WO2014112401A1 - 電極用複合材料及びその製造方法並びに二次電池 - Google Patents
電極用複合材料及びその製造方法並びに二次電池 Download PDFInfo
- Publication number
- WO2014112401A1 WO2014112401A1 PCT/JP2014/050035 JP2014050035W WO2014112401A1 WO 2014112401 A1 WO2014112401 A1 WO 2014112401A1 JP 2014050035 W JP2014050035 W JP 2014050035W WO 2014112401 A1 WO2014112401 A1 WO 2014112401A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- porous carbon
- carbon material
- composite material
- electrode
- pore volume
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present disclosure relates to an electrode composite material, a manufacturing method thereof, and a secondary battery.
- lithium nickelate-based material which is said to have a relatively high capacity, is about 190 mAh / gram to 220 mAh / gram.
- sulfur has a high theoretical capacity density of about 1670 mAh / gram and is one of the promising candidates for a high capacity electrode material.
- sulfur alone has a low electron conductivity and does not contain lithium (Li), so that there is a problem that the negative electrode has a narrow selection range because lithium or an alloy containing lithium must be used for the negative electrode.
- lithium sulfide contains lithium
- alloys such as graphite and silicon can be used for the negative electrode, and the selection range of the negative electrode material is drastically increased.
- lithium sulfide also has low electronic conductivity
- charging and discharging are hardly performed by simply mixing, for example, carbon powder, which is a conductive material, and technology for imparting electronic conductivity to lithium sulfide is indispensable. is there.
- a lithium battery including a positive electrode using sulfur or lithium polysulfide as an active material and a lithium ion conductive solid electrolyte layer is known from JP-A-6-275313.
- a positive electrode material for a lithium battery is produced by the following method (see paragraphs [0011] and [0018] in JP-A-6-275313). That is, first, sulfur or lithium polysulfide is dissolved in carbon disulfide, acetylene black is immersed in this solution, this mixed solution is filtered, and dried under reduced pressure at room temperature, whereby sulfur or lithium polysulfide is added to acetylene black. A positive electrode material carrying s is obtained.
- WO2012 / 102037A1 discloses an invention of a composite material containing a conductive agent and an alkali metal sulfide integrated on the surface of the conductive agent, and this composite material is used for an electrode of a lithium ion battery.
- ketjen black and acetylene black are disclosed as the conductive agent, and the average diameter of the pores of the conductive agent obtained based on the BJH method is 0.1 nm or more and 40 nm or less. It is.
- lithium sulfide Li 2 S
- Li 2 S lithium sulfide
- JP-A-6-27531 a method for producing lithium sulfide
- the manufactured lithium sulfide is used as a raw material for manufacturing a solid electrolyte, but there is no mention of using lithium sulfide as a constituent material of the positive electrode. Moreover, it is difficult to say that the characteristics of the lithium ion battery are sufficient when ketjen black or acetylene black is used as the conductive agent.
- an object of the present disclosure is to provide a composite material for an electrode having an excellent characteristic using lithium sulfide as an active material, a method for manufacturing the same, and a secondary battery including an electrode composed of the composite material for an electrode.
- Pore volume MP PC by MP method 0.1 cm 3 / g or more, preferably 0.15 cm 3 / g or more, the porous carbon material derived from a plant is more preferably 0.20 cm 3 / g or more and, Lithium sulfide supported in the pores of the porous carbon material, including.
- the pore volume MP 0 by the MP method of electrode composites 0.1 cm 3 / g, preferably less 0.08 cm 3 / g or less, more preferably 0.05 cm 3 / g or less.
- the electrode composite material according to the second aspect of the present disclosure for achieving the above-described object A plant-derived porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, including.
- the pore volume MP 0 of the composite material for electrodes by the MP method is less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less, and the electrode
- the pore volume MP 1 by the MP method after washing the composite material for water is larger than the pore volume MP 0 .
- the electrode composite material according to the third aspect of the present disclosure for achieving the above object is as follows: A plant-derived porous carbon material having a pore volume BJH PC of less than 100 nm by the BJH method of 0.3 cm 3 / gram or more, preferably 0.4 cm 3 / gram or more, more preferably 0.5 cm 3 / gram or more, as well as, Lithium sulfide supported in the pores of the porous carbon material, including.
- the electrode composite material according to the fourth aspect of the present disclosure for achieving the above object is as follows: A plant-derived porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, including.
- the pore volume BJH 1 of less than 100 nm by the BJH method after the electrode composite material is washed with water is larger than the pore volume BJH 0 .
- the electrode composite material according to the fifth aspect of the present disclosure for achieving the above object is as follows: A porous carbon material having an inverse opal structure, and Lithium sulfide supported in the pores of the porous carbon material, A composite material for an electrode comprising: The pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is 20% or less of the pore volume BJH PC of less than 100 nm by the BJH method of the porous carbon material.
- the composite material for an electrode according to the sixth aspect of the present disclosure for achieving the above object is: Porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the electrode composite material according to the seventh aspect of the present disclosure for achieving the above object is as follows: Porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including The ratio of the pore volume BJH 100 of 100 nm or more by the BJH method is 30% or less.
- the secondary battery according to the first aspect of the present disclosure for achieving the above object includes an electrode manufactured from the composite material for electrodes according to the first aspect of the present disclosure. Moreover, the secondary battery which concerns on the 2nd aspect of this indication for achieving said objective is equipped with the electrode produced from the composite material for electrodes which concerns on said 2nd aspect of this indication. Furthermore, the secondary battery according to the third aspect of the present disclosure for achieving the above object includes an electrode manufactured from the composite material for an electrode according to the third aspect of the present disclosure. Moreover, the secondary battery which concerns on the 4th aspect of this indication for achieving said objective is equipped with the electrode produced from the composite material for electrodes which concerns on said 4th aspect of this indication.
- the secondary battery according to the fifth aspect of the present disclosure for achieving the above object includes an electrode manufactured from the composite material for electrodes according to the fifth aspect of the present disclosure.
- a secondary battery according to the sixth aspect of the present disclosure for achieving the above object includes an electrode manufactured from the composite material for an electrode according to the sixth aspect of the present disclosure.
- the secondary battery according to the seventh aspect of the present disclosure for achieving the above object includes an electrode manufactured from the composite material for an electrode according to the seventh aspect of the present disclosure.
- pore volume MP PC is 0.1cm by MP method 3 / g or more, preferably 0.15 cm 3 / g or more, more preferably added porous carbon material derived from a plant is 0.20 cm 3 / g or more, by heating the porous carbon material, and porous
- a method for producing a composite material for an electrode to obtain a composite material for an electrode comprising lithium sulfide supported in pores of a carbonaceous material The pore volume MP 0 of the composite material for electrodes by the MP method is less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less.
- a plant-derived porous carbon material is added and heated.
- a method for producing a composite material for an electrode to obtain a porous carbon material, and a composite material for an electrode comprising lithium sulfide supported in pores of the porous carbon material is less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less, The pore volume MP 1 by the MP method after washing of the electrode composite material is larger than the pore volume MP 0 .
- a pore volume BJH PC of less than 100 nm by the BJH method is obtained.
- a plant-derived porous carbon material is added and heated.
- a method for producing a composite material for an electrode to obtain a composite material for an electrode comprising a porous carbon material and lithium sulfide supported in pores of the porous carbon material, Pore volume BJH 0 of less than 100nm by the BJH method of the electrode composite material, 0.3 cm 3 / g, preferably less 0.27 cm 3 / g or less, more preferably 0.25 cm 3 / g or less,
- the pore volume BJH 1 of less than 100 nm by the BJH method after washing the electrode composite material is larger than the pore volume BJH 0 .
- a method for producing a composite material for an electrode according to a fifth aspect of the present disclosure includes: generating lithium hydrosulfide in a solvent; adding a porous carbon material having an inverse opal structure; A method for producing a composite material for an electrode to obtain a porous carbon material and a composite material for an electrode containing lithium sulfide supported in pores of the porous carbon material,
- the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is 20% or less of the pore volume BJH PC of less than 100 nm by the BJH method of the porous carbon material.
- the method for producing a composite material for an electrode according to the sixth aspect of the present disclosure for achieving the above-described object includes, after generating lithium hydrosulfide in a solvent, adding a porous carbon material and heating, A method for producing a composite material for an electrode to obtain a porous carbon material, and a composite material for an electrode comprising lithium sulfide supported in pores of the porous carbon material,
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the method for producing a composite material for an electrode according to the seventh aspect of the present disclosure for achieving the above-described object includes, after generating lithium hydrosulfide in a solvent, adding a porous carbon material and heating, A method for producing a composite material for an electrode to obtain a porous carbon material, and a composite material for an electrode comprising lithium sulfide supported in pores of the porous carbon material,
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material is 30% or less.
- the electrode composite material or the constituent material thereof Since the pore volume based on the MP method or BJH method of the porous carbon material and the electrode composite material is defined, the electrode composite material, the secondary battery, and the electrode according to the sixth aspect of the present disclosure
- a porous carbon material is specified, and furthermore, since an average particle size is specified, the porous carbon material, which is a conductive material, has a high electronic conductivity with respect to lithium sulfide. It is possible to provide a composite material for an electrode for obtaining a secondary battery excellent in charge and discharge cycle characteristics using lithium sulfide as an active material.
- an electrode composite material in the method for producing an electrode composite material according to the first to seventh aspects of the present disclosure, after lithium hydrosulfide is generated in a solvent, a predetermined porous carbon material is added, By heating, an electrode composite material in which lithium sulfide is supported on the pores of the porous carbon material can be obtained, so that a desired electrode composite material having excellent characteristics can be reliably produced. .
- FIG. 1A and FIG. 1B are graphs of pore distributions by the MP method of the electrode composite materials of Example 1A-1, Example 1A-2, and Example 1A-3, and the plant-derived porous carbon material, respectively.
- FIG. 5 is a graph of pore distribution by the BJH method.
- 2A and 2B are a graph of pore distribution by the MP method and a pore distribution graph by the BJH method of the electrode composite material of Comparative Example 1A and Ketjen Black, respectively.
- 3A and 3B are graphs showing the results of X-ray diffraction analysis (XRD) of the composite materials for electrodes of Comparative Example 1A and Example 1A-1, respectively.
- XRD X-ray diffraction analysis
- FIG. 4A and 4B are graphs showing the results of X-ray diffraction analysis (XRD) of the electrode composite materials of Example 1A-2 and Example 1A-3, respectively.
- FIG. 5 is a graph showing a charge / discharge test result of the lithium-sulfur secondary battery of Example 2.
- FIG. 6 is a graph showing the charge / discharge test results of the lithium-sulfur secondary batteries of Comparative Example 2A and Comparative Example 2C.
- FIG. 7 is a graph showing a charge / discharge test result of the lithium-sulfur secondary battery of Comparative Example 2B.
- FIG. 8 is a graph showing charge / discharge test results under different conditions for the lithium-sulfur secondary batteries of Example 2 and Comparative Example 2A.
- FIG. 9 is a graph showing the charge / discharge test results of the lithium-sulfur secondary battery of Example 3.
- FIG. 10 is a graph showing the charge / discharge test results of the lithium-sulfur secondary battery of Example 4.
- FIG. 11 is a graph showing the charge / discharge test results of the lithium-sulfur secondary battery of Example 5.
- FIG. 12 is a graph showing the charge / discharge test results of the lithium-sulfur secondary battery of Example 6.
- Example 1 Composite Material for Electrode According to First to Seventh Aspects of the Present Disclosure and Method for Producing the Same
- Example 2 secondary battery according to first to seventh aspects of the present disclosure
- Example 3 Modification of Example 2
- Example 4 Modification of Example 3
- Example 5 another modification of Example 3) 7
- Example 6 another modification of Example 3
- the electrode composite material according to the first aspect of the present disclosure, the method for manufacturing the electrode composite material according to the first aspect of the present disclosure, and the secondary battery according to the first aspect of the present disclosure are collectively named,
- the electrode composite material according to the second aspect of the present disclosure, the method for manufacturing the electrode composite material according to the second aspect of the present disclosure, or the present disclosure may be simply referred to as “first aspect of the present disclosure”.
- the secondary batteries according to the second aspect of the present disclosure may be collectively referred to simply as “second aspect of the present disclosure”
- the method for manufacturing the electrode composite material according to the third aspect and the secondary battery according to the third aspect of the present disclosure may be collectively referred to simply as “third aspect of the present disclosure”.
- the electrode composite material according to the fourth aspect of the disclosure, the method for producing the electrode composite material according to the fourth aspect of the present disclosure, and the two according to the fourth aspect of the present disclosure The batteries may be collectively referred to simply as “fourth aspect of the present disclosure”, and may be referred to as a composite material for an electrode according to the fifth aspect of the present disclosure, and a composite for an electrode according to the fifth aspect of the present disclosure.
- the secondary battery according to the fifth embodiment of the present disclosure may be simply referred to as “fifth embodiment of the present disclosure” or the electrode according to the sixth embodiment of the present disclosure.
- the composite material for use in the present invention, the method for manufacturing the composite material for electrode according to the sixth aspect of the present disclosure, and the secondary battery according to the sixth aspect of the present disclosure are simply referred to as “sixth aspect of the present disclosure”.
- the electrode composite material according to the seventh aspect of the present disclosure, the method for manufacturing the electrode composite material according to the seventh aspect of the present disclosure, and the secondary battery according to the seventh aspect of the present disclosure may be referred to. Collectively, this may be simply referred to as “seventh aspect of the present disclosure”.
- the electrode composite materials according to the first to seventh aspects of the present disclosure are collectively referred to simply as “electrode composite materials of the present disclosure”, and the first to seventh aspects of the present disclosure.
- the secondary batteries according to the embodiments are collectively referred to simply as “secondary batteries of the present disclosure”, and the methods for manufacturing the composite materials for electrodes according to the first to seventh embodiments of the present disclosure are collectively referred to simply as It may be referred to as “a method for producing a composite material for an electrode according to the present disclosure”.
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material may be 30% or less, and includes such a form.
- the BJH after washing the electrode composite material with water is larger than the value BJH 2 obtained by dividing the pore volume BJH 0 of the electrode composite material by the content of the porous carbon material.
- the pore volume BJH 1 obtained by the method can be a large form.
- the pore volume MP PC of the plant-derived porous carbon material by the MP method is 0.1 cm 3 / gram or more, preferably 0.15 cm 3 / g or more, more preferably 0.20 cm 3 / g or more, a pore volume MP 0 by the MP method of electrode composites 0.1 cm 3 / g, preferably less than 0.08cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less, or the pore volume MP 0 by the MP method of the electrode composite material is less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / g or less, more preferably 0.05 cm 3 / g or less, and a pore volume MP 1 by the MP method after washing the electrode composite pore volume MP 0 It can be also large form.
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, and more. Preferably it is 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material may be 30% or less.
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more. More preferably, it is 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 35 ⁇ m or less.
- the porous carbon material is made from a plant-derived material, and the porous carbon material is refined by the MP method.
- pore volume MP PC is 0.1 cm 3 / g or more, preferably 0.15 cm 3 / g or more, more preferably 0.20 cm 3 / g or more, a pore volume MP 0 by the MP method of the electrode composite material
- the form may be less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less.
- the porous carbon material is made from a plant-derived material, and the electrode composite material is refined by the MP method.
- the pore volume MP 0 is less than 0.1 cm 3 / gram, preferably 0.08 cm 3 / gram or less, more preferably 0.05 cm 3 / gram or less, and the fineness of the electrode composite material by MP method after washing with water.
- the pore volume MP 1 can be configured to be larger than the pore volume MP 0 .
- the porous carbon material is made from a plant-derived material, and the plant-derived porous carbon material BJH
- the pore volume BJH PC of less than 100 nm by the method is 0.3 cm 3 / gram or more, preferably 0.4 cm 3 / gram or more, more preferably 0.5 cm 3 / gram or more.
- the pore volume BJH 0 is 0.3 cm 3 / g less than 100 nm, preferably from 0.27 cm 3 / g or less, and more preferably be in the form it is 0.25 cm 3 / g or less.
- the porous carbon material is made from a plant-derived material, and the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is less than 0.3 cm 3 / gram, preferably 0.27 cm 3 / gram.
- the pore volume BJH 1 less than 100 nm by the BJH method after washing the electrode composite material with water is more preferably 0.25 cm 3 / gram or less, and the pore volume BJH 0 is larger. it can.
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material is 30% or less. It can be in a certain form.
- the value BJH obtained by dividing the pore volume BJH 0 of the composite material for electrodes by the content of the porous carbon material can be larger than 2.
- the plant-derived porous carbon material has a silicon content of 5 mass. % Or more plant-derived material, and in this case, after carbonizing at 400 ° C. to 1400 ° C. and then treating with an acid or alkali, the porous carbon material can be obtained. Further, after treatment with acid or alkali, heat treatment can be performed at a temperature exceeding the temperature in carbonization. Further, in these cases, with acid or alkali, It can be set as the structure which removes the silicon component in the plant-derived material after carbonization by a process.
- lithium hydrosulfide is generated in a solvent by adding lithium hydroxide to the solvent and bubbling with hydrogen sulfide gas. It can be set as the form made by doing. Further, the heating temperature after adding the porous carbon material is preferably 150 ° C. to 230 ° C.
- the plant-derived porous carbon material is derived from a plant having a silicon content of 5% by mass or more. It can be set as the form which uses the material as a raw material.
- the pores (holes) are three-dimensionally ordered. And can be arranged in a macroscopic (macroscopic) arrangement of crystal structures. In this case, pores (holes) are macroscopically (macroscopic) on the material surface. It can also be set as the form arrange
- the peak half-value width of the X-ray diffraction intensity of the ⁇ 220 ⁇ plane of lithium sulfide is 0.37 degrees or less. It can be.
- the value of the specific surface area of the porous carbon material according to the nitrogen BET method may be 100 m 2 / gram or more. it can.
- the electrode can be configured to constitute a positive electrode.
- the secondary battery of the present disclosure including the various preferable forms described above including such a form may be a form including a lithium-sulfur secondary battery.
- the negative electrode includes at least one selected from the group consisting of lithium, sodium, lithium alloy, sodium alloy, carbon, silicon, silicon alloy, silicon compound, aluminum, tin, antimony, magnesium, and lithium / sodium inert sulfur composite. More specifically, the negative electrode active material may be included, and more specifically, lithium titanate, lithium metal, sodium metal, lithium aluminum alloy, sodium aluminum alloy, lithium tin alloy, sodium tin alloy, lithium silicon alloy, Metallic materials such as sodium silicon alloy, lithium antimony alloy, sodium antimony alloy, crystalline graphite such as natural graphite, artificial graphite, carbon black, acetylene black, graphite, activated carbon, carbon fiber, coke, soft carbon, hard carbon It can be mentioned wood and non-crystalline known anode material, such carbon material a carbon material or the like.
- the elements constituting the silicon alloy can include tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium, and constitute a silicon compound.
- the element include oxygen and carbon.
- two or more negative electrode active materials may be used in combination.
- Examples of current collectors constituting secondary batteries include nickel, stainless steel, copper, and titanium.
- the current collector can be composed of foil, plate, mesh, expanded metal, punched metal, or the like.
- the negative electrode may be omitted, and the current collector may also serve as the negative electrode.
- Examples of the separator constituting the secondary battery include a glass separator that absorbs and holds an electrolytic solution, a porous sheet made of a polymer, and a nonwoven fabric.
- Examples of the polymer constituting the porous sheet include polyolefins such as polyethylene and polypropylene, multilayer structures of polyolefin, polyimide, and aramid.
- As the nonwoven fabric known materials such as cotton, rayon, acetate, nylon (registered trademark), polyester, polyolefin, polyimide, and aramid can be used alone or in combination.
- an electrolytic solution in which at least a part of glyme and an alkali metal salt forms a complex [specifically, for example, tetraglyme and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI, (CF 3 SO 2) 2 NLi) mixing products ([Li (G4)] [ TFSI])] or, there may be mentioned lithium nitrate (LiNO 3) and the electrolyte solution mixed product is contained in LiTFSI, limited to Not what you want.
- R is any one of an alkyl group having 1 to 9 carbon atoms which may be substituted with fluorine, a phenyl group which may be substituted with a halogen atom, and a cyclohexyl group which may be substituted with a halogen atom.
- x is 1-6.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.
- the phenyl group which may be substituted with a halogen atom includes 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromo And a phenyl group, a 2,4-dibromophenyl group, a 2-iodophenyl group, a 3-iodophenyl group, a 4-iodophenyl group, a 2,4-iodophenyl group, and the like.
- Examples of the cyclohexyl group that may be used include 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, 4-bromocyclohexyl group. 2,4-dibromocyclohexyl group, 2-iodocyclo Hexyl group, 3-iodo cyclohexyl group, 4-iodo-cyclohexyl group, and a 2,4-di-iodo cyclohexyl group.
- M is an alkali metal
- X is Cl, Br, I, BF 4 , PF 6 , CF 3 SO 3 , ClO 4 , CF 3 CO 2 , AsF 6 , SbF.
- the average particle diameter of the porous carbon material (the average particle diameter of the porous carbon material (raw material) before being combined with lithium sulfide) can be measured by a laser diffraction / scattering method.
- the average particle size of the porous carbon material may be measured using a laser diffraction scattering type particle size distribution measuring instrument LMS series manufactured by Seishin Corporation or a SALD series manufactured by Shimadzu Corporation.
- the average particle diameter refers to the median diameter (also referred to as d50). That is, when the porous carbon material is divided into two with a certain particle diameter, it indicates a diameter in which the larger side and the smaller side are equivalent.
- the average particle diameter of the porous carbon material constituting the electrode can be obtained by observation using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the average particle size of the porous carbon material itself can be measured by the following method using the sample obtained by peeling the porous carbon material from the electrode. That is, it is put into N-methyl-2-pyrrolidone (NMP), stirred at 200 ° C. for 3 hours, and then dried at 300 ° C. for 48 hours in a nitrogen atmosphere. Next, 1 gram of sample is added to 300 milliliters of water and stirred well at 24 ° C. while applying ultrasonic waves. This operation is performed a plurality of times as necessary. Thereafter, centrifugation is performed, the liquid phase is removed, water is added and ultrasonic cleaning is performed twice, and then the particle diameter is measured based on the above average particle diameter measuring method.
- NMP N-methyl-2-pyrrolidone
- the following method may be adopted as a method for rinsing the electrode composite material in the second aspect and the fourth aspect of the present disclosure. That is, 1 gram of the electrode composite material and 300 ml of water are placed in a beaker, subjected to ultrasonic cleaning for 1 hour, centrifuged, and the supernatant is discarded. This operation is repeated a total of two times, and then the obtained solid is dried in the atmosphere at 120 ° C. for 12 hours.
- the composite material for an electrode of the present disclosure is a porous carbon material and a composite material containing lithium sulfide supported on the pores of the porous carbon material, and does not include a binder or a current collector, and is in a powder form or a bulk form And so on.
- Analysis of various elements in the porous carbon material can be performed by an energy dispersion method (EDS) using, for example, an energy dispersive X-ray analyzer (for example, JED-2200F manufactured by JEOL Ltd.).
- EDS energy dispersion method
- the measurement conditions may be, for example, a scanning voltage of 15 kV and an irradiation current of 10 ⁇ A.
- the plant-derived porous carbon material can be obtained by carbonizing a plant-derived material at 400 ° C. to 1400 ° C. and then treating with an acid or alkali.
- a method for producing a plant-derived porous carbon material is referred to as “a method for producing a plant-derived porous carbon material”.
- a material obtained by carbonizing a plant-derived material at 400 ° C. to 1400 ° C., before being treated with an acid or alkali is referred to as “porous carbon material precursor”. Or called “carbonaceous material”.
- the content of silicon (Si) in the porous carbon material obtained by treatment with acid or alkali is less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less. It is desirable to be. In addition, it is preferable that the content rate of the silicon (Si) of a raw material (plant-derived material before carbonization) is 5 mass% or more as mentioned above.
- a step of performing an activation treatment can be included, and after the activation treatment, the treatment with acid or alkali is performed. Also good.
- carbonization is performed.
- the plant-derived material may be heat-treated at a temperature lower than the temperature of (eg, 400 ° C. to 700 ° C.) in a state where oxygen is blocked. Such heat treatment is called “preliminary carbonization treatment”. As a result, the tar component that will be generated in the carbonization process can be extracted.
- the state in which oxygen is shut off is, for example, an inert gas atmosphere such as nitrogen gas or argon gas, or a vacuum atmosphere, or a plant-derived material is in a kind of steamed state. This can be achieved.
- an inert gas atmosphere such as nitrogen gas or argon gas, or a vacuum atmosphere
- a plant-derived material is in a kind of steamed state. This can be achieved.
- carbonization is also possible.
- the plant-derived material may be immersed in alcohol (for example, methyl alcohol, ethyl alcohol, isopropyl alcohol).
- a preliminary carbonization process in the manufacturing method of a plant-derived porous carbon material, you may perform a preliminary carbonization process after that.
- a material that is preferably subjected to a preliminary carbonization treatment in an inert gas for example, a plant that generates a large amount of pyroligneous acid liquid (tar and light oil) can be exemplified.
- examples of materials that are preferably pretreated with alcohol include seaweeds that contain a large amount of iodine and various minerals.
- a plant-derived material is carbonized at 400 ° C. to 1400 ° C.
- carbonization is generally referred to as an organic substance (in the present disclosure).
- a plant-derived material or a raw material for producing a porous carbon material having an inverse opal structure is heat-treated and converted into a carbonaceous material (see, for example, JIS M0104-1984). ).
- an atmosphere for carbonization an atmosphere in which oxygen is shut off can be mentioned.
- a vacuum atmosphere an inert gas atmosphere such as nitrogen gas or argon gas, plant-derived material, or inverse opal
- the atmosphere which makes the raw material for manufacturing the porous carbon material which has a structure a kind of steamed state can be mentioned.
- the rate of temperature rise until reaching the carbonization temperature is not limited, but in such an atmosphere, 1 ° C / min or more, preferably 3 ° C / min or more, more preferably 5 ° C / min or more. be able to.
- the upper limit of the carbonization time can be 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto.
- the lower limit of the carbonization time may be a time during which the plant-derived material is reliably carbonized.
- the plant-derived material may be pulverized as desired to obtain a desired particle size, or may be classified. Plant-derived materials may be washed in advance. Alternatively, the obtained porous carbon material precursor, porous carbon material intermediate, and porous carbon material may be pulverized as desired to obtain a desired particle size or classified. Alternatively, the porous carbon material intermediate or the porous carbon material after the activation treatment may be pulverized as desired to obtain a desired particle size or may be classified.
- heat treatment may be performed at a temperature exceeding the temperature in carbonization after treatment with acid or alkali.
- a kind of shrinkage occurs in the porous carbon material.
- a carbonaceous material can be provided.
- an atmosphere in which oxygen is shut off can be mentioned, and specifically, an atmosphere in which a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, and a porous carbon material intermediate is in a kind of steamed state can be mentioned.
- the rate of temperature rise until reaching the temperature of the heat treatment is not limited, but in such an atmosphere, it is 1 ° C / min or more, preferably 3 ° C / min or more, more preferably 5 ° C / min or more. Can be mentioned.
- the difference between the temperature for carbonization and the temperature for heat treatment may be determined as appropriate by conducting various tests.
- the upper limit of the heat treatment time may be 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto.
- the lower limit of the heat treatment time may be a time that can impart desired characteristics to the porous carbon material.
- There is no limitation on the type, configuration, and structure of the furnace used for the heat treatment and a continuous furnace or a batch furnace (batch furnace) can be used.
- micropores (described later) having a pore diameter smaller than 2 nm can be increased.
- the activation treatment method include a gas activation method and a chemical activation method.
- the gas activation method uses oxygen, water vapor, carbon dioxide gas, air or the like as an activator, and in such a gas atmosphere, at 700 ° C. to 1400 ° C., preferably at 700 ° C. to 1000 ° C.
- the porous carbon material intermediate or the porous carbon material is heated in the porous carbon material intermediate or the porous carbon material by heating the porous carbon material intermediate or the porous carbon material for several tens of minutes to several hours at 800 ° C. to 1000 ° C. It is a method to develop a fine structure by volatile components and carbon molecules. In addition, what is necessary is just to select the heating temperature in an activation process suitably based on the kind of plant-derived material, the kind of gas, a density
- the chemical activation method is activated with zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc., instead of oxygen and water vapor used in the gas activation method, washed with hydrochloric acid, alkaline In this method, the pH is adjusted with an aqueous solution and dried.
- the silicon component in the plant-derived material after carbonization is preferably removed by treatment with an acid or an alkali.
- examples of the silicon component include silicon oxides such as silicon dioxide, silicon oxide, and silicon oxide salts.
- the porous carbon material which has a high specific surface area can be obtained by removing the silicon component in the plant-derived material after carbonization.
- the silicon component in the plant-derived material after carbonization may be removed based on a dry etching method.
- a plant-derived material containing silicon (Si) is used as a raw material, but when converted into a porous carbon material precursor or a carbonaceous material, a plant-derived material is used.
- a high temperature for example, 400 ° C. to 1400 ° C.
- silicon contained in the plant-derived material does not become silicon carbide (SiC) but silicon dioxide (SiO x ).
- silicon components (silicon oxide) such as silicon oxide and silicon oxide salt.
- a high temperature for example, 400 ° C to 1400 ° C
- the porous carbon material is an environmentally compatible material derived from a natural product, and its microstructure is obtained by treating a silicon component (silicon oxide) previously contained in a raw material that is a plant-derived material with an acid or alkali, It is obtained by removing. Therefore, the pore arrangement maintains the bioregularity of the plant.
- the porous carbon material can be made from plant-derived materials.
- plant-derived materials rice husks and straws such as rice (rice), barley, wheat, rye, rice husk and millet, rice beans, tea leaves (for example, leaves such as green tea and tea), Citrus such as sugar cane (more specifically, sugar cane squeezed straw), corn (more specifically, corn core), fruit peel (eg orange peel, grapefruit peel, mandarin peel) But also, but not limited to, vascular plants, fern plants, moss plants, algae And seaweed.
- these materials may be used independently as a raw material, and multiple types may be mixed and used.
- the shape and form of the plant-derived material are not particularly limited, and may be, for example, rice husk or straw itself, or may be a dried product.
- what processed various processes such as a fermentation process, a roasting process, an extraction process, can also be used in food-drinks processing, such as beer and western liquor.
- These processed straws and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, liquor manufacturers, food companies, and food processing companies.
- the porous carbon material has many pores.
- the pores include “mesopores” having a pore diameter of 2 nm to 50 nm, “micropores” having a pore diameter smaller than 2 nm, and “macropores” having a pore diameter exceeding 50 nm.
- the mesopores include, for example, many pores having a pore diameter of 20 nm or less, and particularly many pores having a pore diameter of 10 nm or less. For micropores of 2 nm or less, the greater the pore volume, the better the performance.
- the nitrogen BET method is an adsorption isotherm measured by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (here, a porous carbon material), and the measured data is converted into a BET equation represented by equation (1). Based on this method, the specific surface area, pore volume, and the like can be calculated. Specifically, when calculating the value of the specific surface area by the nitrogen BET method, first, an adsorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on the porous carbon material.
- the specific surface area a sBET is calculated from V m based on the formula (3) (see BELSORP-mini and BELSORP analysis software manuals, pages 62 to 66, manufactured by Nippon Bell Co., Ltd.).
- This nitrogen BET method is a measurement method according to JIS R 1626-1996 “Measurement method of specific surface area of fine ceramic powder by gas adsorption BET method”.
- V a (V m ⁇ C ⁇ p) / [(p 0 ⁇ p) ⁇ 1+ (C ⁇ 1) (p / p 0 ) ⁇ ] (1)
- [P / ⁇ V a (p 0 ⁇ p) ⁇ ] [(C ⁇ 1) / (C ⁇ V m )] (p / p 0 ) + [1 / (C ⁇ V m )] (1 ′)
- V m 1 / (s + i) (2-1)
- C (s / i) +1 (2-2)
- a sBET (V m ⁇ L ⁇ ⁇ ) / 22414 (3)
- V a Adsorption amount
- V m Adsorption amount of monolayer
- p Nitrogen equilibrium pressure
- p 0 Nitrogen saturated vapor pressure
- L Avogadro number
- ⁇ Nitrogen adsorption cross section.
- the pore volume V p is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated to obtain the adsorption amount V at the relative pressure set by the pore volume calculation relative pressure. From this adsorption amount V, the pore volume V p can be calculated based on the formula (4) (see BELSORP-mini and BELSORP analysis software manuals, pages 62 to 65, manufactured by Bell Japan Co., Ltd.). Hereinafter, the pore volume based on the nitrogen BET method may be simply referred to as “pore volume”.
- V p (V / 22414) ⁇ (M g / ⁇ g ) (4)
- V Adsorption amount at relative pressure
- M g Nitrogen molecular weight
- ⁇ g Nitrogen density.
- the pore diameter of the mesopores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the BJH method.
- the BJH method is widely used as a pore distribution analysis method. When pore distribution analysis is performed based on the BJH method, first, desorption isotherms are obtained by adsorbing and desorbing nitrogen as adsorbed molecules on the porous carbon material.
- the thickness of the adsorption layer when the adsorption molecules are attached and detached in stages from the state where the pores are filled with the adsorption molecules (for example, nitrogen), and the pores generated at that time obtains an inner diameter (twice the core radius) of calculating the pore radius r p based on equation (5) to calculate the pore volume based on the equation (6).
- the pore radius and the pore volume variation rate relative to the pore diameter (2r p) from the pore volume (dV p / dr p) pore distribution curve is obtained by plotting the (Nippon Bel Co. Ltd. BELSORP-mini And BELSORP analysis software manual, pages 85-88).
- V pn R n ⁇ dV n -R n ⁇ dt n ⁇ c ⁇ ⁇ A pj (6)
- R n r pn 2 / (r kn ⁇ 1 + dt n ) 2 (7)
- V pn pore volume dV n when the nth attachment / detachment of nitrogen occurs: change amount dt n at that time: change in the thickness t n of the adsorption layer when the nth attachment / detachment of nitrogen occurs
- Amount r kn Core radius c at that time c: Fixed value r pn : Pore radius when the nth attachment / detachment of nitrogen occurs.
- the pore diameter of the micropores can be calculated as the pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the MP method.
- an adsorption isotherm is obtained by adsorbing nitrogen to a porous carbon material.
- this adsorption isotherm is converted into a pore volume with respect to the thickness t of the adsorption layer (t plotted).
- a pore distribution curve can be obtained based on the curvature of this plot (the amount of change in the pore volume with respect to the amount of change in the adsorption layer thickness t) (BELSORP-mini and BELSORP analysis software manuals manufactured by Bell Japan Co., Ltd.). , Pages 72-73, page 82).
- the porous carbon material precursor is treated with an acid or alkali.
- Specific treatment methods include, for example, a method of immersing the porous carbon material precursor in an acid or alkali aqueous solution, or a porous carbon material precursor and an acid. Or the method of making it react with an alkali by a gaseous phase can be mentioned.
- the acid include fluorine compounds exhibiting acidity such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride.
- the amount of fluorine element is 4 times the amount of silicon element in the silicon component contained in the porous carbon material precursor, and the concentration of the fluorine compound aqueous solution is preferably 10% by mass or more.
- the silicon component for example, silicon dioxide
- the silicon dioxide is mixed with hydrofluoric acid as shown in chemical formula (A) or chemical formula (B). It reacts and is removed as hexafluorosilicic acid (H 2 SiF 6 ) or silicon tetrafluoride (SiF 4 ) to obtain a porous carbon material intermediate. Thereafter, washing and drying may be performed.
- sodium hydroxide can be mentioned as an alkali, for example.
- an alkaline aqueous solution the pH of the aqueous solution may be 11 or more.
- the silicon component for example, silicon dioxide
- the silicon dioxide is heated as shown in the chemical formula (C) by heating the aqueous sodium hydroxide solution. It reacts and is removed as sodium silicate (Na 2 SiO 3 ) to obtain a porous carbon material intermediate.
- the sodium hydroxide solid when processing by reacting sodium hydroxide in the gas phase, the sodium hydroxide solid is heated to react as shown in the chemical formula (C) and is removed as sodium silicate (Na 2 SiO 3 ). A porous carbon material intermediate can be obtained. Thereafter, washing and drying may be performed.
- the pores (holes) have a three-dimensional regularity and are arranged in an arrangement that forms a macroscopic (macro) crystal structure. It can be in the form.
- the arrangement of the pores (holes) is not particularly limited as long as the arrangement state corresponds macroscopically to the crystal structure.
- a crystal structure can include a single crystal structure, specifically, The face-centered cubic structure, the body-centered cubic structure, the simple cubic structure, and the like can be exemplified.
- the face-centered cubic structure that is, the close-packed structure increases the surface area of the porous carbon material.
- the pores (holes) are preferably arranged macroscopically in a face-centered cubic structure.
- the pores (holes) are macroscopically arranged in a face-centered cubic structure ( Arranged in an arrangement corresponding to the (111) plane orientation (specifically, a state in which pores (holes) are located at arrangement positions of atoms located on the (111) plane in the face-centered cubic structure) It is preferable that
- the reflection spectrum indicates absorption at substantially a single wavelength on the surface of the porous carbon material, and the entire porous carbon material is monochromatic. That is, for example, when a porous carbon material is placed in a dark place, irradiated with white light at a viewing angle of 0 °, and the wavelength of the reflected light is measured, the obtained reflection spectrum shows pores (holes).
- unimodal absorption is shown at a specific wavelength corresponding to the diameter, it can be said that pores (holes) are almost regularly arranged at predetermined intervals within the material. Specifically, for example, if unimodal absorption is shown at a wavelength of 450 nm, pores (holes) having a diameter of about 280 nm are arranged almost regularly.
- the pores (holes) can be continuously arranged. Further, the shape of the pores (holes) is not particularly limited. For example, as described later, the shape is determined to some extent by the shape of the colloidal crystal used in the production of the porous carbon material. Considering the mechanical strength of the material and the shape controllability of the colloidal crystal at the nanoscale, it is preferably spherical or substantially spherical.
- a porous carbon material having an inverse opal structure is, for example, a polymerizable monomer in a state where a nanoscale colloidal crystal is immersed in a solution of a polymerizable monomer or a solution of a composition containing the polymerizable monomer.
- the colloidal crystal body refers to a colloidal particle aggregated and in an arrangement state corresponding to a crystal structure, and has a three-dimensional regularity. That is, it means a state in which colloidal particles are located at the arrangement positions of atoms in the crystal.
- the pores (voids) correspond to voids created by the individual colloidal particles removed.
- the colloidal crystal body functions as a kind of template.
- the pores (holes) may be voids closed with a carbon material as long as they have the above-described three-dimensional regularity. However, the pores that are continuously arranged expand the surface area. This is preferable. Since the arrangement of the pores (holes) is determined by the colloidal particle packing arrangement in the colloidal crystal, the regularity of the arrangement of the pores (holes) described above includes the regularity of the arrangement of colloidal particles and the arrangement state. Is reflected. When pores (holes) of different sizes are included, it is possible to obtain an arrangement pattern of pores (holes) having more complicated regularity.
- the porous carbon material having an inverse opal structure is, for example, (A) A nanoscale colloidal crystal (an aggregate of colloidal particles such as inorganic particles, inorganic material particles, and inorganic compound particles serving as a template) of a polymerizable monomer solution or a composition containing a polymerizable monomer A step of obtaining a blended composition by immersing in a solution; (B) a step of polymerizing the polymerizable monomer in the blended composition to obtain a composite of a polymer material and a colloidal crystal (hereinafter sometimes referred to as “colloidal crystal composite”); (C) carbonizing the polymer material in the colloidal crystal composite at 800 ° C. to 3000 ° C.
- a nanoscale colloidal crystal an aggregate of colloidal particles such as inorganic particles, inorganic material particles, and inorganic compound particles serving as a template
- a step of obtaining a blended composition by immersing in a solution A step of obtaining a blended composition by immersing
- a colloidal crystal complex (hereinafter sometimes referred to as “carbonized / colloidal crystal complex”) in which the polymer material is carbonized is immersed in a liquid capable of dissolving the colloidal crystal.
- a step of dissolving and removing the colloidal crystal to obtain a porous carbon material made of a carbonized polymer material It can manufacture with the manufacturing method of the porous carbon material containing this.
- the rate of temperature rise until reaching the carbonization temperature is not particularly limited as long as it is in the range of the rate of temperature rise at which the colloidal crystal does not collapse due to local heating.
- the porous carbon material obtained using a colloidal crystal has a three-dimensional regularity and continuity macroscopically in the arrangement
- the shape of the colloidal particles constituting the colloidal crystal is preferably a true sphere or a substantially spherical shape.
- the colloidal particles are preferably composed of inorganic compound particles that are dissolved in, for example, a fluorine compound solution such as hydrofluoric acid, an alkaline solution, or an acidic solution.
- the inorganic compound include carbonates of alkaline earth metals such as calcium carbonate, barium carbonate, and magnesium carbonate; silicates of alkaline earth metals such as calcium silicate, barium silicate, and magnesium silicate; calcium phosphate , Alkaline earth metal phosphates such as barium phosphate and magnesium phosphate; metal oxides such as silica, titanium oxide, iron oxide, cobalt oxide, zinc oxide, nickel oxide, manganese oxide, aluminum oxide; iron hydroxide Metal hydroxides such as nickel hydroxide, aluminum hydroxide, calcium hydroxide and chromium hydroxide; metal silicates such as zinc silicate and aluminum silicate; metal carbonates such as zinc carbonate and basic copper carbonate Can be illustrated. Examples of natural products include shirasu balloon and pearlite.
- the starting material of a porous carbon material having an inverse opal structure is any polymer that can be converted into a carbon material by carbonization is not particularly limited. Specifically, a furfuryl alcohol resin, a phenol / aldehyde resin, a styrene / divinylbenzene copolymer, and a furfuryl alcohol / phenol resin can be exemplified.
- a starting material which can obtain glassy (amorphous) non-graphitizable carbon, graphitizable carbon or graphite (graphitized carbon) is used as the porous carbon material. It is more preferable.
- the concentration of the polymerizable monomer is 0.1 mass% to 99.9 mass. %, And if necessary, 0.001% by mass to 50% by mass of a crosslinking agent is added.
- the reaction conditions such as the initiator concentration and the polymerization method may be selected as appropriate for the polymerizable monomer.
- the polymerizable monomer, the catalyst, the polymerization initiator, the crosslinking agent, and the like are substituted with nitrogen.
- a solution may be prepared by dissolving in an organic solvent, and the colloidal crystal and this solution may be mixed.
- the polymerization may be carried out by heating to an appropriate temperature or irradiating with light.
- the polymer material is based on known solutions such as radical polymerization, acid polycondensation, etc., bulk, emulsion, reverse phase suspension polymerization, etc., for example, polymerization temperature 0 to 100 ° C., polymerization time 10 minutes to 48 hours. Can be obtained at
- a colloidal crystal is formed from colloidal particles.
- a method for forming this colloidal crystal A method of dropping a solution containing colloidal particles (hereinafter referred to as “colloid solution”) onto a substrate and distilling off the solvent contained in the dropped colloid solution can be given.
- the solvent can be distilled off at room temperature, it is preferably carried out by heating to the same temperature as the boiling point of the solvent used or a temperature higher than the boiling point.
- substrate may be heated and a solvent may be distilled off, or a colloidal solution may be dripped on a preheated board
- the substrate may be rotated when or after the colloidal solution is dropped.
- the film thickness and area of the resulting composition can be controlled. In particular, it is possible to easily increase the area while maintaining the three-dimensional regularity.
- a colloidal solution having a solid content concentration of 10% by mass or more can be used, a compound composition having a considerable thickness can be formed on the substrate by one drop, and dripping and distillation.
- the thickness of the blended composition can be controlled.
- the obtained colloidal crystal can be made into a colloidal crystal having a single crystal structure.
- (B) A method in which the colloidal solution is suction filtered to remove the solvent and deposit the blended composition.
- the composition can be deposited on the filter paper or the filter cloth on the suction funnel by sucking and removing the solvent from the colloidal solution by vacuum suction using a suction funnel or the like.
- the obtained colloidal crystal can have a single crystal structure.
- the concentration of the colloidal solution used for suction filtration can be appropriately selected based on the volume of the blended composition to be obtained in a single operation.
- the method of sucking the solvent is not particularly limited, and examples thereof include a method of sucking with aspirator or pump.
- the speed of suction is not particularly limited. For example, the degree of decompression is about 40 mmHg, and the liquid level of the colloidal solution in the suction funnel may be lowered at a constant speed.
- (C) As a method of forming a colloidal crystal, (C) The method of immersing a board
- a blended composition having a desired area and volume can be obtained by adjusting the concentration of the colloidal solution to be used and repeating the operation.
- the speed at which the substrate is pulled up is not particularly limited. However, since the colloidal crystal grows at the interface between the colloidal solution and the atmosphere, it is preferable to pull it up at a slow speed. Further, the speed of evaporating the solvent is not particularly limited, but is preferably slower for the same reason. For example, by using a monodispersed colloidal solution, the resulting colloidal crystal can have a single crystal structure.
- (D) A method of applying an electric field to the colloidal solution and then removing the solvent.
- (E) A method of removing the solvent after allowing the dispersed colloidal solution to stand and allowing the colloidal particles to settle naturally and depositing.
- the properties of the surface of the substrate to be used are not particularly limited, but it is preferable to use a substrate having a smooth surface.
- a solution such as an acidic solution, an alkaline solution, or an acidic solution of a fluorine compound (hereinafter referred to as “colloid for convenience.
- a crystal removal solution a solution such as an acidic solution, an alkaline solution, or an acidic solution of a fluorine compound
- a crystal removal solution a solution such as an acidic solution, an alkaline solution, or an acidic solution of a fluorine compound
- the colloidal crystal is silica, shirasu balloon, or silicate, an aqueous solution of hydrofluoric acid, an acidic solution such as ammonium fluoride, calcium fluoride, or sodium fluoride, or an alkaline solution such as sodium hydroxide. It is only necessary to immerse the carbonized / colloidal crystal composite in the colloidal crystal removal solution.
- the colloidal crystal removal solution may be a fluorine element in an amount of 4 times or more with respect to the silicon element of the carbonized / colloidal crystal composite, but the concentration is preferably 10% by mass or more.
- the alkaline solution is not particularly limited as long as it has a pH of 11 or more.
- the colloidal crystal is composed of a metal oxide or metal hydroxide, it is only necessary to immerse the carbonized / colloidal crystal complex in a colloidal crystal removal solution of an acidic solution such as hydrochloric acid.
- the acidic solution is not particularly limited as long as the pH is 3 or less.
- the colloidal crystal body may be dissolved and removed before carbonization of the polymer material.
- an aprotic polar organic compound for example, an amide compound, a lactam compound, a urea compound, an organic sulfur compound, a cyclic organic phosphorus compound, etc.
- aprotic polar organic compound for example, an amide compound, a lactam compound, a urea compound, an organic sulfur compound, a cyclic organic phosphorus compound, etc.
- amide compounds for example, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N— Examples include dipropylacetamide, N, N-dimethylbenzoic acid amide, and the like.
- lactam compound examples include N-cyclohexylcaprolactam, N-cyclohexylcaprolactam, N-isopropylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-normalpropylcaprolactam, N-normalbutylcaprolactam, N-cyclohexylcaprolactam and the like.
- Alkylcaprolactams N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-normalpropyl-2-pyrrolidone, N- N-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-34, 5-trimethyl-2- Pylori N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethyl-2-piperidone, etc.
- Examples of the urea compound include tetramethylurea, N, N′-dimethylethyleneurea, N, N′-dimethylpropyleneurea, and the like.
- examples of the organic sulfur compound include dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfone, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, and the like.
- Examples of the formula organophosphorus compound include 1-methyl-1-oxophosphorane, 1-normalpropyl-1-oxophosphorane, 1-phenyl-1-oxophosphorane and the like.
- Each of these various aprotic polar organic compounds may be used alone or in combination of two or more, and further mixed with other solvent components to be used as an aprotic organic solvent. It can.
- aprotic organic solvents preferred are N-alkylcaprolactam and N-alkylpyrrolidone, and particularly preferred is N-methyl-2-pyrrolidone (NMP).
- the temperature of the solvent to which lithium hydroxide is added during bubbling with hydrogen sulfide gas is 0 ° C to 200 ° C, preferably 90 ° C. Up to 150 ° C. can be exemplified, and the bubbling time can be exemplified as 0.1 to 10 hours. After bubbling with hydrogen sulfide gas, the porous carbon material is added and the entire system is heated, so that lithium sulfide supported on the pores of the porous carbon material can be obtained. As described above, 150 ° C. to 230 ° C., preferably 170 ° C. to 230 ° C. can be exemplified, and the heating time can be exemplified as 0.1 hour to 1 hour. Examples of the mass of the porous carbon material to be added per gram of lithium hydroxide include 0.01 to 3 grams, preferably 0.1 to 1.5 grams.
- the pore volume of the porous carbon material after the electrode is manufactured can be measured by the following method. That is, the secondary battery is disassembled, the electrode is taken out, and the porous carbon material is peeled off from the electrode. Then, the porous carbon material was put into N-methyl-2-pyrrolidone (NMP), stirred at 200 ° C. for 24 hours, filtered, and the solid phase was reduced under reduced pressure at 120 ° C. for 12 hours. dry. Next, the sample is put into water, ultrasonic waves are applied for 3 hours, and the sample is dried. Then, various measurements may be performed using this sample.
- NMP N-methyl-2-pyrrolidone
- the secondary battery of the present disclosure can be incorporated into, for example, an electronic device.
- the electronic device may be basically any device, and includes both a portable type and a stationary type. Specific examples of the electronic device include a mobile phone, a mobile device, a robot, a personal computer, a game device, a camera-integrated VTR (video tape recorder), an in-vehicle device, various home electric products, an industrial product, and the like.
- the shape, configuration, structure, and form of the secondary battery are essentially arbitrary.
- Example 1 relates to an electrode composite material and a method for manufacturing the same according to the first to seventh aspects of the present disclosure.
- the electrode composite material of Example 1 includes a plant-derived porous carbon material, and lithium sulfide (Li x S, provided that 0 ⁇ x ⁇ 0) supported in pores of the porous carbon material. 2.
- x 2) is included.
- the pore volume MP PC of the porous carbon material by the MP method is 0.1 cm 3 / gram or more, and the pore volume MP 0 of the composite material for an electrode by the MP method is less than 0.1 cm 3 / gram ( The composite material for electrodes according to the first aspect of the present disclosure).
- the pore volume MP 0 by the MP method of the electrode composite material is less than 0.1 cm 3 / gram, and the pore volume MP 1 by the MP method after washing the electrode composite material from the pore volume MP 0 (The composite material for an electrode according to the second aspect of the present disclosure).
- the pore volume BJH PC of less than 100 nm by the BJH method of the porous carbon material is 0.3 cm 3 / gram or more, and the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is 0.3 cm. Less than 3 / gram (the composite material for an electrode according to the third aspect of the present disclosure).
- the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is less than 0.3 cm 3 / gram
- the pore volume BJH 1 of less than 100 nm by the BJH method after washing the electrode composite material is It is larger than the pore volume BJH 0 (the composite material for an electrode according to the fourth aspect of the present disclosure).
- a porous carbon material having an inverse opal structure, and Lithium sulfide supported in the pores of the porous carbon material A composite material for an electrode comprising: The pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is 20% or less of the pore volume BJH PC of less than 100 nm by the BJH method of the porous carbon material.
- the electrode composite material of Example 1 will be described according to the sixth aspect of the present disclosure.
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- Example 1 the electrode composite material of Example 1 will be described according to the seventh aspect of the present disclosure.
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material is 30% or less.
- the pore volume BJH 0 of the electrode composite material is divided by the content of the porous carbon material.
- the pore volume BJH 1 by the BJH method after the electrode composite material is washed with water can be made larger than the measured value BJH 2 .
- the pore volume MP PC of the plant-derived porous carbon material by the MP method is 0.1 cm 3 / gram.
- the pore volume MP 0 of the composite material for electrodes by the MP method may be less than 0.1 cm 3 / gram, or the pore volume MP by the MP method of the composite material for electrodes. 0 is less than 0.1 cm 3 / gram, and the pore volume MP 1 by the MP method after the electrode composite material is washed with water may be larger than the pore volume MP 0 .
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more. More preferably, it is 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material is 30% or less. be able to.
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0. 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the porous carbon material is made from a plant-derived material, and the MP method of the porous carbon material
- the pore volume MP PC due to the electrode is 0.1 cm 3 / gram or more, and the pore volume MP 0 according to the MP method of the electrode composite material may be less than 0.1 cm 3 / gram.
- the porous carbon material is a plant-derived material as a raw material.
- the pore volume MP 0 by the MP method of the electrode composite material is less than 0.1 cm 3 / gram, and the pore volume MP 1 by the MP method after washing the electrode composite material is the pore volume MP A form larger than 0 can be adopted.
- the porous carbon material is a plant-derived material as a raw material.
- the pore volume BJH PC of less than 100 nm by the BJH method of the plant-derived porous carbon material is 0.3 cm 3 / gram or more
- the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is It can be in the form of less than 0.3 cm 3 / gram.
- the porous carbon material is made from a plant-derived material
- the pore volume BJH 0 of less than 100 nm by the BJH method of the electrode composite material is less than 0.3 cm 3 / gram
- the electrode composite material The pore volume BJH 1 of less than 100 nm according to the BJH method after washing with water can be made larger than the pore volume BJH 0 .
- the ratio of the pore volume BJH 100 of 100 nm or more by the BJH method of the electrode composite material is 30% It can be set as the following forms.
- the pore volume BJH 0 of the composite material for an electrode is set as follows.
- the pore volume BJH 1 by the BJH method of the electrode composite material after washing with water can be made larger than the value BJH 2 divided by the content of the porous carbon material.
- the specific surface area value (specific surface area value) of the porous carbon material according to the nitrogen BET method is 100 m 2 / gram or more.
- the plant-derived porous carbon material uses a plant-derived material having a silicon content of 5% by mass or more as a raw material (Example 1A).
- the pores (holes) have a three-dimensional regularity and are arranged in an arrangement that forms a macroscopic (macro) crystal structure, Furthermore, the pores (holes) are arranged macroscopically on the material surface in a (1,1,1) plane orientation of a face-centered cubic lattice (Example 1B).
- the characteristics of the first aspect and the third aspect of the present disclosure are combined, or the second aspect and the fourth aspect of the present disclosure are combined. Combined with the characteristics of Furthermore, these are combined with the characteristics in the fifth to seventh aspects of the present disclosure.
- Example 1 the electrode composite material was manufactured by the method described below. That is, first, lithium hydrosulfide (LiSH) is generated in a solvent. Specifically, lithium hydroxide was added to the solvent and bubbled with hydrogen sulfide gas. More specifically, 4.5 g of lithium hydroxide was added to 300 ml of N-methyl-2-pyrrolidone (NMP) as a solvent, and the whole was heated to 90 ° C. And in this state, it bubbled with hydrogen sulfide. As a result, lithium hydrosulfide (LiSH) was generated by the reaction of lithium hydroxide and hydrogen sulfide, and no solid was present in the solvent.
- LiSH lithium hydrosulfide
- a composite material for an electrode of Example 1A-2 was obtained by performing the same operation except that the same plant-derived porous carbon material (however, the addition amount was 2.25 g) was used. Furthermore, a composite material for an electrode of Example 1A-3 was obtained by performing the same operation except that the same plant-derived porous carbon material (however, the addition amount was 1.5 g) was used.
- Example 1B it replaced with the plant-derived porous carbon material, and performed Example 1B by performing the same operation except having used the porous carbon material (however, the addition amount is 1.5 grams) which has an inverse opal structure.
- -1 electrode composite material was obtained.
- a composite material for an electrode of Example 1B-2 was obtained by carrying out the same operation except that a porous carbon material having the same inverse opal structure (however, the addition amount was 2.25 grams) was used. It was.
- the plant-derived porous carbon material used in Example 1A-1, Example 1A-2, and Example 1A-3 was produced by the following method. That is, porous carbon is obtained by carbonizing (baking) carbon dioxide at 800 ° C. in a nitrogen gas atmosphere using rice husk, which is a plant-derived material having a silicon (Si) content of 5% by mass or more. A material precursor was obtained. Next, the porous carbon material precursor thus obtained is immersed in a 20% by mass aqueous sodium hydroxide solution at 80 ° C overnight to perform an alkali treatment to remove the silicon component in the plant-derived material after carbonization. Then, the porous carbon material intermediate was obtained by washing with water and ethyl alcohol until pH 7 and drying.
- the porous carbon material intermediate was heated to 900 ° C. in a nitrogen gas atmosphere and subjected to activation treatment with water vapor.
- heat treatment was performed at a temperature exceeding the temperature in carbonization (specifically, 800 ° C.). More specifically, in order to perform the heat treatment, the temperature was raised to 1400 ° C. at 5 ° C./min in a nitrogen gas atmosphere, and then held at 1400 ° C. for 1 hour.
- the material obtained in this manner was pulverized to 4 ⁇ m with a jet mill to obtain the plant-derived porous carbon material (raw material 1A) used in Example 1A-1, Example 1A-2, and Example 1A-3. I was able to get it.
- porous carbon material having an inverse opal structure used in Examples 1B-1 to 1B-2 was produced by the following method.
- monodispersed silica spherical fine particles (trade name: Seahoster KE) manufactured by Nippon Shokubai Co., Ltd. or silica spherical fine particles (trade name: Snowtex) manufactured by Nissan Chemical Industries, Ltd.
- a monodispersed silica colloid suspension aqueous solution consisting of an aqueous solution having a concentration of 3% to 40% by weight was prepared.
- the colloidal particle diameter is 50 nm.
- a monodispersed silica colloid suspension aqueous solution was put into an SPC filter holder (manufactured by Shibata Kagaku Co., Ltd.) having a diameter of 30 mm with a filter cloth and sucked under reduced pressure using an aspirator.
- the degree of vacuum was about 40 mmHg.
- a colloidal crystal composed of a silica colloid layer could be obtained on the filter cloth.
- a polycarbonate membrane filter manufactured by Whatman was used as the filter cloth. The filter cloth was peeled off and sintered in air at 1000 ° C. for 2 hours to obtain a thin film of colloidal crystal (a thin-film silica colloid single crystal).
- the compounding composition was obtained by immersing in the solution of the composition containing a polymerizable monomer. Specifically, a thin colloidal crystal is placed on a polytetrafluoroethylene sheet, and 10.0 grams of furfuryl alcohol and 0.05 grams of oxalic acid hexahydrate (both are Wako Pure Chemical Industries, Ltd.) The solution made of the mixture was dropped onto the colloidal crystal. Then, the excess solution overflowing from the colloidal crystal was gently wiped off. Next, it was put in a desiccator and evacuated several times to ensure that the colloidal crystal was impregnated with the solution. Thus, a blended composition could be obtained.
- the polymerizable monomer in the blended composition was polymerized to obtain a colloidal crystal composite, which is a composite of a polymer material (polymer resin) and a colloidal crystal. Specifically, the polymerization was carried out in air at 80 ° C. for 48 hours.
- the polymer material in the colloidal crystal composite was carbonized at 800 ° C. to 3000 ° C. under an inert gas atmosphere. Specifically, the obtained colloidal crystal composite is heated in a tubular furnace in an argon atmosphere or a nitrogen gas atmosphere at 200 ° C. for 1 hour to remove moisture and re-harden the polymer material. went. Next, the temperature is increased at 5 ° C./min in an argon atmosphere, carbonized at a constant temperature of 800 ° C. to 1400 ° C. for 1 hour, and then cooled to obtain a silica / carbon composite. A carbonized and colloidal crystal composite was obtained.
- the carbonized colloidal crystal composite was immersed in a liquid capable of dissolving the colloidal crystal to dissolve and remove the colloidal crystal, and a porous carbon material made of a carbonized polymer material was obtained. .
- the colloidal crystal was dissolved in a 46% hydrofluoric acid aqueous solution at room temperature for 24 hours. Thereafter, washing with pure water and ethyl alcohol was repeated until neutrality to obtain a porous carbon material having an inverse opal structure. If it is necessary to further increase the conductivity, firing at a high temperature (1400 ° C. to 3000 ° C.) may be performed in a nitrogen atmosphere.
- the porous carbon material thus obtained was classified using a sieve having an opening of 75 ⁇ m to obtain a 75 ⁇ m-passing product. This porous carbon material was used as a raw material 1B.
- pores (holes) in the porous carbon material had three-dimensional regularity, that is, 3 It was confirmed that the pores (holes) were arranged in a dimensional arrangement and arranged in a macroscopic manner to form a crystal structure.
- the pores (holes) are macroscopically arranged in a face-centered cubic structure, and further, macroscopically arranged in an arrangement state corresponding to the (111) plane orientation in the face-centered cubic structure.
- the obtained reflection spectrum has a pore (hole) diameter. Since unimodal absorption was exhibited at the corresponding specific wavelength, it was confirmed that the pores (holes) were regularly arranged three-dimensionally even inside the porous carbon material. The pores (holes) were continuously arranged, and the shape of the pores (holes) was spherical or substantially spherical.
- a composite material for an electrode of Comparative Example 1A was obtained by performing the same operation except that 1.5 g of ketjen black (manufactured by Lion Corporation) was used instead of the plant-derived porous carbon material. . Further, in place of the plant-derived porous carbon material, 1.5 g of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) was used, and the same operation was performed, so that the composite material for electrodes of Comparative Example 1B Got.
- FIG. 1A A graph of the pore distribution by the MP method of the electrode composite materials of Example 1A-1, Example 1A-2, and Example 1A-3 and the plant-derived porous carbon material is shown in FIG. 1A, and the BJH method is used.
- FIG. 1B A graph of the pore distribution is shown in FIG. 1B.
- FIG. 2A a graph of the pore distribution by the MP method of the electrode composite material of Comparative Example 1A and Ketjen Black is shown in FIG. 2A
- the graph of the pore distribution by the BJH method is shown in FIG. 2B.
- the horizontal axis of FIG. 1A, FIG. 1B, FIG. 2A, and FIG. 2B is a pore diameter.
- 1B represents data of a plant-derived porous carbon material
- “1A-1” represents data of the electrode composite material of Example 1A-1
- “1A -2 indicates the data of the electrode composite material of Example 1A-2
- 1A-3 indicates the data of the electrode composite material of Example 1A-3
- Comparative Example 1A in FIGS. 2A and 2B.
- “" Shows the data of the composite material for electrodes of Comparative Example 1A
- “KB” shows the data of Ketjen Black.
- XRD X-ray diffraction analysis
- the measurement results of the obtained X-ray diffraction intensity are shown in the graphs of FIGS. 3A, 3B, 4A, and 4B, and it was confirmed that the porous carbon material contains lithium sulfide.
- the X-ray diffraction intensity was measured by sealing with polyethylene.
- the measurement conditions of X-ray diffraction intensity are shown below.
- black circles indicate the peak of X-ray diffraction intensity of lithium sulfide (Li 2 S)
- white circles indicate the peak of X-ray diffraction intensity of polyethylene.
- the X-ray diffraction intensity peak half-value width of the surface is 0.37 degrees or less, more specifically, 0.3 degrees or less.
- X-ray diffractometer RIGAKU RINT-2000 manufactured by Rigaku Corporation Accelerating voltage: 40 kilovolt current: 40 mA slit: Diverging slit 1 degree, scattering slit 1 degree, light receiving slit 0.3 mm Scanning speed: 5 degrees / minute Step width: 0.02 degrees
- “nitrogen BET method”, “particle size”, “MP method”, “BJH method [A] less than 50 nm”, “BJH method [B] from 50 nm to less than 100 nm” , “BJH method [D] 100 nm or more” is a value of specific surface area by nitrogen BET method (unit: m 2 / gram), porous carbon material (porous carbon material (raw material) before complexing with lithium sulfide) Average particle diameter d50 (unit: ⁇ m), pore volume value by MP method (unit: cm 3 / gram), pore volume value by pore diameter less than 50 nm by BJH method (unit: cm 3 / gram), pore size 50nm or more by the BJH method, the value of the pore volume of less than 100nm (unit: cm 3 / g), the value of the pore diameter 100nm or more pore volume by the BJH method: means (unit cm 3 / g
- the unit of the total pore volume is “cm 3 / gram”. Furthermore, based on the pore volume measurement result of the total pore diameter by the BJH method of the composite material for electrodes, the ratio of the pore volume less than 50 nm, the pore volume of 50 nm or more, the ratio of less than 100 nm, and the ratio of the pore volume of 100 nm or more As summarized in Table 2, in the example, the pore volume ratio of 100 nm or more by the BJH method of the electrode composite material is 30% or less.
- “raw material 1A”, “raw material 1B”, “KB raw material”, and “AB raw material” are plant-derived porous carbon materials (raw materials), respectively.
- porous carbon material (raw material 1B) having an inverse opal structure, ketjen black, and acetylene black.
- the content of silicon (Si) in the raw material 1A was less than 3% by mass.
- the values in parentheses in the columns of Example 1B-1, Example 1B-2, Comparative Example 1A, and Comparative Example 1B in the pore size less than 100 nm by the BJH method in Table 1-2 and the BJH method [E] are as follows: , (BJH 0 / BJH PC ) (unit:%).
- the electrode composite material is analyzed to determine the lithium content of the electrode composite material, and the electrode composite material does not contain anything other than lithium sulfide. This was confirmed by X-ray diffraction analysis (XRD), and the lithium sulfide content was calculated from the lithium content.
- XRD X-ray diffraction analysis
- the values of lithium content, lithium sulfide content, porous carbon material content, and pore volume BJH 0 , BJH 2 , BJH 1 are shown in Table 3.
- the pore volume BJH 0 is the content of the porous carbon material.
- the pore volume BJH 1 by the BJH method after washing with water is larger than the value BJH 2 divided by.
- BJH 1 is smaller than BJH 2 .
- the value BJH 2 representing the pore volume of the porous carbon material in the electrode composite material in which the porous carbon material and lithium sulfide are combined is the pore volume BJH 1 (lithium sulfide) obtained by the BJH method after washing. Is less than the removed porous carbon material, which is approximately equal to its own pore volume.
- BJH 1 is smaller than BJH 2 , but this is considered to be because, in Comparative Example 1B, lithium sulfide simply adheres to the surface of acetylene black.
- the specific surface area value by the nitrogen BET method, the value of the total pore volume, the value of the pore volume by the MP method, the total pore diameter by the BJH method of the composite materials for electrodes of the examples (but before washing) The values of the pore volume and the pore volume with a pore diameter of less than 100 nm (BJH method [C]) according to the BJH method are those of the plant-derived porous carbon material and the porous carbon material having an inverse opal structure. It is lower than the value of. This is because lithium sulfide is supported on the pores of the porous carbon material.
- the value of the pore volume of the composite material for electrodes by the MP method (that is, the value of the micropore volume whose pore diameter is smaller than 2 nm) is 0 cm 3 / gram or almost 0 cm 3 / gram, and the pore diameter is 2 nm. It can be seen that the smaller micropores are filled with lithium sulfide.
- the total volume value of mesopores having a pore diameter of 2 nm to 50 nm and macropores having a pore diameter of more than 50 nm and less than 100 nm is the value of the porous carbon material before complexing with lithium sulfide.
- mesopores having a pore diameter of 2 nm to 50 nm and macropores having a pore diameter of more than 50 nm and less than 100 nm are filled with lithium sulfide.
- the specific surface area value by the nitrogen BET method, the value of the total pore volume, the value of the pore volume by the MP method, the pores of the total pore diameter by the BJH method of the composite materials for electrodes of the examples but after washing with water
- Both the value of the volume and the value of the pore volume with a pore diameter of less than 100 nm by the BJH method are higher than the value before washing with water. This is a result of the lithium sulfide carried on the pores of the porous carbon material being removed by washing with water.
- Comparative Example 1b For comparison, 3 grams of lithium sulfide and 1 gram of ketjen black were mixed and ground in a mortar for 1 hour. Then, the material of the comparative example 1b was obtained by heating at 950 degreeC for 1 hour by nitrogen gas atmosphere. The material of Comparative Example 1b was a white solid, and when X-ray diffraction analysis (XRD) of Comparative Example 1b was performed, it was confirmed that carbon had reacted and disappeared.
- XRD X-ray diffraction analysis
- Example 2 relates to a secondary battery according to the first to fifth aspects of the present disclosure.
- the secondary battery of Example 2 includes an electrode manufactured from the electrode composite material of Example 1, and this electrode constitutes the positive electrode of the secondary battery.
- the secondary battery is a lithium-sulfur secondary battery.
- Example 2 a positive electrode of a secondary battery was produced using the electrode composite material (lithium sulfide-porous carbon composite material) of Example 1A-2 and other materials, and further a secondary battery was produced. did. Specifically, a slurry having the composition shown in Table 5 below was prepared. “KB6” is a carbon material manufactured by Lion Corporation, and “PVDF” is an abbreviation for polyvinylidene fluoride and functions as a binder.
- a blended product (positive electrode material, positive electrode active material) having the composition shown in Table 5 above was kneaded in a mortar by adding NMP as a solvent to form a slurry. Then, the kneaded product was applied onto the aluminum foil and dried with hot air at 120 ° C. for 3 hours. Next, hot pressing is performed using a hot pressing device under the conditions of a temperature of 80 ° C. and a pressure of 580 kgf / cm 2 to increase the density of the positive electrode material, prevent the occurrence of damage in contact with the electrolyte, The value was reduced. Thereafter, punching was performed so that the diameter became 15 mm, and vacuum drying was performed at 60 ° C. for 3 hours to remove moisture and solvent.
- the thickness of the positive electrode portion (positive electrode material layer) excluding the aluminum foil thus obtained was 10 ⁇ m to 30 ⁇ m, and the mass was 2 mg to 3 mg.
- a lithium-sulfur secondary battery including a 2016-type coin battery was assembled. Specifically, a positive electrode composed of an aluminum foil and a positive electrode material layer, an electrolyte, a lithium foil having a thickness of 1.0 mm as a negative electrode material, and a nickel mesh as a current collector are laminated to form a lithium composed of a 2016 type coin battery. -A sulfur secondary battery was assembled. As a separator, F20-MBU manufactured by TonenGeneral was used.
- LiTFSI lithium bis (trifluoromethylsulfonyl) imide
- LiNO 3 a mixed solvent of dimethyl ether and 1,3 dioxysan ( Those dissolved in a volume ratio of 1/1) were used.
- the conditions for the charge / discharge test of the lithium-sulfur secondary battery are shown in Table 6-1 below.
- the discharge conditions were 0.05C.
- the curves “A”, “B”, “C”, “D”, and “E” indicate the first charge / discharge, the second charge / discharge, the fifth charge / discharge, The 10th charge / discharge and the 15th charge / discharge are shown. 5 to 12, the horizontal axis represents the charge / discharge capacity, and the unit is “mAh / (lithium sulfide 1 gram)”.
- FIG. 8 shows a graph of a charge / discharge test result of the secondary battery of Example 2 under the conditions shown in Table 6-2.
- Comparative Example 2A a positive electrode of a secondary battery was manufactured using the composite material for electrodes of Comparative Example 1A and other materials, and further a secondary battery was manufactured. Specifically, a slurry having the composition shown in Table 7 below was prepared. “PVA” is an abbreviation for polyvinyl alcohol and functions as a binder. “VGCF” is a vapor growth carbon fiber manufactured by Showa Denko KK In order to prototype the secondary batteries of Comparative Example 2B and Comparative Example 2C, slurries having the formulations shown in Table 8 and Table 9 below were prepared.
- the positive electrode containing aluminum foil was produced based on the method similar to Example 2 using the compounding material (positive electrode material, active material for positive electrodes) of the composition shown in Table 7, Table 8, and Table 9.
- the thickness of the positive electrode portion (positive electrode material layer) excluding the aluminum foil thus obtained was 80 ⁇ m to 100 ⁇ m, and the mass was 8 mg to 12 mg.
- a lithium-sulfur secondary battery comprising a 2016-type coin battery was assembled in the same manner as in Example 2.
- FIG. 6 shows the charge / discharge test results of the lithium-sulfur secondary batteries of Comparative Example 2A and Comparative Example 2C.
- the secondary batteries of Comparative Example 2A and Comparative Example 2C cannot maintain a high potential for a long time, It was confirmed that the capacity was small.
- FIG. 7 shows the result of the charge / discharge test of the lithium-sulfur secondary battery of Comparative Example 2B. In Comparative Example 2B, no discharge was possible.
- FIG. 8 shows a graph of a charge / discharge test result of the secondary battery of Comparative Example 2A under the conditions shown in Table 6-2.
- Example 2 the pore volume based on the MP method or the BJH method of the porous carbon material that is a constituent material of the electrode composite material is defined, and lithium sulfide is formed by the porous carbon material that is a conductive material. Therefore, it is possible to provide a composite material for an electrode for obtaining a secondary battery excellent in charge / discharge cycle characteristics using lithium sulfide as an active material.
- Example 3 is a modification of Example 2.
- the electrode composite material of Example 1A-2 was used.
- a positive electrode of a secondary battery was prepared using the electrode composite material (lithium sulfide-porous carbon composite material) of Example 1A-3 and other materials.
- a secondary battery was produced. Specifically, a slurry having the composition shown in Table 12 below was prepared.
- a lithium-sulfur secondary battery comprising a 2016-type coin battery was assembled in the same manner as in Example 2 using the blended product (positive electrode material, positive electrode active material) having the composition shown in Table 12.
- FIG. 9 shows a graph of the charge / discharge test results.
- 1166 mAh / (lithium sulfide 1 gram) which is the theoretical capacity of lithium sulfide, was obtained in the first discharge.
- Example 4 is a modification of Example 3.
- a 1.0 mm thick lithium foil was used as the negative electrode material, and a nickel mesh was used as the current collector.
- the use of the negative electrode material was omitted, and a stainless steel plate was used as the current collector.
- the electrode composite material of Example 1A-3 was used to prepare a slurry having the composition shown in Table 12, and a secondary battery was produced in the same manner as in Example 3. .
- FIG. 10 shows a graph of the charge / discharge test results, and it was confirmed that the secondary battery of Example 4 functioned as a secondary battery because lithium was deposited on the stainless steel plate during discharge.
- the curves “A”, “B”, and “C” indicate the first charge / discharge, the second charge / discharge, and the third charge / discharge.
- Example 5 is also a modification of Example 3.
- Si was used as the negative electrode material, and a stainless steel plate was used as the current collector.
- the electrode composite material of Example 1A-3 was used to prepare a slurry having the composition shown in Table 12, and a secondary battery was produced in the same manner as in Example 3. .
- an electrolytic solution an electrolytic solution in which at least a part of glyme and an alkali metal salt forms a complex, specifically, a mixture of tetraglyme and lithium bis (trifluoromethylsulfonyl) imide ([Li (G4)] [TFSI]), 100 microliters was used, and GA-55 manufactured by Advantec was used as a separator.
- FIG. 11 shows a graph of the charge / discharge test results, and it was confirmed that the secondary battery of Example 5 functions as a secondary battery.
- the curves “A”, “B”, “C”, “D”, and “E” indicate the first charge / discharge, the second charge / discharge, the third charge / discharge, The fourth charge / discharge and the fifth charge / discharge are shown.
- Example 6 is also a modification of Example 3.
- graphite was used as the negative electrode material, and a stainless steel plate was used as the current collector.
- the electrode composite material of Example 1A-3 was used to prepare a slurry having the composition shown in Table 12, and a secondary battery was produced in the same manner as Example 3. .
- [Li (G4)] [TFSI] 100 microliters was used as the electrolytic solution, and GA-55 was used as the separator.
- FIG. 12 shows a graph of the charge / discharge test results, and it was confirmed that the secondary battery of Example 6 functions as a secondary battery.
- the curves “A”, “B”, “C”, “D”, “E”, and “F” indicate the fifth charge / discharge, the tenth charge / discharge, and the fifteenth charge.
- the 20th charge / discharge, the 25th charge / discharge, and the 30th charge / discharge are shown.
- lithium sulfide having the composition formula Li 2 S was used, but the composition of lithium sulfide is not limited to this.
- the plant-derived porous carbon material and the porous carbon material having an inverse opal structure have been described.
- activated carbon, peat charcoal (peat), medicinal use Charcoal or the like can be used.
- a porous carbon material other than the plant-derived porous carbon material can be used.
- a porous carbon material other than the porous carbon material having an inverse opal structure can also be used.
- at least two of the seven aspects of the first to seventh aspects of the present disclosure can be arbitrarily combined.
- rice husk is used as the raw material of the porous carbon material has been described, but other plants may be used as the raw material.
- examples of other plants include pods, cocoons or stem wakame, vascular plants vegetated on land, fern plants, moss plants, algae and seaweeds, and these may be used alone. Further, a plurality of types may be mixed and used.
- plant-derived materials that are raw materials for porous carbon materials are rice straw (eg, from Kagoshima; Isehikari), and porous carbon materials are carbonized from raw straw as a carbonaceous material.
- a porous carbon material intermediate can be obtained by converting to (porous carbon material precursor) and then performing acid treatment.
- a plant-derived material that is a raw material of the porous carbon material is used as a rice bran, and the rice bran as a raw material is carbonized to be converted into a carbonaceous substance (porous carbon material precursor).
- a porous carbon material intermediate can be obtained.
- porous carbon materials obtained by treatment with an alkali (base) such as an aqueous hydrofluoric acid solution and an aqueous sodium hydroxide solution.
- an alkali base
- the manufacturing method of a porous carbon material can be made substantially the same as that of Example 1.
- the plant-derived material which is the raw material for the porous carbon material
- the porous carbon material intermediate is carbonized from the stem wakame as a raw material to produce a carbonaceous material (porous carbon It can be obtained by converting to a material precursor) and then performing an acid treatment.
- a stem carbon seam is heated at a temperature of about 500 ° C. and subjected to a preliminary carbonization treatment for carbonization.
- the stem wakame is soaked in ethyl alcohol for 48 hours.
- tar components that will be generated at the time of the next carbonization can be reduced or removed.
- 10 grams of this carbide is put in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonizes at 1000 degreeC for 5 hours, and after converting into a carbonaceous substance (porous carbon material precursor), it cools to room temperature. In addition, nitrogen gas is kept flowing during carbonization and cooling.
- this porous carbon material precursor is subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethyl alcohol until pH 7 and dried. Thereby, a porous carbon material intermediate can be obtained.
- Electrode Composite Material Second Aspect >> A plant-derived porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume MP by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing with water 1 Is the pore volume MP 0 Larger composite material for electrodes.
- Electrode Composite Material Third Aspect >> Pore volume less than 100 nm by BJH method BJH PC Is 0.3cm Three Plant-derived porous carbon material that is / gram or more, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume less than 100 nm by BJH method BJH 0 Is 0.3cm Three Composite material for electrodes that is less than / gram.
- Electrode Composite Material Fourth Aspect >> A plant-derived porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume less than 100 nm by BJH method BJH 0 Is 0.3cm Three / Pore volume BJH of less than 100 nm by BJH method after washing with water 1 Is the pore volume BJH 0 Larger composite material for electrodes.
- BJH pore volume BJH of 100 nm or more 100 Is a composite material for an electrode according to [A03] or [A04], which is 30% or less.
- Pore volume BJH 0 BJH divided by the content of porous carbon material 2 Rather than pore volume BJH by BJH method after water washing 1 Is a large composite material for an electrode according to any one of [A03] to [A05].
- Pore volume MP of plant-derived porous carbon material by MP method PC Is 0.1cm Three / G or more, Pore volume MP by MP method 0 Is 0.1cm Three The composite material for an electrode according to any one of [A03] to [A06], which is less than / gram.
- [A10] The composite material for an electrode according to any one of [A01] to [A09], in which the porous carbon material is a plant-derived material having a silicon content of 5% by mass or more.
- the porous carbon material is a plant-derived material having a silicon content of 5% by mass or more.
- the value of the specific surface area of the porous carbon material according to the nitrogen BET method is 100 m. 2
- Electrode Composite Material Fifth Aspect >> A porous carbon material having an inverse opal structure, and Lithium sulfide supported in the pores of the porous carbon material, A composite material for an electrode comprising: Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is a pore volume BJH of less than 100 nm by BJH method of porous carbon material PC 20% or less of the composite material for electrodes.
- Pore volume BJH of 100 nm or more by BJH method 100 The electrode composite material according to [B01], which has a ratio of 30% or less.
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- Electrode Composite Material Sixth Aspect >> Porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including The composite material for an electrode having an average particle size of the porous carbon material of 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- Electrode Composite Material Seventh Aspect >> Porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume BJH of 100 nm or more by BJH method 100 The composite material for electrodes whose ratio is 30% or less.
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less
- the porous carbon material is made from a plant-derived material, Pore volume MP of porous carbon material by MP method PC Is 0.1cm Three / G or more, Pore volume MP by MP method 0 Is 0.1cm Three The composite material for electrodes according to any one of [B01] to [B06], which is less than / gram.
- the porous carbon material is made from a plant-derived material, Pore volume MP by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing with water 1 Is the pore volume MP 0
- the porous carbon material is made from a plant-derived material, Pore volume BJH of plant-derived porous carbon material less than 100 nm by BJH method PC Is 0.3cm Three / G or more, Pore volume less than 100 nm by BJH method BJH 0 Is 0.3cm Three
- the composite material for electrodes according to any one of [B01] to [B08], which is less than / gram.
- the porous carbon material is made from a plant-derived material, Pore volume less than 100 nm by BJH method BJH 0 Is 0.3cm Three / Pore volume BJH of less than 100 nm by BJH method after washing with water 1 Is the pore volume BJH 0
- Pore volume BJH of 100 nm or more by BJH method 100 The electrode composite material according to any one of [B01] to [B10], in which the ratio is 30% or less.
- the electrode composite material according to any one of [B01] to [B11].
- the plant-derived porous carbon material is a composite material for an electrode according to any one of [B01] to [B12], in which a plant-derived material having a silicon content of 5% by mass or more is used as a raw material. .
- the pores In the porous carbon material having an inverse opal structure, the pores have a three-dimensional regularity and are arranged in an arrangement that macroscopically forms a crystal structure.
- any of [B01] to [B06] The composite material for electrodes according to claim 1.
- [B15] The electrode composite material according to [B14], in which the pores are macroscopically arranged on the material surface in a (1,1,1) plane orientation of a face-centered cubic lattice.
- [B16] The composite material for electrodes according to any one of [B01] to [B15], wherein the peak half-value width of the X-ray diffraction intensity of the ⁇ 220 ⁇ plane of lithium sulfide is 0.37 degrees or less.
- the value of the specific surface area of the porous carbon material according to the nitrogen BET method is 100 m.
- ⁇ secondary battery third embodiment >> Pore volume less than 100 nm by BJH method BJH PC Is 0.3cm Three Plant-derived porous carbon material that is / gram or more, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume less than 100 nm by BJH method BJH 0 Is 0.3cm Three A secondary battery comprising an electrode made of a composite material for an electrode that is less than 1 gram.
- Pore volume MP of composite material for electrode by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing of electrode composite material with water 1 Is the pore volume MP 0
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the porous carbon material uses a plant-derived material having a silicon content of 5% by mass or more as a raw material.
- the value of the specific surface area of the porous carbon material according to the nitrogen BET method is 100 m. 2
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- Electrode Composite Material Seventh Aspect >> Porous carbon material, and Lithium sulfide supported in the pores of the porous carbon material, Including Pore volume BJH of 100 nm or more by BJH method 100
- a secondary battery comprising an electrode made of a composite material for an electrode having a ratio of 30% or less.
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the porous carbon material is made from a plant-derived material, Pore volume MP of porous carbon material by MP method PC Is 0.1cm Three / G or more, Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three The secondary battery according to any one of [D01] to [D06], which is less than / gram.
- the porous carbon material is made from a plant-derived material, Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing of electrode composite material with water 1 Is the pore volume MP 0
- the secondary battery according to any one of [D01] to [D07], which is larger than.
- the porous carbon material is made from a plant-derived material, Pore volume BJH of plant-derived porous carbon material less than 100 nm by BJH method PC Is 0.3cm Three / G or more, Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is 0.3cm Three
- the secondary battery according to any one of [D01] to [D08], which is less than / gram.
- the porous carbon material is made from a plant-derived material, Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is 0.3cm Three Pore volume BJH of less than 100 nm by the BJH method after washing the electrode composite material with water 1 Is the pore volume BJH 0
- Porous volume BJH of 100 nm or more by BJH method of composite material for electrode 100 The secondary battery according to any one of [D01] to [D10], in which the ratio is 30% or less.
- [D15] The secondary battery according to [D14], in which the pores are macroscopically arranged in a (1,1,1) plane orientation of a face-centered cubic lattice on the material surface.
- [D16] The secondary battery according to any one of [D01] to [D15], wherein the peak half-value width of the X-ray diffraction intensity of the ⁇ 220 ⁇ plane of lithium sulfide is 0.37 degrees or less.
- the value of the specific surface area of the porous carbon material according to the nitrogen BET method is 100 m 2
- [E01] The secondary battery according to any one of [C01] to [D17], wherein the electrode constitutes a positive electrode.
- [E02] The secondary battery according to any one of [C01] to [E01], comprising a lithium-sulfur secondary battery.
- [E03] The secondary battery according to [E01] or [E02], including an electrolytic solution in which at least a part of glyme and an alkali metal salt forms a complex.
- Pore volume BJH of 100 nm or more by BJH method of electrode composite material 100 The manufacturing method of the composite material for electrodes as described in [F03] or [F04] whose ratio is 30% or less.
- Than pore volume BJH by BJH method after washing electrode composite material with water 1 Is a method for producing a composite material for an electrode according to any one of [F03] to [F05].
- Pore volume MP of plant-derived porous carbon material by MP method PC Is 0.1cm Three / G or more, Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three The manufacturing method of the composite material for electrodes as described in any one of [F03] thru
- Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing of electrode composite material with water 1 Is the pore volume MP 0 The manufacturing method of the composite material for electrodes as described in any one of [F03] thru
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- [F11] The method for producing a composite material for an electrode according to [F10], wherein the porous carbon material is obtained by carbonizing at 400 ° C to 1400 ° C and then treating with an acid or an alkali.
- [F12] The method for producing a composite material for an electrode according to [F11], in which heat treatment is performed at a temperature exceeding the temperature in carbonization after treatment with an acid or an alkali.
- [F13] The method for producing a composite material for an electrode according to any one of [F10] to [F12], wherein a silicon component in the plant-derived material after carbonization is removed by treatment with an acid or an alkali.
- [F14] The method for producing a composite material for an electrode according to any one of [F01] to [F13], wherein the peak half-value width of the X-ray diffraction intensity of the ⁇ 220 ⁇ plane of lithium sulfide is 0.37 degrees or less. .
- the specific surface area of the porous carbon material according to the nitrogen BET method is 100 m. 2
- Electrode Composite Material Fifth Aspect >> After generating lithium hydrosulfide in a solvent, a porous carbon material having an inverse opal structure is added and heated, so that the porous carbon material and lithium sulfide supported in the pores of the porous carbon material are
- An electrode composite material manufacturing method for obtaining an electrode composite material comprising: Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is a pore volume BJH of less than 100 nm by BJH method of porous carbon material PC The manufacturing method of the composite material for electrodes which is 20% or less of.
- Porous volume BJH of 100 nm or more by BJH method of electrode composite material 100 Is 30% or less.
- the average particle size of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less.
- the average particle diameter of the porous carbon material is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, 75 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less
- [G05 ] The manufacturing method of the composite material for electrodes as described in above.
- the porous carbon material is made from a plant-derived material, Pore volume MP of porous carbon material by MP method PC Is 0.1cm Three / G or more, Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three The manufacturing method of the composite material for electrodes as described in any one of [G01] thru
- the porous carbon material is made from a plant-derived material, Pore volume MP of composite material for electrodes by MP method 0 Is 0.1cm Three / Pore volume MP by MP method after washing of electrode composite material with water 1 Is the pore volume MP 0
- the porous carbon material is made from a plant-derived material, Pore volume BJH of plant-derived porous carbon material less than 100 nm by BJH method PC Is 0.3cm Three / G or more, Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is 0.3cm Three The method for producing a composite material for an electrode according to any one of [G01] to [G08], which is less than 1 gram.
- the porous carbon material is made from a plant-derived material, Pore volume BJH of electrode composite material less than 100 nm by BJH method 0 Is 0.3cm Three Pore volume BJH of less than 100 nm by the BJH method after washing the electrode composite material with water 1 Is the pore volume BJH 0
- Electrode composite pore volume BJH 0 BJH divided by the content of porous carbon material 2 Than pore volume BJH by BJH method after washing electrode composite material with water 1 The method for producing a composite material for an electrode according to any one of [G01] to [G11].
- [G15] The method for producing a composite material for an electrode according to [G14], in which heat treatment is performed at a temperature exceeding the temperature in carbonization after treatment with an acid or an alkali.
- [G16] The method for producing a composite material for an electrode according to any one of [G13] to [G15], wherein a silicon component in the plant-derived material after carbonization is removed by treatment with an acid or an alkali.
- the pores In the porous carbon material having an inverse opal structure, the pores have a three-dimensional regularity and are arranged in an arrangement that macroscopically forms a crystal structure.
- [G01] to [G06] The manufacturing method of the composite material for electrodes of Claim 1.
- [G18] The method for producing a composite material for an electrode according to [G17], wherein the pores are macroscopically arranged in a (1,1,1) plane orientation of a face-centered cubic lattice on the material surface.
- [G19] The method for producing a composite material for an electrode according to any one of [G01] to [G18], wherein the peak half-value width of the X-ray diffraction intensity of the ⁇ 220 ⁇ plane of lithium sulfide is 0.37 degrees or less. .
- Specific surface area of porous carbon material measured by nitrogen BET method is 100 m 2
- Lithium hydrosulfide is generated in the solvent by adding lithium hydroxide to the solvent and bubbling with hydrogen sulfide gas.
- [F01] to [G20] A method for producing a composite material.
- [H02] The method for producing the electrode composite material according to any one of [F01] to [H01], wherein the heating temperature after adding the porous carbon material is 150 ° C to 230 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
MP法による細孔容積MPPCが0.1cm3/グラム以上、好ましくは0.15cm3/グラム以上、より好ましくは0.20cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む。そして、電極用複合材料のMP法による細孔容積MP0は、0.1cm3/グラム未満、好ましくは0.08cm3/グラム以下、より好ましくは0.05cm3/グラム以下である。
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む。そして、電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満、好ましくは0.08cm3/グラム以下、より好ましくは0.05cm3/グラム以下であり、且つ、電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい。
BJH法による100nm未満の細孔容積BJHPCが0.3cm3/グラム以上、好ましくは0.4cm3/グラム以上、より好ましくは0.5cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む。そして、電極用複合材料のBJH法による100nm未満の細孔容積BJH0は、0.3cm3/グラム未満、好ましくは0.27cm3/グラム以下、より好ましくは0.25cm3/グラム以下である。
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む。そして、電極用複合材料のBJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満、好ましくは0.27cm3/グラム以下、より好ましくは0.25cm3/グラム以下であり、且つ、電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい。
逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む電極用複合材料であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である。
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である。
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積BJH100の割合が30%以下である。
電極用複合材料のMP法による細孔容積MP0は、0.1cm3/グラム未満、好ましくは0.08cm3/グラム以下、より好ましくは0.05cm3/グラム以下である。
電極用複合材料のMP法による細孔容積MP0が、0.1cm3/グラム未満、好ましくは0.08cm3/グラム以下、より好ましくは0.05cm3/グラム以下であり、
電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい。
電極用複合材料のBJH法による100nm未満の細孔容積BJH0は、0.3cm3/グラム未満、好ましくは0.27cm3/グラム以下、より好ましくは0.25cm3/グラム以下である。
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、0.3cm3/グラム未満、好ましくは0.27cm3/グラム以下、より好ましくは0.25cm3/グラム以下であり、
電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい。
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である。
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である。
電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合が30%以下である。
1.本開示の第1の態様~第7の態様に係る電極用複合材料及びその製造方法並びに二次電池、全般に関する説明
2.実施例1(本開示の第1の態様~第7の態様に係る電極用複合材料及びその製造方法)
3.実施例2(本開示の第1の態様~第7の態様に係る二次電池)
4.実施例3(実施例2の変形)
5.実施例4(実施例3の変形)
6.実施例5(実施例3の別の変形)
7.実施例6(実施例3の更に別の変形)、その他
以下の説明において、本開示の第1の態様~第7の態様に係る電極用複合材料、本開示の第1の態様~第7の態様に係る電極用複合材料の製造方法、本開示の第1の態様~第7の態様に係る二次電池を総称して、単に、『本開示』と呼ぶ場合がある。また、本開示の第1の態様に係る電極用複合材料、本開示の第1の態様に係る電極用複合材料の製造方法、本開示の第1の態様に係る二次電池を総称して、単に、『本開示の第1の態様』と呼ぶ場合があるし、開示の第2の態様に係る電極用複合材料、本開示の第2の態様に係る電極用複合材料の製造方法、本開示の第2の態様に係る二次電池を総称して、単に、『本開示の第2の態様』と呼ぶ場合があるし、本開示の第3の態様に係る電極用複合材料、本開示の第3の態様に係る電極用複合材料の製造方法、本開示の第3の態様に係る二次電池を総称して、単に、『本開示の第3の態様』と呼ぶ場合があるし、本開示の第4の態様に係る電極用複合材料、本開示の第4の態様に係る電極用複合材料の製造方法、本開示の第4の態様に係る二次電池を総称して、単に、『本開示の第4の態様』と呼ぶ場合があるし、本開示の第5の態様に係る電極用複合材料、本開示の第5の態様に係る電極用複合材料の製造方法、本開示の第5の態様に係る二次電池を総称して、単に、『本開示の第5の態様』と呼ぶ場合があるし、本開示の第6の態様に係る電極用複合材料、本開示の第6の態様に係る電極用複合材料の製造方法、本開示の第6の態様に係る二次電池を総称して、単に、『本開示の第6の態様』と呼ぶ場合があるし、本開示の第7の態様に係る電極用複合材料、本開示の第7の態様に係る電極用複合材料の製造方法、本開示の第7の態様に係る二次電池を総称して、単に、『本開示の第7の態様』と呼ぶ場合がある。更には、本開示の第1の態様~第7の態様に係る電極用複合材料を総称して、単に『本開示の電極用複合材料』と呼び、本開示の第1の態様~第7の態様に係る二次電池を総称して、単に『本開示の二次電池』と呼び、本開示の第1の態様~第7の態様に係る電極用複合材料の製造方法を総称して、単に『本開示の電極用複合材料の製造方法』と呼ぶ場合がある。
[p/{Va(p0-p)}]
=[(C-1)/(C・Vm)](p/p0)+[1/(C・Vm)] (1’)
Vm=1/(s+i) (2-1)
C =(s/i)+1 (2-2)
asBET=(Vm・L・σ)/22414 (3)
Va:吸着量
Vm:単分子層の吸着量
p :窒素の平衡時の圧力
p0:窒素の飽和蒸気圧
L :アボガドロ数
σ :窒素の吸着断面積
である。
V :相対圧での吸着量
Mg:窒素の分子量
ρg:窒素の密度
である。
Vpn=Rn・dVn-Rn・dtn・c・ΣApj (6)
但し、
Rn=rpn 2/(rkn-1+dtn)2 (7)
rp:細孔半径
rk:細孔半径rpの細孔の内壁にその圧力において厚さtの吸着層が吸着した場合のコア半径(内径/2)
Vpn:窒素の第n回目の着脱が生じたときの細孔容積
dVn:そのときの変化量
dtn:窒素の第n回目の着脱が生じたときの吸着層の厚さtnの変化量
rkn:その時のコア半径
c:固定値
rpn:窒素の第n回目の着脱が生じたときの細孔半径
である。また、ΣApjは、j=1からj=n-1までの細孔の壁面の面積の積算値を表す。
SiO2+4HF → SiF4+2H2O (B)
(a)ナノスケールのコロイド結晶体(鋳型となる無機粒子、無機材料粒子、無機化合物粒子といったコロイド粒子の集合体)を、重合性単量体の溶液又は重合性単量体を含む組成物の溶液に浸漬することで、配合組成物を得る工程、
(b)配合組成物における重合性単量体を重合させて高分子材料とコロイド結晶体との複合体(以下、『コロイド結晶体複合体』と呼ぶ場合がある)を得る工程、
(c)不活性ガス雰囲気下、800゜C乃至3000゜Cでコロイド結晶体複合体における高分子材料を炭素化する工程、及び、
(d)高分子材料が炭素化されたコロイド結晶体複合体(以下、『炭素化・コロイド結晶体複合体』と呼ぶ場合がある)を、コロイド結晶体を溶解することができる液体に浸漬することでコロイド結晶体を溶解除去し、炭素化された高分子材料から成る多孔質炭素材料を得る工程、
を含む多孔質炭素材料の製造方法によって製造することができる。炭素化の温度に至るまでの昇温速度は、局部的な加熱によりコロイド結晶体が崩壊しない昇温速度範囲であれば、特に限定されない。そして、コロイド結晶体を用いて得られる多孔質炭素材料は、前述したとおり、巨視的に細孔(空孔)の配列に3次元的規則性及び連続性を有する。
(A)コロイド粒子を含む溶液(以下、『コロイド溶液』と呼ぶ)を基板上に滴下し、滴下されたコロイド溶液に含まれる溶媒を留去する方法
を挙げることができる。溶媒の留去は、室温において行うこともできるが、用いられる溶媒の沸点と同じ温度又は沸点以上の温度に加熱することにて行うことが好ましい。尚、基板上にコロイド溶液を滴下した後、基板を加熱して溶媒を留去してもよいし、予め加熱した基板上にコロイド溶液を滴下して溶媒を留去してもよい。コロイド溶液を滴下する際、又は、滴下した後、基板を回転させてもよい。コロイド溶液の滴下、溶媒留去の操作を繰り返すことによって、あるいは又、コロイド溶液の濃度を調整することにより、あるいは又、滴下するコロイド溶液の量を調整することにより、あるいは又、以上の操作を適宜組み合わせることにより、得られる配合組成物の膜厚、面積を制御することができる。特に、3次元的規則性を保持したまま、大面積化が容易に可能である。具体的には、固形分濃度として10質量%以上のコロイド溶液を用いることができることから、一度の滴下にて相当の厚さの配合組成物を基板上に形成することができ、滴下、留去(乾燥)を繰り返すことにより、配合組成物の厚さを制御することができる。更には、例えば、単分散コロイド溶液を用いることにより、得られるコロイド結晶体を単結晶構造のコロイド結晶体とすることができる。
(B)コロイド溶液を吸引濾過して溶媒を除去し、配合組成物を堆積させる方法
を挙げることができる。具体的には、コロイド溶液から、吸引ロートを用いた減圧吸引等によって溶媒を吸引除去することより、吸引ロート上の濾紙又は濾布上に配合組成物を堆積させることができる。この方法においても、例えば、単分散コロイド溶液を用いることにより、得られるコロイド結晶体を単結晶構造とすることができる。吸引濾過に用いるコロイド溶液の濃度は、一度の操作で得ようとする配合組成物の容積に基づき、適宜、選択することができる。また、一旦、全ての溶媒を吸引除去した後、再度、コロイド溶液を追加して同様の操作を繰り返すことにより、所望の容積の配合組成物を得ることができる。このような方法によっても、3次元的規則性を保持したまま、配合組成物の大面積化、大容積化が可能である。溶媒を吸引する方法は、特に限定されず、アスピレータやポンプ等により吸引する方法を挙げることができる。吸引する速度も特に限定されず、例えば、40mmHg程度の減圧度とし、吸引ロート内のコロイド溶液の液面が一定速度で降下する状態とすればよい。
(C)基板をコロイド溶液に浸漬し、基板を引き上げ、溶媒を蒸発させる方法
を挙げることができる。具体的には、固形分濃度が1質量%乃至5質量%の比較的希薄なコロイド溶液に、数十μmの間隔を開けて対向させた平滑な2枚の基板の下部を浸漬し、毛細管現象によりコロイド溶液を基板間に上昇させると共に、溶媒を蒸発除去することで、基板間に配合組成物を析出させることができる。この方法にあっても、用いるコロイド溶液の濃度の調整や、繰り返しの操作を行うことによって、所望の面積、容積の配合組成物を得ることができる。基板を引き上げる速度は特に限定されないが、コロイド溶液と大気との界面においてコロイド結晶体が成長するため、遅い速度で引き上げることが好ましい。また、溶媒を蒸発させる速度も特に限定されないが、同様の理由から遅い方が好ましい。例えば、単分散コロイド溶液を用いることにより、得られるコロイド結晶体を単結晶構造とすることができる。
(D)コロイド溶液に電場を加え、その後、溶媒を除去する方法
(E)分散したコロイド溶液を静置し、コロイド粒子を自然沈降させて堆積させた後、溶媒を除去する方法
(F)移流集積法
等の方法を例示することができる。
逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む電極用複合材料であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である。
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である。
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積BJH100の割合が30%以下である。
X線回折装置:株式会社リガク製 RIGAKU RINT-2000
加速電圧 :40キロボルト
電流 :40ミリアンペア
スリット :発散スリット1度、散乱スリット1度、受光スリット0.3mm
走査速度 :5度/分
ステップ幅 :0.02度
X線源 :CuKα=1.5418オングストローム
BJH2=BJH0/(多孔質炭素材料の含有率)
であり、
多孔質炭素材料の含有率=1-(硫化リチウム含有率)
である。リチウム含有率、硫化リチウム含有率、多孔質炭素材料の含有率、細孔容積BJH0,BJH2,BJH1の値を表3に示すが、細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、水洗後のBJH法による細孔容積BJH1は大きい。一方、比較例1Bにあっては、BJH2よりもBJH1は小さい。ところで、水洗後のBJH法による細孔容積BJH1は、硫化リチウムが除去された多孔質炭素材料、それ自体の細孔容積に概ね等しい。そして、実施例にあっては、多孔質炭素材料と硫化リチウムとの複合化によって、多孔質炭素材料の有する細孔内に硫化リチウムが侵入する。その結果、多孔質炭素材料と硫化リチウムとが複合化された電極用複合材料における多孔質炭素材料の細孔容積を表す値BJH2は、水洗後のBJH法による細孔容積BJH1(硫化リチウムが除去された多孔質炭素材料、それ自体の細孔容積に概ね等しい)よりも小さくなる。一方、比較例1Bにおいて、BJH2よりもBJH1が小さいが、このことは、比較例1Bにあっては、アセチレンブラックの表面に硫化リチウムが単に付着しただけであるためと考えられる。
半値幅
実施例1A-1 0.22度
実施例1A-2 0.22度
実施例1A-3 0.22度
実施例1B-1 0.26度
実施例1B-2 0.26度
質量%
実施例1A-2 78
KB6 12
PVDF 10
電流 :0.05C
カットオフ:放電時1.8ボルト(但し、定電流放電)
充電時3.3ボルト(但し、定電流/定電圧充電)
[表6-2]
電流 :0.05C
カットオフ:放電時1.5ボルト(但し、定電流放電)
充電時3.3ボルト(但し、定電流/定電圧充電)
質量%
比較例1A 87
KB6 3
PVA 10
質量%
比較例1B 78
VGCF 6
PVDF 10
質量%
硫化リチウム 60
KB6 30
PVA 10
電流 :0.05C
カットオフ:放電時1.6ボルト(但し、定電流放電)
充電時2.8ボルト(但し、定電流/定電圧充電)
電流 :0.05C
カットオフ:放電時1.8ボルト(但し、定電流放電)
充電時3.7ボルト(但し、定電流/定電圧充電)
質量%
実施例1A-3 78
KB6 6
VGCF 6
PVDF 10
電流 :0.05C
カットオフ:放電時1.5ボルト(但し、定電流放電)
充電時3.7ボルト(但し、定電流/定電圧充電)
電流 :0.05C
カットオフ:放電時0.0ボルト(但し、定電流放電)
充電時3.7ボルト(但し、定電流/定電圧充電)
電流 :0.05C
カットオフ:放電時0.0ボルト(但し、定電流放電)
充電時4.3ボルト(但し、定電流/定電圧充電)
[A01]《電極用複合材料:第1の態様》
MP法による細孔容積MPPCが0.1cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0は0.1cm3/グラム未満である電極用複合材料。
[A02]《電極用複合材料:第2の態様》
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料。
[A03]《電極用複合材料:第3の態様》
BJH法による100nm未満の細孔容積BJHPCが0.3cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満である電極用複合材料。
[A04]《電極用複合材料:第4の態様》
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満であり、且つ、水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料。
[A05]BJH法による100nm以上の細孔容積BJH100の割合は30%以下である[A03]又は[A04]に記載の電極用複合材料。
[A06]細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、水洗後のBJH法による細孔容積BJH1は大きい[A03]乃至[A05]のいずれか1項に記載の電極用複合材料。
[A07]植物由来の多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
MP法による細孔容積MP0は0.1cm3/グラム未満である[A03]乃至[A06]のいずれか1項に記載の電極用複合材料。
[A08]MP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[A03]乃至[A06]のいずれか1項に記載の電極用複合材料。
[A09]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[A01]乃至[A08]のいずれか1項に記載の電極用複合材料。
[A10]多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[A01]乃至[A09]のいずれか1項に記載の電極用複合材料。
[A11]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[A01]乃至[A10]のいずれか1項に記載の電極用複合材料。
[A12]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[A01]乃至[A11]のいずれか1項に記載の電極用複合材料。
[B01]《電極用複合材料:第5の態様》
逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む電極用複合材料であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である電極用複合材料。
[B02]BJH法による100nm以上の細孔容積BJH100の割合は30%以下である[B01]に記載の電極用複合材料。
[B03]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[B01]又は[B02]に記載の電極用複合材料。
[B04]《電極用複合材料:第6の態様》
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である電極用複合材料。
[B05]《電極用複合材料:第7の態様》
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積BJH100の割合が30%以下である電極用複合材料。
[B06]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[B05]に記載の電極用複合材料。
[B07]多孔質炭素材料は植物由来の材料を原料としており、
多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
MP法による細孔容積MP0は0.1cm3/グラム未満である[B01]乃至[B06]のいずれか1項に記載の電極用複合材料。
[B08]多孔質炭素材料は植物由来の材料を原料としており、
MP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[B01]乃至[B07]のいずれか1項に記載の電極用複合材料。
[B09]多孔質炭素材料は植物由来の材料を原料としており、
植物由来の多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCは0.3cm3/グラム以上であり、
BJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満である[B01]乃至[B08]のいずれか1項に記載の電極用複合材料。
[B10]多孔質炭素材料は植物由来の材料を原料としており、
BJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満であり、且つ、水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい[B01]乃至[B08]のいずれか1項に記載の電極用複合材料。
[B11]BJH法による100nm以上の細孔容積BJH100の割合は30%以下である[B01]乃至[B10]のいずれか1項に記載の電極用複合材料。
[B12]細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、水洗後のBJH法による細孔容積BJH1は大きい[B01]乃至[B11]のいずれか1項に記載の電極用複合材料。
[B13]植物由来の多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[B01]乃至[B12]のいずれか1項に記載の電極用複合材料。
[B14]逆オパール構造を有する多孔質炭素材料において、細孔は、3次元的規則性を有し、巨視的に結晶構造を構成する配置で配列されている[B01]乃至[B06]のいずれか1項に記載の電極用複合材料。
[B15]細孔が巨視的に材料表面に面心立方格子の(1,1,1)面配向で配列している[B14]に記載の電極用複合材料。
[B16]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[B01]乃至[B15]のいずれか1項に記載の電極用複合材料。
[B17]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[B01]乃至[B16]のいずれか1項に記載の電極用複合材料。
[C01]《二次電池:第1の態様》
MP法による細孔容積MPPCが0.1cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0が0.1cm3/グラム未満である電極用複合材料から作製された電極を備えている二次電池。
[C02]《二次電池:第2の態様》
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0が0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料から作製された電極を備えている二次電池。
[C03]《二次電池:第3の態様》
BJH法による100nm未満の細孔容積BJHPCが0.3cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満である電極用複合材料から作製された電極を備えている二次電池。
[C04]《二次電池:第4の態様》
植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満であり、且つ、水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料から作製された電極を備えている二次電池。
[C05]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である「C03]又は[C04]に記載の二次電池。
[C06]電極用複合材料の細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、電極用複合材料の水洗後のBJH法による細孔容積BJH1は大きい[C03]乃至[C05]のいずれか1項に記載の二次電池。
[C07]植物由来の多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
電極用複合材料のMP法による細孔容積MP0が0.1cm3/グラム未満である[C03]乃至[C06]のいずれか1項に記載の二次電池。
[C08]電極用複合材料のMP法による細孔容積MP0が0.1cm3/グラム未満であり、且つ、電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[C03]又は[C06]に記載の二次電池。
[C09]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[C01]乃至[C08]のいずれか1項に記載の二次電池。
[C10]多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[C01]乃至[C09]のいずれか1項に記載の二次電池。
[C11]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[C01]乃至[C10]のいずれか1項に記載の二次電池。
[C12]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[C01]乃至[C11]のいずれか1項に記載の二次電池。
[D01]《二次電池:第5の態様》
逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である電極用複合材料から作製された電極を備えている二次電池。
[D02]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である[D01]に記載の二次電池。
[D03]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[D01]又は[D02]に記載の二次電池。
[D04]《二次電池:第6の態様》
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である電極用複合材料から作製された電極を備えている二次電池。
[D05]《電極用複合材料:第7の態様》
多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積BJH100の割合が30%以下である電極用複合材料から作製された電極を備えている二次電池。
[D06]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[D05]に記載の二次電池。
[D07]多孔質炭素材料は植物由来の材料を原料としており、
多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満である[D01]乃至[D06]のいずれか1項に記載の二次電池。
[D08]多孔質炭素材料は植物由来の材料を原料としており、
電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[D01]乃至[D07]のいずれか1項に記載の二次電池。
[D09]多孔質炭素材料は植物由来の材料を原料としており、
植物由来の多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCは0.3cm3/グラム以上であり、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満である[D01]乃至[D08]のいずれか1項に記載の二次電池。
[D10]多孔質炭素材料は植物由来の材料を原料としており、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満であり、且つ、電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい[D01]乃至[D08]のいずれか1項に記載の二次電池。
[D11]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である[D01]乃至[D10]のいずれか1項に記載の二次電池。
[D12]電極用複合材料の細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、電極用複合材料の水洗後のBJH法による細孔容積BJH1は大きい[D01]乃至[D11]のいずれか1項に記載の二次電池。
[D13]植物由来の多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[D01]乃至[D12]のいずれか1項に記載の二次電池。
[D14]逆オパール構造を有する多孔質炭素材料において、細孔は、3次元的規則性を有し、巨視的に結晶構造を構成する配置で配列されている[D01]乃至[D06]のいずれか1項に記載の二次電池。
[D15]細孔が巨視的に材料表面に面心立方格子の(1,1,1)面配向で配列している[D14]に記載の二次電池。
[D16]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[D01]乃至[D15]のいずれか1項に記載の二次電池。
[D17]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[D01]乃至[D16]のいずれか1項に記載の二次電池。
[E01]電極は正極を構成する[C01]乃至[D17]のいずれか1項に記載の二次電池。
[E02]リチウム-硫黄二次電池から成る[C01]乃至[E01]のいずれか1項に記載の二次電池。
[E03]グライムとアルカリ金属塩との少なくとも一部が錯体を形成している電解液が含まれている[E01]又は[E02]に記載の二次電池。
[F01]《電極用複合材料の製造方法:第1の態様》
溶媒中で水硫化リチウムを生成させた後、MP法による細孔容積MPPCが0.1cm3/グラム以上である植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のMP法による細孔容積MP0が0.1cm3/グラム未満である電極用複合材料の製造方法。
[F02]《電極用複合材料の製造方法:第2の態様》
溶媒中で水硫化リチウムを生成させた後、植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のMP法による細孔容積MP0が0.1cm3/グラム未満であり、
電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料の製造方法。
[F03]《電極用複合材料の製造方法:第3の態様》
溶媒中で水硫化リチウムを生成させた後、BJH法による100nm未満の細孔容積BJHPCが0.3cm3/グラム以上である植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満である電極用複合材料の製造方法。
[F04]《電極用複合材料の製造方法:第4の態様》
溶媒中で水硫化リチウムを生成させた後、植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満であり、
電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料の製造方法。
[F05]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である[F03]又は[F04]に記載の電極用複合材料の製造方法。
[F06]電極用複合材料の細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、電極用複合材料の水洗後のBJH法による細孔容積BJH1は大きい[F03]乃至[F05]のいずれか1項に記載の電極用複合材料の製造方法。
[F07]植物由来の多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満である[F03]乃至[F06]のいずれか1項に記載の電極用複合材料の製造方法。
[F08]電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[F03]乃至[F06]のいずれか1項に記載の電極用複合材料の製造方法。
[F09]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[F01]乃至[F08]のいずれか1項に記載の電極用複合材料の製造方法。
[F10]多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[F01]乃至[F09]のいずれか1項に記載の電極用複合材料の製造方法。
[F11]400゜C乃至1400゜Cにて炭素化した後、酸又はアルカリで処理することで、多孔質炭素材料を得る[F10]に記載の電極用複合材料の製造方法。
[F12]酸又はアルカリで処理した後、炭素化における温度を超える温度で加熱処理を行う[F11]に記載の電極用複合材料の製造方法。
[F13]酸又はアルカリでの処理によって、炭素化後の植物由来の材料中のケイ素成分を除去する[F10]乃至[F12]のいずれか1項に記載の電極用複合材料の製造方法。
[F14]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[F01]乃至[F13]のいずれか1項に記載の電極用複合材料の製造方法。
[F15]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[F01]乃至[F14]のいずれか1項に記載の電極用複合材料の製造方法。
[G01]《電極用複合材料の製造方法:第5の態様》
溶媒中で水硫化リチウムを生成させた後、逆オパール構造の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が、多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCの20%以下である電極用複合材料の製造方法。
[G02]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である[G01]に記載の電極用複合材料の製造方法。
[G03]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[G01]又は[G02]に記載の電極用複合材料の製造方法。
[G04]《電極用複合材料の製造方法:第6の態様》
溶媒中で水硫化リチウムを生成させた後、多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である電極用複合材料の製造方法。
[G05]《電極用複合材料の製造方法:第7の態様》
溶媒中で水硫化リチウムを生成させた後、多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合が30%以下である電極用複合材料の製造方法。
[G06]多孔質炭素材料の平均粒径は、0.1μm以上、好ましくは0.5μm以上、より好ましくは1.0μm以上、75μm以下、好ましくは50μm以下、より好ましくは35μm以下である[G05]に記載の電極用複合材料の製造方法。
[G07]多孔質炭素材料は植物由来の材料を原料としており、
多孔質炭素材料のMP法による細孔容積MPPCは0.1cm3/グラム以上であり、
電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満である[G01]乃至[G06]のいずれか1項に記載の電極用複合材料の製造方法。
[G08]多孔質炭素材料は植物由来の材料を原料としており、
電極用複合材料のMP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい[G01]乃至[G07]のいずれか1項に記載の電極用複合材料の製造方法。
[G09]多孔質炭素材料は植物由来の材料を原料としており、
植物由来の多孔質炭素材料のBJH法による100nm未満の細孔容積BJHPCは0.3cm3/グラム以上であり、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満である[G01]乃至[G08]のいずれか1項に記載の電極用複合材料の製造方法。
[G10]多孔質炭素材料は植物由来の材料を原料としており、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満であり、且つ、電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい[G01]乃至[G08]のいずれか1項に記載の電極用複合材料の製造方法。
[G11]電極用複合材料のBJH法による100nm以上の細孔容積BJH100の割合は30%以下である[G01]乃至[G10]のいずれか1項に記載の電極用複合材料の製造方法。
[G12]電極用複合材料の細孔容積BJH0を多孔質炭素材料の含有率で除した値BJH2よりも、電極用複合材料の水洗後のBJH法による細孔容積BJH1は大きい[G01]乃至[G11]のいずれか1項に記載の電極用複合材料の製造方法。
[G13]植物由来の多孔質炭素材料は、ケイ素の含有率が5質量%以上である植物由来の材料を原料としている[G01]乃至[G12]のいずれか1項に記載の電極用複合材料の製造方法。
[G14]400゜C乃至1400゜Cにて炭素化した後、酸又はアルカリで処理することで、多孔質炭素材料を得る[G13]に記載の電極用複合材料の製造方法。
[G15]酸又はアルカリで処理した後、炭素化における温度を超える温度で加熱処理を行う[G14]に記載の電極用複合材料の製造方法。
[G16]酸又はアルカリでの処理によって、炭素化後の植物由来の材料中のケイ素成分を除去する[G13]乃至[G15]のいずれか1項に記載の電極用複合材料の製造方法。
[G17]逆オパール構造を有する多孔質炭素材料において、細孔は、3次元的規則性を有し、巨視的に結晶構造を構成する配置で配列されている[G01]乃至[G06]のいずれか1項に記載の電極用複合材料の製造方法。
[G18]細孔が巨視的に材料表面に面心立方格子の(1,1,1)面配向で配列している[G17]に記載の電極用複合材料の製造方法。
[G19]硫化リチウムの{220}面のX線回折強度のピーク半値幅は、0.37度以下である[G01]乃至[G18]のいずれか1項に記載の電極用複合材料の製造方法。
[G20]多孔質炭素材料の窒素BET法による比表面積の値は100m2/グラム以上である[G01]乃至[G19]のいずれか1項に記載の電極用複合材料の製造方法。
[H01]溶媒中での水硫化リチウムの生成は、溶媒に水酸化リチウムを添加し、硫化水素ガスでバブリングすることによってなされる[F01]乃至[G20]のいずれか1項に記載の電極用複合材料の製造方法。
[H02]多孔質炭素材料を加えた後の加熱の温度は、150゜C乃至230゜Cである[F01]乃至[H01]のいずれか1項に記載の電極用複合材料の製造方法。
Claims (21)
- MP法による細孔容積が0.1cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積は0.1cm3/グラム未満である電極用複合材料。 - 植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0は0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料。 - BJH法による100nm未満の細孔容積が0.3cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積は0.3cm3/グラム未満である電極用複合材料。 - 植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0は0.3cm3/グラム未満であり、且つ、水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料。 - 逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む電極用複合材料であって、
電極用複合材料のBJH法による100nm未満の細孔容積が、多孔質炭素材料のBJH法による100nm未満の細孔容積の20%以下である電極用複合材料。 - 多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、75μm以下である電極用複合材料。 - 多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積の割合が30%以下である電極用複合材料。 - MP法による細孔容積が0.1cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積が0.1cm3/グラム未満である電極用複合材料から作製された電極を備えている二次電池。 - 植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
MP法による細孔容積MP0が0.1cm3/グラム未満であり、且つ、水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料から作製された電極を備えている二次電池。 - BJH法による100nm未満の細孔容積が0.3cm3/グラム以上である植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積が0.3cm3/グラム未満である電極用複合材料から作製された電極を備えている二次電池。 - 植物由来の多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満であり、且つ、水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料から作製された電極を備えている二次電池。 - 逆オパール構造を有する多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含む電極用複合材料から作製された電極を備えた二次電池であって、
電極用複合材料のBJH法による100nm未満の細孔容積が、多孔質炭素材料のBJH法による100nm未満の細孔容積の20%以下である二次電池。 - 多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
多孔質炭素材料の平均粒径は、0.1μm以上、75μm以下である二次電池。 - 多孔質炭素材料、及び、
多孔質炭素材料の有する細孔に担持された硫化リチウム、
を含み、
BJH法による100nm以上の細孔容積の割合が30%以下である電極用複合材料から作製された電極を備えている二次電池。 - 溶媒中で水硫化リチウムを生成させた後、MP法による細孔容積が0.1cm3/グラム以上である植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のMP法による細孔容積が0.1cm3/グラム未満である電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のMP法による細孔容積MP0が0.1cm3/グラム未満であり、
電極用複合材料の水洗後のMP法による細孔容積MP1は細孔容積MP0よりも大きい電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、BJH法による100nm未満の細孔容積が0.3cm3/グラム以上である植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積が0.3cm3/グラム未満である電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、植物由来の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積BJH0が0.3cm3/グラム未満であり、
電極用複合材料の水洗後のBJH法による100nm未満の細孔容積BJH1は細孔容積BJH0よりも大きい電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、逆オパール構造の多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm未満の細孔容積が、多孔質炭素材料のBJH法による100nm未満の細孔容積の20%以下である電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
多孔質炭素材料の平均粒径は、0.1μm以上、75μm以下である電極用複合材料の製造方法。 - 溶媒中で水硫化リチウムを生成させた後、多孔質炭素材料を加え、加熱することで、多孔質炭素材料、及び、多孔質炭素材料の有する細孔に担持された硫化リチウムを含む電極用複合材料を得る電極用複合材料の製造方法であって、
電極用複合材料のBJH法による100nm以上の細孔容積の割合が30%以下である電極用複合材料の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014557421A JP6292127B2 (ja) | 2013-01-18 | 2014-01-06 | 電極用複合材料の製造方法 |
KR1020157016110A KR20150108352A (ko) | 2013-01-18 | 2014-01-06 | 전극용 복합 재료 및 그 제조 방법 및 이차 전지 |
US14/760,614 US20150357637A1 (en) | 2013-01-18 | 2014-01-06 | Composite material for electrodes, method for producing same, and secondary battery |
CA2897709A CA2897709A1 (en) | 2013-01-18 | 2014-01-06 | Composite material for electrodes, method for producing same, and secondary battery |
CN201480004594.1A CN105122519B (zh) | 2013-01-18 | 2014-01-06 | 电极用复合材料、用于制备复合材料的方法、及二次电池 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-007439 | 2013-01-18 | ||
JP2013007439 | 2013-01-18 | ||
JP2013-249512 | 2013-02-12 | ||
JP2013249512 | 2013-12-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014112401A1 true WO2014112401A1 (ja) | 2014-07-24 |
Family
ID=51209494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/050035 WO2014112401A1 (ja) | 2013-01-18 | 2014-01-06 | 電極用複合材料及びその製造方法並びに二次電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20150357637A1 (ja) |
JP (2) | JP6292127B2 (ja) |
KR (1) | KR20150108352A (ja) |
CN (1) | CN105122519B (ja) |
CA (1) | CA2897709A1 (ja) |
WO (1) | WO2014112401A1 (ja) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016009936A1 (ja) * | 2014-07-15 | 2016-01-21 | 東レ株式会社 | 電極材料、リチウム硫黄電池電極、リチウム硫黄電池および電極材料の製造方法 |
JP2016115417A (ja) * | 2014-12-11 | 2016-06-23 | 株式会社リコー | リチウム硫黄2次電池に用いる正極、リチウム硫黄2次電池 |
JP2016127005A (ja) * | 2014-12-31 | 2016-07-11 | 現代自動車株式会社Hyundai Motor Company | 全固体リチウム電池の陽極及びこれを含む二次電池 |
JP2017222567A (ja) * | 2016-06-14 | 2017-12-21 | 出光興産株式会社 | 硫化リチウム、及びその製造方法 |
JP2017222547A (ja) * | 2016-06-16 | 2017-12-21 | 進和テック株式会社 | 活性炭の製造方法及び活性炭製造システム |
WO2018056126A1 (ja) * | 2016-09-26 | 2018-03-29 | デクセリアルズ株式会社 | 多孔質炭素材料、及びその製造方法、並びに合成反応用触媒 |
US10411261B2 (en) | 2014-08-08 | 2019-09-10 | Kureha Corporation | Carbonaceous material for non-aqueous electrolyte secondary battery anodes |
US10424790B2 (en) | 2014-08-08 | 2019-09-24 | Kureha Corporation | Carbonaceous material for non-aqueous electrolyte secondary battery anode |
JP2020149794A (ja) * | 2019-03-11 | 2020-09-17 | トヨタ自動車株式会社 | 非水系リチウムイオン二次電池 |
US10797319B2 (en) | 2014-08-08 | 2020-10-06 | Kureha Corporation | Production method for carbonaceous material for non-aqueous electrolyte secondary battery anode, and carbonaceous material for non-aqueous electrolyte secondary battery anode |
JP2020534241A (ja) * | 2017-11-08 | 2020-11-26 | エルジー・ケム・リミテッド | 多孔性炭素、これを含む正極及びリチウム二次電池 |
CN114597366A (zh) * | 2022-03-11 | 2022-06-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | 超高活性复合材料、其制备方法及在镁硫电池中的应用 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6180681B1 (ja) * | 2015-09-30 | 2017-08-16 | 株式会社クレハ | 非水電解質二次電池負極用炭素質材料及びその製造方法 |
CN108315028B (zh) * | 2017-01-16 | 2020-12-01 | 中国科学院物理研究所 | 一种具有纵向孔结构的热解硬碳材料及其制备方法和应用 |
JP6646088B2 (ja) * | 2018-02-21 | 2020-02-14 | デクセリアルズ株式会社 | 多孔質炭素材料、及びその製造方法、並びに合成反応用触媒 |
US20210391577A1 (en) * | 2018-10-10 | 2021-12-16 | Hunan Jinye High-tech Co., Ltd. | Lithium-ion battery negative electrode active material, lithium-ion battery negative electrode, lithium ion battery, battery pack and battery-powered vehicle |
JP2022509607A (ja) | 2018-11-13 | 2022-01-21 | ピッツバーグ ステート ユニバーシティ | 活性炭電極材料 |
JP7122981B2 (ja) * | 2019-01-31 | 2022-08-22 | 株式会社日本マイクロニクス | 二次電池 |
JP7383254B2 (ja) | 2019-02-25 | 2023-11-20 | 日産自動車株式会社 | 硫黄活物質含有電極組成物、並びにこれを用いた電極および電池 |
US10840553B2 (en) * | 2019-03-01 | 2020-11-17 | Ses Holdings Pte. Ltd. | Free-solvent-free lithium sulfonamide salt compositions that are liquid at room temperature, and uses thereof in lithium ion battery |
EP3718967A1 (en) * | 2019-04-02 | 2020-10-07 | Heraeus Battery Technology GmbH | Process for the preparation of a porous carbonaceous material, an electrochemical energy storage device and a catalyst |
CN112794320A (zh) * | 2021-01-14 | 2021-05-14 | 广东凯金新能源科技股份有限公司 | 一种高容量高压实低反弹多孔球型碳负极材料及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07330312A (ja) * | 1994-06-03 | 1995-12-19 | Idemitsu Petrochem Co Ltd | 硫化リチウムの製造方法 |
JP2003197196A (ja) * | 2001-12-19 | 2003-07-11 | Samsung Sdi Co Ltd | カソード電極、その製造方法およびこれを採用したリチウム電池 |
WO2008123606A1 (ja) * | 2007-04-04 | 2008-10-16 | Sony Corporation | 多孔質炭素材料及びその製造方法、並びに、吸着剤、マスク、吸着シート及び担持体 |
WO2010035602A1 (ja) * | 2008-09-24 | 2010-04-01 | 独立行政法人産業技術総合研究所 | 硫化リチウム-炭素複合体、その製造方法、及び該複合体を用いるリチウムイオン二次電池 |
JP2010095390A (ja) * | 2008-09-16 | 2010-04-30 | Tokyo Institute Of Technology | メソポーラス炭素複合材料およびこれを用いた二次電池 |
WO2012102037A1 (ja) * | 2011-01-27 | 2012-08-02 | 出光興産株式会社 | アルカリ金属硫化物と導電剤の複合材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100514510C (zh) * | 2004-06-04 | 2009-07-15 | 出光兴产株式会社 | 高性能全固体锂电池 |
WO2010064715A1 (en) * | 2008-12-04 | 2010-06-10 | Canon Kabushiki Kaisha | Mesoporous silica film and process for production thereof |
JP5599573B2 (ja) * | 2009-04-10 | 2014-10-01 | 出光興産株式会社 | 固体電解質粒子からなるガラス及びリチウム電池 |
CN102763250A (zh) * | 2009-10-29 | 2012-10-31 | 小利兰·斯坦福大学托管委员会 | 用于先进的可充电电池组的器件、系统和方法 |
EP2583336A4 (en) * | 2010-06-17 | 2013-12-11 | Linda Faye Nazar | MULTI-COMPONENT ELECTRODES FOR RECHARGEABLE BATTERIES |
WO2012045002A1 (en) * | 2010-09-30 | 2012-04-05 | Energ2 Technologies, Inc. | Enhanced packing of energy storage particles |
EP2707327B1 (en) * | 2011-05-11 | 2017-08-30 | FPInnovations Inc. | Chiral nematic mesoporous carbon |
-
2014
- 2014-01-06 US US14/760,614 patent/US20150357637A1/en not_active Abandoned
- 2014-01-06 KR KR1020157016110A patent/KR20150108352A/ko not_active Application Discontinuation
- 2014-01-06 CA CA2897709A patent/CA2897709A1/en not_active Abandoned
- 2014-01-06 JP JP2014557421A patent/JP6292127B2/ja active Active
- 2014-01-06 CN CN201480004594.1A patent/CN105122519B/zh active Active
- 2014-01-06 WO PCT/JP2014/050035 patent/WO2014112401A1/ja active Application Filing
-
2018
- 2018-02-14 JP JP2018024190A patent/JP6658777B2/ja active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07330312A (ja) * | 1994-06-03 | 1995-12-19 | Idemitsu Petrochem Co Ltd | 硫化リチウムの製造方法 |
JP2003197196A (ja) * | 2001-12-19 | 2003-07-11 | Samsung Sdi Co Ltd | カソード電極、その製造方法およびこれを採用したリチウム電池 |
WO2008123606A1 (ja) * | 2007-04-04 | 2008-10-16 | Sony Corporation | 多孔質炭素材料及びその製造方法、並びに、吸着剤、マスク、吸着シート及び担持体 |
JP2010095390A (ja) * | 2008-09-16 | 2010-04-30 | Tokyo Institute Of Technology | メソポーラス炭素複合材料およびこれを用いた二次電池 |
WO2010035602A1 (ja) * | 2008-09-24 | 2010-04-01 | 独立行政法人産業技術総合研究所 | 硫化リチウム-炭素複合体、その製造方法、及び該複合体を用いるリチウムイオン二次電池 |
WO2012102037A1 (ja) * | 2011-01-27 | 2012-08-02 | 出光興産株式会社 | アルカリ金属硫化物と導電剤の複合材料 |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016009936A1 (ja) * | 2014-07-15 | 2016-01-21 | 東レ株式会社 | 電極材料、リチウム硫黄電池電極、リチウム硫黄電池および電極材料の製造方法 |
US10797319B2 (en) | 2014-08-08 | 2020-10-06 | Kureha Corporation | Production method for carbonaceous material for non-aqueous electrolyte secondary battery anode, and carbonaceous material for non-aqueous electrolyte secondary battery anode |
US10411261B2 (en) | 2014-08-08 | 2019-09-10 | Kureha Corporation | Carbonaceous material for non-aqueous electrolyte secondary battery anodes |
US10424790B2 (en) | 2014-08-08 | 2019-09-24 | Kureha Corporation | Carbonaceous material for non-aqueous electrolyte secondary battery anode |
JP2016115417A (ja) * | 2014-12-11 | 2016-06-23 | 株式会社リコー | リチウム硫黄2次電池に用いる正極、リチウム硫黄2次電池 |
JP2016127005A (ja) * | 2014-12-31 | 2016-07-11 | 現代自動車株式会社Hyundai Motor Company | 全固体リチウム電池の陽極及びこれを含む二次電池 |
US11177472B2 (en) | 2014-12-31 | 2021-11-16 | Hyundai Motor Company | Cathode of all-solid lithium battery and secondary battery using the same |
JP2017222567A (ja) * | 2016-06-14 | 2017-12-21 | 出光興産株式会社 | 硫化リチウム、及びその製造方法 |
JP7014496B2 (ja) | 2016-06-14 | 2022-02-01 | 出光興産株式会社 | 硫化リチウム、及びその製造方法 |
JP2017222547A (ja) * | 2016-06-16 | 2017-12-21 | 進和テック株式会社 | 活性炭の製造方法及び活性炭製造システム |
WO2018056126A1 (ja) * | 2016-09-26 | 2018-03-29 | デクセリアルズ株式会社 | 多孔質炭素材料、及びその製造方法、並びに合成反応用触媒 |
JP2018052750A (ja) * | 2016-09-26 | 2018-04-05 | デクセリアルズ株式会社 | 多孔質炭素材料、及びその製造方法、並びに合成反応用触媒 |
US11504697B2 (en) | 2016-09-26 | 2022-11-22 | Dexerials Corporation | Porous carbon material, method for producing same, and synthesis reaction catalyst |
JP2020534241A (ja) * | 2017-11-08 | 2020-11-26 | エルジー・ケム・リミテッド | 多孔性炭素、これを含む正極及びリチウム二次電池 |
US11367866B2 (en) | 2017-11-08 | 2022-06-21 | Lg Energy Solution, Ltd. | Porous carbon, and positive electrode and lithium secondary battery comprising same |
JP7105877B2 (ja) | 2017-11-08 | 2022-07-25 | エルジー エナジー ソリューション リミテッド | 多孔性炭素、これを含む正極及びリチウム二次電池 |
US11631842B2 (en) | 2017-11-08 | 2023-04-18 | Lg Energy Solution, Ltd. | Porous carbon, and positive electrode and lithium secondary battery comprising same |
JP2020149794A (ja) * | 2019-03-11 | 2020-09-17 | トヨタ自動車株式会社 | 非水系リチウムイオン二次電池 |
JP7071701B2 (ja) | 2019-03-11 | 2022-05-19 | トヨタ自動車株式会社 | 非水系リチウムイオン二次電池 |
CN114597366A (zh) * | 2022-03-11 | 2022-06-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | 超高活性复合材料、其制备方法及在镁硫电池中的应用 |
CN114597366B (zh) * | 2022-03-11 | 2024-04-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | 超高活性复合材料、其制备方法及在镁硫电池中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN105122519B (zh) | 2019-04-09 |
JP6292127B2 (ja) | 2018-03-14 |
KR20150108352A (ko) | 2015-09-25 |
JPWO2014112401A1 (ja) | 2017-01-19 |
CN105122519A (zh) | 2015-12-02 |
CA2897709A1 (en) | 2014-07-24 |
JP6658777B2 (ja) | 2020-03-04 |
US20150357637A1 (en) | 2015-12-10 |
JP2018088420A (ja) | 2018-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6292127B2 (ja) | 電極用複合材料の製造方法 | |
Jagadale et al. | Influence of electrodeposition modes on the supercapacitive performance of Co3O4 electrodes | |
Narsimulu et al. | Surfactant-free microwave hydrothermal synthesis of SnO2 nanosheets as an anode material for lithium battery applications | |
JP6245253B2 (ja) | 空気−金属二次電池 | |
WO2014103480A1 (ja) | 二次電池用の電極材料及びその製造方法、並びに、二次電池 | |
CN106414326B (zh) | 纳米硅材料及其制造方法和二次电池的负极 | |
WO2013073400A1 (ja) | リチウムイオン二次電池用正極及びそれを用いたリチウムイオン二次電池 | |
WO2014167981A1 (ja) | 電極及びその製造方法、並びに、二次電池 | |
Sanad et al. | Chemical activation of nanocrystalline LiNbO3 anode for improved storage capacity in lithium-ion batteries | |
JP5760871B2 (ja) | リチウムイオン二次電池用正極材料、リチウムイオン二次電池用正極部材、リチウムイオン二次電池、及びリチウムイオン二次電池用正極材料の製造方法 | |
WO2014141769A1 (ja) | リチウム-硫黄二次電池及び電極材料 | |
JP6314382B2 (ja) | リチウム−硫黄二次電池用の電極材料及びリチウム−硫黄二次電池並びにリチウム−硫黄二次電池用の電極材料の製造方法 | |
JP6062445B2 (ja) | 負極材料の製造方法及び同方法による負極材料 | |
JP6476019B2 (ja) | 炭素−金属複合体 | |
KR20220071426A (ko) | 나트륨이차전지용 질소-도핑된 탄소가 코팅된 음극 활물질 및 그 제조방법 | |
Yang et al. | Electrochemical properties of spherical hollow composite powders with various Li4Ti5O12/SnO2 ratios prepared by spray pyrolysis | |
Shu et al. | Facile controlled growth of silica on carbon spheres and their superior electrochemical properties | |
JP6065678B2 (ja) | 負極活物質とその製造方法及び蓄電装置 | |
CA2950251C (en) | Silicon material and negative electrode of secondary battery | |
JP2012059570A (ja) | リチウム二次電池用正極活物質及びその製造方法 | |
WO2014156582A1 (ja) | 空気-金属二次電池 | |
CN108689404B (zh) | 活性炭微球、电极及超级电容器 | |
Khatavkar et al. | Liquid phase deposition of nanostructured materials for supercapacitor applications | |
WO2021128197A1 (zh) | 负极材料及包含其的电化学装置和电子装置 | |
EP4020617A1 (en) | Negative electrode material, and electrochemical device and electronic device comprising same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14741024 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014557421 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157016110 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2897709 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14760614 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14741024 Country of ref document: EP Kind code of ref document: A1 |