Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • 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

• This disclosure relates to negative electrode active materials and batteries.
• silicon-containing materials have been attracting attention as negative electrode active materials with high theoretical capacity density.
• conventional silicon-containing materials for example, a material in which silicon particles are dispersed in a SiO2 phase, and a material in which silicon particles are dispersed in a lithium silicate phase containing Li, Si, and O (hereinafter sometimes referred to as "LSX") are known.
• Patent Document 1 also discloses an anode active material for secondary batteries that includes composite particles containing a lithium aluminate phase and a silicon phase dispersed within the lithium aluminate phase.
• the anode active material disclosed in Patent Document 1 includes composite particles (hereinafter sometimes referred to as "LAX particles") in which a silicon phase is dispersed within a lithium aluminate phase that has excellent alkali resistance, thereby reducing side reactions that occur during the initial charging and discharging of lithium ion secondary batteries and suppressing a decrease in the initial charging and discharging efficiency.
• LAX particles composite particles
• negative electrode active materials containing LAX particles can suppress the decrease in initial charge/discharge efficiency in batteries.
• negative electrode active materials containing LAX particles have the problem that the negative electrode active material deteriorates due to the erosion of the lithium aluminate phase caused by a side reaction between the composite particles and the electrolyte, and there is a demand for improving the cycle characteristics of the battery.
• the negative electrode active material of the present disclosure is A composite particle; a coating layer that coats at least a portion of the surface of the composite particle; Equipped with The composite particles include an alkali aluminate phase containing at least one alkali metal element and Al, and a silicon phase dispersed within the alkali aluminate phase,
• the coating layer includes a lithium sulfonate compound and a hydrophobic polymer compound.
• the technology disclosed herein can provide a negative electrode active material that can improve the cycle characteristics of a battery.
• FIG. 1 is a cross-sectional view showing a schematic configuration of an example of a negative electrode active material according to the present embodiment.
• FIG. 2 is a cross-sectional view showing a schematic configuration of another example of the negative electrode active material according to this embodiment.
• FIG. 3 is a cross-sectional view showing a schematic configuration of an example of a battery according to this embodiment.
• FIG. 4 is a cross-sectional view showing a schematic configuration of another example of the battery according to the present embodiment.
• the negative electrode active material 10 includes a composite particle 1 and a coating layer 5 that coats at least a part of the surface of the composite particle 1.
• the composite particle 1 includes an alkali aluminate phase 2 and a silicon phase 3 dispersed in the alkali aluminate phase 2.
• the alkali aluminate phase 2 includes at least one alkali metal element and Al.
• the coating layer 5 includes a lithium sulfonate compound and a hydrophobic polymer compound.
• the coating layer 5 contains a lithium sulfonate compound, which gives the coating layer 5 good ionic conductivity and thus suppresses side reactions in the battery.
• the coating layer 5 contains a hydrophobic polymer compound, which improves the retention of the lithium sulfonate compound on the surface of the composite particle 1, and the surface of the composite particle 1 is effectively coated with the lithium sulfonate compound. This significantly suppresses side reactions between the negative electrode active material 10 and the electrolyte. This improves the cycle characteristics of the battery, as well as the charge/discharge efficiency.
• Composite particle 1 may contain other elements in addition to the alkali aluminate phase 2 and the silicon phase 3.
• composite particle 1 may further contain a conductive layer.
• FIG. 2 is a cross-sectional view showing a schematic configuration of another example of the negative electrode active material according to this embodiment.
• the negative electrode active material 20 includes a composite particle 6 and a coating layer 5 that covers at least a part of the surface of the composite particle 6.
• the composite particle 6 includes an alkali aluminate phase 2 and a silicon phase 3 dispersed within the alkali aluminate phase 2.
• the composite particle 6 further includes a conductive layer 4 that covers at least a part of the surface of the particle composed of the alkali aluminate phase 2 and the silicon phase 3.
• the conductive layer 4 is located between the particle composed of the alkali aluminate phase 2 and the silicon phase 3 and the coating layer 5.
• the particle composed of the alkali aluminate phase 2 and the silicon phase 3 will be referred to as the "mother particle".
• the conductive layer 4 covers at least a part of the surface of the mother particle.
• composite particles The following description of the composite particle can be applied to both the composite particle 1 shown in FIG. 1 and the composite particle 6 shown in FIG.
• the composite particle has, for example, a sea-island structure in which multiple fine silicon phases 3 are dispersed in a matrix of an alkaline aluminate phase 2.
• the composite particle includes, for example, a mother particle composed of an alkaline aluminate phase 2 and a silicon phase 3, and a conductive layer 4 covering at least a part of the surface of the mother particle.
• the composite particle may consist of only the mother particle.
• the average particle size of the composite particles may be 1 ⁇ m or more and 25 ⁇ m or less, or 4 ⁇ m or more and 15 ⁇ m or less.
• the average particle size of composite particles means the particle size (volume average particle size) at which the volume cumulative value is 50% in the particle size distribution measured by the laser diffraction scattering method.
• the "LA-750" manufactured by Horiba Ltd. can be used as a measuring device.
• the thickness of the conductive layer 4 is thin enough that it does not substantially affect the average particle size of the composite particles, so the average particle size of composite particle 1 and the average particle size of composite particle 6 having the conductive layer 4 can be considered to be substantially the same.
• the composite particles can be removed from the battery, for example, by the following method. Note that the following method is just one example.
• a fully discharged battery is disassembled to remove the negative electrode, which is then washed with, for example, anhydrous ethyl methyl carbonate or dimethyl carbonate to remove non-aqueous electrolyte components.
• the negative electrode mixture layer is peeled off from the current collector (e.g., copper foil) that is the negative electrode core, and the mixture layer is crushed in a mortar to obtain a sample powder.
• the sample powder is dried for 1 hour in a dry atmosphere, and immersed, for example, in gently boiling 6M hydrochloric acid for about 10 minutes to remove elements derived from other than the composite particles.
• the sample powder is washed with ion-exchanged water, filtered, and dried, for example, at 200°C for 1 hour.
• a fully discharged state is a state in which the depth of discharge (DOD) is 90% or more (state of charge (SOC) is 10% or less).
• the alkali aluminate phase 2 contains at least one alkali metal element, aluminum (Al), and oxygen (O).
• the alkali aluminate phase 2 is a phase containing alkali aluminate, which is a composite oxide containing at least one alkali metal element and Al.
• the atomic ratio of O to Al in the alkaline aluminate (O/Al) is, for example, 1.6 or more and 4 or less.
• the atomic ratio of alkali metal (MA) to Al in the alkaline aluminate (MA/Al) is, for example, 1/5 or more and 5 or less.
• the stability and ionic conductivity of the alkaline aluminate phase 2 become better.
• the stability of the alkaline aluminate phase 2 includes both the chemical stability (alkali resistance) and the thermal stability of the alkaline aluminate phase 2.
• the alkali metal element may include at least one selected from the group consisting of Li, Na, and K.
• the alkali metal element may include at least one selected from the group consisting of Li and Na, or may include Li.
• the alkali aluminate phase 2 may further contain element M in addition to the alkali metal elements, Al, and O.
• element M is at least one selected from the group consisting of calcium (Ca), magnesium (Mg), zirconium (Zr), iron (Fe), boron (B), phosphorus (P), and lanthanum (La).
• the element M may form a compound.
• the compound may be, for example, an oxide of element M or an aluminate of element M.
• the alkaline aluminate phase 2 may further contain trace amounts of elements such as chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), and molybdenum (Mo).
• the alkali aluminate phase 2 may be amorphous. In this case, the effects of expansion and contraction of the silicon phase 3 can be more effectively mitigated.
• a fine Al2O3 phase having high crystallinity may be dispersed in the alkali aluminate phase 2.
• the Al2O3 phase is distributed in an island shape in the matrix of the alkali aluminate phase 2, for example.
• the expansion and cracking of the alkali aluminate phase 2 due to the expansion and contraction of the silicon phase 3 is easily suppressed, and the effect of improving cycle characteristics is enhanced.
• the content of Al2O3 in the composite particle is, for example, 10 mass% or less.
• Silicon phase 3 is a phase of simple Si, which repeatedly absorbs and releases Li ions as the battery is charged and discharged. Capacity is generated by a Faraday reaction involving silicon phase 3. Silicon phase 3 has a large capacity. Silicon phase 3 also expands and contracts to a large extent as it is charged and discharged. In the negative electrode active material disclosed herein, silicon phase 3 is dispersed within alkaline aluminate phase 2, and therefore the stress caused by the expansion and contraction of silicon phase 3 is alleviated by alkaline aluminate phase 2.
• the silicon phase 3 may be particulate.
• the silicon phase 3 is particulate, for example, at least before the first charge.
• the average particle size of the silicon phase 3 may be 1 nm or more and 1000 nm or less.
• the average particle size of the silicon phase 3 may be 500 nm or less, 200 nm or less, or 50 nm or less.
• the average particle size of the silicon phase 3 may be 400 nm or less, or 100 nm or less.
• the average particle size of the silicon phase 3 can be measured using a scanning electron microscope (SEM) image obtained by observing the cross section of the negative electrode active material in which the cross section of the silicon phase 3 is exposed. Specifically, the average particle size of the silicon phase 3 can be calculated by averaging the maximum diameters of 100 silicon phases 3 randomly selected from the cross-sectional SEM image of the negative electrode active material.
• SEM scanning electron microscope
• the silicon phase 3 may contain crystalline silicon.
• the silicon phase 3 is composed of, for example, multiple crystallites.
• the crystallite size of the silicon phase 3 may be 30 nm or less, 20 nm or less, or 15 nm or less. As a result, the volume change due to the expansion and contraction of the silicon phase 3 accompanying charging and discharging can be reduced, and the effect of improving the cycle characteristics becomes more significant.
• the crystallite size of the silicon phase 3 is calculated by the Scherrer formula from the half-width of the diffraction peak derived from the Si(111) plane in the X-ray diffraction pattern obtained by X-ray diffraction measurement using Cu-K ⁇ radiation.
• the lower limit of the crystallite size of silicon phase 3 is not particularly limited, but an example is 1 nm.
• An example of a suitable crystallite size of silicon phase 3 is 1 nm or more and 15 nm or less, and may be 5 nm or more and 11 nm or less.
• the crystallite size of silicon phase 3 is 1 nm or more, for example, the surface area of silicon phase 3 can be kept small, making it difficult for deterioration of silicon phase 3 accompanied by the generation of irreversible capacity to occur.
• the crystallite size is 15 nm or less, the expansion and contraction of silicon phase 3 can be easily made uniform, and stress generated in the negative electrode active material is effectively alleviated.
• the content of silicon phase 3 in the composite particle may be 30 mass% or more, 35 mass% or more, or 55 mass% or more. From the viewpoint of improving cycle characteristics, the content of silicon phase 3 in the composite particle may be 95 mass% or less, 75 mass% or less, or 70 mass% or less. In this case, the amount of silicon phase 3 exposed on the surface of the composite particle without being covered by the alkali aluminate phase 2 is reduced, and side reactions between the electrolyte and the silicon phase 3 are also suppressed.
• the content of silicon phase 3 in the composite particle may be 30 mass% or more and 90 mass% or less, or 35 mass% or more and 75 mass% or less.
• the content of silicon phase 3 in the composite particles can be determined by quantifying the amount of Si that constitutes silicon phase 3 in the composite particles using Si-NMR, as described below.
• the composite particles may be substantially free of lithium silicate and SiO 2.
• the total content of lithium silicate and SiO 2 in the composite particles may be, for example, 3 mass% or less.
• the mass ratio (mAl) of Al to the total mass of elements other than oxygen (O) constituting the alkali aluminate phase 2 and the silicon phase 3 may be 10 mass% or more and 47 mass% or less, or 11.5 mass% or more and 45.5 mass% or less.
• the mass ratio (mMA) of the alkali metal element to the total mass of elements other than O constituting the alkali aluminate phase 2 and the silicon phase 3 may be 0.7 mass% or more and 13.5 mass% or less, 1.0 mass% or more and 9.5 mass% or less, or 1.5 mass% or more and 3.5 mass% or less.
• the above configuration can improve the stability and ionic conductivity of the alkali aluminate phase 2.
• the above stability includes both chemical stability (alkali resistance) and thermal stability.
• the ratio (mMA/mAl) of the mass ratio of alkali metal elements (mMA) to the mass ratio of Al (mAl) may be 0.01 or more and 0.50 or less, or 0.05 or more and 0.25 or less, from the viewpoint of the stability and ionic conductivity of the alkali aluminate phase 2.
• the mass ratio of Si (mSi) to the total mass of elements other than O constituting the alkaline aluminate phase 2 and the silicon phase 3 may be 40 mass% or more and 90 mass% or less, or 50.8 mass% or more and 85.5 mass% or less.
• the mass ratio (mB) of B to the total mass of elements other than O constituting the alkali aluminate phase 2 and the silicon phase 3 may be 1 mass% or more and 20 mass% or may be 2 mass% or more and 15 mass% or less.
• the ratio (mAl/mB) of the mass ratio of Al (mAl) to the mass ratio of B (mB) may be 1.0 or more and 30.0 or less, 1.0 or more and 20.0 or less, or 1.0 or more and 10.0 or less.
• mAl/mB is 30.0 or less, the effect of reducing the porosity of the composite particle 1 may become more significant. This suppresses deterioration of the particle structure caused by the voids in the composite particle, and effectively improves the cycle characteristics of the battery.
• mAl/mB is 1.0 or more, the decrease in the initial charge/discharge efficiency can be reduced. Therefore, when mAl/mB is within the above range, both improved cycle characteristics and good initial charge/discharge efficiency can be achieved.
• the conductive layer 4 covers at least a portion of the surface of the base particle composed of the alkali aluminate phase 2 and the silicon phase 3.
• the conductive layer 4 may cover the entire surface of the base particle.
• the conductive layer 4 is, for example, a thin film layer containing a conductive material.
• the conductive layer 4 in the composite particle improves the conductivity.
• the conductive material may be a conductive carbon material. That is, the conductive layer 4 may contain carbon.
• the carbon material graphite such as natural graphite, artificial graphite, and graphitized mesophase carbon, amorphous carbon, soft carbon, and hard carbon can be used.
• the carbon material may be amorphous carbon. As described above, it is easy to form a thin conductive layer 4 that covers the surface of the base particle. Examples of amorphous carbon include carbon black, burned pitch, coke, and activated carbon.
• the thickness of the conductive layer 4 is desirably thin enough not to affect the average particle size of the composite particles.
• the thickness of the conductive layer 4 may be 1 nm or more and 200 nm or less, or 5 nm or more and 100 nm or less, taking into consideration the need to ensure electrical conductivity and the diffusibility of ions such as Li ions.
• the thickness of the conductive layer 4 can be measured by SEM observation or transmission electron microscope (TEM) observation of a cross section of the negative electrode active material in which the cross section of the composite particle is exposed.
• the porosity of the composite particle before the first charge and discharge may be 25% or less. Since the conductive layer 4 does not affect the porosity, the porosity of the composite particle 6 is substantially the same as that of the mother particle (composite particle 1). By suppressing the porosity of the composite particle to 25% or less, the number of parts that can become the starting point of cracks and breaks when charging and discharging are repeated is reduced. This suppresses deterioration of the negative electrode active material and further improves the cycle characteristics of the battery.
• the porosity of the composite particle may be 20% or less, or may be 15% or less. The lower limit of the porosity is not particularly limited, but one example is 1%.
• the porosity of a composite particle means the proportion of voids in the cross section of the composite particle.
• the porosity of a composite particle can be measured using an SEM image of the cross section of the negative electrode active material in which the cross section of the composite particle is exposed.
• the porosity of a composite particle is calculated by extracting the void area by binarizing the SEM image using image analysis software (e.g., imageJ) and dividing the total area of the voids by the total area of the particle cross section.
• the porosity of the composite particles can be controlled to some extent by adjusting the sintering temperature in the composite particle manufacturing process, the compressive force applied to the particles during sintering, and mMA/mAl, in addition to adding B to the alkali aluminate phase 2 described above.
• the composite particle may have a Vickers hardness of 300 HV or more. Since the conductive layer 4 does not affect the Vickers hardness, the Vickers hardness of the composite particle 6 is substantially the same as that of the mother particle (composite particle 1). When the composite particle has a high Vickers hardness, it is easy to suppress the volume change of the silicon phase 3 during charging and discharging, and deterioration of the particle structure can be reduced. As a result, the effect of improving the cycle characteristics becomes more significant.
• the Vickers hardness of the composite particle is more preferably 350 HV or more, and may be 400 HV or more, or 500 HV or more.
• the Vickers hardness of the composite particles can be measured using a Vickers hardness tester. Specifically, the composite particles from which the coating layer 5 has been removed from the negative electrode active material are embedded in a thermosetting resin and polished with #400 abrasive paper to expose the cross section of the composite particle 1. The cross section is then mirror-finished with #2000 abrasive paper and buff polishing. The Vickers hardness is measured under conditions of a load of 1 kg and a holding time of 15 seconds.
• the upper limit of the Vickers hardness of the composite particle 1 is not particularly limited, but is, for example, 1500 HV.
• the content of each element in the composite particles is measured by the following methods.
• the oxygen content can be measured using an oxygen, nitrogen, and hydrogen analyzer.
• the Si content can be measured using NMR.
• the carbon content can be measured using a carbon and sulfur analyzer.
• the content of other elements can be measured by inductively coupled plasma atomic emission spectrometry. If it is not possible to measure using inductively coupled plasma atomic emission spectrometry (ICP), it can also be measured using energy dispersive X-ray (EDX). If it is not possible to measure using either ICP or EDX, it can also be measured using Auger electron spectroscopy (AES).
• the composition of the alkali aluminate phase 2 can be determined from the content of each element.
• a fully discharged battery can be disassembled, the negative electrode is removed and washed, the non-aqueous electrolyte components are removed, and the battery is dried, and then the cross section of the negative electrode mixture layer obtained is analyzed using a cross-section polisher.
• ICP Inductively Coupled Plasma Atomic Emission Spectroscopy
• EDX ⁇ Energy Dispersive X-ray (EDX)>
• the measurement is performed by EDX.
• element mapping analysis is performed by EDX.
• the content area of the target element is calculated using image analysis software. The observation magnification is, for example, 2000 to 20000 times.
• 10 composite particles 1 having a maximum particle diameter of 5 ⁇ m or more are randomly selected from the cross-sectional image of the reflected electron image of the negative electrode mixture layer containing the negative electrode active material, and element mapping analysis is performed for each of them by EDX.
• the measured values of the content area of a predetermined element contained in 10 particles are averaged to calculate the content of the target element.
• Desirable measurement conditions for cross-sectional SEM-EDX analysis are shown below.
• Processing equipment JEOL, SM-09010 (Cross Section Polisher) Processing conditions: Acceleration voltage 6 kV Current value: 140 ⁇ A Degree of vacuum: 1 ⁇ 10 ⁇ 3 Pa to 2 ⁇ 10 ⁇ 3 Pa
• Measuring device Hitachi SU-70 electron microscope Acceleration voltage during analysis: 10 kV Field: Free mode Probe current mode: Medium Probe current range: High Anode Ap.: 3 OBJ Ap.: 2 Analysis area: 1 ⁇ m square Analysis software: EDAX Genesis CPS: 20500 Lsec: 50 Time constant: 3.2
• AES ⁇ Auger Electron Spectroscopy
• 10 composite particles having a maximum particle diameter of 5 ⁇ m or more are randomly selected from a cross-sectional image of a backscattered electron image of the negative electrode mixture layer containing the negative electrode active material, and a qualitative and quantitative analysis of elements is performed for each of them using an AES analyzer.
• the content of a predetermined element contained in 10 particles is averaged to calculate the content.
• a coating may be formed on the surface of the composite particle due to decomposition of the non-aqueous electrolyte, etc.
• the composite particle may further have a conductive layer. Therefore, the EDX analysis and AES analysis are performed on a range, for example, 1 ⁇ m inside from the peripheral edge of the cross section of the composite particle so that the thin coating and conductive layer are not included in the measurement range.
• ⁇ Nuclear magnetic resonance spectroscopy (NMR)> The amount of Si constituting the silicon phase 3 can be quantified using Si-NMR. Desirable measurement conditions for Si-NMR are shown below. Measurement equipment: Solid-state nuclear magnetic resonance spectrometer (INOVA-400), manufactured by Varian Probe: Varian 7mm CPMAS-2 MAS: 4.2kHz MAS speed: 4kHz Pulse: DD (45° pulse + signal acquisition time 1H decoupled) Repeat time: 1200 sec to 3000 sec Observation width: 100kHz Observation center: Around -100 ppm Signal acquisition time: 0.05 sec Accumulation count: 560 Sample amount: 207.6 mg
• the carbon content of the composite particles can be measured using a carbon/sulfur analyzer (for example, EMIA-520 model manufactured by Horiba, Ltd.).
• EMIA-520 model manufactured by Horiba, Ltd.
• a sample is weighed out onto a magnetic board, a combustion improver is added, and the board is inserted into a combustion furnace (carrier gas: oxygen) heated to 1350°C, and the amount of carbon dioxide gas generated during combustion is detected by infrared absorption.
• a calibration curve is prepared using, for example, carbon steel (carbon content: 0.49%) manufactured by Bureau of Analysed Samples Ltd., and the carbon content of the sample is calculated.
• the coating layer 5 covers at least a part of the surface of the composite particle.
• the coating layer 5 may cover the entire surface of the composite particle.
• the coating layer 5 contains a lithium sulfonate compound and a hydrophobic polymer compound.
• the lithium sulfonate compound is a lithium salt of a sulfonic acid compound.
• the sulfonic acid compound is an organic compound having a sulfonic acid group (SO 3 H).
• the sulfonic acid compound may be a monosulfonic acid compound or a disulfonic acid compound.
• the lithium sulfonate compound may be a compound represented by the following general formula (1).
• R is an n-valent hydrocarbon group that may have a substituent, and n is 1 or 2.
• the number of carbon atoms in the hydrocarbon group is not particularly limited as long as it is 1 or more.
• the number of carbon atoms in the hydrocarbon group may be, for example, 20 or less, 10 or less, or 5 or less.
• the substituent may be, for example, a halogen or a fluorine atom.
• the hydrocarbon group may be an aliphatic hydrocarbon group.
• R may be an n-valent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• the lithium sulfonate compound may include at least one selected from the group consisting of lithium methanesulfonate, lithium ethanesulfonate, and lithium propanesulfonate.
• the lithium sulfonate compound may include lithium methanesulfonate.
• the mass ratio of the lithium sulfonate compound in the coating layer 5 relative to the composite particles may be 1 mass% or more.
• the amount of lithium sulfonate compound carried may be 1 mass% or more and 10 mass% or less, 1 mass% or more and 6 mass% or less, or 2 mass% or more and 6 mass% or less.
• the amount of the lithium sulfonate compound supported is 1 mass% or more, the surface of the composite particle can be sufficiently coated with the lithium sulfonate compound, and the effect of suppressing side reactions caused by the lithium sulfonate compound is easily obtained.
• the amount of the lithium sulfonate compound supported is 6 mass% or less, a low-resistance coating layer 5 and a low-resistance negative electrode active material are easily obtained.
• a coating layer 5 containing a lithium sulfonate compound and a hydrophobic polymer compound for example, an amount of the lithium sulfonate compound in the above range is supported on the surface of the composite particle.
• the hydrophobic polymer compound may have good binding properties and thermal melting properties.
• the hydrophobic polymer compound can firmly support the lithium sulfonate compound on the surface of the composite particles, and the effect of suppressing side reactions by the lithium sulfonate compound can be stably obtained.
• the hydrophobic polymer compound is almost insoluble in water.
• the hydrophobic polymer compound may contain a fluororesin.
• the fluororesin may contain at least one selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene, perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and ethylene chlorotrifluoroethylene copolymer.
• PVDF polyvinylidene fluoride
• PFA perfluoroalkoxyalkane
• perfluoroethylene propene copolymer ethylene tetrafluoroethylene copolymer
• polychlorotrifluoroethylene polychlorotrifluoroethylene
• ethylene chlorotrifluoroethylene copolymer ethylene chlorotrifluoroethylene copolymer.
• the fluororesin may contain PVDF.
• PVDF polyvinylidene fluoride
• the hydrophobic polymer compound may include a polymer containing vinylidene fluoride units, in addition to polyvinylidene fluoride.
• polymers containing vinylidene fluoride units include copolymers of vinylidene fluoride with other monomers. Examples of other monomers include hexafluoropropylene (HFP) and tetrafluoroethylene (TFE).
• Polymers containing vinylidene fluoride units include polyvinylidene fluoride and its modified products, vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, etc.
• the content of vinylidene fluoride units is, for example, 30 mol% or more, and may be 50 mol% or more.
• the mass ratio of the hydrophobic polymer compound in the coating layer 5 relative to the composite particle (hereinafter referred to as the "amount of hydrophobic polymer compound carried") may be 1 mass% or more.
• the amount of hydrophobic polymer compound carried may be 1 mass% or more and 10 mass% or less, 1 mass% or more and 6 mass% or less, or 2 mass% or more and 6 mass% or less.
• the hydrophobic polymer compound supported When the amount of the hydrophobic polymer compound supported is 1 mass% or more, the hydrophobic polymer compound can sufficiently improve the retention of the lithium sulfonate compound on the surface of the composite particles. When the amount of the hydrophobic polymer compound supported is 6 mass% or less, a low-resistance coating layer 5 and a low-resistance negative electrode active material are easily obtained.
• the amount of the lithium sulfonate compound and the amount of the fluororesin are determined by the following method.
• the negative electrode active material is washed with N-methyl-2-pyrrolidone (NMP) to dissolve the fluororesin, and the difference in mass before and after dissolution is calculated as the mass of the fluororesin.
• NMP N-methyl-2-pyrrolidone
• the remainder that does not dissolve in NMP is then washed with water to dissolve the lithium sulfonate compound.
• the mass of the lithium sulfonate compound dissolved in water is calculated using quantitative analysis such as ICP emission spectroscopy.
• the remaining mass that is not dissolved in water and NMP is calculated as the mass of the composite particle. If the composite particle has a conductive layer 4, the remaining mass that is not dissolved in water and NMP is quantitatively analyzed for carbon using a carbon-sulfur analyzer or the like, and the calculated amount of carbon is derived from the carbon material of the conductive layer 4.
• the amount of fluororesin supported is calculated using the mass of the fluororesin and the mass of the composite particles calculated above according to the formula: (mass of fluororesin/mass of composite particles) x 100.
• the amount of lithium sulfonate compound supported is calculated using the mass of the lithium sulfonate compound and the mass of the composite particles calculated above according to the formula: (mass of lithium sulfonate compound/mass of composite particles) x 100.
• the thickness of the coating layer 5 is desirably thin enough not to substantially affect the average particle size of the negative electrode active material. From the viewpoint of protecting the composite particles from the electrolyte, the thickness of the coating layer 5 may be 1 nm or more. From the viewpoint of suppressing an increase in resistance, the thickness of the coating layer 5 may be 300 nm or less. The thickness of the coating layer 5 may be smaller than the thickness of the conductive layer 4. The thickness of the coating layer 5 can be measured by SEM or TEM observation of a cross section of the negative electrode active material.
• the negative electrode active material When the negative electrode active material is subjected to surface analysis by X-ray photoelectron spectroscopy (XPS), a peak derived from the lithium sulfonate compound is observed in the surface layer (including the outermost surface) of the coating layer 5. Specifically, the peak has a binding energy of approximately 165 eV to 170 eV and an intensity (c/s) of 200 to 1000.
• XPS X-ray photoelectron spectroscopy
• the negative electrode active material of the present disclosure is produced, for example, by a production method including step I of obtaining composite particles and step II of forming a coating layer 5 on the surface of the composite particles.
• Step I includes the following steps 1 to 4.
• First step a step of obtaining a raw material alkali aluminate (hereinafter referred to as "raw material aluminate").
• Second step A step of compounding the raw aluminate and raw silicon to obtain a composite intermediate in which the raw silicon is dispersed in the raw aluminate.
• Third step a step of heat treating the composite intermediate to obtain a sintered body containing an alkali aluminate phase 2 and a silicon phase 3 dispersed within the alkali aluminate phase 2.
• Fourth step A step of pulverizing the sintered body to obtain composite particles 1 (mother particles).
• the first step includes, for example, a step of mixing an aluminum compound, a compound containing an alkali metal element, and, if necessary, a compound containing element M to obtain a mixture, and a step of calcining the mixture to obtain a raw aluminate.
• the calcination is performed, for example, in an oxidizing atmosphere.
• the calcination temperature may be 400°C or more and 1200°C or less, or 700°C or more and 1100°C or less.
• aluminum compounds examples include aluminum oxide, aluminum hydroxide, aluminum carbonate, etc.
• One type of aluminum compound may be used alone, or two or more types may be used in combination.
• Examples of compounds containing an alkali metal element include lithium carbonate, lithium oxide, lithium hydroxide, lithium hydride, sodium carbonate, sodium oxide, sodium hydroxide, sodium hydride, potassium carbonate, potassium oxide, potassium hydroxide, potassium hydride, etc.
• Compounds containing an alkali metal element may be used alone or in combination of two or more.
• the compound containing element M is, for example, a boron compound.
• boron compounds include boron oxide, boric acid, borax, sodium tetraborate, etc.
• One type of boron compound may be used alone, or two or more types may be used in combination.
• the first step aluminum compounds that have not reacted with the compound containing an alkali metal element during the preparation of the raw aluminate may remain in the raw aluminate.
• the amount of aluminum compound used is large relative to the compound containing an alkali metal element, the aluminum compounds are likely to remain.
• the aluminum compound remaining in the raw aluminate is Al2O3
• an Al2O3 phase dispersed in the alkali aluminate phase 2 may be formed in the composite particles finally obtained.
• a mixture of raw aluminate and raw silicon is pulverized while applying shear force to obtain a finely divided composite intermediate.
• the raw silicon is, for example, coarse silicon particles having an average particle size of several ⁇ m to several tens of ⁇ m.
• the silicon particles may be prepared so that the crystallite size of the silicon phase 3 calculated from the half-width of the diffraction peak derived from the Si(111) plane in the X-ray diffraction pattern of the negative electrode active material or composite particle 1 using Scherrer's formula is 15 nm or less. It is also possible to synthesize silicon nanoparticles and raw aluminate nanoparticles and mix them together without using a pulverizer.
• the composite intermediate is sintered while applying pressure to the microparticulated composite intermediate, for example, by hot pressing, to obtain a sintered body.
• the pressure applied to the composite intermediate is, for example, 100 MPa or more, and may be 100 MPa or more and 300 MPa or less.
• the higher the pressure in the third step the smaller the porosity of the composite particles tends to be.
• the sintering conditions in the third step also affect the crystallites of the silicon phase 3, and generally the higher the sintering temperature, the larger the crystallite size.
• the firing temperature is 450°C or higher and 1000°C or lower. If the firing temperature is within this range, it is easy to form a structure in which minute silicon phases 3 are dispersed within the alkaline aluminate phase 2 with low crystallinity. The raw material aluminate is stable at this temperature and hardly reacts with silicon.
• the firing temperature may be 550°C or higher and 950°C or lower, or 650°C or higher and 900°C or lower. In order to reduce the porosity of the composite particles to 25% or less, it is desirable to fire at a temperature of 650°C or higher.
• the firing time is, for example, 1 hour or more and 10 hours or less.
• the fourth step is to pulverize the composite particles 1 (parent particles) so that they have a desired particle size distribution.
• the parent particles are pulverized so that the median diameter is 1 ⁇ m or more and 25 ⁇ m or less.
• Step I may further include the following fifth step after the first to fourth steps.
• Fifth step a step of forming a conductive layer 4 on the surface of the base particle consisting of the alkali aluminate phase 2 and the silicon phase 3.
• the conductive material constituting the conductive layer 4 is preferably a conductive carbon material.
• methods for coating the surface of the base particles with a carbon material include a CVD method using hydrocarbon gases such as acetylene and methane as raw materials, and a method in which coal pitch, petroleum pitch, phenolic resin, etc. is mixed with the base particles and heated to carbonize them. Carbon black may also be attached to the surface of the base particles.
• the mixture of the base particles and the carbon material is heated in an inert atmosphere (e.g., an atmosphere of argon, nitrogen, etc.) at 700°C or higher and 950°C or lower to form a conductive layer 4 on the surface of the base particles.
• an inert atmosphere e.g., an atmosphere of argon, nitrogen, etc.
• Step II is a step of forming a coating layer 5 on the surface of the composite particle.
• the composite particles are granulated using the composite particles, the lithium sulfonate compound, and the hydrophobic polymer compound, and the granulated powder is then crushed and classified to a desired size, thereby obtaining a negative electrode active material having a desired average particle size and a coating layer 5 formed on the surface of the composite particles.
• Granulation is carried out, for example, by dispersing the composite particles, the lithium sulfonate compound powder, and the hydrophobic polymer compound in water, and then spray drying the dispersion. This forms a coating layer, which is a mixed layer of the lithium sulfonate compound and the hydrophobic polymer compound, on the surface of the composite particles.
• the amount of the lithium sulfonate compound added may be 1% by mass or more and 6% by mass or less relative to the composite particles.
• the amount of the hydrophobic polymer compound added may be 1% by mass or more and 6% by mass or less relative to the composite particles.
• the particle size of the lithium sulfonate compound and the hydrophobic polymer compound dispersed in water is smaller than the particle size of the composite particles. In this case, it is easy to uniformly cover the surface of the composite particles with the lithium sulfonate compound and the hydrophobic polymer compound.
• the average particle size of the lithium sulfonate compound may be 1 ⁇ m or more and 100 ⁇ m or less, or 1 ⁇ m or more and 10 ⁇ m or less.
• the average particle size of the hydrophobic polymer compound may be 200 nm or more and 1 ⁇ m or less.
• the method of forming the coating layer 5 on the surface of the composite particles is not limited to the above.
• the composite particles, a powder of a lithium sulfonate compound, and a powder of a hydrophobic polymer compound may be dry mixed to obtain a mixture, and then the mixture may be heat-treated to form the coating layer 5 on the surface of the composite particles.
• the mixing process produces an intermediate (mixture) in which the mixture of the lithium sulfonate compound and the hydrophobic polymer compound is attached to the surface of the composite particles.
• a ball mill method can be used for the dry mixing process.
• the amount and particle size of the lithium sulfonate compound and the hydrophobic polymer compound added may be the same as those described above.
• the heat treatment is preferably performed at a temperature equal to or higher than the melting point of the hydrophobic polymer compound and equal to or lower than the decomposition temperature of the hydrophobic polymer compound.
• the heat treatment temperature may be equal to or higher than the melting point (150°C to 170°C) of PVDF and equal to or lower than the decomposition temperature (340°C), and is preferably, for example, equal to or higher than 200°C and equal to or lower than 250°C.
• the heat treatment may be performed in an inert atmosphere.
• the heat treatment time is, for example, about 1 hour to 3 hours.
• the hydrophobic polymer compound in the mixture is liquefied by the heat treatment, and penetrates and diffuses around the composite particles and the particles of the lithium sulfonate compound so as to fill the gaps between the composite particles and the particles of the lithium sulfonate compound, and the gaps between the particles of the lithium sulfonate compound. This enhances the retention of the lithium sulfonate compound on the surface of the composite particles.
• a coating layer 5 which is a mixed layer of the lithium sulfonate compound and the hydrophobic polymer compound, is formed.
• the mixture after the heat treatment is crushed to obtain a negative electrode active material having a desired average particle size.
• the battery according to the present embodiment includes a negative electrode, a positive electrode, and an electrolyte.
• the negative electrode contains the negative electrode active material according to the present embodiment.
• the negative electrode contains the negative electrode active material according to the present embodiment, and therefore the cycle characteristics are improved, and the initial charge/discharge efficiency is improved.
• FIG. 3 is a longitudinal cross-sectional view showing a schematic example of a battery according to this embodiment.
• Battery 100 is a cylindrical battery that includes a cylindrical battery case, a wound electrode group 24, and an electrolyte (not shown).
• the electrode group 24 is housed within the battery case and is in contact with the electrolyte.
• the battery case is composed of a case body 25, which is a cylindrical metal container with a bottom, and a sealing body 26 that seals the opening of the case body 25.
• a gasket 37 is disposed between the case body 25 and the sealing body 26. The gasket 37 ensures that the battery case is airtight.
• insulating plates 27 and 28 are disposed on both ends of the electrode group 24 in the direction of the winding axis of the electrode group 24.
• the case body 25 has, for example, a step 31.
• the step 31 can be formed by partially pressing the side wall of the case body 25 from the outside.
• the step 31 may be formed in an annular shape on the side wall of the case body 25 along the circumferential direction of an imaginary circle defined by the case body 25.
• the sealing body 26 is supported, for example, by the surface of the step 31 on the opening side.
• the sealing body 26 includes a filter 32, a lower valve body 33, an insulating member 34, an upper valve body 35, and a cap 36. In the sealing body 26, these components are layered in this order.
• the sealing body 26 is attached to the opening of the case body 25 so that the cap 36 is located on the outside of the case body 25 and the filter 32 is located on the inside of the case body 25.
• Each of the above-mentioned components constituting the sealing body 26 is, for example, disk-shaped or ring-shaped.
• the above-mentioned components are electrically connected to each other, except for the insulating member 34.
• the electrode group 24 has a positive electrode 21, a separator 22, and a negative electrode 23.
• the positive electrode 21, the separator 22, and the negative electrode 23 are all strip-shaped.
• the width direction of the strip-shaped positive electrode 21 and negative electrode 23 is, for example, parallel to the winding axis of the electrode group 24.
• the separator 22 is disposed between the positive electrode 21 and the negative electrode 23.
• the positive electrode 21 and the negative electrode 23 are wound in a spiral shape with the separator 22 interposed between these electrodes.
• the positive electrodes 21 and negative electrodes 23 are stacked alternately in the radial direction of an imaginary circle defined by the case body 25, with a separator 22 interposed between these electrodes.
• the positive electrode 21 is electrically connected to the cap 36, which also serves as a positive electrode terminal, via the positive electrode lead 29.
• One end of the positive electrode lead 29 is connected, for example, near the center of the positive electrode 21 in the longitudinal direction of the positive electrode 21.
• the positive electrode lead 29 extends from the positive electrode 21 to the filter 32 through a through hole formed in the insulating plate 27.
• the other end of the positive electrode lead 29 is welded, for example, to the surface of the filter 32 facing the electrode group 24.
• the negative electrode 23 is electrically connected to the case body 25, which also serves as a negative electrode terminal, via the negative electrode lead 30.
• One end of the negative electrode lead 30 is connected, for example, to an end of the negative electrode 23 in the longitudinal direction of the negative electrode 23.
• the other end of the negative electrode lead 30 is welded, for example, to the inner bottom surface of the case body 25.
• the components of the battery 100 are described in detail below.
• the positive electrode 21 includes a material that has the property of absorbing and releasing metal ions (e.g., lithium ions).
• the positive electrode 21 includes, for example, a positive electrode active material.
• the positive electrode 21 may include a positive electrode current collector and a positive electrode mixture layer supported on the surface of the positive electrode current collector.
• the positive electrode mixture layer includes a positive electrode active material.
• the positive electrode active material include lithium-containing transition metal oxides, lithium-containing transition metal phosphates, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, and transition metal oxynitrides.
• the manufacturing cost of the battery can be reduced and the average discharge voltage can be increased.
• the lithium-containing transition metal oxides include lithium cobalt oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, and lithium nickel manganese oxide.
• the lithium-containing transition metal phosphates include lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, and lithium nickel phosphate. At least one selected from these positive electrode active materials can be used.
• the positive electrode mixture layer may contain a conductive additive, an ion conductor, and a binder as necessary.
• the conductive assistant and ion conductor are used to reduce the resistance of the electrode.
• the conductive assistant include carbon materials and conductive polymer compounds.
• the carbon materials include carbon black, graphite, acetylene black, carbon nanotubes, carbon nanofibers, graphene, fullerene, and graphite oxide.
• the conductive polymer compounds include polyaniline, polypyrrole, and polythiophene. At least one selected from these conductive assistants can be used.
• Binders are used to improve the binding of the materials that make up the electrodes.
• binders include polymeric materials such as polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene-butadiene copolymer rubber, polypropylene, polyethylene, and polyimide. At least one selected from these binders can be used.
• the positive electrode current collector is, for example, a sheet or film made of a metal material such as aluminum, an aluminum alloy, stainless steel, titanium, or a titanium alloy.
• the sheet or film may be porous or non-porous.
• Metal foil, metal mesh, or the like may be used as the sheet or film.
• a carbon material may be applied to the surface of the positive electrode current collector as a conductive auxiliary material.
• the negative electrode 23 includes the negative electrode active material according to this embodiment.
• the negative electrode 23 includes, for example, a negative electrode current collector and a negative electrode mixture layer supported on the surface of the negative electrode current collector.
• the negative electrode current collector is a foil made of a metallic material such as stainless steel, nickel, nickel alloy, copper, or copper alloy.
• the negative electrode mixture layer contains the negative electrode active material according to this embodiment.
• the negative electrode mixture layer may contain other materials such as a conductive assistant, an ion conductor, and a binder, as necessary.
• the materials described above for the positive electrode mixture layer can also be used as the conductive assistant, the ion conductor, and the binder for the negative electrode mixture layer.
• the electrolyte may contain a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
• concentration of the lithium salt in the electrolyte may be, for example, 0.5 mol/L or more and 2 mol/L or less. By controlling the lithium salt concentration within the above range, an electrolyte having excellent ionic conductivity and appropriate viscosity can be obtained. However, the lithium salt concentration is not limited to the above.
• Cyclic carbonates, chain carbonates, cyclic ethers, chain ethers, nitriles, amides, etc. may be used as non-aqueous solvents. One selected from these solvents may be used, or two or more may be used in combination.
• lithium salt examples include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bisperfluoroethylsulfonylimide (LiN(SO 2 C 2 F 5 ) 2 ), LiAsF 6 , LiCF 3 SO 3 , and lithium difluoro(oxalato)borate.
• LiPF 6 lithium hexafluorophosphate
• LiBF 4 lithium tetrafluoroborate
• LiClO 4 lithium perchlorate
• LiFSI lithium bis(fluorosulfonyl)imide
• LiTFSI lithium bis(trifluoromethanesulfonyl)imide
• the separator 22 has high ion permeability and has appropriate mechanical strength and insulating properties.
• the separator 22 may be made of a microporous thin film, a woven fabric, a nonwoven fabric, or the like.
• the separator 22 may be made of a polymer, for example.
• the polymer may be a polyolefin, such as polypropylene or polyethylene.
• the electrolyte may be impregnated into a polymer provided as a separator, for example.
• the battery of the present disclosure may have a structure in which the electrolyte and the polymer are used in combination.
• the battery of the present disclosure may further include a solid electrolyte as an electrolyte. That is, the battery of the present disclosure may have a hybrid structure in which an electrolytic solution and a solid electrolyte are used in combination.
• solid electrolyte materials are halide solid electrolytes, sulfide solid electrolytes, oxide solid electrolytes, and organic polymer solid electrolytes.
• halide solid electrolyte refers to a solid electrolyte containing a halogen element as the main component of the anions.
• Sulfide solid electrolyte refers to a solid electrolyte containing sulfur as the main component of the anions.
• Oxide solid electrolyte refers to a solid electrolyte containing oxygen as the main component of the anions.
• the main component of the anions refers to the anion with the largest substance amount among all the anions that make up the solid electrolyte.
• the configuration example shown in FIG. 3 is described, that is, a cylindrical nonaqueous electrolyte secondary battery in which a wound electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween and an electrolyte solution are housed in an exterior body.
• the battery according to this disclosure is not limited to this configuration example.
• the battery according to this disclosure may be in any form, such as a square type, a coin type, a button type, a laminate type, etc.
• an electrode group of another form such as an electrode group in which a positive electrode and a negative electrode are stacked with a separator interposed therebetween, may be used.
• FIG. 4 is a cross-sectional view showing a schematic configuration of another example of a battery according to this embodiment.
• the battery 200 includes a positive electrode 210, an electrolyte layer 220, and a negative electrode 230.
• the negative electrode 230 contains the negative electrode active material according to this embodiment.
• the electrolyte layer 220 is disposed between the positive electrode 210 and the negative electrode 230.
• the battery 200 is, for example, an all-solid-state battery.
• the positive electrode 210 includes a positive electrode current collector 211 and a positive electrode mixture layer 212 supported on the surface of the positive electrode current collector 211.
• the positive electrode mixture layer 212 is located between the positive electrode current collector 211 and the electrolyte layer 220.
• the positive electrode current collector 211 and the positive electrode mixture layer 212 can be made of the materials described above for the positive electrode 21 in the battery 100.
• the positive electrode mixture layer 212 may contain a solid electrolyte.
• solid electrolytes include the solid electrolytes described above as the electrolyte in the battery 100.
• the electrolyte layer 220 is a layer that contains an electrolyte.
• the electrolyte is, for example, a solid electrolyte.
• the electrolyte layer 220 may be a solid electrolyte layer. Examples of solid electrolytes include the solid electrolytes described above as the electrolyte in the battery 100.
• the electrolyte layer 220 may further include a binder.
• a binder the materials described above for the positive electrode mixture layer of the battery 100 can also be used for the electrolyte layer 220.
• the negative electrode 230 includes a negative electrode current collector 231 and a negative electrode mixture layer 232 supported by the negative electrode current collector 231.
• the negative electrode mixture layer 232 contains the negative electrode active material according to this embodiment.
• the negative electrode mixture layer 232 is located between the negative electrode current collector 231 and the electrolyte layer 220.
• the materials described above for the negative electrode 23 in the battery 100 can be used for the negative electrode current collector 231 and the negative electrode mixture layer 232.
• the negative electrode mixture layer 232 may contain a solid electrolyte.
• solid electrolytes include the solid electrolytes described above as the electrolyte in the battery 100.
• the battery 200 can be configured as a battery of various shapes, such as a coin type, a cylindrical type, a rectangular type, a sheet type, a button type, a flat type, a laminated type, etc.
• a composite particle A composite particle; a coating layer that coats at least a portion of the surface of the composite particle; Equipped with The composite particles include an alkali aluminate phase containing at least one alkali metal element and Al, and a silicon phase dispersed within the alkali aluminate phase,
• the coating layer includes a lithium sulfonate compound and a hydrophobic polymer compound. Negative electrode active material.
• This configuration improves the battery's cycle characteristics.
• the lithium sulfonate compound is represented by the general formula (1):
• R is an n-valent aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. With this configuration, the cycle characteristics of the battery can be improved.
• the fluororesin includes at least one selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene, and ethylenechlorotrifluoroethylene copolymer.
• a negative electrode comprising the negative electrode active material according to any one of techniques 1 to 12; A positive electrode and an electrolyte; battery.
• This configuration has the effect of improving cycle characteristics.
• the raw aluminate (average particle size 10 ⁇ m) and raw silicon (3N, average particle size 10 ⁇ m) were mixed in a mass ratio of 40:60.
• the resulting mixture was loaded into the pot (SUS, volume: 500 mL) of a planetary ball mill (Fritsch, P-5).
• 24 SUS balls (diameter 20 mm) were placed in the pot, the lid was closed, and the mixture was milled in an inert atmosphere at 200 rpm for 50 hours. This produced a powdered mixture.
• mother particles (LAX particles) were obtained in which a silicon phase was dispersed in an alkali aluminate phase containing a specified amount of Li and B.
• the resulting granulated powder was crushed using a mill (IKA MultiDrive basic) and then classified using an ultrasonic oscillator (Artech Ultrasonic Systems), forming a coating layer on the surface of the composite particles that was a composite layer of MSL and PVDF.
• Example 1 The average particle size of the particles of Example 1 was 7 ⁇ m.
• Example 2 Particles of Example 2 were produced in the same manner as in Example 1, except that the amount of MSL and the amount of PVDF used in forming the coating layer were each changed to 4 parts by mass per 100 parts by mass of the composite particles.
• Example 3 Particles of Example 3 were produced in the same manner as in Example 1, except that the amount of MSL and the amount of PVDF used in forming the coating layer were each changed to 6 parts by mass per 100 parts by mass of the composite particles.
• Example 4 Particles of Example 4 were produced in the same manner as in Example 1, except that the amount of MSL and the amount of PVDF used in forming the coating layer were each changed to 8 parts by mass per 100 parts by mass of the composite particles.
• Comparative Example 1 Particles of Comparative Example 1 were prepared in the same manner as in Example 1, except that no coating layer was formed on the surface of the composite particles. That is, the particles of Comparative Example 1 were composite particles that were LAX particles having a conductive layer in Example 1.
• Li2CO3 and SiO2 were mixed so that the atomic ratio: Si / Li was 1.05 to obtain a mixture.
• the mixture was fired at 800°C for 10 hours in an inert gas atmosphere to obtain lithium silicate ( Li2Si2O5 ).
• the fired product was then pulverized to obtain lithium silicate with an average particle size of 10 ⁇ m .
• Lithium silicate (average particle size 10 ⁇ m) and raw silicon (3N, average particle size 10 ⁇ m) were mixed in a mass ratio of 40:60.
• the mixture was filled into a pot (SUS, volume: 500 mL) of a planetary ball mill (Fritsch, P-5).
• SUS planetary ball mill
• 24 SUS balls (diameter 20 mm) were placed in the pot, the lid was closed, and the mixture was milled at 200 rpm for 50 hours in an inert atmosphere.
• the powder mixture was removed from the inert atmosphere, and sintered at 600°C for 4 hours while applying pressure from a hot press in the inert atmosphere. This resulted in a sintered body.
• the sintered mixture was crushed and passed through a 40 ⁇ m mesh. Then, using a sieve, mother particles (LSX particles) with an average particle size of 10 ⁇ m were obtained, in which the silicon phase was dispersed within the lithium silicate phase.
• a conductive layer was formed on the surface of the obtained base particles in the same manner as in Example 1. Then, using a sieve, composite particles with an average particle size of 5 ⁇ m, which were LSX particles with a conductive layer, were obtained. These composite particles were designated as particles of Comparative Example 2.
• the particles and graphite were mixed in a mass ratio of 10:90 to obtain a mixture.
• the mixture was used as the negative electrode active material.
• the negative electrode slurry was applied to both sides of the copper foil, which is the negative electrode current collector, and the coating was dried and then rolled.
• the negative electrode was cut to a predetermined size to produce a negative electrode in which a negative electrode mixture layer was formed on both sides of the negative electrode current collector. At this time, a negative electrode current collector exposed portion was provided on a part of the negative electrode.
• NMP N-methyl-2-pyrrolidone
• a lithium transition metal composite oxide represented by LiNi 0.88 Co 0.09 Al 0.03 O 2 was used as the positive electrode active material.
• the positive electrode slurry was applied to both sides of the aluminum foil that was the positive electrode current collector, and the coating was dried and then rolled. The positive electrode was cut to a predetermined size, and a positive electrode in which a positive electrode mixture layer was formed on both sides of the positive electrode current collector was produced. At this time, a positive electrode current collector exposed portion was provided on a part of the positive electrode.
• LiPF 6 lithium hexafluorophosphate
• EC ethylene carbonate
• EMC ethyl methyl carbonate
• DMC dimethyl carbonate
• E in the formula is the value (%) of the initial charge and discharge efficiency of each of Examples 1 to 4, Comparative Examples 1 to 2, and Reference Example 1, and E0 is the value (%) of the initial charge and discharge efficiency of Comparative Example 1.
• the batteries of Examples 1 to 4 had smaller cycle deterioration rates than the batteries of Comparative Examples 1 to 2 and Reference Example 1. That is, the batteries of Examples 1 to 4 had better cycle characteristics than the batteries of Comparative Examples 1 to 2 and Reference Example 1. Furthermore, the batteries of Examples 1 to 4 had smaller amounts of side reactions than the battery of Comparative Example 1. That is, the batteries of Examples 1 to 4 showed higher initial charge/discharge efficiency than the battery of Comparative Example 1. Furthermore, the batteries of Examples 2 to 4 had smaller amounts of side reactions than the battery of Comparative Example 2.
• the technology disclosed herein is useful for batteries such as lithium-ion secondary batteries.

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