WO2013073400A1 - Électrode positive pour des batteries rechargeables au lithium-ion, et batterie rechargeable au lithium-ion qui utilise cette dernière - Google Patents

Électrode positive pour des batteries rechargeables au lithium-ion, et batterie rechargeable au lithium-ion qui utilise cette dernière Download PDF

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Publication number
WO2013073400A1
WO2013073400A1 PCT/JP2012/078629 JP2012078629W WO2013073400A1 WO 2013073400 A1 WO2013073400 A1 WO 2013073400A1 JP 2012078629 W JP2012078629 W JP 2012078629W WO 2013073400 A1 WO2013073400 A1 WO 2013073400A1
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aluminum silicate
positive electrode
lithium ion
ion secondary
secondary battery
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PCT/JP2012/078629
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English (en)
Japanese (ja)
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紘揮 三國
潔 川合
克倫 古田土
裕史 中嶋
片山　秀昭
児島　克典
愛知　且英
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新神戸電機株式会社
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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 positive electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same.
  • Lithium-ion secondary batteries are lighter and have higher input / output characteristics than other secondary batteries such as nickel metal hydride batteries and lead-acid batteries. It is attracting attention as an output power source.
  • impurities for example, magnetic impurities such as Fe, Ni, Cu, etc.
  • impurities for example, magnetic impurities such as Fe, Ni, Cu, etc.
  • the operating temperature of lithium ion secondary batteries may be 40 ° C to 80 ° C, such as in the car in summer.
  • the metal in the Li-containing metal oxide constituting the positive electrode is eluted from the positive electrode, and the characteristics of the battery are deteriorated. For this reason, examination of the trap of impurities and examination of the stabilization of the positive electrode have been made (for example, refer to Patent Document 1).
  • a lithium compound containing Fe or Mn as a metal element is used as a positive electrode active material, and the effective pore diameter is larger than the ion radius of the metal element and 0.5 nm (5 mm) or less.
  • Patent Document 2 a lithium compound containing Fe or Mn as a metal element is used as a positive electrode active material, and the effective pore diameter is larger than the ion radius of the metal element and 0.5 nm (5 mm) or less.
  • an object of the present invention is to provide a positive electrode for a lithium ion secondary battery excellent in metal ion adsorption and metal ion selectivity and a lithium ion secondary battery using the positive electrode.
  • ⁇ 4> The positive electrode for a lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 3>, wherein the element molar ratio Si / Al of the aluminum silicate is 0.4 or more and 0.6 or less. .
  • the aluminum silicate has an area ratio (peak B / peak A) between peak A around -78 ppm and peak B around -85 ppm in the range of 2.0 to 9.0.
  • the positive electrode for a lithium ion secondary battery according to any one of the above items ⁇ 3> to ⁇ 5>.
  • ⁇ 7> The positive electrode for a lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 6>, wherein the aluminum silicate has a BET specific surface area of 250 m 2 / g or more.
  • ⁇ 8> The positive electrode for a lithium ion secondary battery according to any one of ⁇ 1> to ⁇ 7>, wherein the aluminum silicate is provided by a dispersion containing the aluminum silicate.
  • the present invention it is possible to provide a positive electrode for a lithium ion secondary battery excellent in metal ion adsorption and metal ion selectivity and a lithium ion secondary battery using the same.
  • FIG. 2 is a 27Al-NMR spectrum of an aluminum silicate according to Example 1 and Example 2.
  • FIG. 2 is a 29Si-NMR spectrum of aluminum silicate according to Example 1 and Example 2.
  • FIG. 2 is a transmission electron microscope (TEM) photograph of aluminum silicate according to Example 1.
  • FIG. 2 is a transmission electron microscope (TEM) photograph of aluminum silicate according to Example 2.
  • FIG. It is a figure which shows typically what is called tubular imogolite which is an example of this embodiment.
  • 2 is a powder X-ray diffraction spectrum of aluminum silicate according to Example 1 and Example 2.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
  • the positive electrode for a lithium ion secondary battery of the present invention is provided with an aluminum silicate having an Si / Al element molar ratio Si / Al of 0.3 or more and less than 1.0 on the surface.
  • An aluminum silicate having an element molar ratio Si / Al of 0.3 to less than 1.0 (hereinafter sometimes referred to as “specific aluminum silicate”) has many metal ions per unit mass. And has a feature of highly selectively adsorbing metal ions with a high specific surface area.
  • Specified aluminum silicate is an oxide salt of Si and Al and has different valences, so there are many OH groups, and this has ion exchange ability. Therefore, it has a feature of having many metal ion adsorption sites per unit mass and highly selectively adsorbing metal ions with a high specific surface area.
  • the specific aluminum silicate has a specific property of adsorbing unnecessary metal ions even though it hardly adsorbs lithium ions essential for charging and discharging of a lithium ion battery.
  • unnecessary metal ions refer to nickel ions other than lithium ions, manganese ions, copper ions, and the like. These unnecessary metal ions are derived from impurity ions present in the constituent materials of the battery and metal ions eluted from the positive electrode at a high temperature.
  • the specific aluminum silicate is an inorganic oxide, it has excellent thermal stability and stability in a solvent. For this reason, it can exist stably even during charging and discharging.
  • impurity ions are ionized at the positive electrode, and metal ions are eluted from the positive electrode when the operating temperature of the battery is high. This is effective from the viewpoint of maintaining conductivity between substances.
  • the element ratio Si / Al between Si and Al is 0.3 or more and less than 1.0 in terms of metal ion adsorption ability and metal ion selectivity. It is preferably 4 or more and 0.6 or less, and more preferably 0.45 or more and 0.55 or less.
  • the Si / Al molar ratio is less than 0.3, the amount of Al that does not contribute to the enhancement of metal ion adsorption capacity becomes excessive, and the ion adsorption capacity of impurities is poor. If it is 1.0 or more, the amount of Si that does not contribute to the improvement of metal ion selectivity tends to be excessive, and the metal ion selectivity is lowered.
  • the element ratio Si / Al of Si and Al can be measured by an ordinary method using an ICP emission spectrometer (for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.).
  • ICP emission spectrometer for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.
  • the specific aluminum silicate according to the present embodiment preferably has a peak in the vicinity of 3 ppm in the 27Al-NMR spectrum.
  • the 27Al-NMR measuring apparatus for example, AV400WB type manufactured by Bruker BioSpin can be used, and specific measuring conditions are as follows.
  • FIG. 1 shows a 27Al-NMR spectrum of a specific aluminum silicate according to Example 1 and Example 2 described later as an example of the specific aluminum silicate according to the present embodiment.
  • the specific aluminum silicate according to this embodiment preferably has a peak in the vicinity of 3 ppm in the 27Al-NMR spectrum.
  • the peak around 3 ppm is estimated to be a peak derived from 6-coordinated Al.
  • the peak near 55 ppm is estimated to be a peak derived from tetracoordinated Al.
  • the area ratio of the peak near 55 pm to the peak near 3 ppm in the 27Al-NMR spectrum is 25% or less. Preferably, it is 20% or less, more preferably 15% or less.
  • the specific aluminum silicate according to the present embodiment has an area ratio of a peak near 55 pm to a peak near 3 ppm in the 27Al-NMR spectrum from the viewpoint of metal ion adsorptivity and metal ion selectivity of 1%. Preferably, it is preferably 5% or more, more preferably 10% or more.
  • the specific aluminum silicate according to this embodiment preferably has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29Si-NMR spectrum.
  • Aluminum silicate showing such a specific 29Si-NMR spectrum is excellent in metal ion adsorption and metal ion selectivity.
  • a 29Si-NMR measuring apparatus for measuring a 29Si-NMR spectrum for example, an AV400WB type manufactured by Bruker BioSpin can be used, and specific measurement conditions are as follows.
  • Resonance frequency 79.5 MHz
  • Measuring method MAS (single pulse)
  • MAS rotation speed 6 kHz
  • Measurement area 24 kHz
  • Number of data points 2048 resolution (measurement area / number of data points): 5.8 Hz
  • Pulse width 4.7 ⁇ sec
  • Delay time 600 seconds
  • Chemical shift value criteria TMSP-d4 (3- (trimethylsilyl) (2,2,3,3-2H4) sodium propionate) 1.52
  • window function exponential function
  • Line Broadening coefficient 50 Hz
  • FIG. 2 shows 29Si-NMR spectra of specific aluminum silicate according to Example 1 and Example 2 described later as an example of the specific aluminum silicate according to the present embodiment.
  • the specific aluminum silicate according to this embodiment preferably has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29Si-NMR spectrum.
  • the peak A that appears in the vicinity of ⁇ 78 ppm is derived from a specific aluminum silicate having a crystal structure such as imogolite and allophanes, and is considered to be caused by a structure of HO—Si— (OAl) 3.
  • the peak B appearing around ⁇ 85 ppm is considered to be a specific aluminum silicate having a clay structure or a specific aluminum silicate having an amorphous structure. Therefore, the specific aluminum silicate having peaks near 78 ppm and -85 ppm is a mixture or composite of the specific aluminum silicate having a crystal structure and the specific aluminum silicate having a viscosity structure or an amorphous structure. It is estimated to be.
  • aluminum silicate having a peak A that appears in the vicinity of ⁇ 78 ppm has many OH groups per unit mass. For this reason, it has been found that the aluminum silicate having the peak A that appears in the vicinity of ⁇ 78 ppm is excellent in water adsorption ability.
  • the inventors have newly found that this aluminum silicate has an excellent ability to adsorb metal ions, and in particular selectively adsorbs metal ions which adversely affect the battery. For this reason, in the lithium ion battery containing this specific aluminum silicate, the occurrence of short circuit is remarkably reduced, and as a result, it can be considered that the life characteristics are excellent.
  • the specific aluminum silicate according to this embodiment may not have a peak around ⁇ 110 ppm derived from the layered clay mineral.
  • having no peak means that the displacement from the baseline in the vicinity of ⁇ 110 ppm is below the noise level.
  • the specific aluminum silicate according to this embodiment has an area ratio of a peak A around ⁇ 78 ppm and a peak B around ⁇ 85 ppm in the 29Si-NMR spectrum (from the viewpoint of improving metal ion adsorption ability and metal ion selectivity).
  • Peak B / Peak A) is preferably 0.4 to 9.0, more preferably 1.5 to 9.0, still more preferably 2.0 to 9.0. It is more preferably 0.0 to 7.0, still more preferably 2.0 to 5.0, and particularly preferably 2.0 to 4.0.
  • a baseline is first drawn in the 29Si-NMR spectrum.
  • a straight line connecting -55 ppm and -140 ppm is taken as a baseline.
  • the area of peak A near ⁇ 78 ppm is the area of the region surrounded by the straight line passing through ⁇ 81 ppm perpendicular to the chemical shift axis and the base line, and the area of peak B is chemical through ⁇ 81 ppm. This is the area of a region surrounded by a straight line perpendicular to the shift axis and the base line.
  • FIG. 3 and 4 show an example of a transmission electron microscope (TEM) photograph of the specific aluminum silicate according to the present embodiment.
  • the specific aluminum silicate shown in FIG. 3 is a specific aluminum silicate according to Example 1 described later.
  • the specific aluminum silicate shown in FIG. 4 is a specific aluminum silicate according to Example 2 described later.
  • the specific aluminum silicate according to Example 1 does not have a tubular product having a length of 50 nm or more when observed at a magnification of 100,000 with a transmission electron microscope (TEM).
  • the specific aluminum silicate according to Example 2 is tubular so-called imogolite, as shown in FIG.
  • the specific aluminum silicate according to the present embodiment is a tubular product having a length of 50 nm or more when observed with a transmission electron microscope (TEM) at a magnification of 100,000 from the viewpoint of metal ion adsorption ability and metal ion selectivity. Is preferably absent.
  • TEM transmission electron microscope
  • Observation of a specific aluminum silicate with a transmission electron microscope (TEM) is performed at an acceleration voltage of 100 kV.
  • TEM transmission electron microscope
  • a solution after heating before the second washing step (desalting and solid separation) in the manufacturing method described later is dropped on a support for preparing a TEM observation sample, and then dried to form a thin film.
  • an observation sample is prepared using an appropriately diluted solution after the heat treatment so that a sufficient contrast can be obtained.
  • the specific aluminum silicate in which a tubular product as shown in FIG. 3 is not observed is manufactured by performing a heat treatment of silicate ions and aluminum ions at a specific concentration or more.
  • FIG. 5 is a drawing schematically showing a tubular so-called imogolite (first specific aluminum silicate described in a manufacturing method described later) 10 which is an example of the specific aluminum silicate according to the present embodiment.
  • the fiber structure tends to be formed by the tubular bodies 10 a, and the outer wall (outer periphery) of the tubular body 10 a forming the inner wall 20 in the tube of the tubular body 10 a and the gap 30 between the tubular body 10 a ridges. Surface) can be used as an adsorption site for metal ions.
  • the length of the tubular body 10a in the tube portion length direction is, for example, 1 nm to 10 ⁇ m.
  • the tubular body 10a has, for example, a circular tubular shape, and has an outer diameter of, for example, 1.5 nm to 3.0 nm and an inner diameter of, for example, 0.7 nm to 1.4 nm.
  • Powder X-ray diffraction is measured using CuK ⁇ rays as an X-ray source.
  • a powder X-ray diffractometer manufactured by Rigaku Corporation: Geigerflex RAD-2X (trade name) can be used.
  • FIG. 6 shows a powder X-ray diffraction spectrum of the specific aluminum silicate according to Example 1 and Example 2 described later as an example of the specific aluminum silicate according to the present embodiment.
  • precipitation of aluminum hydroxide can be suppressed by making the heating temperature at the time of heat processing into 160 degrees C or less.
  • content of aluminum hydroxide can be adjusted by adjusting pH at the time of the desalting process by centrifugation.
  • the specific aluminum silicate according to this embodiment has a BET specific surface area of preferably 250 m 2 / g or more, more preferably 280 m 2 / g or more, and 300 m from the viewpoint of improving the metal ion adsorption ability. More preferably, it is 2 / g or more.
  • the BET specific surface area is 250 m 2 / g or more, the adsorbed amount of impurity ions and eluted ions per unit mass is increased, so that the efficiency is good and a high effect is obtained with a small amount.
  • the upper limit of the BET specific surface area is not particularly limited, but if the specific surface area is too large, the amount of moisture adsorbed in the air per unit mass will increase, so the BET specific surface area should be 1500 m 2 / g or less. Is preferably 1200 m 2 / g or less, more preferably 1000 m 2 / g or less.
  • the BET specific surface area of the specific aluminum silicate is measured from the nitrogen adsorption ability at 77K according to JIS Z 8830.
  • the evaluation apparatus for example, AUTOSORB-1 (trade name) manufactured by QUANTACHROME can be used.
  • AUTOSORB-1 trade name manufactured by QUANTACHROME
  • pretreatment for removing moisture by heating is first performed.
  • the measurement cell charged with 0.05 g of the measurement sample is depressurized to 10 Pa or less with a vacuum pump, heated at 110 ° C., held for 3 hours or more, and kept at a normal temperature while maintaining the depressurized state. Cool naturally to (25 ° C).
  • the evaluation temperature is 77K
  • the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • Certain aluminum silicates according to the present embodiment is preferably, 0.12 cm 3 / g or more that the total pore volume is 0.1 cm 3 / g or more More preferably, it is still more preferably 0.15 cm 3 / g or more.
  • the upper limit of the total pore volume is not particularly limited, but if the total pore volume is too large, the amount of moisture adsorbed in the air per unit mass increases, so the total pore volume is 1.5 cm 3. / G or less is preferable, 1.2 cm 3 / g or less is more preferable, and 1.0 cm 3 / g or less is still more preferable.
  • the total pore volume of the specific aluminum silicate is based on the BET specific surface area.
  • the gas adsorption amount closest to the relative pressure 1 is set to the liquid. Calculate by conversion.
  • the average pore diameter of the specific aluminum silicate according to this embodiment is preferably 1.5 nm or more. Since it moves to the site
  • the average pore diameter of the specific aluminum silicate is obtained on the basis of the BET specific surface area and the total pore volume, assuming that all the pores are composed of one cylindrical pore.
  • the specific aluminum silicate according to this embodiment preferably has a moisture content of 10% by mass or less, and more preferably 5% by mass or less.
  • a lithium ion secondary battery is constituted by having a water content of 10% by mass or less, generation of gas due to water causing electrolysis can be suppressed, and battery expansion can be suppressed.
  • the water content can be measured by the Karl Fischer method.
  • a commonly used drying method can be applied without any particular limitation. For example, a method of drying at about 100 ° C. to 300 ° C. for about 6 hours to 24 hours under atmospheric pressure can be mentioned.
  • the method for producing a specific aluminum silicate according to the present invention comprises (a) a step of mixing a solution containing silicate ions and a solution containing aluminum ions to obtain a reaction product, and (b) the reaction product, A step of desalting and separating the solid, (c) a step of subjecting the solid separated in step (b) to a heat treatment in an aqueous medium in the presence of an acid, and (d) a heat treatment in step (c). And a step of desalting and solid separation of the product obtained as described above, and having other steps as necessary.
  • the specific aluminum silicate from which the coexisting ions that inhibit the formation of the regular structure are removed is heat-treated in the presence of an acid, whereby the specific aluminum silicate having a regular structure is formed. It can be considered that the specific aluminum silicate has a regular structure, the affinity for unnecessary metal ions is improved, and the metal ion selectivity is enhanced while efficiently adsorbing the metal ions.
  • Step of obtaining reaction product In the step of obtaining reaction product, a solution containing silicate ions and a solution containing aluminum ions are mixed to contain a specific aluminum silicate and coexisting ions which are reaction products. A mixed solution is obtained.
  • silicate solution When synthesizing a specific aluminum silicate, silicate ions and aluminum ions are required as raw materials.
  • the silicic acid source constituting the solution containing silicate ions (hereinafter also referred to as “silicate solution”) is not particularly limited as long as silicate ions are generated when solvated. Examples thereof include, but are not limited to, tetraalkoxysilanes such as sodium orthosilicate, sodium metasilicate, and tetraethoxysilane.
  • the aluminum source constituting the solution containing aluminum ions is not particularly limited as long as aluminum ions are generated when solvated.
  • examples thereof include, but are not limited to, aluminum chloride, aluminum perchlorate, aluminum nitrate, and aluminum sec-butoxide.
  • a material that can easily be solvated with the silicate source and the aluminum source as raw materials can be appropriately selected and used.
  • water, ethanol or the like can be used. It is preferable to use water from the viewpoint of reducing the coexisting ions in the solution during the heat treatment and ease of handling.
  • the element ratio Si / Al of the Si and Al in the mixed solution is 0.3 to less than 1.0 in molar ratio in accordance with the element ratio Si / Al of Si and Al in the specific aluminum silicate obtained. It adjusts so that it may become 0.4 or more and 0.6 or less, More preferably, it adjusts so that it may become 0.45 or more and 0.55 or less.
  • the element ratio Si / Al is 0.3 or more and less than 1.0, a specific aluminum silicate having a desired regular structure is easily synthesized.
  • the silicon atom concentration of the silicate solution is not particularly limited. Preferably, it is 1 mmol / L to 1000 mmol / L.
  • productivity is improved and specific aluminum silicate can be produced efficiently. Moreover, productivity improves more according to a silicon atom concentration as the silicon atom concentration of a silicic acid solution is 1000 mmol / L or less.
  • the aluminum atom concentration of the aluminum solution is not particularly limited. Preferably, it is 100 mmol / L to 1000 mmol / L.
  • the productivity is improved and specific aluminum silicate can be efficiently produced. Further, when the aluminum atom concentration is 1000 mmol / L or less, the productivity is further improved according to the aluminum atom concentration.
  • a solution containing silicate ions and a solution containing aluminum ions are mixed to produce a specific aluminum silicate containing coexisting ions as a reaction product, and then the specific aluminum silicate containing the coexisting ions is desalted.
  • a first washing step for solid separation In the first washing step, at least a part of the coexisting ions is removed from the mixed solution to reduce the coexisting ion concentration in the mixed solution. By performing the first cleaning step, it is easy to form a desired specific aluminum silicate in the synthesis step.
  • desalting and solid separation include anions other than silicate ions derived from a silicate source and an aluminum source (for example, chloride ions and nitrate ions) and cations other than aluminum ions (for example, sodium ions).
  • anions other than silicate ions derived from a silicate source and an aluminum source for example, chloride ions and nitrate ions
  • cations other than aluminum ions for example, sodium ions
  • the first cleaning step is preferably performed so that the concentration of the coexisting ions is not more than a predetermined concentration.
  • the electrical conductivity of the dispersion is 4.0 S / m. It is preferable to carry out so that it is less than or equal to 1.0 mS / m or more and 3.0 S / m or less, more preferably 1.0 mS / m or more and 2.0 S / m or less. Is more preferable.
  • the desired specific aluminum silicate tends to be more easily formed in the synthesis step.
  • the electrical conductivity is measured at normal temperature (25 ° C.) using FORI 55 manufactured by HORIBA Co., Ltd. and a general electrical conductivity cell of 9382-10D.
  • the first washing step includes a step of dispersing the specific aluminum silicate in an aqueous medium to obtain a dispersion, a step of adjusting the pH of the dispersion to 5 to 7, and a step of precipitating the specific aluminum silicate Are preferably included.
  • the first washing step when the first washing step is performed using centrifugation, it can be performed as follows.
  • the pH is adjusted to 5 to 8 by adding alkali or the like to the mixed solution.
  • the supernatant solution After centrifuging the pH-adjusted solution, the supernatant solution is discharged and the solid is separated as a gel-like precipitate.
  • the separated solid is redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 8, but preferably 5.5 to 6.8, and more preferably 5.8 to 6.5.
  • the alkali used for pH adjustment is not particularly limited. For example, sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and its standard rotor NA-16, it can be set at 3000 rpm (1450 G) or more for 5 to 10 minutes at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of the reduction of coexisting ions and ease of handling, water is preferably used, and pure water is more preferably used. It should be noted that pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the first washing step may be appropriately set according to the remaining amount of coexisting ions. For example, it can be 1 to 6 times. If the washing is repeated about three times, the residual amount of coexisting ions is so small that it does not affect the synthesis of the desired specific aluminum silicate.
  • PH measurement at the time of pH adjustment can be performed with a pH meter using a general glass electrode.
  • a general glass electrode Specifically, for example, trade name: MODEL (F-51) manufactured by HORIBA, Ltd. can be used.
  • a specific aluminum silicate having a regular structure is formed by heat-treating a solution (dispersion) containing the specific aluminum silicate with reduced coexisting ions in the first washing step in the presence of an acid. be able to.
  • the synthesis step may be performed as a dilute solution by appropriately diluting the solid separated in the first washing step, or may be carried out as a high-concentration solution after solid separation in the first washing step.
  • a specific aluminum silicate having a structure in which a regular structure is extended into a tubular shape as shown in FIG. 4 (hereinafter also referred to as “first specific aluminum silicate”). ) Can be obtained. Further, by carrying out the synthesis step in a high concentration solution, a specific aluminum silicate having a viscosity structure and an amorphous structure in addition to a regular structure as shown in FIG. Silicate "). In addition, it replaces with the 2nd specific aluminum silicate growing in the tubular thing 50 nm or more in length, and it is estimated that the formation of a viscosity structure and an amorphous structure is increasing.
  • Both the first and second specific aluminum silicates have a specific regular structure, thereby exhibiting excellent metal ion adsorption ability and metal ion selectivity.
  • the silicon atom concentration can be 20 mmol / L or less and the aluminum atom concentration can be 60 mmol / L or less.
  • the silicon atom concentration is 0.1 mmol / L or more and 10 mmol / L or less and the aluminum atom concentration is 0.1 mmol / L or more and 34 mmol / L or less.
  • the atomic concentration is from 0.1 mmol / L to 2 mmol / L and the aluminum atomic concentration is from 0.1 mmol / L to 7 mmol / L.
  • the first specific aluminum silicate can be efficiently produced.
  • the silicon atom concentration can be 100 mmol / L or more and the aluminum atom concentration can be 100 mmol / L or more.
  • the silicon atom concentration is preferably 120 mmol / L or more and 2000 mmol / L or less
  • the aluminum atom concentration is preferably 120 mmol / L or more and 2000 mmol / L or less
  • the silicon atom concentration is 150 mmol. More preferably, the aluminum atom concentration is 150 mmol / L or more and 1500 mmol / L or less.
  • the second specific aluminum silicate can be efficiently produced, and the productivity of the specific aluminum silicate is also improved. To do.
  • the silicon atom concentration and the aluminum atom concentration are the silicon atom concentration and the aluminum element concentration after adjusting the pH to a predetermined range by adding an acidic compound described later.
  • the silicon atom concentration and the aluminum atom concentration are measured using an ICP emission spectrometer (for example, ICP emission spectrometer manufactured by Hitachi, Ltd .: P-4010).
  • a solvent may be added.
  • the solvent one that can easily be solvated with the raw material can be appropriately selected and used. Specifically, water, ethanol, etc. can be used, but the coexisting ions in the solution during the heat treatment can be reduced. From the viewpoint of ease of handling, it is preferable to use water.
  • the synthesis step at least one acidic compound is added before the heat treatment.
  • the pH after adding the acidic compound is not particularly limited. From the viewpoint of efficiently obtaining the desired specific aluminum silicate, the pH is preferably from 3 to less than 7, and more preferably from 3 to 5.
  • the acidic compound added in the synthesis step is not particularly limited, and may be an organic acid or an inorganic acid. Among these, it is preferable to use an inorganic acid. Specific examples of the inorganic acid include hydrochloric acid, perchloric acid, nitric acid and the like. Considering the reduction of coexisting ion species in the solution during the subsequent heat treatment, it is preferable to use an acidic compound that generates an anion similar to the anion contained in the used aluminum source.
  • a specific aluminum silicate having a desired structure can be obtained by performing a heat treatment after adding an acidic compound.
  • the heating temperature is not particularly limited. From the viewpoint of efficiently obtaining the desired specific aluminum silicate, the temperature is preferably from 80 ° C to 160 ° C.
  • the heating temperature is 160 ° C. or lower, precipitation of boehmite (aluminum hydroxide) tends to be suppressed.
  • the heating temperature is 80 ° C. or higher, the synthesis rate of the desired specific aluminum silicate is improved, and the desired specific aluminum silicate tends to be produced more efficiently.
  • the heating time is not particularly limited. From the viewpoint of more efficiently obtaining a specific aluminum silicate having a desired structure, it is preferably within 96 hours (4 days).
  • the desired specific aluminum silicate can be more efficiently produced.
  • the second washing step only needs to be able to remove at least a part of anions other than silicate ions and cations other than aluminum ions, and may be the same operation as the first washing step before the synthesis step or a different operation. Good.
  • the second washing step is preferably performed so that the concentration of coexisting ions is not more than a predetermined concentration.
  • the electrical conductivity of the dispersion is 4.0 S / m. It is preferable to carry out so that it is less than or equal to 1.0 mS / m or more and 3.0 S / m or less, more preferably 1.0 mS / m or more and 2.0 S / m or less. Is more preferable.
  • the second washing step is performed using centrifugation, for example, it can be performed as follows.
  • the pH is adjusted to 5 to 10 by adding alkali or the like to the mixed solution.
  • the supernatant solution is discharged and the solid is separated as a gel-like precipitate.
  • the solid separated is then redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 10, preferably 8 to 10.
  • the alkali used for pH adjustment is not particularly limited.
  • sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and its standard rotor NA-16, it can be set at 3000 rpm (1450 G) or more for 5 to 10 minutes at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of ease of handling, it is preferable to use water, and it is more preferable to use pure water.
  • pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the second washing step may be set according to the residual amount of coexisting ions, but is preferably 1 to 6 times, and if the washing is repeated about 3 times, the coexistence in the specific aluminum silicate The remaining amount of ions is sufficiently reduced.
  • the concentration of chloride ions and sodium ions that particularly affect the adsorption ability of metal ions is reduced. That is, when the aluminum silicate after washing in the second washing step is prepared by dispersing the aluminum silicate in water to prepare an aqueous dispersion having a concentration of 400 mg / L, the chloride ion concentration in the aqueous dispersion is 100 mg. / L or less and a sodium ion concentration of 100 mg / L or less are preferable. When the chloride ion concentration is 100 mg / L or less and the sodium ion concentration is 100 mg / L or less, the adsorption ability can be further improved.
  • the chloride ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less.
  • the sodium ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less. Chloride ion concentration and sodium ion concentration can be adjusted according to the number of treatments in the washing step and the type of alkali used for pH adjustment.
  • the chloride ion concentration and sodium ion concentration are measured under normal conditions by ion chromatography (for example, DX-320 and DX-100 manufactured by Dionex).
  • concentration of the dispersion of the specific aluminum silicate is based on the mass of the solid obtained by drying the separated solid at 110 degrees for 24 hours.
  • the “dispersion after the second washing step” described here means a dispersion in which the volume is returned to the volume before the second washing step after the second washing step by using a solvent.
  • a solvent that easily solvates with the raw material can be appropriately selected and used. Specifically, water, ethanol or the like can be used, but the residual amount of coexisting ions in the specific aluminum silicate It is preferable to use water from the viewpoint of reduction of the amount and ease of handling.
  • the BET specific surface area of the specific aluminum silicate according to the present invention is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, and discharging the supernatant solution) Then, the specific aluminum silicate remaining as a gel-like precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or a plurality of times.
  • the total pore volume of the specific aluminum silicate is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, and discharging the supernatant solution).
  • the specific aluminum silicate remaining as a gel-like precipitate can be adjusted by a method of redispersing in a solvent and returning to the volume before centrifugation once or a plurality of times.
  • the average pore diameter of the specific aluminum silicate is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, and discharging the supernatant solution).
  • the specific aluminum silicate remaining as a gel-like precipitate can be adjusted by a method of redispersing in a solvent and returning to the volume before centrifugation once or a plurality of times.
  • the positive electrode for a lithium ion secondary battery of the present invention is provided with the specific aluminum silicate on the surface thereof. Since the specific aluminum silicate is applied to the surface of the positive electrode, impurity ions ionized at the positive electrode are captured, so that it is possible to suppress the metal ions from being reduced and the metal from being precipitated at the negative electrode. Thereby, the short circuit of a battery is suppressed. Moreover, since it is suppressed that a metal ion elutes from a positive electrode, the electroconductivity between positive electrode active materials can be hold
  • a layer containing a positive electrode active material (hereinafter sometimes referred to as a “positive electrode layer”) is provided on a current collector.
  • a positive electrode provided with a layer containing a specific aluminum silicate on the surface can be given.
  • the layer containing specific aluminum silicate if the specific aluminum silicate is provided to the surface of the positive electrode layer, it may not be layered.
  • a normal current collector used for a positive electrode for a lithium ion secondary battery can be applied.
  • a normal current collector used for a positive electrode for a lithium ion secondary battery can be applied.
  • aluminum, titanium, stainless steel A band-like material made of a metal such as steel or an alloy such as a foil shape, a perforated foil shape, or a mesh shape can be used.
  • Positive electrode layer The positive electrode layer is provided on the current collector and contains a positive electrode active material.
  • a positive electrode active material usually used for a positive electrode for a lithium ion secondary battery can be applied.
  • a positive electrode active material usually used for a positive electrode for a lithium ion secondary battery can be applied.
  • metal compounds, metal oxides, metal sulfides that can be doped or intercalated with lithium ions Or a conductive polymer material for example, metal compounds, metal oxides, metal sulfides that can be doped or intercalated with lithium ions Or a conductive polymer material.
  • lithium cobaltate LiCoO 2
  • lithium nickelate LiNiO 2
  • lithium manganate LiMnO 2
  • lithium manganese spinel LiMn 2 O 4
  • lithium vanadium compound V 2 O 5 , V 6 O 13 , VO 2 , MnO 2
  • TiO 2 , MoV 2 O 8 TiS 2 , V 2 S 5 , VS 2 , MoS 2 , MoS 3 , Cr 3 O 8 , Cr 2 O 5
  • olivine type LiMPO 4 M: Co, Ni, Mn Fe
  • polyacetylene polyaniline
  • polypyrrole polythiophene
  • polyacene polyacene
  • polyacetylene polyaniline
  • polypyrrole polythioph
  • the positive electrode layer may contain a binder.
  • the binder include styrene-butadiene copolymer; ethylenically unsaturated carboxylic acid ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, hydroxyethyl (meth ) Acrylate, etc.), and (meth) acrylic copolymers obtained by copolymerizing ethylenically unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc.); polyvinylidene fluoride , Polymer compounds such as polyethylene oxide, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polyimide, and polyamideimide.
  • Examples of a method for forming the positive electrode layer on the current collector include a method in which a positive electrode mixture slurry containing the positive electrode active material, the binder, and a solvent is applied on the current collector and dried.
  • the paste-like positive electrode mixture slurry may be formed into a sheet shape, a pellet shape, or the like and integrated with the current collector.
  • the viscosity of the positive electrode mixture slurry is preferably adjusted as appropriate in accordance with the coating method.
  • the solvent examples include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, phosphoric acid esters, and ethers. , Nitriles, water and the like.
  • a highly polar solvent In order to obtain the solubility of the binder and the dispersion stability of the conductive agent, it is preferable to use a highly polar solvent.
  • the solvent include amide solvents obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, Examples include, but are not limited to, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide, and the like. Two or more types can be used in combination.
  • a thickener may be added to the positive electrode mixture slurry in order to adjust the viscosity.
  • the thickener for example, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein and the like can be used.
  • a conductive agent may be mixed in the positive electrode mixture slurry as necessary.
  • the conductive agent include carbon blacks such as ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black; natural graphite such as flake graphite, graphite such as artificial graphite, and expanded graphite
  • Conductive fibers such as carbon fibers and metal fibers
  • metal powders such as copper, silver, nickel, and aluminum
  • organic conductive materials such as polyphenylene derivatives
  • the method for applying the positive electrode mixture slurry to the current collector is not particularly limited, and a known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application
  • the integration of the positive electrode mixture slurry and the current collector formed into a sheet shape, a pellet shape, or the like can be performed by a known method such as a roll, a press, or a combination thereof.
  • the thickness of the positive electrode layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
  • the layer containing the specific aluminum silicate is provided on the positive electrode layer, and may be formed by any method.
  • the specific aluminum silicate can be uniformly dispersed on the positive electrode, and thereby, unnecessary metal ions can be effectively adsorbed. Preferably it is formed.
  • the dispersion can be prepared, for example, by kneading the specific aluminum silicate together with a binder and a solvent by a dispersing device such as a stirrer, a ball mill, a super sand mill, or a pressure kneader. This dispersion can be applied onto the positive electrode layer to form a layer containing a specific aluminum silicate.
  • a dispersing device such as a stirrer, a ball mill, a super sand mill, or a pressure kneader.
  • the method for applying the dispersion on the positive electrode layer is not particularly limited.
  • known methods such as a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, and a screen printing method can be used.
  • After the application it is preferable to perform a rolling process using a flat plate press, a calender roll or the like, if necessary.
  • Examples of the solvent for the dispersion include water, 1-methyl-2-pyrrolidone, alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2 -Methyl-2-propanol, etc.), and water is more preferable from the viewpoint of reducing environmental burden.
  • alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2 -Methyl-2-propanol, etc.
  • the content of the specific aluminum silicate in the dispersion is, for example, preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass. More preferably, the content is from 20% by mass to 20% by mass.
  • Application amount of the specific aluminum silicate in the positive electrode for a lithium ion secondary battery it is preferably, 0.05g / m 2 ⁇ 30g / m 2 is 0.01g / m 2 ⁇ 50g / m 2 about More preferably, it is more preferably 0.1 g / m 2 to 20 g / m 2 .
  • the dispersion preferably further contains a binder.
  • the specific aluminum silicate is fixed to the positive electrode by adding a binder to the dispersion of the specific aluminum silicate. For this reason, when producing a battery, since specific aluminum silicate does not fall off and can exist on a positive electrode also at the time of charging / discharging, an unnecessary metal ion can be adsorb
  • the binder to be contained in the dispersion is not particularly limited, but is preferably a binder used for the positive electrode material layer as a binder from the viewpoint of a battery constituent material.
  • the content ratio of the binder in the layer containing the specific aluminum silicate is preferably 0.1 parts by mass to 15 parts by mass with respect to 100 parts by mass in total of the specific aluminum silicate and the binder. More preferably, it is 3 to 10 parts by mass.
  • the content ratio of the binder is 0.1 parts by mass or more
  • the specific aluminum silicate is effectively fixed to the positive electrode, and the effect of providing the specific aluminum silicate is continuously obtained.
  • suction efficiency per mass can be raised because it is 15 mass parts or less.
  • a thickener may be added to the dispersion to adjust the viscosity.
  • the thickener for example, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein and the like can be used.
  • an underlayer for improving the adhesion between the current collector and the positive electrode layer may be provided between the current collector and the positive electrode layer.
  • the underlayer preferably contains a polymer that does not dissolve or swell in the solvent of the electrolytic solution, and may contain a conductive substance in order to reduce the electrical resistance of the electrode and ensure conductivity.
  • the lithium ion secondary battery of this invention is comprised including the above-mentioned positive electrode, a negative electrode, and electrolyte solution.
  • the specific aluminum silicate is provided on the surface.
  • Negative electrode As an aspect of a negative electrode, the thing provided with the layer (henceforth a "negative electrode layer”) containing a negative electrode active material on the electrical power collector is mentioned, for example.
  • a normal current collector used for a negative electrode for a lithium ion secondary battery can be applied.
  • aluminum, copper, nickel, titanium, stainless steel Or the like may be used in the form of a foil, a punched foil, a mesh or the like.
  • a porous material such as porous metal (foamed metal) or carbon paper can also be used.
  • the negative electrode layer is provided on the current collector and contains a negative electrode active material.
  • negative electrode active material normal materials used for negative electrodes for lithium ion secondary batteries can be applied.
  • carbon materials, metal compounds, metal oxides, metal sulfides capable of doping or intercalating lithium ions can be used.
  • conductive polymer materials For example, natural graphite, artificial graphite, silicon, lithium titanate and the like can be used alone or in combination.
  • the negative electrode may contain a binder.
  • the binder is not particularly limited.
  • styrene-butadiene copolymer (meth) acrylic copolymer [ethylenically unsaturated carboxylic acid ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc.), (meth) acrylonitrile, ethylenically unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc.) Copolymer obtained], polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, polyimide, polyamideimide, and the like.
  • carboxylic acid ester for example, methyl (meth) acrylate, ethyl (meth) acrylate
  • a negative electrode mixture slurry is prepared by kneading the negative electrode active material and the binder together with a solvent by a dispersing device such as a stirrer, a ball mill, a super sand mill, and a pressure kneader. And a method of applying this onto the current collector and drying it.
  • the paste-like negative electrode mixture slurry may be formed into a sheet shape, a pellet shape, or the like and integrated with the current collector.
  • the binder content in the negative electrode layer of the negative electrode is preferably 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass in total of the negative electrode active material and the binder, and is 1 part by mass to 10 parts by mass. It is more preferable.
  • the content ratio of the binder is 0.5% by mass or more, the adhesion is good, and the negative electrode is prevented from being broken due to expansion / contraction during charge / discharge. On the other hand, it can suppress that electrode resistance becomes large because it is 20 mass% or less.
  • a conductive agent may be mixed in the negative electrode mixture slurry as necessary.
  • the conductive agent include carbon black, graphite, acetylene black, or conductive oxides and nitrides.
  • the amount of the conductive agent used may be about 0.1% by mass to 20% by mass with respect to the negative electrode active material.
  • a thickener may be added to the negative electrode mixture slurry in order to adjust the viscosity.
  • the thickener for example, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein and the like can be used.
  • the method for applying the negative electrode mixture slurry to the current collector is not particularly limited.
  • known methods such as a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, and a screen printing method can be used.
  • After the application it is preferable to perform a rolling process using a flat plate press, a calender roll or the like, if necessary.
  • the integration of the negative electrode mixture slurry and the current collector formed into a sheet shape, a pellet shape or the like can be performed by a known method such as a roll, a press, or a combination thereof.
  • the thickness of the negative electrode layer is generally 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 300 ⁇ m or less.
  • the negative electrode layer formed on the current collector and the negative electrode layer integrated with the current collector are preferably heat-treated according to the binder used.
  • heat treatment is preferably performed at 100 to 180 ° C.
  • heat treatment is preferably performed at 150 to 450 ° C.
  • This heat treatment increases the strength by removing the solvent and curing the binder, and improves the adhesion between the particles and between the particles and the current collector.
  • These heat treatments are preferably performed in an inert atmosphere such as helium, argon, nitrogen, or a vacuum atmosphere in order to prevent oxidation of the current collector during the treatment.
  • the negative electrode is pressure-pressed (pressure treatment) after the heat treatment.
  • the electrode density can be adjusted by applying pressure treatment.
  • the electrode density is preferably 1.0 g / cm 3 to 2.0 g / cm 3 .
  • Electrolyte used for the lithium ion secondary battery of the present invention is not particularly limited, and a known one can be used.
  • a non-aqueous lithium ion secondary battery is obtained by using an electrolytic solution in which an electrolyte is dissolved in an organic solvent.
  • lithium salts that generate anions that are difficult to solvate such as LiC (CF 3 SO 2 ) 3 , LiCl, and LiI.
  • the concentration of the electrolyte is not particularly limited.
  • the electrolyte is preferably 0.3 to 5 mol, more preferably 0.5 to 3 mol, and particularly preferably 0.8 to 1.5 mol with respect to 1 L of the electrolyte. preferable.
  • organic solvent examples include carbonates (propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate.
  • the organic solvent may be used alone or as a mixed solvent of two or more.
  • the lithium ion secondary battery of the present invention may have a separator.
  • a separator for example, a nonwoven fabric mainly composed of polyolefin such as polyethylene and polypropylene, cloth, microporous film, or a combination thereof can be used.
  • the positive electrode and the negative electrode of the lithium ion secondary battery to be manufactured are not in direct contact, it is not necessary to use a separator.
  • the structure of the lithium ion secondary battery of the present invention is not particularly limited. Usually, a positive electrode and a negative electrode, and a separator provided as necessary are wound in a flat spiral shape to form a wound electrode group. In general, these are laminated as a flat plate to form a laminated electrode plate group, and the electrode plate group is generally enclosed in an exterior body.
  • the lithium ion secondary battery of the present invention is not particularly limited, but is used as a paper-type battery, a button-type battery, a coin-type battery, a laminated battery, a cylindrical battery, a square battery, or the like.
  • Examples 1 to 4 and Comparative Examples 1 to 3 below metal ion adsorption ability of specific aluminum silicate in water was evaluated as a preliminary test.
  • the model electrolyte was used as a model electrolyte. The metal ion adsorption ability was evaluated.
  • Example 7 a lithium ion secondary battery was produced, and the initial capacity, charge / discharge characteristics, and impedance were measured.
  • Example 1 ⁇ Preparation of aluminum silicate> A concentration: 350 mmol / L sodium orthosilicate aqueous solution (500 mL) was added to a 700 mmol / L aluminum chloride aqueous solution (500 mL), and the mixture was stirred for 30 minutes. To this solution, 330 mL of an aqueous sodium hydroxide solution having a concentration of 1 mol / L was added to adjust the pH to 6.1.
  • centrifugal separation was performed for 5 minutes at a rotation speed of 3,000 rpm using a TOMY Corporation: Suprema 23 and standard rotor NA-16 as a centrifugal separator. After centrifugation, the supernatant solution was discharged, the gel precipitate was redispersed in pure water, and returned to the volume before centrifugation. Such desalting treatment by centrifugation was performed three times.
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was dispersed in pure water so as to have a concentration of 60 g / L, using HORIBA: F-55 and conductivity cell: 9382-10D.
  • the electrical conductivity measured at room temperature (25 ° C.) was 1.3 S / m.
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was dispersed in pure water so as to have a concentration of 60 g / L, using HORIBA: F-55 and conductivity cell: 9382-10D.
  • the electrical conductivity measured at room temperature (25 ° C.) was 0.6 S / m.
  • sample A The gel precipitate obtained after the third desalting of the desalting treatment was dried at 60 ° C. for 16 hours to obtain 30 g of powder. This powder was designated as sample A.
  • As the evaluation device AUTASORB-1 (trade name) manufactured by QUANTACHROME was used. When performing these measurements, after pre-treatment of the sample described later, the evaluation temperature is 77K, and the evaluation pressure range is less than 1 in relative pressure (equilibrium pressure with respect to the saturated vapor pressure).
  • the measurement cell charged with 0.05 g of sample A was automatically degassed and heated with a vacuum pump.
  • the detailed conditions of this treatment were set such that the pressure was reduced to 10 Pa or less, heated at 110 ° C., held for 3 hours or more, and then naturally cooled to room temperature (25 ° C.) while maintaining the reduced pressure.
  • the BET specific surface area of Sample A was 363 m 2 / g, the total pore volume was 0.22 cm 3 / g, and the average pore diameter was 2.4 nm.
  • FIG. 1 shows the 27Al-NMR spectrum of Sample A. As shown in FIG. 1, it had a peak around 3 ppm. A slight peak was observed around 55 ppm. The area ratio of the peak near 55 ppm to the peak near 3 ppm was 15%.
  • FIG. 2 shows the 29Si-NMR spectrum of Sample A. As shown in FIG. 2, there were peaks at around -78 ppm and around -85 ppm.
  • FIG. 3 shows a transmission electron microscope (TEM) photograph of sample A observed at a magnification of 100,000.
  • the TEM observation was performed using a transmission electron microscope (H-7100FA, manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 100 kV.
  • a sample A to be observed with TEM was prepared as follows. That is, the solution after heating (aluminum silicate concentration of 47 g / L) before the final desalting treatment process was diluted 10 times with pure water and subjected to ultrasonic irradiation for 5 minutes. It was prepared by dropping it onto a support and then drying it naturally to form a thin film.
  • Metal ion adsorption capacity in water was evaluated by ICP emission spectroscopic analysis (ICP emission spectrophotometer: P-4010 (manufactured by Hitachi, Ltd.)).
  • a 100 ppm metal ion solution was prepared for each of Li + , Ni 2+, or Mn 2+ using each metal sulfate and pure water. It added so that the sample A might be 1.0 mass% with respect to the prepared solution, and it left still, after mixing sufficiently. Then, each metal ion concentration before and after the addition of sample A was measured by ICP emission spectroscopic analysis.
  • Sample B was commercially available activated carbon (manufactured by Wako Pure Chemical Industries, Ltd., activated carbon, crushed, 2 to 5 mm). Regarding the metal ion adsorption capacity in water, the concentrations after addition of Sample B were 50 ppm for Ni 2+ , 60 ppm for Mn 2+ , and 100 ppm for Li + .
  • Sample C was a commercially available silica gel (manufactured by Wako Pure Chemical Industries, Ltd., small granular (white)). Regarding the metal ion adsorption ability in water, the concentrations after addition of Sample C were 100 ppm for Ni 2+ , 100 ppm for Mn 2+ , and 80 ppm for Li + .
  • Example 2 ⁇ Preparation of aluminum silicate> A concentration: 74 mmol / L sodium orthosilicate aqueous solution (500 mL) was added to an aluminum chloride aqueous solution (500 mL) having a concentration of 180 mmol / L, followed by stirring for 30 minutes. To this solution, 93 mL of a 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 7.0.
  • centrifugal separation was performed for 5 minutes at a rotation speed of 3,000 rpm using a TOMY Corporation: Suprema 23 and standard rotor NA-16 as a centrifugal separator. After centrifugation, the supernatant solution was discharged, the gel precipitate was redispersed in pure water, and returned to the volume before centrifugation. Such desalting treatment by centrifugation was performed three times.
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was adjusted so as to have a concentration of 60 g / L, and it was used at normal temperature using FORI 55: F-55 and conductivity cell: 9382-10D.
  • the electrical conductivity was measured at 25 ° C. and found to be 1.3 S / m.
  • Pure water was added to the gel-like precipitate obtained after the supernatant was discharged for the third time in the desalting treatment to make the volume 12 L.
  • the silicon atom concentration and the aluminum atom concentration in the solution at this time were measured using an ICP emission spectrometer: P-4010 (manufactured by Hitachi, Ltd.), the silicon atom concentration was 2 mmol / L and the aluminum atom concentration was 4 mmol. / L.
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was adjusted so as to have a concentration of 60 g / L, and it was used at normal temperature using FORI 55: F-55 and conductivity cell: 9382-10D.
  • the electric conductivity was measured at 25 ° C., it was 0.6 S / m.
  • the BET specific surface area of Sample E was 323 m 2 / g, the total pore volume was 0.22 cm 3 / g, and the average pore diameter was 2.7 nm.
  • FIG. 1 shows the 27Al-NMR spectrum of Sample E. As shown in FIG. 1, it had a peak around 3 ppm. A slight peak was observed around 55 ppm. The area ratio of the peak around 55 ppm to the peak around 3 ppm was 4%.
  • FIG. 2 shows the 29Si-NMR spectrum of Sample E. As shown in FIG. 2, there were peaks near ⁇ 78 ppm and ⁇ 85 ppm. The peak areas around ⁇ 78 ppm and ⁇ 85 ppm were measured by the above method. As a result, when the area of peak A near ⁇ 78 ppm was 1.00, the area of peak B near ⁇ 85 ppm was 0.44.
  • FIG. 4 the transmission electron microscope (TEM) photograph when the sample E is observed by 100,000 times by the same method as Example 1 is shown.
  • TEM transmission electron microscope
  • Example 3 The sample A prepared in Example 1 was used, and the ability to adsorb metal ions in water was evaluated by the method described in Example 1 except that the addition amount of Sample A was changed as shown in the following table. The results are shown in the table below.
  • Example 4 Using the sample A prepared in Example 1, the metal ion adsorption ability in water was evaluated by the method described in Example 1 except that the metal ion species was changed to Cu 2+ and the metal ion adjustment concentration was changed to 400 ppm. . The pH at this time was 5.1. The concentration after addition of Sample A was 160 ppm for Cu 2+ .
  • DEC diethyl carbonate
  • EC ethylene carbonate
  • the specific aluminum silicates of Examples 1 and 2 exhibited Ni 2+ ion adsorption ability superior to silica gel, zeolite 4A, and zeolite 13X.
  • Example 6 The Ni 2+ ion adsorption ability in the model electrolyte was evaluated by the method described in Example 5 except that the amount of sample A added was changed as shown in the table below. The results are shown in the table below.
  • the positive electrode active material used in this example is LiMn 2 O 4 powder having an average particle size of 20 ⁇ m and a maximum particle size of 80 ⁇ m.
  • This positive electrode active material, natural graphite, and a 1-methyl-2-pyrrolidone solution of polyvinylidene fluoride were mixed and sufficiently kneaded to obtain a positive electrode slurry.
  • the mixing ratio of LiMn 2 O 4 , natural graphite, and polyvinylidene fluoride was 90: 6: 4 by mass ratio.
  • This slurry was applied to the surface of a positive electrode current collector made of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method so that the coating amount after drying was 250 g / m 2 .
  • This positive electrode was dried at 100 ° C. for 2 hours.
  • Specified aluminum silicate dispersion obtained by adding polyvinylidene fluoride as a binder to 15% by mass aqueous dispersion of the specific aluminum silicate (sample A) prepared in Example 1 to 5% by mass with respect to sample A was applied onto the positive electrode sheet by a doctor blade method and vacuum dried at 120 ° C. to prepare a positive electrode A.
  • the amount of sample A applied to the positive electrode A was 5 g / m 2 .
  • the negative electrode was produced by the following method. Artificial graphite powder having an average particle size of 10 ⁇ m was used as the negative electrode active material. Artificial graphite powder and polyvinylidene fluoride were mixed at a mass ratio of 90:10, 1-methyl-2-pyrrolidone was added as an organic solvent, and the mixture was sufficiently kneaded to prepare a negative electrode slurry. This slurry was applied to the surface of a negative electrode current collector made of a copper foil having a thickness of 10 ⁇ m by a doctor blade method so that the coating amount after drying was 75 g / m 2, and dried at 100 ° C. for 2 hours. A negative electrode was produced.
  • a polyethylene porous sheet having a thickness of 25 ⁇ m was used as a separator, and a solution obtained by dissolving LiPF 6 in a mixed solvent of 1: 1 volume ratio of diethyl carbonate and ethylene carbonate to a concentration of 1 mol / l was used as an electrolytic solution.
  • An aluminum laminate cell was produced.
  • An aluminum laminate cell uses a three-layer laminate film made of nylon film-aluminum foil-modified polyolefin film as an exterior material, and the lithium ion secondary in which the positive electrode, negative electrode, separator, electrolyte, etc. are enclosed in the exterior material. It is a battery.
  • the cell with sample A applied to the positive electrode showed similar initial capacity compared to the cell without sample A applied.
  • the battery was charged with a constant current until it reached 4.2 V with a current value of 0.2 C, and then was charged with a constant voltage at 4.2 V until the current value reached 0.01 mA. After standing for 30 minutes after the completion of charging, constant current discharge was performed at a current value of 0.5 C until the lithium ion secondary battery reached 3V.
  • the discharge capacity was measured with the current values of 1C, 2C, 3C, and 5C after charging under the same charging conditions, and the dependence of the discharge capacity on the discharge conditions was evaluated.
  • the cell in which the sample A was applied to the positive electrode had a lower discharge capacity reduction rate than the cell in which the sample A was not applied.
  • the cell in which the sample A was applied to the positive electrode had a smaller rate of increase in impedance after being left for 1 week at 50 ° C. than the cell in which the sample A was not applied.
  • Sample A applied to the positive electrode surface contributes to the extension of cell life and safety. This is presumed to be due to the adsorption of impurities eluted from the positive electrode from the evaluation results of the ion adsorption ability of sample A.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention se rapporte à une électrode positive pour des batteries rechargeables au lithium-ion, qui présente une excellente adsorbabilité des ions métalliques et une excellente sélectivité des ions métalliques. Une électrode positive pour des batteries rechargeables au lithium-ion selon la présente invention est pourvue d'un sel de silicate d'aluminium, qui présente un rapport molaire élémentaire entre le silicium (Si) et l'aluminium (Al), à savoir Si/Al, qui est égal ou supérieur à 0,3 mais inférieur à 1,0 sur la surface.
PCT/JP2012/078629 2011-11-15 2012-11-05 Électrode positive pour des batteries rechargeables au lithium-ion, et batterie rechargeable au lithium-ion qui utilise cette dernière WO2013073400A1 (fr)

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JP5879943B2 (ja) * 2011-11-15 2016-03-08 日立化成株式会社 リチウムイオン二次電池
WO2016098553A1 (fr) * 2014-12-17 2016-06-23 日立化成株式会社 Pile rechargeable au lithium-ion
KR102156472B1 (ko) * 2014-12-17 2020-09-15 히타치가세이가부시끼가이샤 리튬 이온 이차 전지
JP6960176B2 (ja) * 2018-03-12 2021-11-05 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤、これを用いた電極及び電極の製造方法
JP6678358B2 (ja) * 2018-03-12 2020-04-08 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤、これを用いた電極及び電極の製造方法
JP6635616B2 (ja) * 2018-10-10 2020-01-29 Ａｔｔａｃｃａｔｏ合同会社 非水電解質二次電池用の正極及びこれを用いた電池
JP7537752B2 (ja) * 2019-09-06 2024-08-21 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤、これを用いた電極及び電極の製造方法

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JPH11260416A (ja) * 1998-03-11 1999-09-24 Ngk Insulators Ltd リチウム二次電池
JP2000077103A (ja) * 1998-08-31 2000-03-14 Hitachi Ltd リチウム二次電池および機器
JP2001064010A (ja) * 1999-08-30 2001-03-13 Agency Of Ind Science & Technol 高濃度な無機溶液からのチューブ状アルミニウムケイ酸塩の合成法
JP2008179533A (ja) * 2006-12-27 2008-08-07 National Institute Of Advanced Industrial & Technology 中湿度領域において優れた水蒸気吸放湿特性を有する非晶質アルミニウムケイ酸塩
WO2009084632A1 (fr) * 2007-12-27 2009-07-09 National Institute Of Advanced Industrial Science And Technology Complexe de silicate d'aluminium et adsorbant haute performance comprenant celui-ci
JP2012146477A (ja) * 2011-01-12 2012-08-02 Hitachi Ltd 非水電解液電池
WO2012124222A1 (fr) * 2011-03-11 2012-09-20 日立化成工業株式会社 Silicate d'aluminium, adsorbant d'ions métalliques, et procédé de production associé

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11260416A (ja) * 1998-03-11 1999-09-24 Ngk Insulators Ltd リチウム二次電池
JP2000077103A (ja) * 1998-08-31 2000-03-14 Hitachi Ltd リチウム二次電池および機器
JP2001064010A (ja) * 1999-08-30 2001-03-13 Agency Of Ind Science & Technol 高濃度な無機溶液からのチューブ状アルミニウムケイ酸塩の合成法
JP2008179533A (ja) * 2006-12-27 2008-08-07 National Institute Of Advanced Industrial & Technology 中湿度領域において優れた水蒸気吸放湿特性を有する非晶質アルミニウムケイ酸塩
WO2009084632A1 (fr) * 2007-12-27 2009-07-09 National Institute Of Advanced Industrial Science And Technology Complexe de silicate d'aluminium et adsorbant haute performance comprenant celui-ci
JP2012146477A (ja) * 2011-01-12 2012-08-02 Hitachi Ltd 非水電解液電池
WO2012124222A1 (fr) * 2011-03-11 2012-09-20 日立化成工業株式会社 Silicate d'aluminium, adsorbant d'ions métalliques, et procédé de production associé

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