ m, when observed with an electron microscope.
  • a polyacrylonitrile powder having a specific surface area of 30 m 2 / g or more is used.
  • a polyacrylonitrile powder having a specific surface area of 30 m 2 / g or more By using a polyacrylonitrile powder having a specific surface area of 30 m 2 / g or more, the discharge capacity of a lithium ion secondary battery using the obtained sulfur-based positive electrode active material as the positive electrode is maximized. The reason for this is not clear, but since the discharge capacity is saturated by setting the specific surface area to 30 m 2 / g or more as shown in FIG. 4, the bonding reaction and desorption reaction of polyacrylonitrile and sulfur This is thought to be because the pore diameter becomes smaller and sulfur becomes harder to enter as the specific surface area increases or the specific surface area increases.
  • the mixing ratio of the sulfur powder and the polyacrylonitrile powder is preferably about 200 to 600 parts by mass, more preferably about 200 to 500 parts by mass with respect to 100 parts by mass of the polyacrylonitrile powder. More preferably, the amount is about 400 to 450 parts by mass.
  • a sulfur-based positive electrode active material having a sulfur content of 30 to 70% by mass can be produced.
  • the mixed raw material may be a simple mixture of sulfur powder and polyacrylonitrile powder, but the mixture may be in the form of pellets.
  • the mixed raw material may be composed of only polyacrylonitrile and sulfur, or may be blended with a general material that can be blended with the positive electrode active material (such as a conductive aid).
  • the above-described mixed raw material of sulfur powder and polyacrylonitrile powder is used and heated in a non-oxidizing atmosphere while preventing the outflow of sulfur.
  • sulfur in the vapor state reacts with polyacrylonitrile, so that polyacrylonitrile modified by sulfur or incorporating sulfur is obtained.
  • a method of heating in a sealed atmosphere can be adopted.
  • the sealed atmosphere may be maintained in a sealed state to the extent that sulfur vapor generated by heating is not dissipated.
  • the non-oxidizing atmosphere may be a reduced pressure state with a low oxygen concentration such that the oxidation reaction does not proceed; an inert gas atmosphere such as nitrogen or argon; a sulfur gas atmosphere or the like.
  • the raw material is put in a container that maintains the sealing property to the extent that sulfur vapor is not dissipated, and the container is decompressed. Or what is necessary is just to heat as inert gas atmosphere.
  • a mixed raw material of sulfur powder and polyacrylonitrile powder may be heated in a vacuum packaged state with a material that does not react with sulfur vapor such as an aluminum laminate film.
  • the packaged mixed raw material is placed in a pressure vessel such as an autoclave filled with water and heated, and the generated steam is used from the outside of the packaging material. It is preferable that the pressure is applied. According to this method, since pressure is applied by water vapor from the outside of the packaging material, the packaging material is prevented from being swollen and damaged by sulfur vapor.
  • the heating temperature is preferably about 250 to 500 ° C, more preferably about 250 to 400 ° C, and further preferably about 250 to 300 ° C.
  • the heating time is not particularly limited and varies depending on the actual heating temperature. Usually, it may be held for about 10 minutes to 10 hours, preferably about 30 minutes to 6 hours, within the above temperature range. . According to the production method of the present invention, it is possible to form a sulfur-based positive electrode active material in such a short time.
  • sulfur powder and polyacrylonitrile powder are contained in a reaction vessel having an opening for discharging hydrogen sulfide generated by the reaction while sulfur vapor is refluxed.
  • a method of heating the raw material powder can be employed.
  • the opening for discharging the hydrogen sulfide may be provided at a position where the generated sulfur vapor is liquefied and recirculated almost completely and the outflow of sulfur vapor from the opening can be prevented.
  • the opening for discharging the hydrogen sulfide may be provided at a position where the generated sulfur vapor is liquefied and recirculated almost completely and the outflow of sulfur vapor from the opening can be prevented.
  • the opening for discharging the hydrogen sulfide may be provided at a position where the generated sulfur vapor is liquefied and recirculated almost completely and the outflow of sulfur vapor from the opening can be prevented.
  • the opening for discharging the hydrogen sulfide may be provided at a position where the generated sulfur vapor is
  • the amount of sulfur blended with respect to polyacrylonitrile is excessive, a sufficient amount of sulfur can be easily taken into the polyacrylonitrile in the heat treatment step. And even if it mix
  • the mixing ratio of polyacrylonitrile and sulfur in the mixture is 1: 2 to 1: 5 by mass ratio
  • the target object after the heat treatment process is heated at 200 ° C. to 250 ° C. while reducing the pressure. (Single element sulfur removal step) By taking a sufficient amount of sulfur into polyacrylonitrile, it is possible to suppress the adverse effects due to the remaining single sulfur.
  • the sulfur type positive electrode active material of this invention can be manufactured with the manufacturing method of this invention.
  • the sulfur-based positive electrode active material of the present invention is used for a positive electrode of a lithium ion secondary battery having a positive electrode, a negative electrode, and an electrolyte. It can also be used for the positive electrode of a sodium ion secondary battery.
  • the sulfur-based positive electrode active material of the present invention comprises a carbon skeleton derived from polyacrylonitrile and sulfur (S) contained in the carbon skeleton, and has a sulfur content of 30 to 70% by mass. .
  • S polyacrylonitrile and sulfur
  • the weight loss by thermogravimetric analysis of the sulfur-based positive electrode active material of the present invention when heated from room temperature to 900 ° C. at a rate of temperature increase of 20 ° C./min is 10% or less at 400 ° C.
  • a weight decrease is observed from around 120 ° C., and when it exceeds 200 ° C., a large weight loss based on the disappearance of sulfur is recognized.
  • the sulfur-based positive electrode active material of the present invention as a result of X-ray diffraction by CuK ⁇ ray, the peak based on sulfur disappears and only a broad peak with a diffraction angle (2 ⁇ ) of around 20-30 ° C. is confirmed.
  • FIG. 2 shows an example of a Raman spectrum of the sulfur-based positive electrode active material of the present invention obtained by using 200 parts by mass of sulfur with respect to 100 parts by mass of polyacrylonitrile.
  • the sulfur-based positive electrode active material in the Raman spectrum, there is a main peak near 1331cm -1 of Raman shift, and, 1548cm -1 in the range of 200cm -1 ⁇ 1800cm -1, 939cm -1 , 479cm -1, There are peaks near 381 cm ⁇ 1 and 317 cm ⁇ 1 .
  • the above-mentioned Raman shift peak is observed at the same peak position when the ratio of sulfur to polyacrylonitrile is changed, and characterizes the sulfur-based positive electrode active material of the present invention.
  • Each of the peaks described above can exist in a range of approximately ⁇ 8 cm ⁇ 1 with the peak position as the center.
  • the number of peaks may change or the position of the peak top may be shifted due to a difference in wavelength or resolution of incident light.
  • the positive electrode for lithium ion secondary batteries of this invention contains the sulfur type positive electrode active material of this invention mentioned above.
  • the positive electrode for a lithium ion secondary battery can have the same structure as a general positive electrode for a lithium ion secondary battery, except for the positive electrode active material.
  • the positive electrode for a lithium ion secondary battery of the present invention can be manufactured by applying a positive electrode material, which is a mixture of the sulfur-based positive electrode active material of the present invention, a conductive additive, a binder, and a solvent, to a current collector.
  • Conductive aids include vapor grown carbon fiber (Vapor Grown Carbon Fiber: VGCF), carbon powder, carbon black (CB), acetylene black (AB), ketjen black (KB), graphite, aluminum, titanium and other positive electrodes Examples thereof include fine metal powders stable in potential.
  • polyvinylidene fluoride PolyVinylidene fluoride DiFluoride: PVDF
  • PVDF polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • PI polyimide
  • PAI polyamideimide
  • CMC carboxymethylcellulose
  • PVC polyvinyl chloride
  • PMA methacrylic resin
  • PAN Polyacrylonitrile
  • PPO modified polyphenylene oxide
  • PEO polyethylene oxide
  • PE polyethylene
  • PP polypropylene
  • the solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylformaldehyde, alcohol, water and the like.
  • These conductive assistants, binders and solvents may be used as a mixture of plural kinds.
  • the amount of these materials is not particularly limited. For example, it is preferable to add about 20 to 100 parts by mass of a conductive additive and about 10 to 20 parts by mass of a binder with respect to 100 parts by mass of the sulfur-based positive electrode active material.
  • a mixture of the sulfur-based positive electrode active material of the present invention, the above-described conductive additive and binder is kneaded with a mortar or a press machine to form a film, and the film-like mixture is collected with a press machine or the like.
  • the positive electrode for a lithium ion secondary battery of the present invention can also be produced by pressure bonding to an electric body.
  • current collectors include aluminum foil, aluminum mesh, punched aluminum sheet, aluminum expanded sheet, stainless steel foil, stainless steel mesh, punched stainless steel sheet, stainless steel expanded sheet, nickel foam, nickel non-woven fabric, copper foil, copper Examples thereof include a mesh, a punched copper sheet, a copper expanded sheet, a titanium foil, a titanium mesh, a carbon nonwoven fabric, and a carbon woven fabric.
  • the carbon non-woven fabric / woven fabric current collector made of carbon having a high degree of graphitization is suitable as a current collector for a sulfur-based positive electrode active material because it does not contain hydrogen and has low reactivity with sulfur.
  • pitches that is, by-products such as petroleum, coal, coal tar, etc.
  • PAN polyacrylonitrile fiber
  • the positive electrode for a lithium ion secondary battery of the present invention contains the above-described sulfur-based positive electrode active material of the present invention as a positive electrode active material. Therefore, the lithium ion secondary battery using the positive electrode for lithium ion secondary batteries of the present invention has a large charge / discharge capacity and excellent cycle characteristics.
  • lithium ion secondary battery (Lithium ion secondary battery)
  • the structure of a lithium ion secondary battery using the sulfur-based positive electrode active material of the present invention for the positive electrode will be described.
  • a lithium ion secondary battery using the sulfur-based positive electrode active material of the present invention for the positive electrode is simply abbreviated as a lithium ion secondary battery.
  • the positive electrode is as described above.
  • the negative electrode material As the negative electrode material, known carbon-based materials such as metallic lithium and graphite, silicon-based materials such as silicon thin films, and alloy-based materials such as copper-tin and cobalt-tin can be used.
  • a negative electrode material that does not contain lithium for example, a carbon-based material, a silicon-based material, an alloy-based material, or the like among the negative electrode materials described above, short-circuiting between the positive and negative electrodes due to generation of dendrites is unlikely to occur. This is advantageous.
  • these negative electrode materials not containing lithium are used in combination with the positive electrode of the present invention, neither the positive electrode nor the negative electrode contains lithium.
  • the lithium pre-doping method may be a known method.
  • a half battery is assembled using metallic lithium as the counter electrode, and lithium is inserted by an electrolytic doping method in which lithium is electrochemically doped, or a metallic lithium foil is attached to the electrode.
  • an electrolytic doping method in which lithium is electrochemically doped, or a metallic lithium foil is attached to the electrode.
  • the positive electrode is predoped with lithium, the above-described electrolytic doping method can be used.
  • a silicon-based material that is a high-capacity negative electrode material is particularly preferable, and among these, thin-film silicon that is advantageous in terms of capacity per volume due to thin electrode thickness is more preferable.
  • an electrolyte in which an alkali metal salt as an electrolyte is dissolved in an organic solvent can be used.
  • the organic solvent is preferably at least one selected from non-aqueous solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl ether, ⁇ -butyrolactone, and acetonitrile.
  • LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiI, LiClO 4, or the like can be used.
  • the concentration of the electrolyte may be about 0.5 mol / l to 1.7 mol / l.
  • the electrolyte is not limited to liquid.
  • the electrolyte is in a solid state (for example, a polymer gel).
  • the lithium ion secondary battery may include a member such as a separator in addition to the above-described negative electrode, positive electrode, and electrolyte.
  • the separator is interposed between the positive electrode and the negative electrode, allows ions to move between the positive electrode and the negative electrode, and prevents an internal short circuit between the positive electrode and the negative electrode. If the lithium ion secondary battery is a sealed type, the separator is also required to have a function of holding an electrolytic solution.
  • the separator it is preferable to use a thin, microporous or non-woven membrane made of polyethylene, polypropylene, polyacrylonitrile, aramid, polyimide, cellulose, glass or the like.
  • the shape of the lithium ion secondary battery is not particularly limited, and can be various shapes such as a cylindrical shape, a stacked shape, and a coin shape.
  • the reaction apparatus 1 includes a reaction vessel 2, a lid 3, a thermocouple 4, an alumina protective tube 40, two alumina tubes (gas introduction tube 5, gas discharge tube 6), and argon gas. It has a pipe 50, a gas tank 51 containing argon gas, a trap pipe 60, a trap tank 62 containing a sodium hydroxide aqueous solution 61, an electric furnace 7, and a temperature controller 70 connected to the electric furnace.
  • a bottomed cylindrical glass tube (quartz glass) was used as the reaction vessel 2.
  • the mixed raw material 9 was accommodated in the reaction vessel 2.
  • the opening of the reaction vessel 2 was closed with a glass lid 3 having three through holes.
  • an alumina protective tube 40 (alumina SSA-S, manufactured by Nikkato Co., Ltd.) containing the thermocouple 4 was attached.
  • a gas introduction pipe 5 (alumina SSA-S, manufactured by Nikkato Co., Ltd.) was attached to the other through hole.
  • a gas exhaust pipe 6 (alumina SSA-S, manufactured by Nikkato Co., Ltd.) was attached to the remaining one of the through holes.
  • the reaction vessel 2 had an outer diameter of 60 mm, an inner diameter of 50 mm, and a length of 300 mm.
  • the alumina protective tube 40 had an outer diameter of 4 mm, an inner diameter of 2 mm, and a length of 250 mm.
  • the gas introduction pipe 5 and the gas discharge pipe 6 had an outer diameter of 6 mm, an inner diameter of 4 mm, and a length of 150 mm.
  • the tips of the gas introduction pipe 5 and the gas discharge pipe 6 were exposed to the outside of the lid 3 (inside the reaction vessel 2). The length of this exposed part was 3 mm.
  • the tips of the gas introduction pipe 5 and the gas discharge pipe 6 are approximately 100 ° C. or lower in a heat treatment process described later. For this reason, the sulfur vapor generated in the heat treatment step does not flow out of the gas introduction pipe 5 and the gas discharge pipe 6, but is returned (refluxed) to the reaction vessel 2.
  • the temperature of the mixed raw material 9 in the reaction vessel 2 was indirectly measured at the tip of the thermocouple 4 placed in the alumina protective tube 40.
  • the temperature measured by the thermocouple 4 was fed back to the temperature controller 70 of the electric furnace 7.
  • An argon gas pipe 50 was connected to the gas introduction pipe 5.
  • the argon gas pipe 50 was connected to a gas tank 51 containing argon gas.
  • One end of a trap pipe 60 was connected to the gas discharge pipe 6.
  • the other end of the trap pipe 60 was inserted into the sodium hydroxide aqueous solution 61 in the trap tank 62.
  • the trap pipe 60 and the trap tank 62 are traps for hydrogen sulfide gas generated in a heat treatment process to be described later.
  • Heating was stopped when the mixed raw material 9 reached 360 ° C. After stopping the heating, the temperature of the mixed raw material 9 increased to 400 ° C. and then decreased. Therefore, in this heat treatment step, the mixed raw material 9 was heated to 400 ° C. Thereafter, the mixed raw material 9 was naturally cooled, and when the mixed raw material 9 was cooled to room temperature (about 25 ° C.), the product (that is, the object to be treated after the heat treatment step) was taken out from the reaction vessel 2. The heating time at this time was about 5 minutes at 400 ° C., and sulfur was refluxed.
  • Elemental sulfur removal process In order to remove elemental sulfur (free sulfur) remaining in the object to be treated after the heat treatment process, the following processes were performed.
  • the object to be treated after the heat treatment step was pulverized with a mortar. 2 g of the pulverized product was placed in a glass tube oven and heated at 200 ° C. for 3 hours while being vacuumed. The temperature elevation temperature at this time was 10 ° C./min. By this process, the elemental sulfur remaining in the object to be treated after the heat treatment process was evaporated and removed, and the sulfur-based positive electrode active material of Example 1 not including elemental sulfur (or including a small amount of elemental sulfur) was obtained.
  • Negative electrode As the negative electrode, a 0.5 mm thick metal lithium foil (Honjo Metal Co., Ltd.) punched to ⁇ 14 mm was used.
  • Electrolytic Solution As the electrolytic solution, a non-aqueous electrolyte in which LiPF 6 was dissolved in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed was used. Ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1. The concentration of LiPF 6 in the electrolytic solution was 1.0 mol / l.
  • Test Example 1 Various mixed raw materials were prepared by changing various mixing ratios of the polyacrylonitrile powder and the sulfur powder. Polyacrylonitrile powders having a specific surface area of 33 m 2 / g were all used.
  • Example 1 Using these mixed raw materials, a heat treatment step was performed in the same manner as in Example 1 using the same apparatus as in Example 1, and a single sulfur removal step was performed in the same manner as in Example 1 to obtain a plurality of types of sulfur-based positive electrode active materials. Got. When the sulfur content of these sulfur-based positive electrode active materials was measured in the same manner as in Example 1, the sulfur content was distributed between 20% by mass and 80% by mass.
  • Example 1 a plurality of types of positive electrodes for lithium ion secondary batteries were formed in the same manner as in Example 1, and a plurality of types of lithium ion secondary batteries were obtained in the same manner as in Example 1. It was.
  • each lithium ion secondary battery was charged and discharged at a current value corresponding to 50 mA per 1 g of the positive electrode active material. At this time, the discharge end voltage was 1.0 V, and the charge end voltage was 3.0 V. The discharge capacity at the second time when charging / discharging was repeated twice was measured, and the relationship with the sulfur content is shown in FIG.
  • the discharge capacity of each lithium ion secondary battery has a peak peaked at Example 1, and a discharge capacity of about 500 mAh / g or more can be obtained by setting the sulfur content in the range of 30 to 70 mass%. It is clear to show. It is also clear that when the sulfur content is in the range of 45 to 55 mass%, a discharge capacity of about 700 mAh / g or more is exhibited.
  • Test Example 2 The mixing ratio of the polyacrylonitrile powder and the sulfur powder was constant at a mass ratio of 1: 4, and six types (A to F) of polyacrylonitrile powders having different specific surface areas were used as shown in FIG. Six kinds of mixed raw materials were prepared.
  • Example 1 Using these mixed raw materials, a heat treatment step was performed in the same manner as in Example 1 using the same apparatus as in Example 1, and a single sulfur removal step was performed in the same manner as in Example 1 to obtain a plurality of types of sulfur-based positive electrode active materials. Got. For these sulfur-based positive electrode active materials, the sulfur content was measured in the same manner as in Example 1, and the results are shown in Table 1.
  • Example 1 a plurality of types of positive electrodes for lithium ion secondary batteries were formed in the same manner as in Example 1, and a plurality of types of lithium ion secondary batteries were obtained in the same manner as in Example 1. It was.
  • each lithium ion secondary battery was charged and discharged at a current value corresponding to 50 mA per 1 g of the positive electrode active material. At this time, the discharge end voltage was 1.0 V, and the charge end voltage was 3.0 V.
  • FIG. 4 shows the relationship between the specific surface area of the polyacrylonitrile powder used by measuring the discharge capacity at the second time when charging and discharging were repeated twice.
  • the sulfur-based positive electrode active material produced using polyacrylonitrile powder with a specific surface area of 30m 2 / g or more has a high sulfur content of 38% by mass, and the sulfur-based positive electrode active material is used. It can be seen that the lithium ion secondary battery had a substantially saturated discharge capacity. That is, it is clear that a high-capacity lithium ion secondary battery can be obtained by using, as a positive electrode, a sulfur-based positive electrode active material produced using a polyacrylonitrile powder having a specific surface area of 30 m 2 / g or more.
  • a sulfur-based positive electrode active material having a sulfur content of 30 to 70% by mass or even 45 to 55% by mass is manufactured and used for the positive electrode. It is clear that a lithium ion secondary battery having a capacity can be manufactured stably.
  • Reactor 2 Reaction vessel 3: Lid 4: Thermocouple 5: Gas introduction pipe 6: Gas discharge pipe 7: Electric furnace

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un matériau actif d'électrode positive contenant du soufre, dans lequel un atome de soufre est lié à un squelette carboné dérivé d'un polyacrylonitrile et qui présente une teneur en soufre de 30 à 70 % en masse, caractérisé en ce qu'il peut être produit en chauffant un mélange de polyacrylonitrile et d'une poudre de soufre. Une batterie rechargeable lithium- produite en incorporant le matériau actif d'électrode positive contenant du soufre selon l'invention dans une électrode positive développe une capacité pouvant atteindre, voire dépasser 400 mAh/g.
PCT/JP2012/002613 2011-06-28 2012-04-16 Matériau actif d'électrode positive contenant du soufre et procédé pour sa production, et électrode positive pour batterie rechargeable lithium-ion WO2013001693A1 (fr)

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WO2016159212A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau de soufre organique et procédé de production associé
WO2016158675A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau à base de soufre organique et son procédé de fabrication
US9531009B2 (en) 2013-01-08 2016-12-27 Sion Power Corporation Passivation of electrodes in electrochemical cells
US9559348B2 (en) 2013-01-08 2017-01-31 Sion Power Corporation Conductivity control in electrochemical cells
CN109923693A (zh) * 2016-08-31 2019-06-21 威廉马歇莱思大学 用于电池的阳极、阴极和隔膜、以及其制造方法和用途
CN111755688A (zh) * 2019-03-29 2020-10-09 住友橡胶工业株式会社 硫系活性物质
WO2022004696A1 (fr) * 2020-06-29 2022-01-06 株式会社Adeka Polyacrylonitrile modifié par un soufre, matière active d'électrode contenant celui-ci, électrode pour batterie secondaire contenant cette matière active d'électrode, procédé de fabrication de cette électrode, et batterie secondaire à électrolyte non aqueux mettant en œuvre cette électrode
WO2022004697A1 (fr) * 2020-06-29 2022-01-06 株式会社Adeka Polyacrylonitrile modifié au soufre, matériau actif d'électrode en contenant, électrode de batterie rechargeable contenant ledit matériau actif d'électrode, procédé de production de ladite électrode et batterie rechargeable à électrolyte non aqueux qui utilise ladite électrode
US11515516B2 (en) 2015-12-22 2022-11-29 Baoshan Iron & Steel Co., Ltd. Method of preparing cathode matertal for a battery
WO2023085245A1 (fr) * 2021-11-11 2023-05-19 株式会社Adeka Composition, électrode, batterie et matériau actif d'électrode
WO2023095755A1 (fr) 2021-11-26 2023-06-01 株式会社Adeka Électrode de batterie secondaire à électrolyte non aqueux comprenant un collecteur de courant contenant un métal poreux et un matériau actif à base d'organosulfure, une batterie secondaire à électrolyte non aqueux contenant ladite électrode, et un matériau actif à base d'organosulfure pour la fabrication de ladite électrode
WO2024057992A1 (fr) * 2022-09-15 2024-03-21 株式会社Adeka Matériau comprenant un soufre, matériau de batterie comprenant un soufre, électrode, et batterie
WO2024057991A1 (fr) * 2022-09-15 2024-03-21 株式会社Adeka Procédé de fabrication de matériau comprenant un soufre
US11984576B1 (en) 2019-10-01 2024-05-14 William Marsh Rice University Alkali-metal anode with alloy coating applied by friction

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9531009B2 (en) 2013-01-08 2016-12-27 Sion Power Corporation Passivation of electrodes in electrochemical cells
US9559348B2 (en) 2013-01-08 2017-01-31 Sion Power Corporation Conductivity control in electrochemical cells
US10906869B2 (en) 2015-03-31 2021-02-02 National Institute Of Advanced Industrial Science And Technology Organic sulfur material and method for producing same
WO2016158675A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau à base de soufre organique et son procédé de fabrication
JPWO2016159212A1 (ja) * 2015-03-31 2017-12-28 国立研究開発法人産業技術総合研究所 有機硫黄材料及びその製造方法
JPWO2016158675A1 (ja) * 2015-03-31 2018-02-01 国立研究開発法人産業技術総合研究所 有機硫黄材料及びその製造方法
WO2016159212A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau de soufre organique et procédé de production associé
US10710960B2 (en) 2015-03-31 2020-07-14 National Institute Of Advanced Industrial Science And Technology Carbon sulfur material and method for producing same
US11515516B2 (en) 2015-12-22 2022-11-29 Baoshan Iron & Steel Co., Ltd. Method of preparing cathode matertal for a battery
CN109923693A (zh) * 2016-08-31 2019-06-21 威廉马歇莱思大学 用于电池的阳极、阴极和隔膜、以及其制造方法和用途
CN111755688A (zh) * 2019-03-29 2020-10-09 住友橡胶工业株式会社 硫系活性物质
US11984576B1 (en) 2019-10-01 2024-05-14 William Marsh Rice University Alkali-metal anode with alloy coating applied by friction
WO2022004696A1 (fr) * 2020-06-29 2022-01-06 株式会社Adeka Polyacrylonitrile modifié par un soufre, matière active d'électrode contenant celui-ci, électrode pour batterie secondaire contenant cette matière active d'électrode, procédé de fabrication de cette électrode, et batterie secondaire à électrolyte non aqueux mettant en œuvre cette électrode
WO2022004697A1 (fr) * 2020-06-29 2022-01-06 株式会社Adeka Polyacrylonitrile modifié au soufre, matériau actif d'électrode en contenant, électrode de batterie rechargeable contenant ledit matériau actif d'électrode, procédé de production de ladite électrode et batterie rechargeable à électrolyte non aqueux qui utilise ladite électrode
WO2023085245A1 (fr) * 2021-11-11 2023-05-19 株式会社Adeka Composition, électrode, batterie et matériau actif d'électrode
WO2023095755A1 (fr) 2021-11-26 2023-06-01 株式会社Adeka Électrode de batterie secondaire à électrolyte non aqueux comprenant un collecteur de courant contenant un métal poreux et un matériau actif à base d'organosulfure, une batterie secondaire à électrolyte non aqueux contenant ladite électrode, et un matériau actif à base d'organosulfure pour la fabrication de ladite électrode
WO2024057992A1 (fr) * 2022-09-15 2024-03-21 株式会社Adeka Matériau comprenant un soufre, matériau de batterie comprenant un soufre, électrode, et batterie
WO2024057991A1 (fr) * 2022-09-15 2024-03-21 株式会社Adeka Procédé de fabrication de matériau comprenant un soufre

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