WO2022259914A1 - 負極活物質、負極及びリチウムイオン二次電池 - Google Patents
負極活物質、負極及びリチウムイオン二次電池 Download PDFInfo
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- WO2022259914A1 WO2022259914A1 PCT/JP2022/022103 JP2022022103W WO2022259914A1 WO 2022259914 A1 WO2022259914 A1 WO 2022259914A1 JP 2022022103 W JP2022022103 W JP 2022022103W WO 2022259914 A1 WO2022259914 A1 WO 2022259914A1
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- negative electrode
- active material
- electrode active
- particles
- silicon monoxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a negative electrode active material, a negative electrode, and a lithium ion secondary battery.
- lithium-ion secondary batteries are becoming more and more popular because they are easy to make smaller and have higher capacity, and they have a higher energy density than lead-acid batteries and nickel-cadmium batteries.
- the lithium-ion secondary battery described above includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and the negative electrode contains a negative electrode active material involved in charge-discharge reactions.
- the negative electrode active material expands and contracts during charging and discharging, and cracks are likely to occur mainly near the surface layer of the negative electrode active material.
- an ionic substance is generated inside the active material, making the negative electrode active material fragile.
- a new surface is generated thereby increasing the reaction area of the active material.
- a decomposition reaction of the electrolytic solution occurs on the new surface, and a film, which is a decomposition product of the electrolytic solution, is formed on the new surface, so that the electrolytic solution is consumed.
- cycle characteristics tend to deteriorate.
- silicon and amorphous silicon dioxide are simultaneously deposited using a vapor phase method (see Patent Document 1, for example).
- a carbon material electroconductive material
- an active material containing silicon and oxygen is produced, and an active material layer with a high oxygen ratio is formed in the vicinity of the current collector (for example, see Patent Document 3).
- the silicon active material contains oxygen so that the average oxygen content is 40 atomic % or less, and the oxygen content is increased near the current collector. (see, for example, Patent Document 4).
- a nanocomposite containing Si phase, SiO 2 , and M y O metal oxide is used to improve the initial charge/discharge efficiency (see, for example, Patent Document 5).
- the molar ratio of oxygen to silicon in the negative electrode active material is set to 0.1 to 1.2, and the difference between the maximum and minimum molar ratios near the interface between the active material and the current collector is is 0.4 or less (see Patent Document 7, for example).
- a metal oxide containing lithium is used (see, for example, Patent Document 8).
- a hydrophobic layer such as a silane compound is formed on the surface layer of the silicon material (see Patent Document 9, for example).
- Patent Document 10 silicon oxide is used, and conductivity is imparted by forming a graphite film on the surface layer.
- Patent Document 10 broad peaks appear at 1330 cm ⁇ 1 and 1580 cm ⁇ 1 with respect to the shift values obtained from the RAMAN spectrum of the graphite film, and their intensity ratio I 1330 /I 1580 is 1.5 ⁇ I 1330 /I 1580 ⁇ 3.
- particles having a silicon microcrystalline phase dispersed in silicon dioxide are used (see, for example, Patent Document 11).
- silicon oxide in which the atomic ratio of silicon and oxygen is controlled to 1:y (0 ⁇ y ⁇ 2) is used (see Patent Document 12, for example).
- Non-Patent Document 1 The silicon oxide proposed by Hohl is a composite of Si 0+ to Si 4+ and has various oxidation states (Non-Patent Document 2).
- Kapaklis also proposed a disproportionated structure in which Si and SiO 2 are separated by applying a thermal load to silicon oxide (Non-Patent Document 3).
- Miyachi et al. pay attention to Si and SiO 2 that contribute to charging and discharging among silicon oxides having a disproportionated structure (Non-Patent Document 4).
- silicon oxide powder with a defined particle size distribution of mode diameter, D50 and D90 is used (for example, Patent Document 13).
- D50 indicates cumulative 50% diameter
- D90 indicates cumulative 90% diameter
- other numerical values are the same.
- D90, D90/D10, and fine powder amount of 1 ⁇ m or less of silicon oxide powder subjected to wet classification with water after ball mill pulverization are specified (for example, Patent Document 14).
- silicon oxide powder having a defined D50/D10 of the silicon oxide powder before forming the carbon film and a BET specific surface area of the negative electrode active material after forming the carbon film is used (for example, Patent document 15).
- the specific surface area calculated from the particle size distribution of the negative electrode active material assuming that the particles are spherical and the BET specific surface area of the negative electrode active material A ratio is defined (eg, US Pat.
- D10 and D90 of a negative electrode active material made of silicon oxide after forming a carbon film are specified (eg, Patent Document 17).
- JP 2013-101770 A Japanese Patent Application Laid-Open No. 2001-185127 Japanese Patent Application Laid-Open No. 2002-042806 JP 2006-164954 A JP 2006-114454 A JP 2009-070825 A JP 2008-282819 A JP 2008-251369 A JP 2008-177346 A JP 2007-234255 A JP 2009-212074 A JP 2009-205950 A JP-A-06-325765 JP 2015-149171 A JP 2011-65934 A WO2012/077268 WO2014/002356 JP 2013-101770 A
- Lithium-ion secondary batteries that use silicon-based materials with high charge-discharge capacity are expected to have cycle characteristics that are close to those of lithium-ion secondary batteries that use carbon-based active materials.
- silicon-based materials silicon oxide has the potential to obtain higher cycle characteristics, and various improvements have been made. In repeating charging and discharging, the suppression of decomposition of the electrolytic solution on the surface of the negative electrode active material was insufficient, and cycle characteristics that could withstand a practical level were not obtained.
- Patent Document 14 specifies D90/D10 and the amount of fine powder of 1 ⁇ m or less by performing wet classification with water, using SiO x powder with a change in the surface Si oxidation state and a greatly different value of x. Relative evaluation of efficiency and cycle characteristics versus particle size distribution is not possible.
- the BET specific surface area of the negative electrode active material is greatly affected not only by the surface state of the silicon oxide particles serving as the base material, but also by the state of the carbon film formed on the surface of the negative electrode active material. It is insufficient as a factor to suppress the reaction. Furthermore, although there is a description that there is no difference in cycle characteristics (10 cycles) between an example having a D50 of about 5 ⁇ m and a comparative example having a D50 of 9.36 ⁇ m, generally in coin battery evaluation, charging and discharging cycles are performed. Since the Li positive electrode deteriorates with repetition, it is not suitable for a long-term cycle test exceeding 50 cycles. Therefore, in order to evaluate the deterioration of the negative electrode due to the reaction between the electrolyte and the negative electrode active material, more than 100 charge-discharge cycles are required. must be done in
- Patent Documents 16 and 17 do not mention the particle size distribution and BET surface area of SiO x before forming the carbon film, and Patent Document 17 has a small D90 of 5 ⁇ m or less.
- the present invention has been made in view of the problems described above, and an object of the present invention is to provide a negative electrode active material capable of improving cycle characteristics when used as a negative electrode active material for a negative electrode of a secondary battery.
- the present invention provides a negative electrode active material containing silicon monoxide particles, wherein the silicon monoxide particles have a cumulative volume distribution of 0.5. 1% particle size D0.1 is 1.2 ⁇ m ⁇ D0.1 ⁇ 3.0 ⁇ m, cumulative 10% particle size D10 is 3.5 ⁇ m ⁇ D10 ⁇ 7.0 ⁇ m, cumulative 50% particle size D50 is 6.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m, the cumulative 99.9% particle diameter D99.9 satisfies 25.0 ⁇ m ⁇ D99.9 ⁇ 50.0 ⁇ m, and the silicon monoxide particles have a BET specific surface area Sm of 1.0 m 2 /g ⁇ S Provided is a negative electrode active material that satisfies m ⁇ 3.5 m 2 /g.
- the negative electrode active material of the present invention has such a particle size distribution and BET specific surface area that in a long-term cycle test in which charging and discharging are repeated, the reaction with the electrolyte solution on the particle surface of the negative electrode active material is suppressed, and the battery cycle Characteristics can be greatly improved.
- the cumulative 0.1% particle diameter D0.1 preferably satisfies 2.0 ⁇ m ⁇ D0.1 ⁇ 3.0 ⁇ m.
- the cumulative 10% particle diameter D10 preferably satisfies 4.8 ⁇ m ⁇ D10 ⁇ 7.0 ⁇ m.
- the cumulative 50% particle size D50 preferably satisfies 8.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m.
- the reaction with the electrolytic solution on the particle surface is more effectively suppressed, and the cycle characteristics of the battery can be greatly improved.
- the BET specific surface area Sm is preferably 1.0 m 2 /g ⁇ S m ⁇ 2.2 m 2 /g.
- the silicon monoxide particles are preferably coated with a carbon film.
- the present invention also provides a negative electrode that includes the negative electrode active material described above.
- the present invention also provides a lithium ion secondary battery comprising the above negative electrode, positive electrode, separator, and electrolyte.
- the negative electrode active material of the present invention has a specific particle size distribution and BET specific surface area, so that in a long-term cycle test in which charging and discharging are repeated, the reaction with the electrolyte solution on the particle surface of the negative electrode active material is suppressed, and the cycle characteristics of the battery In particular, the cycle characteristics in long-term cycle tests can be greatly improved.
- 4 is a graph showing the number of cycles at which 70% discharge capacity is maintained with respect to D0.1 of silicon monoxide particles. 4 is a graph showing the number of cycles of maintaining 70% discharge capacity with respect to D10 of silicon monoxide particles. 4 is a graph showing the number of cycles of maintaining 70% discharge capacity with respect to D50 of silicon monoxide particles. It is a graph which shows the number of discharge capacity 70% maintenance cycles with respect to D99.9 of silicon monoxide particles. 4 is a graph showing the number of cycles at which 70% discharge capacity is maintained with respect to the BET specific surface area of silicon monoxide particles. 4 is a graph showing the number of cycles at which 70% discharge capacity is maintained with respect to the BET specific surface area of carbon-coated silicon monoxide particles.
- the present inventors have made intensive studies on controlling the particle size of the silicon monoxide particles that constitute the negative electrode active material. As a result, not only the particle size distribution of the silicon monoxide particles that serve as the base material, but also the BET specific surface area of the silicon monoxide particles is set in an appropriate range, thereby maintaining the initial charge-discharge characteristics while greatly improving the cycle characteristics. It has been found that it is possible to improve to , leading to the present invention.
- the negative electrode active material of the present invention is a negative electrode active material containing silicon monoxide particles. Furthermore, the silicon monoxide particles satisfy the following conditions in the volume standard distribution measured by a laser diffraction particle size distribution analyzer.
- ⁇ Cumulative 0.1% particle diameter D0.1 is 1.2 ⁇ m ⁇ D0.1 ⁇ 3.0 ⁇ m
- ⁇ Cumulative 10% particle diameter D10 is 3.5 ⁇ m ⁇ D10 ⁇ 7.0 ⁇ m
- - Cumulative 50% particle diameter D50 is 6.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m
- ⁇ Cumulative 99.9% particle diameter D99.9 is 25.0 ⁇ m ⁇ D99.9 ⁇ 50.0 ⁇ m
- the silicon monoxide particles contained in the negative electrode active material of the present invention have a BET specific surface area Sm that satisfies 1.0 m 2 /g ⁇ S m ⁇ 3.5 m 2 /g.
- the BET specific surface area is a value measured by the BET one-point method, which measures the N 2 gas adsorption amount.
- the silicon monoxide particles contained in the negative electrode active material of the present invention are 2.0 ⁇ m ⁇ D0.1 ⁇ 3.0 ⁇ m, 4.8 ⁇ m ⁇ D10 ⁇ 7.0 ⁇ m, and 8.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m.
- BET specific surface area S m satisfies at least one of 1.0 m 2 /g ⁇ S m ⁇ 2.2 m 2 /g.
- Silicon oxide is a generic term for amorphous silicon oxide, and silicon oxide before disproportionation is represented by the general formula SiOx (0.5 ⁇ x ⁇ 1.6).
- This silicon oxide can be obtained, for example, by heating a mixture of silicon dioxide and metal silicon and then cooling and precipitating silicon monoxide gas produced, thereby obtaining silicon monoxide (SiO) in which x is 1 or close to 1. For example, 0.9 ⁇ x ⁇ 1.1.
- the silicon monoxide particles within the specific particle size range of the present invention described above, they can be appropriately adjusted by treatments such as pulverization and classification.
- Well-known equipment can be used for grinding.
- ball mills, media agitation mills, and rollers are used to pulverize crushed materials by moving pulverizing media such as balls and beads, and using the impact force, friction force, and compression force resulting from the kinetic energy.
- a jet mill that pulverizes the crushed material by colliding it with the lining material at high speed or colliding with each other, and crushing it by the impact force caused by the impact, and the impact caused by the rotation of the rotor with fixed hammers, blades, pins, etc.
- Dry classification mainly uses air flow, and the processes of dispersion, separation (separation of fine and coarse particles), collection (separation of solid and gas), and discharge are performed sequentially or simultaneously, and interference between particles, particle
- pretreatment adjustment of moisture, dispersibility, humidity, etc.
- pulverization and classification are performed at once, and a desired particle size distribution can be obtained.
- the cumulative 0.1% diameter D0.1 of the silicon monoxide particles is, as described above, 1.2 to 3.0 ⁇ m, preferably 2.0 to 3.0 ⁇ m. Also, the cumulative 10% diameter D10 of the silicon monoxide particles is set to 3.5 to 7.0 ⁇ m, preferably 4.8 to 7.0 ⁇ m. Also, the cumulative 50% diameter D50 of the silicon monoxide particles is 6.0 to 15.0 ⁇ m, preferably 8.0 to 15.0 ⁇ m.
- the cumulative 99.9% diameter D99.9 of the silicon monoxide particles is 25.0 to 50.0 ⁇ m.
- D99.9 is more than 50.0 ⁇ m, the coarse particles expand and contract due to charging and discharging, and there is a risk that the conductive path will be lost in the negative electrode active material layer.
- the separator may be damaged by coarse particles due to pressing or the like. Therefore, as described above, D99.9 should not exceed 50 ⁇ m by setting D0.1 to 3.0 ⁇ m or less, D10 to 7.0 ⁇ m or less, and D50 to 15.0 ⁇ m or less. can be done.
- the BET specific surface area of the silicon monoxide particles contained in the negative electrode active material of the present invention is 1.0 to 3.5 m 2 /g, preferably 1.0 to 2.2 m 2 /g, as described above. do.
- the reaction area between the electrolytic solution and the silicon monoxide particles is reduced. Cycle characteristics can be greatly improved.
- the reason why the BET specific surface area is 1.0 m 2 /g or more is that the BET specific surface area is 1.0 m 2 /g for silicon monoxide particles that satisfy D50 of 6.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m. This is because it is industrially difficult to produce silicon monoxide particles of less than
- a method of imparting conductivity to the silicon monoxide particles and improving battery characteristics a method of mixing with conductive particles such as graphite, a method of coating the surface of the composite particles with a carbon film, and both.
- a method of combining the Among them it is preferable to use coated particles in which the surfaces of silicon monoxide particles are coated with a carbon film.
- Chemical vapor deposition (CVD) is a suitable method for coating with a carbon coating.
- CVD chemical vapor deposition
- silicon monoxide particles are exposed to carbon at a temperature range of 600 to 1,200° C. in an organic gas and/or steam atmosphere that can be thermally decomposed to produce carbon.
- a method of forming a carbon coating by chemical vapor deposition may be mentioned.
- Chemical vapor deposition can be applied under both normal pressure and reduced pressure.
- generally known apparatuses such as a batch type furnace, a continuous furnace such as a rotary kiln and a roller hearth kiln, and a fluidized bed can be used as the apparatus used in the step of forming the carbon coating.
- the vapor deposition apparatus is a batch type furnace in which the particles are left stationary, the carbon can be more uniformly coated by carrying out the vapor deposition under reduced pressure, and the battery characteristics can be improved.
- the thermal decomposition temperature, deposition rate, and characteristics of the carbon film formed after vapor deposition largely depend on the substance used. may differ.
- the uniformity of the carbon film on the surface of a substance with a high deposition rate is not sufficient, and on the other hand, if a high temperature is required for decomposition, the silicon crystals in the silicon monoxide particles to be coated grow too large during deposition at a high temperature. As a result, the discharge efficiency and cycle characteristics may deteriorate.
- the crystallite size of silicon is determined by the Scherrer method from the half width of the Si (111) peak in powder XRD measurement, and is preferably 50 nm or less, more preferably 10 nm or less. The smaller the crystallite size, the more the disproportionation of silicon oxide due to charging and discharging is suppressed, and higher cycle characteristics can be obtained.
- the Si crystallite size of the silicon monoxide particles in the negative electrode active material can be confirmed, for example, using the following XRD apparatus.
- ⁇ XRD Bruker D8 ADVANCE
- the X-ray source was Cu K ⁇ rays, using a Ni filter, an output of 40 kV/40 mA, a slit width of 0.3°, a step width of 0.008°, and a counting time of 0.15 seconds per step from 10 to 40°. Measure up to
- Raw materials for organic gases that can be thermally decomposed to produce carbon include hydrocarbons such as methane, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane, and hexane, benzene, toluene, xylene, styrene, ethylbenzene, Diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, cumarone, pyridine, anthracene, phenanthrene and other monocyclic to tricyclic aromatic hydrocarbons, gas light oil obtained in the tar distillation process, creosote oil, anthracene oil and naphtha cracked tar oil. These can be used singly or in combination of two or more. From an economical point of view, it is preferable to use a hydrocarbon gas with a composition of CxHy.
- the coating amount of the carbon coating is preferably 1.0% by mass or more and 5.0% by mass or less with respect to the entire carbon-coated coated particles. Although it depends on the particles to be coated, by setting the carbon coating amount to 1.0% by mass or more, generally sufficient conductivity can be maintained. In addition, by setting the carbon coating amount to 5.0% by mass or less, the proportion of carbon in the negative electrode active material can be moderated without excessively increasing, and it can be used as a negative electrode active material for lithium ion secondary batteries. The charge/discharge capacity can be ensured when the battery is used.
- a lithium ion secondary battery can be produced by producing a negative electrode using the negative electrode active material in which silicon monoxide particles are coated with a carbon film.
- a conductive agent such as carbon or graphite
- the type of the conductive agent is not particularly limited, and any electronically conductive material that does not cause decomposition or deterioration in the constructed battery may be used.
- metal particles and metal fibers such as Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn, Si, natural graphite, artificial graphite, various coke particles, mesophase carbon, vapor growth carbon fiber, pitch Graphite such as carbon-based carbon fiber, PAN-based carbon fiber, and various resin sintered bodies can be used.
- An example of the method for preparing the negative electrode is as follows.
- the above negative electrode active material, optionally a conductive agent, other additives such as a binder such as carboxymethyl cellulose (hereinafter referred to as CMC), and a solvent such as an organic solvent or water are kneaded to form a paste. and apply this mixture to the current collector sheet.
- CMC carboxymethyl cellulose
- a solvent such as an organic solvent or water
- the current collector sheet materials such as copper foil and nickel foil, which are usually used as current collectors for negative electrodes, can be used without particular limitations on thickness and surface treatment.
- the molding method for molding the mixture into a sheet is not particularly limited, and a known method can be used.
- a lithium ion secondary battery is a lithium ion secondary battery having at least a positive electrode, a negative electrode, and a lithium ion conductive non-aqueous electrolyte, wherein the negative electrode uses the negative electrode active material according to the present invention. It is.
- the lithium ion secondary battery of the present invention is characterized in that it comprises a negative electrode using the negative electrode active material comprising the above-described coated particles, and other materials such as the positive electrode, electrolyte, separator, etc., and battery shape, etc. are known. can be used and is not particularly limited.
- the negative electrode active material of the present invention has good battery characteristics (charge/discharge capacity and cycle characteristics) when used as a negative electrode active material for lithium ion secondary batteries, and is particularly excellent in cycle durability. is.
- transition metal oxides such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , MnO 2 , TiS 2 and MoS 2 , lithium, and chalcogen compounds are used.
- a non-aqueous solution containing a lithium salt such as lithium hexafluorophosphate or lithium perchlorate is used.
- a lithium salt such as lithium hexafluorophosphate or lithium perchlorate
- the non-aqueous solvent propylene carbonate, ethylene carbonate, diethyl carbonate, dimethoxyethane, ⁇ -butyrolactone, 2-methyltetrahydrofuran, etc. may be used singly or in combination of two or more.
- Various other non-aqueous electrolytes and solid electrolytes can also be used.
- a jaw crusher manufactured by Maekawa Kogyosho
- a ball mill manufactured by Makino
- the particles were finely pulverized in a jet mill (KJ800 manufactured by Kurimoto, Ltd.) under the conditions of a compressed air pressure of 0.52 MPa and a classifier rotation speed of 4,500 rpm, and collected with a cyclone.
- a jet mill KJ800 manufactured by Kurimoto, Ltd.
- a compressed air pressure 0.52 MPa
- a classifier rotation speed 4500 rpm
- a cyclone collected with a cyclone.
- D0.1 was 1.2 ⁇ m
- D10 was 3.5 ⁇ m
- D50 was
- the silicon monoxide particles were 7.9 ⁇ m
- D99.9 was 28.1 ⁇ m
- BET specific surface area was 2.9 m 2 /g.
- the particles were spread on a tray so that the powder layer had a thickness of 10 mm, and charged into a batch heating furnace. Then, the temperature inside the furnace was raised to 1,000° C. at a heating rate of 200° C./hr while reducing the pressure in the furnace with an oil rotary vacuum pump. After the temperature reached 1,000° C., 0.3 L/min of methane was passed through the furnace, and carbon coating treatment was performed for 10 hours. After the methane was stopped, the temperature inside the furnace was lowered and cooled, and the collected agglomerates were pulverized to obtain black particles.
- the resulting black particles are conductive particles having a D50 of 7.9 ⁇ m, a BET specific surface area of 2.2 m 2 /g, a carbon coating amount of 2.8% by mass relative to the black particles, and a silicon crystallite size of 5.0 nm. Met.
- negative electrode active material graphite, conductive aid 1 (carbon nanotube, CNT), conductive aid 2 (carbon fine particles having a median diameter of about 50 nm), sodium polyacrylate, and CMC were mixed at 9.3:83.7:1. After mixing at a dry mass ratio of :1:4:1, the mixture was diluted with pure water to obtain a negative electrode mixture slurry.
- This slurry was applied to a copper foil having a thickness of 15 ⁇ m and dried in a vacuum atmosphere at 100° C. for 1 hour. After drying, the deposition amount of the negative electrode active material layer per unit area (also referred to as area density) on one side of the negative electrode was 7.0 mg/cm 2 .
- an electrolyte salt lithium hexafluorophosphate: LiPF 6
- vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added in amounts of 1.0% by mass and 2.0% by mass, respectively.
- a Li foil with a thickness of 1 mm was punched into a diameter of 16 mm and attached to an aluminum clad.
- the obtained electrode was punched out to have a diameter of 15 mm, and was faced to the Li counter electrode with a separator interposed therebetween.
- the initial efficiency was measured under the following conditions. First, the charge rate was set to 0.03C. Charging was performed in CCCV mode. CV was 0 V and final current was 0.04 mA. CC discharge was performed at a discharge rate of 0.03 C and a discharge voltage of 1.2 V in the same manner.
- initial efficiency (initial discharge capacity/initial charge capacity) ⁇ 100.
- LCO lithium cobalt oxide
- the cycle characteristics were investigated as follows. First, two cycles of charge and discharge were performed at 0.2C in an atmosphere of 25°C for battery stabilization, and the discharge capacity of the second cycle was measured. The battery cycle characteristics were calculated from the discharge capacity at the third cycle, and the battery test was stopped when the discharge capacity maintenance rate reached 70%. Charging and discharging were performed at 0.7C for charging and 0.5C for discharging. The charge voltage was 4.3V, the discharge final voltage was 2.5V, and the charge final rate was 0.07C.
- the resulting silicon monoxide particles were coated with a carbon film to obtain conductive particles having a D50 of 6.1 ⁇ m, a BET specific surface area of 3.2 m 2 /g, and a carbon coating amount of 3.5% by mass relative to the black particles. .
- a negative electrode was produced in the same manner as in Example 1, and battery evaluation was performed.
- Conductive particles were produced in the same manner as in Example 1, except that the silicon monoxide particles obtained in Comparative Example 2 were used and the methane aeration time was set to 7 hours. Conductive particles having a D50 of 6.0 ⁇ m, a BET specific surface area of 3.2 m 2 /g, and a carbon coating amount of 2.7% by mass based on the black particles were obtained. Using the obtained conductive particles, a negative electrode was produced in the same manner as in Example 1, and battery evaluation was performed.
- Example 4 The ball mill powder having a D50 of 100 ⁇ m obtained in Example 1 was pulverized by a jet mill under the conditions of a classifier compressed air pressure of 0.40 MPa and a rotation speed of 2200 rpm, and collected by a cyclone. Silicon monoxide particles having a D0.1 of 3.5 ⁇ m, a D10 of 7.2 ⁇ m, a D50 of 18.9 ⁇ m, a D99.9 of 53.4 ⁇ m, and a BET specific surface area of 1.3 m 2 /g of the particles collected by the cyclone. there were.
- the resulting silicon monoxide particles were coated with a carbon film to obtain conductive particles having a D50 of 19.0 ⁇ m, a BET specific surface area of 1.2 m 2 /g, and a carbon coating amount of 2.0% by mass relative to the black particles. .
- a negative electrode was produced in the same manner as in Example 1, and battery evaluation was performed.
- the silicon monoxide particles had a D0.1 of 0.3 ⁇ m, a D10 of 1.5 ⁇ m, a D50 of 9.1 ⁇ m, a D99.9 of 57.0 ⁇ m, and a BET specific surface area of 2.8 m 2 /g.
- a carbon film was coated in the same manner as in Example 1 without performing fine pulverization and classification operations with a jet mill, and the D50 was 9.3 ⁇ m, the BET specific surface area was 2.5 m 2 /g, and the carbon coating amount with respect to black particles was 3. 1% by weight of conductive particles was obtained. Using the obtained conductive particles, a negative electrode was produced in the same manner as in Example 1, and battery evaluation was performed.
- Table 1 shows the conditions of Examples and Comparative Examples.
- Table 2 shows powder physical properties and battery characteristics.
- FIG. 1 shows the number of cycles of maintaining 70% discharge capacity of the negative electrode active material coated with carbon with respect to D0.1 of silicon monoxide particles not coated with carbon
- FIG. 2 shows silicon monoxide without carbon coating.
- FIG. 4 shows the number of cycles to maintain 70% discharge capacity of the carbon-coated negative electrode active material with respect to silicon monoxide particles D99.9 in the non-carbon-coated state
- FIG. 5 shows the state without carbon coating.
- the number of cycles is 800 or more when the cumulative 0.1% particle diameter D0.1 of the silicon monoxide particles is in the range of 1.2 ⁇ m ⁇ D0.1 ⁇ 3.0 ⁇ m. Further, from FIG. 2, it can be seen that the number of cycles is 800 or more when the cumulative 10% particle diameter D10 of the silicon monoxide particles is in the range of 3.5 ⁇ m ⁇ D10 ⁇ 7.0 ⁇ m. Further, from FIG. 3, it can be seen that the number of cycles is 800 or more when the cumulative 50% particle diameter D50 of the silicon monoxide particles is in the range of 6.0 ⁇ m ⁇ D50 ⁇ 15.0 ⁇ m. Further, from FIG.
- the number of cycles is 800 or more when the cumulative 99.9% particle diameter D99.9 of the silicon monoxide particles is in the range of 25.0 ⁇ m ⁇ D99.9 ⁇ 50.0 ⁇ m. Further, from FIG. 5, it can be seen that the number of cycles is 800 or more when the BET specific surface area Sm of the silicon monoxide particles is in the range of 1.0 m 2 /g ⁇ S m ⁇ 3.5 m 2 /g.
- Examples 1 to 10 are lithium ion secondary batteries with greatly improved cycle characteristics while maintaining initial charge/discharge characteristics as compared to Comparative Examples 1 to 5.
- the particle size distribution of the silicon monoxide particles did not satisfy the optimum conditions, and the BET specific surface area was high.
- the negative electrode active material comprising silicon monoxide particles having a particle size distribution of D99.9 exceeding 50 ⁇ m deteriorates the cycle characteristics. It is presumed that the coarse particles expanded and contracted due to charging and discharging, and the conductive path was lost.
- the present invention is not limited to the above embodiments.
- the above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and produces similar effects is the present invention. It is included in the technical scope of the invention.
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Abstract
Description
本発明の負極活物質は、一酸化珪素粒子を含む負極活物質である。さらに、当該一酸化珪素粒子は、レーザー回折法粒度分布測定装置で測定した体積基準分布において、以下の条件を満たす。
・累積0.1%粒子径D0.1が1.2μm≦D0.1≦3.0μm、
・累積10%粒子径D10が3.5μm≦D10≦7.0μm、
・累積50%粒子径D50が6.0μm≦D50≦15.0μm、
・累積99.9%粒子径D99.9が25.0μm≦D99.9≦50.0μm
さらに、本発明の負極活物質に含まれる一酸化珪素粒子は、BET比表面積Smが1.0m2/g≦Sm≦3.5m2/gを満たすものである。
・XRD:Bruker社 D8 ADVANCE
X線源はCu Kα線、Niフィルターを使用して,出力40kV/40mA、スリット幅0.3°、ステップ幅0.008°、1ステップあたり0.15秒の計数時間にて10-40°まで測定する。
上記負極活物質を用いて負極を作製する場合、さらにカーボンや黒鉛等の導電剤を添加することができる。この場合においても導電剤の種類は特に限定されず、構成された電池において、分解や変質を起こさない電子伝導性の材料であればよい。具体的にはAl,Ti,Fe,Ni,Cu,Zn,Ag,Sn,Si等の金属粒子や金属繊維又は天然黒鉛、人造黒鉛、各種のコークス粒子、メソフェーズ炭素、気相成長炭素繊維、ピッチ系炭素繊維、PAN系炭素繊維、各種の樹脂焼成体等の黒鉛を用いることができる。
リチウムイオン二次電池は、少なくとも、正極と、負極と、リチウムイオン導電性の非水電解質とを有するリチウムイオン二次電池であって、上記負極に、本発明に係る負極活物質が用いられたものである。本発明のリチウムイオン二次電池は、上記被覆粒子からなる負極活物質を用いた負極からなる点に特徴を有し、その他の正極、電解質、セパレータ等の材料及び電池形状等は公知のものを使用することができ、特に限定されない。上述のように、本発明の負極活物質は、リチウムイオン二次電池用の負極活物質として用いた場合の電池特性(充放電容量及びサイクル特性)が良好で、特にサイクル耐久性に優れたものである。
まず、二酸化珪素と金属珪素との混合物を加熱して生成した一酸化珪素ガスを冷却・析出することで、xがほぼ1.0の一酸化珪素(SiOx)を得た。次に、このSiOx(x=1.0)をジョークラッシャー(前川工業所製)で粗砕し、さらに、ボールミル(マキノ製)で15分間粉砕し、D50が100μmの一酸化珪素粒子を得た。この粒子をジェットミル(栗本鐵工所製KJ800)で、圧縮空気の圧力0.52MPa、分級機の回転数4,500rpmの条件で微粉砕し、サイクロンで回収した。この粒子をレーザー回折法粒度分布測定装置(島津製作所SALD-3100)で屈折率2.05-0.00iの条件で測定したところ、D0.1が1.2μm、D10が3.5μm、D50が7.9μm、D99.9が28.1μm、BET比表面積が2.9m2/gの一酸化珪素粒子であった。
次に、以下の方法で、得られた炭素被膜粒子を負極活物質として用いた電池評価を行った。
得られた電極を直径15mmに打ち抜き、セパレータを介してLi対極と向い合せ電解液注液後、2032コイン電池を作製した。
実施例1と同じSiOx(x=1.0)を同様にボールミルでD50を100μmにした。次のジェットミル工程で分級機の回転数、粉砕圧および雰囲気制御を行い、表1に示される粉体物性を有する一酸化珪素粒子を作製した。実施例1と同様の方法で、一酸化珪素粒子に炭素膜を被覆させて導電性粒子を作製し、得られた導電性粒子を用いて負極を作製し、電池評価を行った。
実施例1と同じSiOx(x=1.0)を同様にボールミルで100μmにした。次のジェットミル工程で分級機の圧縮空気の圧力0.52MPa、回転数を5000rpmの条件で微粉砕し、サイクロンで回収した。サイクロンで回収した粒子のD0.1が1.8μm、D10が4.5μm、D50が6.6μm、D99.9が18.9μm、BET比表面積が3.3m2/gの一酸化珪素粒子であった。実施例1と同様の方法で、一酸化珪素粒子に炭素膜を被覆させて導電性粒子を作製し、得られた導電性粒子を用いて負極を作製し、電池評価を行った。
実施例1と同じSiOx(x=1.0)を用いて30分間ボールミルで粉砕し、D50を20μmにした。次のジェットミル工程では、分級機の圧縮空気の圧力0.45MPa、回転数を5500rpmの条件で微粉砕し、サイクロンで回収した。サイクロンで回収した粒子のD0.1が0.4μm、D10が2.5μm、D50が5.8μm、D99.9が18.5μm、BET比表面積が3.7m2/gの一酸化珪素粒子であった。得られた一酸化珪素粒子に炭素膜を被覆し、D50が6.1μm、BET比表面積が3.2m2/g、黒色粒子に対する炭素被覆量3.5質量%の導電性粒子が得られた。得られた導電性粒子を用いて、実施例1と同様の方法で負極を作製し、電池評価を行った。
比較例2で得られた一酸化珪素粒子を用いることおよびメタン通気時間を7時間とすること以外は、実施例1と同様にして、導電性粒子を作製した。D50が6.0μm、BET比表面積が3.2m2/g、黒色粒子に対する炭素被覆量2.7質量%の導電性粒子が得られた。得られた導電性粒子を用いて、実施例1と同様の方法で負極を作製し、電池評価を行った。
実施例1で得られたD50が100μmのボールミル粉を用いて、ジェットミルで分級機の圧縮空気の圧力0.40MPa、回転数を2200rpmの条件で微粉砕し、サイクロンで回収した。サイクロンで回収した粒子のD0.1が3.5μm、D10が7.2μm、D50が18.9μm、D99.9が53.4μm、BET比表面積が1.3m2/gの一酸化珪素粒子であった。得られた一酸化珪素粒子に炭素膜を被覆し、D50が19.0μm、BET比表面積が1.2m2/g、黒色粒子に対する炭素被覆量2.0質量%の導電性粒子が得られた。得られた導電性粒子を用いて、実施例1と同様の方法で負極を作製し、電池評価を行った。
実施例1と同じSiOx(x=1.0)を用いてボールミルで1時間粉砕した。この一酸化珪素粒子はD0.1が0.3μm、D10が1.5μm、D50が9.1μm、D99.9が57.0μm、BET比表面積が2.8m2/gであった。ジェットミルによる微粉砕・分級操作をせずに、実施例1と同様に炭素膜を被覆し、D50が9.3μm、BET比表面積が2.5m2/g、黒色粒子に対する炭素被覆量3.1質量%の導電性粒子が得られた。得られた導電性粒子を用いて、実施例1と同様の方法で負極を作製し、電池評価を行った。
Claims (8)
- 一酸化珪素粒子を含む負極活物質であって、
前記一酸化珪素粒子は、レーザー回折法粒度分布測定装置で測定した体積基準分布において、
累積0.1%粒子径D0.1が1.2μm≦D0.1≦3.0μm、
累積10%粒子径D10が3.5μm≦D10≦7.0μm、
累積50%粒子径D50が6.0μm≦D50≦15.0μm、
累積99.9%粒子径D99.9が25.0μm≦D99.9≦50.0μm
を満たし、
前記一酸化珪素粒子は、BET比表面積Smが1.0m2/g≦Sm≦3.5m2/gを満たすものであることを特徴とする負極活物質。 - 前記累積0.1%粒子径D0.1が、2.0μm≦D0.1≦3.0μmを満たすものであることを特徴とする請求項1に記載の負極活物質。
- 前記累積10%粒子径D10が、4.8μm≦D10≦7.0μmを満たすものであることを特徴とする請求項1又は請求項2に記載の負極活物質。
- 前記累積50%粒子径D50が、8.0μm≦D50≦15.0μmを満たすものであることを特徴とする請求項1から請求項3のいずれか1項に記載の負極活物質。
- 前記BET比表面積Smが、1.0m2/g≦Sm≦2.2m2/gであることを特徴とする請求項1から請求項4のいずれか1項に記載の負極活物質。
- 前記一酸化珪素粒子が炭素被膜で被覆されたものであることを特徴とする請求項1から請求項5のいずれか1項に記載の負極活物質。
- 請求項1から請求項6のいずれか1項に記載の負極活物質を含むことを特徴とする負極。
- 請求項7に記載の負極と、正極と、セパレータと、電解質とを具備することを特徴とするリチウムイオン二次電池。
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