WO2018034155A1 - 非水電解質二次電池の負極活物質用の炭素質材料、非水電解質二次電池用負極、非水電解質二次電池ならびに炭素質材料の製造方法 - Google Patents
非水電解質二次電池の負極活物質用の炭素質材料、非水電解質二次電池用負極、非水電解質二次電池ならびに炭素質材料の製造方法 Download PDFInfo
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- H01M4/04—Processes of manufacture in general
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a carbonaceous material suitable for a negative electrode active material of a nonaqueous electrolyte secondary battery, a negative electrode for a nonaqueous electrolyte secondary battery containing the carbonaceous material, a nonaqueous electrolyte secondary battery having the negative electrode, and the carbonaceous material
- the present invention relates to a material manufacturing method.
- Patent Document 2 describes a carbonaceous material obtained by carbonizing a plant-derived carbon precursor after immersing it in an acid such as hydrochloric acid or water.
- Patent Document 3 describes a carbonaceous material obtained by subjecting a plant-derived organic material to a main firing after heat treatment in an inert gas atmosphere containing a halogen compound.
- Patent Document 4 is obtained by subjecting dry-distilled coal to halogenation treatment, preliminary pore adjustment treatment, dehalogenation treatment and pore adjustment treatment for the purpose of improving the charge / discharge characteristics of the lithium ion secondary battery.
- a carbon material for a lithium secondary battery is disclosed.
- JP-A-9-161801 Japanese Patent Laid-Open No. 10-21919 International Publication No. 2014/034858 Pamphlet JP 11-135108 A
- the present invention provides a carbonaceous material suitable for a negative electrode active material of a non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery) having a high charge / discharge capacity and charge / discharge efficiency and a low resistance, and the carbonaceous material. It is an object of the present invention to provide a negative electrode containing, a nonaqueous electrolyte secondary battery having the negative electrode, and a method for producing the carbonaceous material. Furthermore, another object of the present invention is to provide a negative electrode for a non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery) having a high charge / discharge capacity and charge / discharge efficiency and a low resistance maintained even after repeated charge / discharge. To provide a carbonaceous material suitable for an active material, a negative electrode including the carbonaceous material, a nonaqueous electrolyte secondary battery having the negative electrode, and a method for producing the carbonaceous material.
- a negative electrode including the carbonace
- a negative electrode for a nonaqueous electrolyte secondary battery comprising the carbonaceous material according to any one of [1] to [5].
- the non-aqueous electrolyte secondary battery using the negative electrode containing the carbonaceous material of the present invention has a high charge / discharge capacity, charge / discharge efficiency, and low resistance.
- a non-aqueous electrolyte secondary battery using a negative electrode containing a carbonaceous material has a high charge / discharge capacity and charge / discharge efficiency, and a low resistance that is maintained even after repeated charge / discharge. .
- FIG. 3 is a diagram showing a Raman spectrum of the carbonaceous material of Example 1.
- FIG. 6 is a diagram showing a Raman spectrum of a carbonaceous material of Comparative Example 1.
- FIG. 4 is a diagram showing a 7 Li nucleus-solid NMR spectrum of the carbonaceous material of Example 1.
- 7 is a graph showing a 7 Li nucleus-solid NMR spectrum of the carbonaceous material of Comparative Example 1.
- FIG. It is a figure which shows the Raman spectrum of the carbonaceous material of Example 6.
- It is a figure which shows the Raman spectrum of the carbonaceous material of the comparative example 5.
- 7 is a graph showing a 7 Li nucleus-solid NMR spectrum of the carbonaceous material of Example 6.
- FIG. 7 is a graph showing a 7 Li nucleus-solid NMR spectrum of a carbonaceous material of Comparative Example 5.
- the carbonaceous material of the present invention is derived from a plant, and for example, can be produced by heat-treating a plant-derived char under an inert gas stream containing a halogen compound.
- char generally indicates a powdery solid rich in carbon that is not melt-softened that is obtained when coal is heated.
- carbon that is not melt-softened that is obtained by heating organic matter It also shows a powdery solid rich in.
- plant raw material The plant used as the raw material for plant-derived char (hereinafter also referred to as “plant raw material”) is not particularly limited.
- coconut husks, coconut beans, tea leaves, sugar cane, fruits (eg, mandarin oranges, bananas), cocoons, rice husks, hardwoods, conifers, and bamboo can be exemplified.
- waste for example, used tea leaves
- part of plant materials for example, bananas and tangerine peels.
- coconut shells are preferred because they are easily available in large quantities.
- the coconut shell is not particularly limited, and examples thereof include palm coconut (coconut palm), coconut palm, salak, and coconut palm. These coconut shells can be used alone or in combination of two or more.
- Palm palm and palm palm coconut shells which are biomass wastes that are used as foods, detergent raw materials, biodiesel oil raw materials and the like and are generated in large quantities, are particularly preferred.
- the half-value width of the peak near 1360 cm ⁇ 1 of the Raman spectrum observed by laser Raman spectroscopy is 190 to 240 cm ⁇ 1 .
- the peak in the vicinity of 1360 cm ⁇ 1 is a Raman peak generally referred to as a D band, and is a peak due to disorder or defects in the graphite structure.
- Peak around 1360 cm -1 is usually, 1345cm -1 ⁇ 1375cm -1, is observed preferably in the range of 1350cm -1 ⁇ 1370cm -1.
- the half width of this peak is related to the amount of disorder / defects in the graphite structure contained in the carbonaceous material. If the full width at half maximum is smaller than the above lower limit, the graphite structure contained in the carbonaceous material has too few turbulences and defects, and due to the development of the graphite structure, the number of micropores between crystals decreases and lithium ions are occluded. Less. Therefore, problems such as a decrease in charge / discharge capacity occur. From this point of view, the half-value width of the peak around 1360 cm -1 is more preferable is preferably 195cm -1 or more, and 200 cm -1 or more.
- the half width is larger than the above upper limit, the graphite structure contained in the carbonaceous material has many turbulences / defects, more amorphous, more carbon edges, and a carbon-terminal reactive group that reacts with lithium. Will increase. Therefore, the utilization efficiency of lithium ions is lowered, and the charge / discharge efficiency is lowered. From this point of view, the half-value width of the peak around 1360 cm -1 is preferably not 235 cm -1 or less, more preferably 230 cm -1 or less.
- the measurement of the Raman spectrum is performed using a Raman spectrometer (for example, a Raman spectrometer “LabRAM ARAMIS (VIS)” manufactured by HORIBA, Ltd.).
- a Raman spectrometer for example, a Raman spectrometer “LabRAM ARAMIS (VIS)” manufactured by HORIBA, Ltd.
- the measurement target particle is set on the observation stage stage, the magnification of the objective lens is 100 times, the focus is adjusted, and the exposure time is 1 while irradiating the measurement cell with argon ion laser light of 532 nm. Measured with a second, 100 integrations, and a measurement range of 50-2000 cm ⁇ 1 .
- the specific surface area determined by the nitrogen adsorption BET multipoint method is 10 to 100 m 2 / g.
- the specific surface area is smaller than the above lower limit, the amount of lithium ions adsorbed on the carbonaceous material decreases, and the charge capacity of the nonaqueous electrolyte secondary battery decreases.
- the contact area between the carbonaceous material and the electrolytic solution is reduced and lithium ions are difficult to move, sufficient input / output characteristics cannot be obtained.
- the specific surface area determined by the nitrogen adsorption BET multipoint method is preferably 10 m 2 / g or more, and more preferably 15 m 2 / g or more.
- the specific surface area determined by the nitrogen adsorption BET multipoint method is preferably 100 m 2 / g or less, and more preferably 90 m 2 / g or less.
- the specific surface area by the nitrogen adsorption BET multipoint method can be measured by the method described later.
- the low magnetic field side with respect to the resonance peak of LiCl as the reference material It is preferable to observe a main resonance peak shifted by 115 to 145 ppm.
- a large shift value of the main resonance peak toward the low magnetic field indicates that a large amount of lithium is present in a cluster.
- the shift value toward the low magnetic field side is more preferably 142 ppm or less from the viewpoint of easily dissociating clusters and achieving quick charge / discharge, and is preferably 138 ppm or less. Even more preferred.
- a small shift value of the main resonance peak toward the low magnetic field indicates that the amount of lithium existing between the carbon layers is large. From the viewpoint of easily increasing the charge / discharge capacity, the shift value toward the low magnetic field is more preferably 120 ppm or more.
- the main resonance peak is observed means that the lithium species providing the main resonance peak is present at 3% or more which is the detection limit of the 7 Li nucleus-solid NMR analysis method described later. To do.
- “dope lithium until fully charged” means that a non-aqueous electrolyte secondary battery having an electrode containing a carbonaceous material as a positive electrode and an electrode containing metallic lithium as a negative electrode is assembled and terminated. It means that charging is carried out with a voltage of usually 0.1 to 0 mV, preferably 0.05 to 0 mV, more preferably 0.01 to 0 mV.
- the fully charged carbonaceous material usually has a capacity of 300 to 600 mAh / g, preferably 350 to 580 mAh / g.
- the details of the method for measuring the 7 Li nucleus-solid NMR spectrum are as described later, and can be measured using a nuclear magnetic resonance apparatus (for example, “AVANCE300” manufactured by BRUKER).
- AVANCE300 manufactured by BRUKER
- the method for adjusting the chemical shift value of the main resonance peak toward the low magnetic field to the above range is not limited at all.
- plant-derived char is charged with an inert gas containing a halogen compound at a temperature of 1100 to 1300 ° C.
- a method of performing heat treatment while supplying at an amount of 14 L / min or more per 50 g can be used.
- the calcium element content is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 35 ppm or less.
- the calcium element content is not more than the above upper limit, it is easy to suppress problems such as short-circuiting of the battery, which may occur when the calcium element is eluted into the electrolytic solution and re-deposited.
- the pores of the carbonaceous material are not easily blocked, the charge / discharge capacity of the battery is easily maintained.
- the content of calcium element in the carbonaceous material is preferably as low as possible, and it is particularly preferable that the carbonaceous material does not substantially contain calcium element.
- substantially not contained means that it is 10 ⁇ 6 mass% or less which is the detection limit of the elemental analysis method (inert gas melting-heat conduction method) described later.
- the method for adjusting the calcium element content to the above range is not limited at all. For example, a method of heat treating plant-derived char while supplying an inert gas containing a halogen compound can be used.
- the potassium element content is preferably 50 ppm or less, more preferably 30 ppm or less, and even more preferably 10 ppm or less.
- the potassium element content is not more than the above upper limit, it is easy to suppress problems such as short-circuiting of the battery, which may occur when the potassium element is eluted into the electrolytic solution and re-deposited.
- the pores of the carbonaceous material are not easily blocked, the charge / discharge capacity of the battery is easily maintained.
- the potassium element content in the carbonaceous material is preferably as low as possible, and it is particularly preferable that the carbonaceous material does not substantially contain potassium element.
- substantially not contained means that it is 10 ⁇ 6 mass% or less which is the detection limit of the elemental analysis method (inert gas melting-heat conduction method) described later.
- the method for adjusting the potassium element content to the above range is not limited at all, but a method of heat treating plant-derived char while supplying an inert gas containing a halogen compound can be used.
- the potassium element content can be measured in the same manner as the measurement of the calcium element content.
- the carbonaceous material of the present invention preferably has a true density ⁇ Bt by the butanol method of 1.35 to 1.70 g / cm 3 from the viewpoint of increasing the capacity per mass of the battery, and is 1.40 to 1. More preferably, it is 65 / cm 3 , and even more preferably 1.44 to 1.60 / cm 3 .
- ⁇ Bt a true density ⁇ Bt by the butanol method of 1.35 to 1.70 g / cm 3 from the viewpoint of increasing the capacity per mass of the battery, and is 1.40 to 1. More preferably, it is 65 / cm 3 , and even more preferably 1.44 to 1.60 / cm 3 .
- Details of the measurement of the true density ⁇ Bt are as described in the examples, and can be measured by a butanol method according to the method defined in JIS R 7212.
- a carbonaceous material having such a true density can be produced, for example, by firing plant-derived char at 1100 to 1300 ° C.
- the mesopore volume calculated by the DFT method is preferably 0.005 to 0.1 mL / g, more preferably 0.01 to 0.085 mL / g, and still more preferably 0.00. 01-0.07 mL / g.
- the mesopore volume is equal to or more than the above lower limit, the electrolyte can easily permeate and resistance can be lowered, and pore clogging due to decomposition products generated during repeated charge and discharge can be suppressed, thereby increasing resistance. It is preferable because it is easy to avoid.
- mesopore volume is equal to or less than the above upper limit because a decrease in bulk density can be suppressed and the electrode density is easily increased.
- mesopores are pores having a pore diameter (pore diameter) of 2 nm to 50 nm in the DFT method.
- the micropore volume calculated by the DFT method is preferably 0.001 to 0.1 mL / g, more preferably 0.003 to 0.05 mL / g, and still more preferably 0.00. 005 to 0.04 mL / g. It is preferable for the micropore volume to be equal to or greater than the above lower limit because adsorption and desorption of Li ions are easily generated. Moreover, it is preferable for the micropore volume to be equal to or less than the above upper limit because it is easy to suppress the reaction between the carbonaceous material and moisture generated during charge / discharge due to moisture adsorption or the like. In the present specification, micropores are pores having a pore diameter (pore diameter) of less than 2 nm in the DFT method.
- the DFT method uses molecular dynamics and computer simulation methods to calculate the equilibrium density profile of the gas adsorbed on the surface and pores of the object to be adsorbed. It is an analysis technique that can be calculated. Since this analysis method can be applied to the entire region of micropores and mesopores, the micropore volume, mesopore volume, and micropore / mesopore distribution can be measured simultaneously. In the present invention, the micropore volume and the mesopore volume can be calculated by applying the DFT method to the nitrogen adsorption / desorption isotherm measured by the nitrogen adsorption method.
- the ratio of the mesopore volume to the micropore volume (calculated by the formula of mesopore volume / micropore volume, which is calculated by the above-described method. Is also preferably 1.0 or more.
- the mesopore volume / micropore volume is less than 1.0, it tends to be difficult to obtain a carbonaceous material suitable for producing a battery having a low internal resistance. In particular, the resistance value is low when charging and discharging are repeated. There is a tendency not to maintain. From such a viewpoint, the mesopore volume / micropore volume is more preferably 1.3 or more, and further preferably 1.5 or more.
- the reason why the above effect is obtained is not clear, but some of the micropores are blocked by repeated charging and discharging, and the resistance becomes high and lithium ions can no longer be occluded. Such clogging is unlikely to occur in mesopores having larger pore diameters. Therefore, it is considered that a low resistance value is maintained when the mesopore volume is more than a certain value.
- the upper limit of said mesopore volume / micropore volume may be 3.0 or less, for example.
- the average particle diameter (D 50 ) of the carbonaceous material of the present invention is preferably 2 to 30 ⁇ m from the viewpoint of coatability during electrode production. It is preferable that the average particle diameter is not less than the above lower limit because an increase in specific surface area due to fine powder in the carbonaceous material and an increase in reactivity with the electrolytic solution are suppressed, and an increase in irreversible capacity is easily suppressed. Moreover, when manufacturing a negative electrode using the obtained carbonaceous material, the space
- the average particle diameter (D 50 ) of the carbonaceous material of the present invention is more preferably 3 ⁇ m or more, even more preferably 4 ⁇ m or more, particularly preferably 5 ⁇ m or more, and most preferably 7 ⁇ m or more.
- the average particle diameter is not more than the above upper limit, since there are few free diffusion steps of lithium ions in the particles and rapid charge / discharge is easily obtained.
- the average particle size is more preferably 20 ⁇ m or less, even more preferably 18 ⁇ m or less, particularly preferably 16 ⁇ m or less, and most preferably 15 ⁇ m or less.
- D 50 is the particle diameter at which the cumulative volume is 50%.
- the particle size distribution is measured by a laser scattering method using a particle diameter / particle size distribution measuring device (“Microtrack MT3300EXII” manufactured by Microtrack Bell Co., Ltd.). Can be obtained.
- the carbonaceous material of the present invention includes, for example, a step of heat-treating plant-derived char at 1100 to 1300 ° C. in an inert gas stream containing a halogen compound, and the supply amount of the inert gas containing the halogen compound is plant It can be obtained by a production method of 14 L / min or more per 50 g of the derived char.
- the present invention also provides the above manufacturing method.
- this process is also referred to as “gas phase demineralization process”.
- the carbonaceous material of the present invention is derived from plants as described above.
- a carbonaceous material manufactured from plant-derived char can be doped with a large amount of Li ions, and thus is basically suitable as a negative electrode material for a non-aqueous electrolyte secondary battery.
- plant-derived char contains a large amount of metal elements contained in plants.
- coconut shell char contains about 0.3% potassium element and about 0.03% calcium element. If a carbonaceous material containing a large amount of such metal elements is used as the negative electrode, it may adversely affect the electrochemical characteristics and safety of the nonaqueous electrolyte secondary battery.
- the plant-derived char also contains alkali metals other than potassium (for example, sodium), alkaline earth metals (for example, magnesium, calcium), transition metals (for example, iron, copper), and other metals. If the carbonaceous material contains these metals, impurities may elute into the electrolyte during dedoping from the negative electrode of the non-aqueous electrolyte secondary battery, which may adversely affect battery performance and harm safety. is there. Further, the pores of the carbonaceous material are blocked by ash, which may adversely affect the charge / discharge capacity of the battery.
- the halogen compound used in the vapor phase decalcification step is not particularly limited, and examples thereof include at least one compound containing an element selected from the group consisting of fluorine, chlorine and iodine.
- fluorine, chlorine examples thereof include bromine, iodine, hydrogen fluoride, hydrogen chloride, hydrogen bromide, iodine bromide, chlorine fluoride (ClF), iodine chloride (ICl), iodine bromide (IBr), and bromine chloride (BrCl).
- a compound that generates these halogen compounds by thermal decomposition, or a mixture thereof can also be used.
- the halogen compound is preferably hydrogen chloride or hydrogen bromide, more preferably hydrogen chloride.
- the inert gas used in the vapor phase decalcification step is not particularly limited as long as it does not react with the carbon component constituting the plant-derived char at the temperature of the heat treatment.
- nitrogen, helium, argon, krypton, or Those mixed gas is mentioned.
- the inert gas is preferably nitrogen.
- the concentration of the impurity gas (especially oxygen) contained in the inert gas is preferably as low as possible. However, the oxygen concentration that is usually allowed is preferably 0 to 2000 ppm, more preferably 0 to 1000 ppm.
- the vapor phase deashing step is performed in an inert gas stream containing a halogen compound, so that not only the reduction of metal elements but also the hydrogen elements and oxygen elements at the ends of the carbon structure are reduced. And active sites in the carbonaceous material can be reduced.
- the heat treatment temperature in the vapor phase decalcification step may be changed depending on the kind of plant-derived char as a raw material, but is preferably 1100 to 1300 ° C., more preferably 1120 from the viewpoint of obtaining a desired carbon structure and a decalcification effect. It is ⁇ 1250 ° C., and more preferably 1150 to 1200 ° C. If the heat treatment temperature is too low, the deashing efficiency may decrease and the deashing may not be sufficiently performed. Moreover, activation by a halogen compound may not be performed sufficiently. On the other hand, if the heat treatment temperature becomes too high, the heat shrinking effect is superior to the activation effect by the halogen compound, and the BET specific surface area becomes excessively small, which may be undesirable.
- the heat treatment time in the vapor phase deashing step is not particularly limited, but is, for example, 5 to 300 minutes, preferably 10 to 200 minutes, more preferably from the viewpoint of the economic efficiency of the reaction equipment and the structure retention of the carbon content. Is 20 to 150 minutes, more preferably 30 to 150 minutes.
- the supply amount of an inert gas stream containing a halogen compound in the heat treatment is preferably 14 L / min or more, more preferably 15 L / min or more, and even more preferably 16 L / min or more per 50 g of plant-derived char. It is preferable to perform the heat treatment at a supply amount equal to or higher than the above lower limit because the gas generated from the char itself in the heat treatment is sufficiently removed and a carbonaceous material having a half-value width in the above range is easily obtained.
- the upper limit of the supply amount is preferably 25 L / min or less, more preferably 20 L / min or less. It is preferable to perform the heat treatment at a supply amount equal to or less than the above upper limit because the halogen compound is easily adsorbed by the plant-derived char and easily reacted with the metal element, and a sufficient decalcification effect is easily obtained.
- gases such as carbon monoxide and hydrogen are generated from the char itself. Since these gases have high reactivity, it has been difficult to control the reaction between the gas and char generated during the heat treatment. For example, by performing the heat treatment with a large supply amount of inert gas (faster supply speed) as described above, it is possible to remove the reactive gas generated from the char itself before reacting with the char. . Therefore, a carbonaceous material having a more controlled carbon structure can be produced.
- the present invention it is preferable to perform a step of heating the carbonaceous material in an inert gas atmosphere (hereinafter also referred to as “deoxidation treatment”) in the absence of a halogen compound after the vapor phase deashing step.
- deoxidation treatment a step of heating the carbonaceous material in an inert gas atmosphere
- Metal elements such as calcium element can be efficiently removed by contact with the halogen compound in the vapor phase decalcification step.
- the halogen is contained in the carbonaceous material by contact with the halogen compound. Therefore, it is preferable to perform a deoxidation treatment in which the carbonaceous material is heated in the absence of a halogen compound, and the halogen contained in the carbonaceous material can be removed by such treatment.
- the deoxidation treatment is usually performed by heating at 800 ° C.
- the deoxidation treatment temperature is the same as the temperature in the gas phase deashing step. It is preferred to carry out at the same or higher temperature.
- the temperature of the deoxidation treatment is preferably 850 to 1300 ° C, more preferably 900 to 1250 ° C, and still more preferably 1000 to 1200 ° C.
- the supply of the halogen compound is shut off and the heat treatment is continuously performed to perform the deoxidation treatment, thereby removing the halogen in the carbonaceous material. be able to.
- the time for the deoxidation treatment is not particularly limited, and is preferably 5 minutes to 300 minutes, more preferably 10 minutes to 200 minutes, still more preferably 20 minutes to 150 minutes, and most preferably 30 minutes to 100 minutes.
- Examples of the inert gas used in the deoxidation treatment include a gas used in a gas phase deashing process. From the viewpoint of simplifying the production process, it is preferable that the inert gas in the gas phase deashing step and the inert gas in the deoxidation treatment are the same.
- the supply amount (circulation amount) of the inert gas is not limited, but is preferably the same as the supply amount of the inert gas in the gas phase deashing step from the viewpoint of production.
- the apparatus used for the heat treatment in the vapor phase demineralization step is not particularly limited as long as it can be heated while mixing plant-derived char and an inert gas containing a halogen compound.
- a fluidized furnace a continuous type or a batch type in-bed flow method using a fluidized bed or the like can be used.
- the heat treatment may be further performed at a temperature of about 850 ° C. to 1280 ° C., for example.
- the treatment time is, for example, 5 minutes to 300 minutes, more preferably 10 minutes to 200 minutes, even more preferably 10 minutes to 150 minutes, and most preferably 10 minutes to 100 minutes.
- the deoxidation treatment is performed after the vapor phase deashing step. Preferably does not include a further heat treatment step at the treatment temperature after the deoxidation treatment step.
- the average particle diameter of the carbonaceous material is adjusted through a pulverization process and a classification process as necessary.
- the pulverization step and the classification step may be performed before the gas phase deashing step or after the gas phase deashing step. From the viewpoint of easily improving the uniformity of the vapor phase decalcification, it is preferable to grind the plant-derived char before the vapor phase demineralization step. Moreover, when performing the alkali soaking process mentioned later, the plant-derived char is pulverized before the alkali soaking process and the vapor phase deashing process.
- the specific surface area of the char obtained after the pulverization step is preferably 100 to 800 m 2 / g, more preferably 200 to 700 m 2 / g, for example, 200 to 600 m 2 / g. It is preferable to carry out the pulverization step so as to obtain a char having a specific surface area in the above range. It is preferable that the specific surface area of the char after the pulverization step is equal to or more than the above lower limit because the fine pores of the carbonaceous material are reduced and the hygroscopicity of the carbonaceous material is easily lowered.
- the specific surface area of the char and the char after the pulverization step means a specific surface area (BET specific surface area) determined by a nitrogen adsorption BET multipoint method. Specifically, it can measure using the method mentioned later.
- the average particle diameter (D 50 ) of the char obtained after the pulverization step is adjusted so that the carbonaceous material having the average particle diameter (D 50 ) described above is finally obtained.
- the plant-derived char shrinks by about 0 to 20% by the gas phase deashing process. Therefore, in order to make the average particle size after the gas phase demineralization step 2-30 ⁇ m, the average particle size of the char after the pulverization step is set to be larger than the desired average particle size after the gas phase demineralization step. It is preferable to adjust the particle size to be about 0 to 20% larger.
- the average particle diameter (D 50 ) of the char after the pulverization step is 2 from the viewpoint of easily improving the uniformity of the gas phase deashing. It is preferable to grind so as to be in the range of ⁇ 100 ⁇ m. When the average particle size is 2 ⁇ m or more, the fine powder is difficult to be scattered in the furnace at the time of vapor phase demineralization, the recovery rate of the generated carbonaceous material is excellent, and the load on the apparatus can be further suppressed.
- the average particle diameter (D 50 ) of the char after the pulverization step is more preferably 3 ⁇ m or more, even more preferably 4 ⁇ m or more, particularly preferably 5 or more, and most preferably 6 ⁇ m or more.
- the average particle size of the char after the pulverization step is 100 ⁇ m or less, which facilitates contact with the halogen compound, leads to an increase in demineralization efficiency and an improvement in activation effect, and gas generated from plant-derived char during heat treatment. It is preferable because it is easy to remove.
- the average particle size of the pulverized char is more preferably 80 ⁇ m or less, even more preferably 60 ⁇ m or less, particularly preferably 40 ⁇ m or less, very preferably 30 ⁇ m or less, and most preferably 20 ⁇ m or less.
- the average particle size of the char after grinding step (D 50) can be measured by the same method as that described for the average particle diameter of the carbonaceous material (D 50).
- the pulverizer used in the pulverization step is not particularly limited, and for example, a jet mill, a ball mill, a hammer mill, or a rod mill can be used. From the viewpoint of pulverization efficiency, a method of pulverization in the presence of a pulverization medium such as a ball mill and a bead mill is preferable. From the viewpoint of equipment load, the use of a ball mill is preferable.
- char classification may be performed as necessary. By performing classification, it becomes easy to obtain a char having the above-described specific surface area and average particle diameter, and the average particle diameter and average particle diameter of the obtained carbonaceous material can be adjusted more accurately. It is preferable that the specific surface area and the average particle diameter after pulverizing and classifying plant-derived char are within the above ranges.
- the average particle diameter of the carbonaceous material can be adjusted more accurately by the classification process. For example, particles having a particle diameter of 1 ⁇ m or less can be removed.
- the content of particles having a particle diameter of 1 ⁇ m or less is 3% by volume or less in the carbonaceous material of the present invention.
- the removal of particles having a particle diameter of 1 ⁇ m or less is not particularly limited as long as it is after pulverization, but it is preferable to perform the pulverization simultaneously with classification.
- the content of particles having a particle diameter of 1 ⁇ m or less is preferably 3% by volume or less, and 2.5% by volume or less from the viewpoint of reducing the specific surface area and reducing the irreversible capacity. It is more preferable that the content is 2% by volume or less.
- the classification method is not particularly limited, and examples thereof include classification using a sieve, wet classification, and dry classification.
- the wet classifier for example, a classifier using principles such as gravity classification, inertia classification, hydraulic classification, centrifugal classification, and the like can be given.
- the dry classifier include a classifier using a principle such as sedimentation classification, mechanical classification, and centrifugal classification.
- the pulverization step and the classification step can be performed using one apparatus.
- the pulverization step and the classification step can be performed using a jet mill having a dry classification function.
- an apparatus in which the pulverizer and the classifier are independent can be used. In this case, pulverization and classification can be performed continuously, but pulverization and classification can also be performed discontinuously.
- An alkali deposition step of adding a compound containing an alkali metal element may be performed before the vapor phase demineralization step of heat-treating the plant-derived char.
- carbon erosion by the alkali metal element is promoted in the temperature rising process up to the vapor phase deashing step, and micropore formation is brought about.
- diffusion of the alkali metal added to the plant-derived char at a temperature near the melting point of the compound containing the alkali metal element is started, and at a temperature around 500 ° C.
- the dehydration reaction in the compound containing the alkali metal element and the char carbon erosion reaction by the compound containing the alkali metal element are started, and further the volatilization of the alkali metal element occurs at a temperature near the boiling point of the alkali metal element.
- the char after the pulverization step in this embodiment is also referred to as “pulverization char” below.
- a compound containing an alkali metal element is added to the pulverized char obtained in the pulverization step to obtain a char to which the alkali metal element is added (hereinafter also referred to as “alkali-added char”).
- the compound containing an alkali metal element is a compound containing an alkali metal element (lithium, sodium, potassium, rubidium, cesium, etc.), for example, an alkali metal element halide (fluoride, chloride, bromide, etc.), water Examples thereof include oxides, carbonates, and hydrogen carbonates.
- compounds containing alkali metal elements include lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, carbonic acid.
- examples thereof include lithium, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate and the like.
- the compound containing an alkali metal element is a compound containing sodium or potassium from a viewpoint of micropore formation ability and safety
- the compound containing an alkali metal element is preferably an alkali metal element hydroxide, carbonate or bicarbonate.
- the compound containing an alkali metal element is more preferably sodium or sodium hydroxide or carbonate, and even more preferably sodium hydroxide or sodium carbonate.
- the method for adding a compound containing an alkali metal element to the pulverized char is not particularly limited.
- a compound containing an alkali metal element may be added to the pulverized char dry or wet. Wet addition is preferable from the viewpoint of easily attaching a compound containing an alkali metal element to the pulverized char.
- an alkali-attached char can be obtained by adding and mixing a compound containing a solid alkali metal element to the pulverized char.
- the compound is preferably added in a powder form and mixed.
- a solution containing an alkali metal element is dissolved in a solvent to prepare a solution, and this solution is then supported on a pulverized char.
- the pulverized char can be supported on the pulverized char by immersing the pulverized char in the solution, spraying the solution onto the pulverized char (spray spraying or the like), or adding and mixing the solution to the pulverized char.
- the mixture of the solvent and the pulverized char may be supported by adding a solid alkali metal element.
- the solvent may be evaporated if necessary. By such treatment, an alkali-attached char can be obtained.
- the solvent is not particularly limited.
- alcohol solvent ethanol, methanol, ethylene glycol, isopropyl alcohol, etc.
- ester solvent ethyl acetate, butyl acetate, ethyl lactate, etc.
- ether solvent tetrahydrofuran, dimethoxyethane, 1, 4) -Dioxane, etc.
- ketone solvents acetone, 2-butanone, cyclopentanone, cyclohexanone, etc.
- aliphatic hydrocarbon solvents penentane, hexane, heptane, etc.
- aromatic hydrocarbon solvents toluene, xylene, mesitylene, etc.
- examples include nitrile solvents (such as acetonitrile), and chlorinated hydrocarbon solvents (such as dichloromethane, chloroform, chlorobenzene), and mixtures thereof.
- the method for evaporating the solvent is not particularly limited, and examples thereof include heat treatment and reduced pressure treatment, and combinations thereof.
- the temperature of the heat treatment may be a temperature at which the pulverized char is not easily oxidized, and varies depending on the type of solvent, but is, for example, 40 to 200 ° C., preferably 50 to 150 ° C., more preferably 60 to 100 ° C.
- the amount (attachment amount) of the compound containing an alkali metal element to be attached to the pulverized char is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably with respect to the mass of the obtained alkali-added char. 3% by mass or more, particularly preferably 5% by mass or more, for example 10% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 17% by mass or less, particularly preferably 16% by mass.
- it is 15 mass% or less, for example.
- the amount of the compound containing an alkali metal element to be attached to the pulverized char is equal to or more than the above lower limit, it is easy to promote the formation of micropores in the subsequent vapor phase deashing step.
- the amount of the compound containing an alkali metal element to be attached to the pulverized char is not more than the above upper limit, excessive micropore formation can be suppressed, and a non-aqueous electrolyte secondary battery having a low resistance with a high charge / discharge capacity is obtained. Easy to get carbonaceous material to give.
- the average particle diameter (D 50 ) of the alkali-adhered char obtained in the alkali-adhering step is preferably 2 to 100 ⁇ m, more preferably 3 to 80 ⁇ m, still more preferably 4 to 60 ⁇ m, particularly preferably 4 to 40 ⁇ m, and most preferably. It is 5 to 30 ⁇ m, most preferably 6 to 20 ⁇ m. It is preferable that the average particle diameter of the alkali-impregnated char is equal to or more than the above lower limit because powder scattering can be reduced even when firing is performed at a high air flow rate. It is preferable that the average particle diameter of the alkali-added char is not more than the above upper limit because the attached alkali compound is easily removed in the gas phase deashing step.
- the specific surface area of the alkali-attached char obtained in the alkali-attaching step is preferably 100 to 800 m 2 / g, more preferably 200 to 700 m 2 / g, and still more preferably 200 to 600 m 2 / g. It is preferable that the specific surface area of the alkali-added char is equal to or more than the above lower limit because the fine pores of the carbonaceous material are reduced and the hygroscopicity of the carbonaceous material is easily lowered.
- the specific surface area of the alkali-added char is not more than the above upper limit, the specific surface area of the obtained carbonaceous material is likely to be within the above range, and it is easy to improve the utilization efficiency of lithium ions in the nonaqueous electrolyte secondary battery. Become.
- the specific surface area of the alkali-added char can be measured by the BET method (nitrogen adsorption BET multipoint method).
- the average particle size of the alkali-added char may be adjusted by pulverization and / or classification.
- Examples of the pulverization method and the classification method include the same methods as described above.
- the production method of the present invention may include a removal step of removing a compound containing an alkali metal element, but even if the production method of the present invention does not include the removal step, the alkali metal in the obtained carbonaceous material. It is possible to keep the element content low. The reason for this is not clear, but a reaction product having a relatively low melting point is formed by the reaction between the halogen compound introduced in the gas phase decalcification step and the alkali metal element, and the reaction product is volatilized by heat treatment in the gas phase deashing step. It may have been removed.
- the present invention is not limited to the above description.
- the alkali addition step is performed in addition to the vapor phase deashing step, it is not limited to the mechanism described later, but reacts with a compound containing an alkali metal element to which a functional group on the char surface such as —OH group or —COOH group is attached. These functional groups are considered to be removed by the subsequent heat treatment / vapor phase deashing step. As a result, it is considered that the oxygen element content and the hydrogen element content in the carbonaceous material are reduced, the irreversible reaction during charge / discharge is suppressed, and the charge / discharge efficiency and the discharge capacity are easily increased.
- the oxygen element content in the carbonaceous material is preferably 0.8% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.65% by mass or less, and particularly preferably 0.6% by mass. % Or less.
- the content of hydrogen element in the carbonaceous material is preferably 0.16% by mass or less, more preferably 0.14% by mass or less, still more preferably 0.12% by mass or less, and particularly preferably 0.1% by mass. It is as follows.
- the content of oxygen element and hydrogen element in the carbonaceous material can be measured, for example, by an inert gas dissolution method.
- the negative electrode for a nonaqueous electrolyte secondary battery of the present invention includes the carbonaceous material of the present invention.
- the negative electrode of the present invention is obtained by adding a binder (binder) to the carbonaceous material of the present invention, adding an appropriate amount of an appropriate solvent, kneading to form an electrode mixture, and then applying it to a current collector plate made of a metal plate, etc. It can be manufactured by pressure molding after drying.
- an electrode having high conductivity can be produced without adding a conductive auxiliary.
- a conductive aid can be added as necessary when preparing the electrode mixture.
- the conductive assistant conductive carbon black, vapor grown carbon fiber (VGCF), nanotube, or the like can be used.
- the amount of conductive auxiliary agent added varies depending on the type of conductive auxiliary agent used, but if the amount added is too small, the expected conductivity may not be obtained, and if too large, the dispersion in the electrode mixture will be poor. May be.
- the binder is not particularly limited as long as it does not react with an electrolytic solution such as PVDF (polyvinylidene fluoride), polytetrafluoroethylene, and a mixture of SBR (styrene-butadiene rubber) and CMC (carboxymethylcellulose).
- PVDF is preferable because PVDF attached to the surface of the active material hardly inhibits lithium ion migration and provides favorable input / output characteristics.
- a polar solvent such as N-methylpyrrolidone (NMP) is preferably used, but an aqueous emulsion such as SBR or CMC can be dissolved in water.
- NMP N-methylpyrrolidone
- an aqueous emulsion such as SBR or CMC can be dissolved in water.
- the amount of the binder added is too large, the resistance of the obtained electrode increases, so that the internal resistance of the battery increases and the battery characteristics may be deteriorated.
- bonding between the particles of negative electrode material and a collector may become inadequate.
- the preferred addition amount of the binder varies depending on the type of binder used, but for example, it is preferably 3 to 13% by mass, and more preferably 3 to 10% by mass for a PVDF binder.
- a binder using water as a solvent is often used by mixing a plurality of binders such as a mixture of SBR and CMC, and the total amount of all binders used is preferably 0.5 to 5% by mass. More preferably, it is 4% by mass.
- the electrode active material layer is basically formed on both sides of the current collector plate, but may be formed on one side as necessary.
- the thickness of the active material layer (per one side) is preferably 10 to 80 ⁇ m, more preferably 20 to 75 ⁇ m, and still more preferably 30 to 75 ⁇ m, from the viewpoint of output during battery discharge.
- the nonaqueous electrolyte secondary battery of the present invention includes the negative electrode for a nonaqueous electrolyte secondary battery of the present invention.
- a nonaqueous electrolyte secondary battery having a negative electrode for a nonaqueous electrolyte secondary battery containing the carbonaceous material of the present invention has a high charge / discharge capacity and charge / discharge efficiency, and a low resistance.
- a non-aqueous electrolyte secondary battery having a negative electrode for a non-aqueous electrolyte secondary battery containing a carbonaceous material is maintained even after high charge / discharge capacity and charge / discharge efficiency and repeated charge / discharge. Low resistance.
- the positive electrode material a layered oxide system (represented as LiMO 2 , where M is a metal: for example, LiCoO 2 , LiNiO 2 , LiMnO 2 , or LiNi x Co y Mo z O 2 (where x, y , Z represents a composition ratio)), olivine system (represented by LiMPO 4 , M is a metal: for example LiFePO 4, etc.), spinel system (represented by LiM 2 O 4 , M is a metal: for example LiMn 2 O 4, etc. ) Of the composite metal chalcogen compound is preferable, and these chalcogen compounds may be mixed and used as necessary.
- These positive electrode materials are molded together with an appropriate binder and a carbon material for imparting conductivity to the electrode, and a positive electrode is formed by forming a layer on the conductive current collector.
- the nonaqueous solvent electrolyte used in combination with these positive electrode and negative electrode is generally formed by dissolving an electrolyte in a nonaqueous solvent.
- the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, diethoxyethane, ⁇ -butyllactone, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, and 1,3-dioxolane. Can be used singly or in combination of two or more.
- LiClO 4 LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiCl, LiBr, LiB (C 6 H 5 ) 4 , or LiN (SO 3 CF 3 ) 2 is used.
- a non-aqueous electrolyte secondary battery is generally immersed in an electrolytic solution with the positive electrode and the negative electrode formed as described above facing each other through a liquid-permeable separator made of a nonwoven fabric or other porous material as necessary. Is formed.
- a non-woven fabric usually used for a secondary battery or a permeable separator made of another porous material can be used.
- a solid electrolyte made of a polymer gel impregnated with an electrolytic solution can be used instead of or together with the separator.
- the carbonaceous material of the present invention is suitable as a carbonaceous material for a battery (typically a non-aqueous electrolyte secondary battery for driving a vehicle) mounted on a vehicle such as an automobile.
- the vehicle can be a target such as a vehicle that is normally used as an electric vehicle, a hybrid vehicle with a fuel cell or an internal combustion engine, and the like, but at least a power supply device including the battery. And an electric drive mechanism that is driven by power supply from the power supply device, and a control device that controls the electric drive mechanism.
- the vehicle may further include a power generation brake and a regenerative brake, and may include a mechanism that converts energy generated by braking into electricity and charges the nonaqueous electrolyte secondary battery.
- the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
- the measuring method of the physical-property value of the carbonaceous material of this invention is described below, the physical-property value described in this specification including an Example is based on the value calculated
- FIG. 1 and FIG. 2 show Raman spectra of carbon electrodes produced using the carbonaceous materials of Example 1 and Comparative Example 1, respectively.
- Argon ion laser light wavelength 532 nm
- Laser power on the sample 15 mW Resolution: 5-7cm -1
- Measurement range 50-2000cm -1
- Exposure time 1 second Integration count: 100 times
- Peak intensity measurement Baseline correction Automatic correction with Polynom-3 order Peak search & fitting processing GaussLoren
- v m is obtained by substituting the actually measured adsorption amount (v) at a predetermined phase body pressure (p / p 0 ) by the multi-point method by nitrogen adsorption at the liquid nitrogen temperature.
- the specific surface area of the sample was calculated by the formula.
- v m is the adsorption amount necessary for forming a monomolecular layer on the surface of the sample (cm 3 / g), v adsorption amount is measured (cm 3 / g), p 0 is saturation vapor pressure, p is an absolute pressure, c is a constant (reflecting the heat of adsorption), N is an Avogadro number of 6.022 ⁇ 10 23 , and a (nm 2 ) is an area occupied by an adsorbate molecule on the sample surface (molecular occupation cross section).
- the amount of nitrogen adsorbed on plant-derived char or carbonaceous material at liquid nitrogen temperature was measured using “Autosorb-iQ-MP” manufactured by Cantachrome.
- a plant-derived char or carbonaceous material which is a measurement sample, is filled in a sample tube, and the sample tube is cooled to ⁇ 196 ° C., and then the pressure is reduced once. 999%) is adsorbed.
- the amount of nitrogen adsorbed on the sample when the equilibrium pressure was reached at each desired relative pressure was defined as the amount of adsorbed gas v.
- an electrolytic solution a mixed solvent obtained by mixing ethylene glycol dimethyl ether and propylene carbonate at a volume ratio of 1: 1 was added LiClO 4 at a ratio of 1 mol / liter.
- a polypropylene microporous membrane was used as the separator.
- a separator was sandwiched between the carbon electrode and the negative electrode, and an electrolyte was injected to produce a coin cell.
- MAS- 7 Li-NMR was measured using a nuclear magnetic resonance apparatus (“AVANCE300” manufactured by BRUKER). In the measurement, lithium chloride was used as a reference material, and the peak of lithium chloride was set to 0 ppm.
- the NMR spectra of the carbon electrodes produced using the carbonaceous materials of Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4, respectively.
- the method for measuring the calcium element content and the potassium element content was measured, for example, by the following method.
- a carbon sample containing predetermined calcium element and potassium element is prepared in advance, and the relationship between the intensity of calcium K ⁇ ray and the content of calcium element and the intensity of potassium K ⁇ ray and the content of potassium element are measured using a fluorescent X-ray analyzer.
- a calibration curve for the relationship was created.
- the intensity of calcium K ⁇ ray and potassium K ⁇ ray in the fluorescent X-ray analysis was measured for the sample, and the calcium element content and the potassium element content were determined from the calibration curve prepared earlier.
- X-ray fluorescence analysis was performed using “ZSX Primus- ⁇ ” manufactured by Rigaku Corporation under the following conditions.
- a sample measurement area was set within a circumference of 30 mm in diameter using an upper irradiation system holder.
- a sample to be measured 2.0 g
- a polymer binder 2.0 g
- a pellet having a diameter of 40 mm was produced by applying a load of 15 ton to the molding machine for 1 minute.
- the produced pellets were wrapped in a polypropylene film and placed in a sample holder for measurement.
- the X-ray source was set to 40 kV and 75 mA.
- LiF (200) was used as a spectral crystal, and a gas flow type proportional coefficient tube was used as a detector, and 2 ⁇ was measured in a range of 110 to 116 ° at a scanning speed of 30 ° / min.
- LiF (200) was used as the spectral crystal, and a gas flow proportional coefficient tube was used as the detector, and the range of 2 ⁇ between 133 and 140 ° was measured at a scanning speed of 4 ° / min.
- the true density ⁇ Bt was measured by the butanol method according to the method defined in JIS R 7212.
- the mass (m 1 ) of a specific gravity bottle with a side tube having an internal volume of about 40 mL was accurately measured.
- the sample was put flat on the bottom so as to have a thickness of about 10 mm, and the mass (m 2 ) was accurately measured.
- 1-butanol was gently added to a depth of about 20 mm from the bottom.
- light vibration was applied to the specific gravity bottle, and it was confirmed that large bubbles were not generated.
- the bottle was placed in a vacuum desiccator and gradually evacuated to 2.0 to 2.7 kPa.
- distilled water excluding the gas which was boiled and dissolved just before use was taken in a specific gravity bottle, immersed in a constant temperature water bath in the same manner as described above, and after aligning the marked lines, the mass (m 5 ) was measured.
- the true density ⁇ Bt was calculated by the following formula. At this time, d is the specific gravity of water at 30 ° C. (0.9946).
- the average particle size (particle size distribution) of plant-derived char and carbonaceous material was measured by the following method.
- the sample was put into an aqueous solution containing 5% by mass of a surfactant (“Toriton X100” manufactured by Wako Pure Chemical Industries, Ltd.), treated with an ultrasonic cleaner for 10 minutes or more, and dispersed in the aqueous solution.
- the particle size distribution was measured using this dispersion.
- the particle size distribution measurement was performed using a particle diameter / particle size distribution measuring apparatus (“Microtrack MT3300EXII” manufactured by Microtrack Bell Co., Ltd.).
- D 50 is the cumulative volume is a particle diameter at 50%, using this value as the average particle size.
- the coconut shell was pulverized and subjected to dry distillation at 500 ° C. in a nitrogen gas atmosphere to obtain an coconut shell char having a particle size of 0.5 to 2.0 mm. Thereafter, the coconut shell char was pulverized using a ball mill to obtain an coconut shell pulverized char having an average particle diameter (D 50 ) of 10 ⁇ m.
- the specific surface area determined by the BET multipoint method was 389 m 2 / g.
- Example 1 The coconut shell char obtained in Production Example 1 was heat-treated at 1200 ° C. for 60 minutes in a nitrogen gas stream containing 2% by volume of hydrogen chloride gas.
- the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas was 18 L / min per 50 g of coconut shell char.
- deoxidation treatment was performed by heat treatment at 1200 ° C. for 60 minutes to obtain a carbonaceous material.
- the supply amount of nitrogen gas in the deoxidation treatment was 18 L / min per 50 g of coconut shell char.
- the average particle diameter D 50 was obtained carbonaceous material 9 .mu.m.
- Example 2 A carbonaceous material was obtained in the same manner as in Example 1 except that nitrogen gas containing 1% by volume of hydrogen chloride gas was used instead of nitrogen gas containing 2% by volume of hydrogen chloride gas.
- Example 3 The carbonaceous material was prepared in the same manner as in Example 1 except that the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas and the supply amount of nitrogen gas in the deoxidation treatment were 16 L / min per 50 g of the coconut shell char. Obtained.
- Example 4 A carbonaceous material was obtained in the same manner as in Example 3 except that nitrogen gas containing 1% by volume of hydrogen chloride gas was used instead of nitrogen gas containing 2% by volume of hydrogen chloride gas.
- Example 5 The coconut shell char obtained in Production Example 1 was mixed with an aqueous solution in which 10% by mass of NaOH was dissolved based on the mass of the coconut shell char. After 30 minutes of ultrasonic irradiation, the solution was allowed to penetrate into the char, and then dried under reduced pressure at 80 ° C. for 8 hours under a reduced pressure of 1 Torr. The obtained mixture was heat-treated at 1200 ° C. for 60 minutes under a nitrogen gas stream containing 1% by volume of hydrogen chloride gas.
- the supply amount of nitrogen gas containing 1% by volume of hydrogen chloride gas is 16.2 L / min per 50 g of a mixture of 50.0 g of coconut shell char and 5.55 g of NaOH, and 18 L / min per 50 g of coconut shell char. there were. Thereafter, only the supply of hydrogen chloride gas was stopped, and deoxidation treatment was performed by heat treatment at 1200 ° C. for 60 minutes to obtain a carbonaceous material.
- the supply amount of nitrogen gas in the deoxidation treatment was 16.2 L / min per 50 g of a mixture of 50.0 g of coconut shell char and 5.55 g of NaOH, and 18 L / min per 50 g of coconut shell char.
- Example 1 The carbonaceous material was prepared in the same manner as in Example 1 except that the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas and the supply amount of nitrogen gas in the deoxidation treatment were 10 L / min per 50 g of the coconut shell char. Obtained.
- Comparative Example 2 A carbonaceous material was obtained in the same manner as in Comparative Example 1 except that the heat treatment temperature was 900 ° C.
- Table 1 shows the physical properties of the carbonaceous materials obtained in Examples 1 to 5 and Comparative Examples 1 to 4.
- an electrochemical measurement device (“1255WB high-performance electrochemical measurement system manufactured by Solartron”) is used, and an amplitude of 10 mV is given at 25 ° C. with a frequency of 10 mHz to 1 MHz. Constant voltage AC impedance was measured by frequency, and real part resistance at frequencies of 1 k, 1, and 0.1 Hz was measured as impedance resistance.
- the electrode produced above was used as a working electrode, and metallic lithium was used as a counter electrode and a reference electrode.
- a solvent propylene carbonate and ethylene glycol dimethyl ether were mixed and used at a volume ratio of 1: 1. 1 mol / L of LiClO 4 was dissolved in this solvent and used as an electrolyte.
- a polypropylene film was used as the separator.
- a coin cell was produced in a glove box under an argon atmosphere. About the lithium secondary battery of the said structure, the charge / discharge test was done after measuring direct-current resistance value before initial charge using the charge / discharge test apparatus (the Toyo System Co., Ltd. make, "TOSCAT").
- Lithium was doped at a rate of 70 mA / g with respect to the mass of the active material, and was doped until 1 mV with respect to the lithium potential. Further, a constant voltage of 1 mV with respect to the lithium potential was applied for 8 hours to complete the doping. The capacity (mAh / g) at this time was defined as the charge capacity. Next, dedoping was performed at a rate of 70 mA / g with respect to the mass of the active material until 2.5 V with respect to the lithium potential, and the capacity discharged at this time was defined as the discharge capacity. The percentage of discharge capacity / charge capacity was defined as charge / discharge efficiency (initial charge / discharge efficiency), which was used as an index of utilization efficiency of lithium ions in the battery. The obtained results are shown in Table 2.
- Batteries produced using the carbonaceous materials of Examples 1 to 5 had a low resistance value, high discharge capacity, and good charge / discharge efficiency.
- a sufficiently low resistance value is not achieved in a battery manufactured using the carbonaceous materials of Comparative Examples 1 to 4 that do not have a half-value width in a predetermined range or have a specific surface area in a predetermined range.
- a sufficiently low resistance value is not achieved in a battery manufactured using the carbonaceous materials of Comparative Examples 1 to 4 that do not have a half-value width in a predetermined range or have a specific surface area in a predetermined range.
- the discharge capacity and charge / discharge efficiency are sufficient.
- Example 6 The coconut shell char obtained in Production Example 2 was heat-treated at 1200 ° C. for 70 minutes in a nitrogen gas stream containing 2% by volume of hydrogen chloride gas.
- the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas was 18 L / min per 50 g of coconut shell char.
- deoxidation treatment was performed by heat treatment at 1200 ° C. for 70 minutes to obtain a carbonaceous material.
- the supply amount of nitrogen gas in the deoxidation treatment was 18 L / min per 50 g of coconut shell char.
- the average particle diameter D 50 was obtained carbonaceous material 10 [mu] m.
- Example 7 A carbonaceous material was obtained in the same manner as in Example 6 except that nitrogen gas containing 1% by volume of hydrogen chloride gas was used instead of nitrogen gas containing 2% by volume of hydrogen chloride gas.
- Example 8 A carbonaceous material was prepared in the same manner as in Example 6 except that the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas and the supply amount of nitrogen gas in the deoxidation treatment were 16 L / min per 50 g of the coconut shell char. Obtained.
- Example 9 A carbonaceous material was obtained in the same manner as in Example 8 except that nitrogen gas containing 1% by volume of hydrogen chloride gas was used instead of nitrogen gas containing 2% by volume of hydrogen chloride gas.
- Example 10 The coconut shell char obtained in Production Example 2 was mixed with an aqueous solution in which 10% by mass of NaOH was dissolved based on the mass of the coconut shell char. After 30 minutes of ultrasonic irradiation, the solution was allowed to penetrate into the char, and then dried under reduced pressure at 80 ° C. for 8 hours under a reduced pressure of 1 Torr. The obtained mixture was heat-treated at 1200 ° C. for 70 minutes under a nitrogen gas stream containing 2% by volume of hydrogen chloride gas.
- the supply amount of nitrogen gas containing 1% by volume of hydrogen chloride gas was 16.2 L / min per 50 g of a mixture of 50 g of coconut shell char and 5.55 g of NaOH, and 18 L / min per 50 g of coconut shell char. . Thereafter, only the supply of hydrogen chloride gas was stopped, and deoxidation treatment was performed by heat treatment at 1200 ° C. for 70 minutes to obtain a carbonaceous material.
- the supply amount of nitrogen gas in the deoxidation treatment was 16.2 L / min per 50 g of a mixture of 50 g of coconut shell char and 5.55 g of NaOH, and 18 L / min per 50 g of coconut shell char.
- Example 5 The carbonaceous material was prepared in the same manner as in Example 6 except that the supply amount of nitrogen gas containing 2% by volume of hydrogen chloride gas and the supply amount of nitrogen gas in the deoxidation treatment were 10 L / min per 50 g of coconut shell char. Obtained.
- Comparative Example 6 A carbonaceous material was obtained in the same manner as in Comparative Example 5 except that the temperature of the heat treatment was 900 ° C.
- Table 3 and Table 4 show the physical properties of the carbonaceous materials obtained in Examples 6 to 10 and Comparative Examples 5 to 8.
- an electrochemical measurement device (“1255WB high-performance electrochemical measurement system manufactured by Solartron”) is used, and an amplitude of 10 mV is given at 25 ° C. with a frequency of 10 mHz to 1 MHz. Constant voltage AC impedance was measured by frequency, and real part resistance at frequencies of 1 k, 1, and 0.1 Hz was measured as impedance resistance.
- the electrode produced above was used as a working electrode, and metallic lithium was used as a counter electrode and a reference electrode.
- a solvent propylene carbonate and ethylene glycol dimethyl ether were mixed and used at a volume ratio of 1: 1. 1 mol / L of LiClO 4 was dissolved in this solvent and used as an electrolyte.
- a polypropylene film was used as the separator.
- a coin cell was produced in a glove box under an argon atmosphere. About the lithium secondary battery of the said structure, the charge / discharge test was done after measuring direct-current resistance value before initial charge using the charge / discharge test apparatus (the Toyo System Co., Ltd. make, "TOSCAT").
- Lithium was doped at a rate of 70 mA / g with respect to the mass of the active material, and was doped until 1 mV with respect to the lithium potential. Further, a constant voltage of 1 mV with respect to the lithium potential was applied for 8 hours to complete the doping. The capacity (mAh / g) at this time was defined as the charge capacity. Next, dedoping was performed at a rate of 70 mA / g with respect to the mass of the active material until 2.5 V with respect to the lithium potential, and the capacity discharged at this time was defined as the discharge capacity. The percentage of discharge capacity / charge capacity was defined as charge / discharge efficiency (initial charge / discharge efficiency), which was used as an index of utilization efficiency of lithium ions in the battery. Moreover, after repeating said charging / discharging 3 times, the impedance was measured. Table 4 shows the obtained results.
- Batteries produced using the carbonaceous materials of Examples 6 to 10 had a low resistance value, high discharge capacity, and good charge / discharge efficiency before the first charge and after three charge / discharge cycles.
- the battery manufactured using the carbonaceous material of Comparative Examples 5 to 8 that does not have a predetermined range of half width or does not have a predetermined range of mesopore volume / micropore volume ratio, It cannot be said that a sufficiently low resistance value is not achieved before charging and after three times of charging / discharging, or that the discharge capacity and charging / discharging efficiency are sufficient.
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Abstract
Description
さらに、本発明の別の目的は、高い充放電容量および充放電効率と、繰返しの充放電後においても維持される低い抵抗を有する非水電解質二次電池(例えばリチウムイオン二次電池)の負極活物質に適した炭素質材料、該炭素質材料を含む負極、該負極を有する非水電解質二次電池ならびに該炭素質材料の製造方法を提供することである。
すなわち、本発明は以下の好適な態様を包含する。
〔1〕非水電解質二次電池の負極活物質用の炭素質材料であって、該炭素質材料は植物に由来し、レーザーラマン分光法により観測されるラマンスペクトルの1360cm-1付近のピークの半値幅の値が190~240cm-1であり、窒素吸着BET多点法により求めた比表面積が10~100m2/gである、炭素質材料。
〔2〕前記炭素質材料に満充電状態となるまでリチウムをドープし、7Li核-固体NMR分析を行ったとき、基準物質であるLiClの共鳴ピークに対して低磁場側に115~145ppmシフトした主共鳴ピークが観測される、〔1〕に記載の炭素質材料。
〔3〕カルシウム元素含量が50ppm以下である、〔1〕または〔2〕に記載の炭素質材料。
〔4〕ブタノール法により求めた真密度が1.35~1.70g/cm3である、〔1〕~〔3〕のいずれかに記載の炭素質材料。
〔5〕DFT法によりそれぞれ算出されるマイクロ孔容積に対するメソ孔容積の比が1.0以上である、〔1〕~〔4〕のいずれかに記載の炭素質材料。
〔6〕〔1〕~〔5〕のいずれかに記載の炭素質材料を含む非水電解質二次電池用負極。
〔7〕〔6〕に記載の非水電解質二次電池用負極を有する非水電解質二次電池。
〔8〕植物由来のチャーを、ハロゲン化合物を含む不活性ガス気流下、1100~1300℃で熱処理する工程を含み、該ハロゲン化合物を含む不活性ガスの供給量は植物由来のチャー50gあたり14L/分以上である、〔1〕~〔5〕のいずれかに記載の炭素質材料の製造方法。
カルシウム元素含量を上記の範囲に調整する方法は何ら限定されないが、例えば、植物由来のチャーを、ハロゲン化合物を含む不活性ガスを供給しながら熱処理する方法を用いることができる。
ラマン分光器(堀場製作所製「LabRAM ARAMIS(VIS)」)を用い、炭素質材料である測定対象粒子を観測台ステージ上にセットし、対物レンズの倍率を100倍とし、ピントを合わせ、アルゴンイオンレーザ光を照射しながら測定した。測定条件の詳細は以下のとおりである。実施例1と比較例1の炭素質材料を用いて作製した炭素電極のラマンスペクトルを、それぞれ図1および図2に示す。
アルゴンイオンレーザ光の波長:532nm
試料上のレーザーパワー:15mW
分解能:5-7cm-1
測定範囲:50-2000cm-1
露光時間:1秒
積算回数:100回
ピーク強度測定:ベースライン補正 Polynom-3次で自動補正
ピークサーチ&フィッテイング処理 GaussLoren
後述する実施例および比較例で調製した炭素質材料94質量部、ポリフッ化ビニリデン6質量部に、N-メチル-2-ピロリドンを加えてペースト状物を得た。該ペースト状物を、フィルム上に均一な厚みで塗布し、乾燥、プレスした。得られたプレス物をフィルムから剥離させて、直径14mmの円板状に打ち抜き炭素電極を得、これを正極として用いた。負極として、厚さ0.2mmの金属リチウム薄膜を直径14mmの円板状に打ち抜いたものを用いた。電解液として、エチレングリコールジメチルエーテルとプロピレンカーボネートを容量比1:1で混合した混合溶媒に1モル/リットルの割合でLiClO4を加えたものを用いた。セパレータとして、ポリプロピレン製微細孔膜を用いた。炭素電極と負極との間にセパレータを挟み、電解液を注入してコインセルを作製した。
カルシウム元素含量およびカリウム元素含量の測定方法は、例えば以下の方法により測定した。予め所定のカルシウム元素およびカリウム元素を含有する炭素試料を調製し、蛍光X線分析装置を用いて、カルシウムKα線の強度とカルシウム元素含量との関係およびカリウムKα線の強度とカリウム元素含量との関係に関する検量線を作成した。ついで試料について蛍光X線分析におけるカルシウムKα線およびカリウムKα線の強度を測定し、先に作成した検量線よりカルシウム元素含量およびカリウム元素含量を求めた。蛍光X線分析は、株式会社リガク製「ZSX Primus-μ」を用いて、以下の条件で行った。上部照射方式用ホルダーを用い、試料測定面積を直径30mmの円周内とした。被測定試料2.0gとポリマーバインダ2.0g(Chemplex社製 Spectro Blend 44μ Powder)を乳鉢で混合し、成形機に入れた。成形機に15tonの荷重を1分間かけて、直径40mmのペレットを作製した。作製したペレットをポリプロピレン製のフィルムで包み、試料ホルダーに設置して測定を行った。X線源は40kV、75mAに設定した。カルシウム元素については、分光結晶にLiF(200)、検出器にガスフロー型比例係数管を使用し、2θが110~116°の範囲を、走査速度30°/分で測定した。カリウム元素については、分光結晶にLiF(200)、検出器にガスフロー型比例係数管を使用し、2θが133~140°の範囲を、走査速度4°/分で測定した。
真密度ρBtは、JIS R 7212に定められた方法に従い、ブタノール法により測定した。内容積約40mLの側管付比重びんの質量(m1)を正確に量った。次に、その底部に試料を約10mmの厚さになるように平らに入れた後、その質量(m2)を正確に量った。これに1-ブタノールを静かに加えて、底から20mm 程度の深さにした。次に比重びんに軽い振動を加えて、大きな気泡の発生がなくなったのを確かめた後、真空デシケーター中に入れ、徐々に排気して2.0~2.7kPaとした。その圧力に20分間以上保ち、気泡の発生が止まった後に、比重びんを取り出し、さらに1-ブタノールを満たし、栓をして恒温水槽(30±0.03℃に調節してあるもの)に15分間以上浸し、1-ブタノールの液面を標線に合わせた。次に、これを取り出して外部をよくぬぐって室温まで冷却した後、質量(m4)を正確に量った。次に、同じ比重びんに1-ブタノールだけを満たし、前記と同じようにして恒温水槽に浸し、標線を合わせた後、質量(m3)を量った。また使用直前に沸騰させて溶解した気体を除いた蒸留水を比重びんにとり、前記と同様に恒温水槽に浸し、標線を合わせた後、質量(m5)を量った。真密度ρBtは次の式により計算した。このとき、dは水の30℃における比重(0.9946)である。
カンタクローム社製「Autosorb-iQ-MP」を使用し、炭素質材料を減圧下、300℃で12時間加熱した後、77Kにおける炭素質材料の窒素吸脱着等温線を測定した。得られた脱着等温線に対し、DFT法を適用し、マイクロ孔容積およびメソ孔容積を算出した。
植物由来のチャーおよび炭素質材料の平均粒子径(粒度分布)は、以下の方法により測定した。試料を界面活性剤(和光純薬工業株式会社製「ToritonX100」)が5質量%含まれた水溶液に投入し、超音波洗浄器で10分以上処理し、水溶液中に分散させた。この分散液を用いて粒度分布を測定した。粒度分布測定は、粒子径・粒度分布測定装置(マイクロトラック・ベル株式会社製「マイクロトラックMT3300EXII」)を用いて行った。D50は、累積体積が50%となる粒子径であり、この値を平均粒子径として用いた。
椰子殻を粉砕し、窒素ガス雰囲気下、500℃で乾留して、0.5~2.0mmの粒子径を有する椰子殻チャーを得た。その後、ボールミルを用いて椰子殻チャーを粉砕し、10μmの平均粒子径(D50)を有する椰子殻粉砕チャーを得た。BET多点法により求められる比表面積は389m2/gであった。
製造例1で得た椰子殻チャーを、塩化水素ガスを2体積%含む窒素ガス気流下、1200℃で60分間熱処理した。塩化水素ガスを2体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり18L/分であった。その後、塩化水素ガスの供給のみを停止し、1200℃で60分間熱処理することにより脱酸処理を行い、炭素質材料を得た。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり18L/分であった。その後、ボールミルで粉砕することで、平均粒径D50が9μmの炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスに代えて塩化水素ガスを1体積%含む窒素ガスを使用したこと以外は実施例1と同様にして、炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスの供給量および脱酸処理における窒素ガスの供給量を、椰子殻チャー50gあたり16L/分としたこと以外は実施例1と同様にして、炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスに代えて塩化水素ガスを1体積%含む窒素ガスを使用したこと以外は実施例3と同様にして、炭素質材料を得た。
製造例1で得た椰子殻チャーを、椰子殻チャーの質量に基づき10質量%のNaOHを溶解した水溶液と混合した。30分間超音波照射をして溶液をチャーに浸透させた後に、1Torrの減圧下で80℃、8時間減圧乾燥した。得られた混合物を、塩化水素ガスを1体積%含む窒素ガス気流下、1200℃で60分間熱処理した。塩化水素ガスを1体積%含む窒素ガスの供給量は、50.0gの椰子殻チャーと5.55gのNaOHの混合物50gあたり16.2L/分であり、椰子殻チャー50gあたりでは18L/分であった。その後、塩化水素ガスの供給のみを停止し、1200℃で60分間熱処理することにより脱酸処理を行い、炭素質材料を得た。脱酸処理における窒素ガスの供給量は、50.0gの椰子殻チャーと5.55gのNaOHの混合物50gあたり16.2L/分であり、椰子殻チャー50gあたりでは18L/分であった。
塩化水素ガスを2体積%含む窒素ガスの供給量および脱酸処理における窒素ガスの供給量を、椰子殻チャー50gあたり10L/分としたこと以外は実施例1と同様にして、炭素質材料を得た。
熱処理の温度を900℃としたこと以外は比較例1と同様にして、炭素質材料を得た。
製造例1で得た椰子殻チャーを、塩化水素ガスを2体積%含む窒素ガス気流下、900℃で60分間熱処理した。塩化水素ガスを2体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。その後、塩化水素ガスの供給のみを停止し、900℃で60分間熱処理することにより脱酸処理を行った。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。得られた炭素質材料を、窒素ガス気流下、1200℃で60分間さらに熱処理した。さらなる熱処理における窒素ガスの供給量は、椰子殻チャー50gあたり1.0L/分であった。
製造例1で得た椰子殻チャーを、塩化水素ガスを1体積%含む窒素ガス気流下、975℃で70分間熱処理した。塩化水素ガスを1体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。その後、塩化水素ガスの供給のみを停止し、975℃で40分間熱処理することにより脱酸処理を行った。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。得られた炭素質材料を、窒素ガス気流下、1000℃で360分間さらに熱処理した。さらなる熱処理における窒素ガスの供給量は、椰子殻チャー50gあたり1.5L/分であった。
実施例1~5、比較例1~4で得た炭素質材料をそれぞれ用いて、以下の手順に従って負極の作製を行った。
炭素質材料96質量部、PVDF(ポリフッ化ビニリデン)4質量部およびNMP(N-メチルピロリドン)90質量部を混合し、スラリーを得た。厚さ14μmの銅箔に、得られたスラリーを塗布し、乾燥後プレスして、厚さ75μmの電極を得た。得られた電極の密度は、0.8~1.0g/cm3であった。
上記で作成した電極を用いて、電気化学測定装置(ソーラトロン社製「1255WB型高性能電気化学測定システム」)を用い、25℃で、0Vを中心に10mVの振幅を与え、周波数10mHz~1MHzの周波数で定電圧交流インピーダンスを測定し、周波数1k、1、0.1Hzにおける実部抵抗をインピーダンス抵抗として測定した。
上記で作製した電極を作用極とし、金属リチウムを対極および参照極として使用した。溶媒として、プロピレンカーボネートとエチレングリコールジメチルエーテルとを、体積比で1:1となるように混合して用いた。この溶媒に、LiClO4を1mol/L溶解し、電解質として用いた。セパレータにはポリプロピレン膜を使用した。アルゴン雰囲気下のグローブボックス内でコインセルを作製した。
上記構成のリチウム二次電池について、充放電試験装置(東洋システム株式会社製、「TOSCAT」)を用いて、初期充電前に直流抵抗値を測定後、充放電試験を行った。リチウムのドーピングは、活物質質量に対し70mA/gの速度で行い、リチウム電位に対して1mVになるまでドーピングした。さらにリチウム電位に対して1mVの定電圧を8時間印加して、ドーピングを終了した。このときの容量(mAh/g)を充電容量とした。次いで、活物質質量に対し70mA/gの速度で、リチウム電位に対して2.5Vになるまで脱ドーピングを行い、このとき放電した容量を放電容量とした。放電容量/充電容量の百分率を充放電効率(初期の充放電効率)とし、電池内におけるリチウムイオンの利用効率の指標とした。得られた結果を表2に示す。
椰子殻を破砕し、窒素ガス雰囲気下、500℃で乾留して、0.5~2.0mmの粒子径を有する椰子殻チャーを得た。その後、ボールミルを用いて椰子殻チャーを粉砕し、10μmの平均粒子径(D50)を有する椰子殻粉砕チャーを得た。BET多点法により求められる比表面積は391m2/gであった。
製造例2で得た椰子殻チャーを、塩化水素ガスを2体積%含む窒素ガス気流下、1200℃で70分間熱処理した。塩化水素ガスを2体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり18L/分であった。その後、塩化水素ガスの供給のみを停止し、1200℃で70分間熱処理することにより脱酸処理を行い、炭素質材料を得た。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり18L/分であった。その後、ボールミルで粉砕することで、平均粒径D50が10μmの炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスに代えて塩化水素ガスを1体積%含む窒素ガスを使用したこと以外は実施例6と同様にして、炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスの供給量および脱酸処理における窒素ガスの供給量を、椰子殻チャー50gあたり16L/分としたこと以外は実施例6と同様にして、炭素質材料を得た。
塩化水素ガスを2体積%含む窒素ガスに代えて塩化水素ガスを1体積%含む窒素ガスを使用したこと以外は実施例8と同様にして、炭素質材料を得た。
製造例2で得た椰子殻チャーを、椰子殻チャーの質量に基づき10質量%のNaOHを溶解した水溶液と混合した。30分間超音波照射をして溶液をチャーに浸透させた後に、1Torrの減圧下で80℃、8時間減圧乾燥した。得られた混合物を、塩化水素ガスを2体積%含む窒素ガス気流下、1200℃で70分間熱処理した。塩化水素ガスを1体積%含む窒素ガスの供給量は、50gの椰子殻チャーと5.55gのNaOHの混合物50gあたり16.2L/分であり、椰子殻チャー50gあたりでは18L/分であった。その後、塩化水素ガスの供給のみを停止し、1200℃で70分間熱処理することにより脱酸処理を行い、炭素質材料を得た。脱酸処理における窒素ガスの供給量は、50gの椰子殻チャーと5.55gのNaOHの混合物50gあたり16.2L/分であり、椰子殻チャー50gあたりでは18L/分であった。
塩化水素ガスを2体積%含む窒素ガスの供給量および脱酸処理における窒素ガスの供給量を、椰子殻チャー50gあたり10L/分としたこと以外は実施例6と同様にして、炭素質材料を得た。
熱処理の温度を900℃としたこと以外は比較例5と同様にして、炭素質材料を得た。
製造例2で得た椰子殻チャーを、塩化水素ガスを2体積%含む窒素ガス気流下、900℃で60分間熱処理した。塩化水素ガスを2体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。その後、塩化水素ガスの供給のみを停止し、900℃で60分間熱処理することにより脱酸処理を行った。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。得られた炭素質材料を、窒素ガス気流下、1200℃で60分間さらに熱処理した。さらなる熱処理における窒素ガスの供給量は、椰子殻チャー50gあたり1.0L/分であった。
製造例2で得た椰子殻チャーを、塩化水素ガスを1体積%含む窒素ガス気流下、975℃で70分間熱処理した。塩化水素ガスを1体積%含む窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。その後、塩化水素ガスの供給のみを停止し、975℃で40分間熱処理することにより脱酸処理を行った。脱酸処理における窒素ガスの供給量は、椰子殻チャー50gあたり10L/分であった。得られた炭素質材料を、窒素ガス気流下、1000℃で360分間さらに熱処理した。さらなる熱処理における窒素ガスの供給量は、椰子殻チャー50gあたり1.5L/分であった。
実施例6~10、比較例5~8で得た炭素質材料をそれぞれ用いて、以下の手順に従って負極の作製を行った。
炭素質材料96質量部、PVDF(ポリフッ化ビニリデン)4質量部およびNMP(N-メチルピロリドン)90質量部を混合し、スラリーを得た。厚さ14μmの銅箔に、得られたスラリーを塗布し、乾燥後プレスして、厚さ75μmの電極を得た。得られた電極の密度は、0.8~1.0g/cm3であった。
上記で作成した電極を用いて、電気化学測定装置(ソーラトロン社製「1255WB型高性能電気化学測定システム」)を用い、25℃で、0Vを中心に10mVの振幅を与え、周波数10mHz~1MHzの周波数で定電圧交流インピーダンスを測定し、周波数1k、1、0.1Hzにおける実部抵抗をインピーダンス抵抗として測定した。
上記で作製した電極を作用極とし、金属リチウムを対極および参照極として使用した。溶媒として、プロピレンカーボネートとエチレングリコールジメチルエーテルとを、体積比で1:1となるように混合して用いた。この溶媒に、LiClO4を1mol/L溶解し、電解質として用いた。セパレータにはポリプロピレン膜を使用した。アルゴン雰囲気下のグローブボックス内でコインセルを作製した。
上記構成のリチウム二次電池について、充放電試験装置(東洋システム株式会社製、「TOSCAT」)を用いて、初期充電前に直流抵抗値を測定後、充放電試験を行った。リチウムのドーピングは、活物質質量に対し70mA/gの速度で行い、リチウム電位に対して1mVになるまでドーピングした。さらにリチウム電位に対して1mVの定電圧を8時間印加して、ドーピングを終了した。このときの容量(mAh/g)を充電容量とした。次いで、活物質質量に対し70mA/gの速度で、リチウム電位に対して2.5Vになるまで脱ドーピングを行い、このとき放電した容量を放電容量とした。放電容量/充電容量の百分率を充放電効率(初期の充放電効率)とし、電池内におけるリチウムイオンの利用効率の指標とした。また、上記の充放電を3回繰り返した後で、インピーダンスの測定を行った。得られた結果を表4に示す。
Claims (8)
- 非水電解質二次電池の負極活物質用の炭素質材料であって、該炭素質材料は植物に由来し、レーザーラマン分光法により観測されるラマンスペクトルの1360cm-1付近のピークの半値幅の値が190~240cm-1であり、窒素吸着BET多点法により求めた比表面積が10~100m2/gである、炭素質材料。
- 前記炭素質材料に満充電状態となるまでリチウムをドープし、7Li核-固体NMR分析を行ったとき、基準物質であるLiClの共鳴ピークに対して低磁場側に115~145ppmシフトした主共鳴ピークが観測される、請求項1に記載の炭素質材料。
- カルシウム元素含量が50ppm以下である、請求項1または2に記載の炭素質材料。
- ブタノール法により求めた真密度が1.35~1.70g/cm3である、請求項1~3のいずれかに記載の炭素質材料。
- DFT法によりそれぞれ算出されるマイクロ孔容積に対するメソ孔容積の比が1.0以上である、請求項1~4のいずれかに記載の炭素質材料。
- 請求項1~5のいずれかに記載の炭素質材料を含む非水電解質二次電池用負極。
- 請求項6に記載の非水電解質二次電池用負極を有する非水電解質二次電池。
- 植物由来のチャーを、ハロゲン化合物を含む不活性ガス気流下、1100~1300℃で熱処理する工程を含み、該ハロゲン化合物を含む不活性ガスの供給量は植物由来のチャー50gあたり14L/分以上である、請求項1~5のいずれかに記載の炭素質材料の製造方法。
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JP2020004589A (ja) * | 2018-06-27 | 2020-01-09 | 株式会社クラレ | 炭素質材料の製造方法 |
US20230197968A1 (en) * | 2020-04-20 | 2023-06-22 | Kuraray Co., Ltd. | Carbonaceous material, method for producing same, and electrochemical device |
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EP3503271A1 (en) | 2019-06-26 |
TW201824620A (zh) | 2018-07-01 |
US11345601B2 (en) | 2022-05-31 |
JP6463875B2 (ja) | 2019-02-06 |
KR20190039072A (ko) | 2019-04-10 |
KR102405983B1 (ko) | 2022-06-07 |
EP3503271A4 (en) | 2020-04-08 |
TWI729187B (zh) | 2021-06-01 |
CN109565049B (zh) | 2022-05-17 |
CN109565049A (zh) | 2019-04-02 |
US20190194024A1 (en) | 2019-06-27 |
JPWO2018034155A1 (ja) | 2019-01-10 |
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