WO2014077113A1 - 負極活物質およびその製造方法、並びにリチウム二次電池 - Google Patents
負極活物質およびその製造方法、並びにリチウム二次電池 Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a negative electrode containing lithium-containing silicon oxide and a method for producing the same, and further to a lithium secondary battery using the negative electrode. Moreover, it is related with the evaluation method of a negative electrode active material.
- Patent Document 1 As a preferable method for producing an oxide or silicate of silicon containing lithium, lithium, silicon, and other simple elements such as silicon and other metal elements or non-metal elements, or a compound thereof, have a predetermined molar ratio. And a method of synthesizing by heating in air or an atmosphere containing oxygen, and an electrochemical reaction between silicon oxide such as silicon dioxide SiO 2 or silicon monoxide SiO and lithium or a substance containing lithium Therefore, a method of occluding lithium ions in a silicon oxide is described (Patent Document 1, paragraphs 0011 and 0016).
- Patent Documents 2 to 7 when a sufficient relaxation time is set for silicon oxide and measured by solid-state NMR (29SiDD / MAS), the spectrum shows a broad peak (A1) centered at -70 ppm and -110 ppm.
- the peak area ratio (A1 / A2) is measured in a range of 0.1 ⁇ A1 / A2 ⁇ 1.0. It is described that the filled silicon oxide is preferable as the electrode material.
- Patent 2999741 Japanese Patent No. 3952118 JP 2001-216916 A Japanese Patent No. 4752992 Japanese Patent No. 4288455 JP 2004-063433 A JP 2009-259723 A
- Patent Documents 2 to 7 describe determining the suitability as a negative electrode active material by measuring solid oxide (29SiDD / MAS) of silicon oxide. Since it is a measurement for a substance, it is not an evaluation in a lithium-doped state.
- silicon oxide When silicon oxide is used for the negative electrode of the battery, it is doped with lithium by charging.
- Patent Document 1 described above there are various methods for doping lithium with respect to silicon oxide, and evaluation of silicon oxide containing no lithium as in Patent Documents 2 to 7 is possible. Then, there is a limit in finding a negative electrode active material with excellent performance.
- the 29 Si-DDMAS spectrum of the silicon oxide changes, and the change varies greatly depending on the amount of lithium doped and the doping method. That is, in the 29 Si-DDMAS spectrum of silicon oxide after lithium doping, peaks appear in addition to the vicinity of ⁇ 70 ppm, ⁇ 84 ppm, and ⁇ 110 ppm described in Patent Documents 2 to 7, and these peaks are within an appropriate range. Without control, it is difficult to obtain a battery with excellent performance.
- an object of the present invention is to provide a lithium secondary battery negative electrode and a lithium secondary battery having excellent characteristics.
- the present invention is a negative electrode active material containing silicon oxide,
- silicon solid state NMR 29 Si-DDMAS
- a sum S2 of peak areas of a group of signals, each having a peak at ⁇ 100 ppm and ⁇ 120 ppm, attributed to Si having a Si (OH) 4-n (OSi) n (n 3,4) structure
- a group of signals having peaks at ⁇ 66 ppm, ⁇ 74 ppm, ⁇ 85 ppm, and ⁇ 96 ppm, respectively, belonging to Si having a structure of Si (OLi) 4-n (OSi) n (n 0, 1, 2, 3).
- a lithium secondary battery negative electrode and a lithium secondary battery having excellent characteristics can be provided. Furthermore, according to one embodiment of the present invention, a method for producing a lithium secondary battery negative electrode having excellent characteristics can be provided.
- FIG. 3 is a schematic cross-sectional view showing the structure of a laminated laminate type secondary battery.
- a solid NMR (29 Si-DDMAS) spectrum of silicon oxide doped with Li which is a diagram showing an example of a fitting thereto.
- Solid-state NMR 29 Si-DDMAS (Dipolar Decoupling / Magic Angle Spinning) peaks corresponding to the major Si present in Li-doped silicon oxide (including doped by charging) are divided into the following three groups: .
- S1 peak group A group of signals having peaks at chemical shifts of 0 to ⁇ 15 ppm, ⁇ 55 ppm, ⁇ 84 ppm and ⁇ 88 ppm, respectively (hereinafter, sometimes referred to as S1 peak group for simplicity). These peaks are attributed to Si having a Si—Si bond. The sum of the peak areas of the S1 peak group is defined as S1.
- each peak is represented by an arbitrary Gaussian function, and the original data is fitted by superimposing these Gaussian functions. After the superposition of the original data and the Gaussian function coincides, the intensity of each peak can be obtained by calculating the area of each peak.
- spinning sidebands generated by MAS Magnetic Angle Spinning
- Spinning sidebands and true peaks can be distinguished by measuring whether a peak shift occurs when the rotational speed of the MAS is changed. If a peak shift occurs, it is a spinning sideband, and if it does not occur, it is a true peak.
- the signal having a peak at ⁇ 84 ppm belonging to the S1 peak group and the ⁇ 85 ppm belonging to the S3 peak group are extremely close to each other.
- priority is given to a signal having a peak at ⁇ 85 ppm belonging to the S3 peak group among these two peaks, and the intensity of this peak increases when the matching rate with the original data is the same.
- the superposition is preferentially adopted.
- Origin OriginLab Corporation data analysis software, http://www.lightstone.co.jp/origin/pa.html Reference
- NLSF Nonlinear Least Squares Fitter-Nonlinear Curve Fitting Mechanism
- the solid NMR measurement is performed on the negative electrode after constituting the negative electrode using a negative electrode active material containing silicon oxide and charging at least once. That is, in the present invention, the performance of the negative electrode active material can be evaluated by measuring Si-NMR in a state in which it is charged at least once and occludes Li.
- a battery using a negative electrode active material can be evaluated by constituting a battery using a negative electrode active material, charging at least once, taking out the negative electrode, and performing NMR measurement as a measurement sample.
- NMR measurement As shown in the examples, it is preferable to actually make a battery and charge it at least once (for example, once) to measure NMR, but it is preferable to make a simulated battery instead. Also good.
- the NMR of the active material tends to deviate from the range of Formula 1 or Formula 2. Therefore, when the NMR of silicon oxide, which is a negative electrode active material in a charged state that has been charged and discharged twice or more, satisfies Formula 1 and Formula 2, the active material can be expressed by Formula 1 and Formula 1 even when charged once. It is estimated that Equation 2 is satisfied. Therefore, it is usually sufficient to measure NMR for the negative electrode after being charged once.
- the present invention provides both a negative electrode active material before charging (an active material before charging that satisfies Equations 1 and 2 after at least one charge) and a negative electrode active material after at least one charge. It is included as a scope of rights.
- silicon oxide and “negative electrode active material” may mean both before and after charging, or only one, but are apparent from the respective contexts. .
- the silicon having a Si—Si bond that gives the S1 peak group includes crystalline silicon, amorphous silicon, nanocluster silicon, and the like deposited in silicon oxide.
- filling a secondary battery shows a favorable charging / discharging cycling characteristic.
- the proportion of silicon having Si—Si bonds exceeds 0.55, the volume change of the silicon oxide accompanying charge / discharge increases, and as a result, the active material is liable to peel off and peel off from the electrode. Tends to get worse.
- the secondary battery negative electrode is obtained with excellent initial charge / discharge efficiency and charge / discharge cycle characteristics.
- the method for producing the negative electrode active material (active material before charging) of the present embodiment is not particularly limited, but is produced by lithium doping silicon oxide (hereinafter referred to as lithium pre-doping) before incorporation into the battery. It is preferable.
- Typical lithium pre-doping methods are (i) a method utilizing diffusion of lithium by heat (hereinafter referred to as thermal pre-doping), and (ii) a method for electrochemically doping lithium (hereinafter referred to as electrochemical pre-doping). However, other methods may be used.
- the thermal pre-doping method is performed by heating in a state where the silicon oxide and the lithium source are in contact with each other.
- the timing of contact is arbitrary, in one preferable embodiment, after producing a negative electrode using silicon oxide (it does not need to be the final shape as a negative electrode), it is mentioned later specifically.
- silicon oxide is applied onto a current collector together with a binder and optionally a conductivity imparting agent to form a predetermined shape, and then lithium is in a metal state or a compound having an activity close to that of a metal. Contact the negative electrode.
- the lithium source is preferably in the form of a sheet.
- the sheet-like lithium source include rolled lithium foil and vapor-deposited lithium foil.
- the base material of the sheet include metals such as copper and plastic films such as PET.
- Heating is performed after the lithium source is brought into contact with the electrode. At that time, if the melting point (180.5 ° C.) of the metallic lithium is exceeded, the molten lithium flows out to a place other than the electrode, and efficient diffusion is not performed. It is preferable.
- the heating temperature is preferably 70 ° C. or higher and 180.5 ° C. or lower, and more preferably 80 ° C. or higher and 150 ° C. or lower.
- the heating time depends on the heating temperature, it is generally 1 to 48 hours, preferably 8 to 16 hours. Since metallic lithium reacts violently with moisture, all operations are preferably performed in a low humidity environment.
- the thermal pre-doping may be performed by mixing silicon oxide (or a mixture containing silicon oxide and other battery materials) and a lithium source at any stage before forming the negative electrode, followed by heat treatment. it can.
- heat processing temperature is not specifically limited, For example, they are 70 degreeC or more and 800 degrees C or less.
- the lithium source include lithium metal, organic lithium compounds, lithium hydride, and lithium aluminum hydride. Even in the case of performing thermal pre-doping before forming the negative electrode, lithium metal is preferable as the lithium source, and the heating temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher and 150 ° C. or lower.
- the electrochemical pre-doping method uses a silicon oxide to produce a negative electrode (it may not be in the final shape as a negative electrode).
- a binder if necessary, together with a conductivity-imparting agent, applied onto a current collector to form a predetermined shape, which is then used as one electrode (working electrode), and metallic lithium or a substance containing lithium is added to the other electrode (
- As a counter electrode an electrochemical cell is constructed by contacting a lithium ion conductive non-aqueous electrolyte so that both electrodes face each other, and the working electrode is energized with an appropriate current in the direction of the cathode reaction to electrochemically convert lithium ions into silicon. This can be done by doping the oxide.
- the negative electrode active material satisfying the predetermined conditions defined in the present embodiment can be obtained by appropriately selecting these lithium pre-doping conditions and combining different conditions as necessary.
- the ratio of the areas of the S1 to S3 peak groups may be different. all right. That is, it was found that the state of silicon present in the silicon oxide differs depending on the lithium pre-doping conditions. Moreover, it turned out that the state of lithium distribution changes with conditions of lithium dope.
- a suitable combination of thermal pre-doping and electrochemical pre-doping More preferably, after the thermal pre-doping is performed, the electrochemical pre-doping is performed.
- the total lithium doping amount is 5% to 70%, preferably 15% to 40% so that silicon clusters do not grow. It is preferable to dope like this.
- thermal pre-doping lithium is doped relatively evenly into the silicon oxide. Once lithium is doped to some extent by thermal pre-doping, the required amount of lithium can be doped by electrochemical pre-doping while suppressing the growth of silicon clusters.
- Si (OLi) 4-n (OSi) n (n 0, 1, 2, 3)
- the ratio of silicon having a structure can be 0.21% or more.
- the silicon oxide before pre-doping is preferably in the range of about 0.5 to 1.6, more preferably 0.9 to 1.45, when expressed by SiO x .
- a desired silicon oxide can be obtained by appropriately selecting from such silicon oxides and performing the above-described pre-doping.
- Such a silicon oxide generally has a form in which small clusters of Si are dispersed in the oxide.
- the size and distribution of the Si clusters change, and Si- The area ratio of the S1 peak group attributed to Si having Si bonds changes.
- the lithium secondary battery of the present invention contains at least a silicon oxide satisfying the formulas 1 and 2 as described above as the negative electrode active material. Components of the negative electrode other than silicon oxide and other components of the battery will be described.
- the metal contained in the current collector is preferably a metal that does not form an alloy with Li.
- Examples of the current collector include copper, nickel, and alloys thereof.
- Examples of the shape of the current collector include foil, flat plate, and mesh.
- the current collector it is particularly preferable to use a foil or mesh mainly composed of copper.
- the ratio of copper in the current collector is preferably 97 to 100% by mass from the viewpoint of conductivity and heat resistance.
- the negative electrode active material contains at least a silicon oxide satisfying the formulas 1 and 2 as described above. Therefore, as the negative electrode active material, only the silicon oxide satisfying the above-described formulas 1 and 2 may be contained, but in addition to this, a known negative electrode active material may be used in combination.
- the active material other than silicon oxide include, for example, carbon materials such as graphite, coke, and hard carbon, lithium alloys such as lithium-aluminum alloy, lithium-lead alloy, and lithium-tin alloy, lithium metal, and SnO 2.
- SnO, TiO 2 , Nb 2 O 3, and the like are metal oxides whose base potential is lower than that of the lithium manganese composite oxide.
- an active material other than silicon oxide for example, a material containing graphite as a negative electrode active material in addition to the silicon oxide satisfying the formulas 1 and 2 is preferable. It is also preferred that the silicon oxide is coated with graphite.
- the content of the active material in the active material layer is preferably 40% by mass or more and 99% by mass or less, and 50% by mass or more and 95% by mass from the viewpoint of improving energy density. More preferably, it is 65 mass% or less, More preferably, it is 65 mass% or more and 90 mass% or less.
- the active material layer may contain a conductivity-imparting agent from the viewpoint of improving conductivity.
- a conductivity-imparting agent there are no particular restrictions on the conductivity-imparting agent, but known ones can be used, for example.
- the conductivity-imparting agent include carbon materials.
- the carbon material include graphite, amorphous carbon, diamond-like carbon, carbon black, ketjen black, acetylene black, vapor grown carbon fiber, fullerene, carbon nanotube, and a composite thereof.
- One of these conductivity-imparting agents may be used alone, or two or more thereof may be used in combination.
- graphite with high crystallinity has high electrical conductivity, and is excellent in adhesion to a current collector made of a metal such as copper and voltage flatness.
- amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
- the content of the conductive agent in the active material layer is preferably 1% by mass or more and 25% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. More preferably.
- the content is 1% by mass or more, sufficient conductivity can be maintained.
- the ratio of active material mass can be enlarged by making this content into 25 mass% or less, the capacity
- the binder is not particularly limited, and examples thereof include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, Polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
- the amount of the binder for the negative electrode to be used is preferably 7 to 20 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
- the binder is preferably polyimide or polyamideimide from the viewpoint of binding properties with the conductive intermediate layer. Moreover, it is preferable to use a polyamic acid as a precursor of a binder, and it is more preferable to use the same polyamic acid as the polyamic acid used for a conductive intermediate layer.
- the positive electrode active material is not particularly limited as long as lithium ions can be inserted during charge and desorbed during discharge.
- a known material can be used.
- the positive electrode active material is preferably a lithium transition metal oxide.
- the lithium transition metal oxide is not particularly limited.
- lithium manganate having a layered structure such as LiMnO 2 and Li x Mn 2 O 4 (0 ⁇ x ⁇ 2) or manganese having a spinel structure is used.
- LicoO 2 LiCoO 2 ; LiCoO 2 , LiNiO 2 or parts of these transition metals replaced with other metals; no more than half of specific transition metals such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 Examples thereof include lithium transition metal oxides; those having an olivine structure such as LiFePO 4 ; those lithium transition metal oxides in which Li is excessive in comparison with the stoichiometric composition.
- These materials can be used individually by 1 type or in combination of 2 or more types.
- the positive electrode according to the present embodiment may include a positive electrode conductivity imparting agent and a positive electrode binder in addition to the positive electrode active material.
- the positive electrode conductivity-imparting agent in addition to the carbon material mentioned as the negative electrode conductivity-imparting agent, a metal substance such as aluminum, a conductive oxide powder, or the like can be used.
- the positive electrode binder is not particularly limited.
- polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber Polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
- PVdF polyvinylidene fluoride
- PVdF polyvinylidene fluoride
- the content of the positive electrode binder in the positive electrode active material layer is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass. More preferably, it is% or less.
- production of electrode peeling can be prevented by making this content into 1 mass% or more.
- the ratio of positive electrode active material mass can be enlarged by making this content into 25 mass% or less, the capacity
- nickel, copper, silver, aluminum, and alloys thereof are preferable from the viewpoint of electrochemical stability.
- the shape include foil, flat plate, and mesh. In particular, aluminum foil is preferable.
- a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
- the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
- the positive electrode can be produced, for example, by preparing a positive electrode slurry by mixing lithium manganese composite oxide, a conductive agent and a positive electrode binder, and forming the positive electrode slurry on a positive electrode current collector.
- electrolyte for example, a liquid electrolyte (electrolytic solution) can be used.
- electrolytic solution containing an electrolyte salt and a nonaqueous electrolytic solvent is used.
- the nonaqueous electrolytic solvent is not particularly limited, but from the viewpoint of being stable at a lithium metal potential, cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate; dimethyl carbonate, diethyl carbonate, ethyl Examples thereof include chain carbonates such as methyl carbonate and dipropyl carbonate; and lactones such as ⁇ -butyrolactone.
- a non-aqueous electrolyte can be used individually by 1 type or in combination of 2 or more types.
- electrolyte salt is not particularly limited, for example, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li (CF 3 SO 2 ) 2 and LiN (CF 3 SO 2 ) 2 and the like.
- the electrolyte salt can be used singly or in combination of two or more.
- an ionic liquid can be used as the electrolytic solution.
- the ionic liquid include quaternary ammonium-imide salts.
- a solid electrolyte may be used instead of a liquid electrolyte.
- a separator in particular is not restrict
- a well-known separator is employable.
- a porous film such as polypropylene or polyethylene or a nonwoven fabric can be used.
- a polyimide or aramid film, a cellulose film, or the like can be used.
- the exterior body can be used without particular limitation as long as it is stable to the electrolyte and has a sufficient water vapor barrier property.
- a metal can such as iron or aluminum alloy, a laminate film, or the like can be used.
- the laminate film is preferably a laminate film obtained by vapor-depositing aluminum or silica from the viewpoint of water vapor barrier properties.
- the configuration of the secondary battery according to the present embodiment is not particularly limited, and for example, an electrode element in which a positive electrode and a negative electrode are opposed to each other and an electrolytic solution may be included in an exterior body. it can.
- the shape of the secondary battery is not particularly limited, and examples thereof include a cylindrical shape, a flat wound rectangular shape, a laminated rectangular shape, a coin shape, a flat wound laminated shape, and a laminated laminated shape.
- FIG. 1 is a schematic cross-sectional view showing a structure of an electrode element included in a laminated secondary battery using a laminate film as an exterior body.
- This electrode element is formed by alternately stacking a plurality of positive electrodes c and a plurality of negative electrodes a with a separator b interposed therebetween.
- the positive electrode current collector e of each positive electrode c is welded to and electrically connected to each other at an end portion not covered with the positive electrode active material, and a positive electrode terminal f is welded to the welded portion.
- the negative electrode current collector d of each negative electrode a is welded and electrically connected to each other at an end portion not covered with the negative electrode active material, and a negative electrode terminal g is welded to the welded portion.
- the electrode element having such a planar laminated structure does not have a portion with a small R (a region close to the core of the concentric winding structure or a folded region corresponding to the end of the flat winding structure), Compared to an electrode element having a rotating structure, there is an advantage that it is less likely to be adversely affected by the volume change of the electrode accompanying charge / discharge. That is, it is effective as an electrode element using an active material that easily causes volume expansion.
- an electrode element having a wound structure since the electrode is curved, the structure is easily distorted when a volume change occurs.
- a negative electrode active material having a large volume change due to charge / discharge such as silicon oxide
- a secondary battery using an electrode element having a wound structure is considered to have a large capacity drop due to charge / discharge. .
- SiO (trade name: “SIO05PB”, High Purity Chemical Research Laboratories), carbon black (trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation), and polyamic acid (trade name: “U-Varnish”) A ”and Ube Industries, Ltd.) were weighed at a mass ratio of 80: 5: 15, respectively.
- NMP n-methylpyrrolidone
- the slurry was applied onto a copper foil using a doctor blade. Then, it heated at 120 degreeC for 7 minute (s), and dried NMP. Then, it heated at 350 degreeC for 30 minute (s) using the electric furnace in nitrogen atmosphere, and produced the negative electrode.
- the lithium foil was brought into contact with the negative electrode and kept at 85 ° C. for 8 hours under a nitrogen atmosphere. From the change in weight of the negative electrode, the amount of lithium doped in the negative electrode was determined. The amount of lithium doped per 1 mol of SiO was 1.62 mol.
- lithium was electrochemically doped into the negative electrode using a beaker cell.
- the counter electrode of the beaker cell contains a metal lithium foil, the electrolyte contains 1.0 mol / l LiPF 6 and a mixed solvent of ethylene carbonate and diethyl carbonate (7: 3 (volume ratio)) as a nonaqueous electrolytic solvent.
- the solution was used.
- the amount of lithium doped in the negative electrode was determined from the amount of coulomb.
- the amount of lithium doped per 1 mol of SiO was 1.78 mol.
- Lithium cobaltate manufactured by Nichia Corporation
- carbon black trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation
- polyvinylidene fluoride trade name: “# 2400”, Co., Ltd.
- Kureha Lithium cobaltate
- carbon black trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation
- polyvinylidene fluoride trade name: “# 2400”, Co., Ltd.
- Kureha Lithium cobaltate (manufactured by Nichia Corporation), carbon black (trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation), and polyvinylidene fluoride (trade name: “# 2400”, Co., Ltd.) Kureha) were weighed at a mass ratio of 95: 2: 3, respectively.
- These and NMP were mixed to form a slurry.
- the mass ratio of NMP to solid content was 52:48.
- the slurry was applied to an aluminum foil having a thickness of 15 ⁇ m using a doctor blade.
- An aluminum terminal and a nickel terminal were welded to each of the produced positive electrode and negative electrode. These were overlapped via a separator to produce an electrode element. Note that the masses of the positive electrode and the negative electrode were adjusted so that the lithium doping amount with respect to SiO, which is the negative electrode active material, was an arbitrary value when fully charged. Further, a nickel terminal was welded to a reference electrode in which copper foil and lithium metal were bonded together, and was superimposed on the negative electrode via a separator. The electrode element and the reference electrode were covered with a laminate film, and an electrolyte solution was injected into the laminate film. Thereafter, the laminate film was heat-sealed and sealed while reducing the pressure inside the laminate film.
- a polypropylene film was used as the separator.
- a polypropylene film on which aluminum was deposited was used.
- the electrolytic solution a solution containing 1.0 mol / l LiPF 6 as an electrolyte and a mixed solvent of ethylene carbonate and diethyl carbonate (7: 3 (volume ratio)) as a nonaqueous electrolytic solvent was used.
- NMR measurement After charging the produced secondary battery once, the battery was disassembled in an argon atmosphere, the negative electrode was taken out, the negative electrode layer was peeled off from the current collector, put into a sample tube, and a sample for NMR measurement. did. Using this sample, solid-state NMR (29SiDD / MAS) was measured, and peaks were analyzed by the method described in the text to determine the areas of S1, S2, and S3. Table 1 shows the results of S1 / (S1 + S2 + S3) and S3 / (S1 + S2 + S3).
- Example 2 The heating time when the negative electrode was thermally doped with lithium was set to 6 hours. The amount of dope was 1.39 mol. Further, the lithium dope amount using the beaker cell was changed by 2.01 mol. Otherwise, a battery was prepared and evaluated in the same manner as in Example 1.
- Example 3 The heating time when the negative electrode was thermally doped with lithium was set to 4 hours.
- the dope amount was 1.21 mol.
- the amount of lithium dope using a beaker cell was changed by 2.19 mol. Otherwise, a battery was prepared and evaluated in the same manner as in Example 1.
- Example 4 The heating time for thermally doping lithium into the negative electrode was set to 2 hours. The dope amount was 1.02 mol. Further, the lithium doping amount using the beaker cell was changed by 2.38 mol. Otherwise, a battery was prepared and evaluated in the same manner as in Example 1.
- Comparative Examples 1 and 2 have high initial charge / discharge efficiency, but the capacity retention rate after 200 cycles is low, and Comparative Example 3 has high capacity retention rate after 200 cycles. Is low.
- Comparative Example 3 has high capacity retention rate after 200 cycles. Is low.
- both the initial charge / discharge efficiency and the capacity retention rate after 200 cycles were high, and the present invention can provide a secondary battery having high energy density and good charge / discharge cycle characteristics.
- Comparative Examples 1 and 2 have a higher proportion of silicon having Si—Si bonds than Comparative Example 3.
- the ratio of silicon having Si—Si bonds is suppressed to the same level as in Comparative Example 3.
Abstract
Description
少なくとも1回充電した後のケイ素酸化物について、ケイ素の固体NMR(29Si-DDMAS)測定を行ったとき、
Si-Si結合を有するSiに帰属される、0~-15ppm、-55ppm、-84ppmおよび-88ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S1と、
Si(OH)4-n(OSi)n(n=3,4)構造を持つSiに帰属される、-100ppmおよび-120ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S2と、
Si(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiに帰属される、-66ppm、-74ppm、-85ppmおよび-96ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S3と
が下記の式1および式2:
(式1) 0.42≦S1/(S1+S2+S3) ≦0.55
(式2) 0.21≦S3/(S1+S2+S3) ≦0.26
を満たすことを特徴とする。
S1~S3の求め方について説明する。Liをドープしたケイ素酸化物(充電によるドープを含む)中に存在する主要なSiに対応する固体NMR(29Si-DDMAS(Dipolar Decoupling/Magic Angle Spinning))ピークを、次の3つのグループに分ける。
化学シフト0~-15ppm、-55ppm、-84ppmおよび-88ppmにそれぞれピークを持つ一群のシグナル(以下、簡単のためにS1ピーク群と呼ぶことがある。)。これらのピークは、Si-Si結合を有するSiに帰属される。S1ピーク群のピーク面積の和をS1とする。
化学シフト-100ppm、-120ppmにピークを持つ一群のシグナル(以下、簡単のためにS2ピーク群と呼ぶことがある。)。これらのピークは、Si(OH)4-n(OSi)n(n=3,4)構造を持つSiに帰属される。S2ピーク群のピーク面積の和をS2とする。
化学シフト-66ppm、-74ppm、-85ppm、-96ppmにピークを持つ一群のシグナル(以下、簡単のためにS3ピーク群と呼ぶことがある。)。これらのピークは、Si(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiに帰属される。S3ピーク群のピーク面積の和をS3とする。
Liをドープしたケイ素酸化物(充電によるドープを含む)の固体NMR(29Si-DDMAS)スペクトルは、図2に1例を示すように、S1~S3ピーク群が重なりあっている。
本発明者らは鋭意検討したところ、リチウム含有ケイ素酸化物の負極活物質としての特性、すなわち、初回充放電効率と充放電サイクル特性は、ケイ素酸化物中の、Si-Si結合を有するSi、Si(OH)4-n(OSi)n(n=3,4)構造を持つSi、およびSi(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiの比率に関係することを発見した。
(式1) 0.42≦S1/(S1+S2+S3) ≦0.55
を満たすとき、二次電池は良好な充放電サイクル特性を示す。Si-Si結合を有するケイ素の占める割合が0.55を超えると、充放電に伴うケイ素酸化物の体積変化が大きくなり、その結果、電極からの活物質の剥離、剥落が起こりやすくなりサイクル特性が悪くなりやすい。
(式2) 0.21≦S3/(S1+S2+S3) ≦0.26
を満たすとき、二次電池は良好な充放電効率を示す。
(集電体)
集電体に含まれる金属は、Liと合金を形成しない金属であることが好ましい。集電体としては、例えば、銅、ニッケル、それらの合金等が挙げられる。集電体の形状としては、箔、平板状、メッシュ状が挙げられる。
本発明では、負極活物質として、前述のとおり式1および式2を満たすケイ素酸化物を少なくとも含有する。従って、負極活物質として、前述の式1および式2を満たすケイ素酸化物のみを含有してもよいが、これに加えて、公知の負極活物質を組み合わせて用いてもよい。
また、活物質層は、導電性を向上させる観点から、導電付与剤を含んでも良い。導電付与剤としては、特に制限されるものはないが、例えば、公知のものを用いることができる。導電付与剤としては、例えば炭素材料が挙げられる。炭素材料としては、例えば、黒鉛、非晶質炭素、ダイヤモンド状炭素、カーボンブラック、ケッチェンブラック、アセチレンブラック、気相成長炭素繊維、フラーレン、カーボンナノチューブ、これらの複合物等が挙げられる。これらの導電付与剤は一種を単独で用いてもよく、二種以上を併せて用いてもよい。なお、結晶性の高い黒鉛は、電気伝導性が高く、銅などの金属からなる集電体との接着性および電圧平坦性が優れている。一方、結晶性の低い非晶質炭素は、体積膨張が比較的小さいため、負極全体の体積膨張を緩和する効果が高く、かつ結晶粒界や欠陥といった不均一性に起因する劣化が起きにくい。
結着剤としては、特に制限されるものではないが、例えば、ポリフッ化ビニリデン、ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体、ビニリデンフルオライド-テトラフルオロエチレン共重合体、スチレン-ブタジエン共重合ゴム、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミドイミド等を用いることができる。使用する負極用結着剤の量は、トレードオフの関係にある「十分な結着力」と「高エネルギー化」の観点から、負極活物質100質量部に対して、7~20質量部が好ましい。
本実施形態において、正極活物質は、リチウムイオンを充電時に挿入、放電時に脱離することができれば、特に限定されるものでなく、例えば公知のものを用いることができる。また、正極活物質としては、リチウム遷移金属酸化物であることが好ましい。リチウム遷移金属酸化物としては、特に制限されるものではないが、例えば、LiMnO2、LixMn2O4(0<x<2)等の層状構造を持つマンガン酸リチウムまたはスピネル構造を有するマンガン酸リチウム;LiCoO2、LiNiO2またはこれらの遷移金属の一部を他の金属で置き換えたもの;LiNi1/3Co1/3Mn1/3O2などの特定の遷移金属が半数を超えないリチウム遷移金属酸化物;LiFePO4などのオリビン構造を有するもの;これらのリチウム遷移金属酸化物において化学量論組成よりもLiを過剰にしたもの等が挙げられる。特に、LiαNiβCoγAlδO2(1≦α≦1.2、β+γ+δ=1、β≧0.7、γ≦0.2)またはLiαNiβCoγMnδO2(1≦α≦1.2、β+γ+δ=1、β≧0.6、γ≦0.2)が好ましい。これらの材料は、一種を単独で、または二種以上を組み合わせて使用することができる。
電解質としては、例えば、液状の電解質(電解液)を用いることができる。好ましい1実施形態においては、特に制限されるものではないが、例えば、電解質塩と非水電解溶媒とを含む電解液を使用する。
セパレータは、特に制限されるものではなく、例えば、公知のセパレータを採用することができる。セパレータとしては、例えば、ポリプロピレン、ポリエチレン等の多孔質フィルムや不織布を用いることができる。また、ポリイミドやアラミドのフィルム、セルロースのフィルム等を用いることもできる。
外装体としては、電解液に安定で、かつ十分な水蒸気バリア性を有するものであれば特に制限されずに用いることができる。外装体としては、例えば鉄やアルミ合金等の金属缶、ラミネートフィルム等を用いることができる。ラミネートフィルムとしては、水蒸気バリア性の観点からアルミニウムやシリカを蒸着したラミネートフィルムであることが好ましい。
本実施形態に係る二次電池の構成は、特に制限されるものではなく、例えば、正極および負極が対向配置された電極素子と、電解液とが外装体に内包されている構成とすることができる。二次電池の形状は、特に制限されるものではないが、例えば、円筒型、扁平捲回角型、積層角型、コイン型、扁平捲回ラミネート型、又は積層ラミネート型が挙げられる。
(負極の作製)
コバルト酸リチウム(日亜化学工業(株)製)と、カーボンブラック(商品名:「#3030B」、三菱化学(株)製)と、ポリフッ化ビニリデン(商品名:「#2400」、(株)クレハ製)とを、それぞれ95:2:3の質量比で計量した。これらと、NMPとを混合し、スラリーとした。NMPと固形分との質量比は52:48とした。該スラリーを厚さ15μmのアルミニウム箔にドクターブレードを用いて塗布した。該スラリーの塗布されたアルミニウム箔を120℃で5分間加熱してNMPを乾燥させ、正極を作製した。
作製した正極および負極のそれぞれに、アルミニウム端子、ニッケル端子を溶接した。これらを、セパレータを介して重ね合わせて電極素子を作製した。なお、正極と負極の質量は、満充電状態時に負極活物質であるSiOに対するリチウムのドープ量が任意の値になるように調整した。また、銅箔とリチウム金属とを貼り合わせた参照極にニッケル端子を溶接し、セパレータを介して負極と重ね合わせた。電極素子と参照極とをラミネートフィルムで外装し、ラミネートフィルム内部に電解液を注入した。その後、ラミネートフィルム内部を減圧しながらラミネートフィルムを熱融着して封止した。これにより平板型の初回充電前の二次電池を作製した。なお、セパレータにはポリプロピレンフィルムを用いた。ラミネートフィルムにはアルミニウムを蒸着したポリプロピレンフィルムを用いた。電解液には、電解質として1.0mol/lのLiPF6と、非水電解溶媒としてエチレンカーボネート及びジエチルカーボネートの混合溶媒(7:3(体積比))を含む溶液を用いた。
作製した二次電池に対し、電池電圧が2.5~4.2Vの範囲で充放電サイクル試験を行った。充電は、CCCV方式で行い、4.2Vに達した後は電圧を一定に一時間保った。放電は、CC方式(一定電流0.2C)で行った。ここで、0.2C電流とは、任意の満充電状態の電池を定電流放電させた場合、完全に放電させるまで5時間かかる電流のことを意味する。初回充放電効率とサイクル特性の結果を表1に示す。
作製した二次電池に対して、1回充電を行った後、電池をアルゴン雰囲気中で、分解して、負極を取り出して集電体から負極層を剥がしサンプルチューブに入れてNMR測定用試料とした。この試料を用いて、固体NMR(29SiDD/MAS)を測定し、本文記載のとおりの方法により、ピークの解析を行ってS1、S2、S3の面積を求めた。S1/(S1+S2+S3)とS3/(S1+S2+S3)の結果を表1に示す。
負極にリチウムを熱ドープする際の加熱時間を6時間にした。そのドープ量は1.39モルであった。またビーカーセルを用いたリチウムドープ量を、2.01モル変更した。それ以外は、実施例1と同様に電池を作製し評価を行った。
負極にリチウムを熱ドープする際の加熱時間を4時間にした。そのドープ量は1.21モルであった。またビーカーセルを用いたリチウムドープ量を、2.19モル変更した。それ以外は、実施例1と同様に電池を作製し評価を行った。
負極にリチウムを熱ドープする際の加熱時間を2時間にした。そのドープ量は1.02モルであった。またビーカーセルを用いたリチウムドープ量を、2.38モル変更した。それ以外は、実施例1と同様に電池を作製し評価を行った。
負極にリチウムを熱ドープする際の加熱時間を18時間にした。そのドープ量は3.14モルであった。ビーカーセルを用いたリチウムドープを行わなかった。それ以外は、実施例1と同様に電池を作製し評価を行った。
負極に加熱によるリチウムドープは行わなかった。またビーカーセルを用いたリチウムドープ量を、3.40モル変更した。それ以外は、実施例1と同様に電池を作製し評価を行った。
負極に加熱よるリチウムドープ、ビーカーセルによるリチウムドープのいずれも行わなかった。それ以外は、実施例1と同様に電池を作製し評価を行った。
Claims (10)
- ケイ素酸化物を含有する負極活物質であって、
少なくとも1回充電した後のケイ素酸化物について、ケイ素の固体NMR(29Si-DDMAS)測定を行ったとき、
Si-Si結合を有するSiに帰属される、0~-15ppm、-55ppm、-84ppmおよび-88ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S1と、
Si(OH)4-n(OSi)n(n=3,4)構造を持つSiに帰属される、-100ppmおよび-120ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S2と、
Si(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiに帰属される、-66ppm、-74ppm、-85ppmおよび-96ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S3と
が下記の式1および式2:
(式1) 0.42≦S1/(S1+S2+S3) ≦0.55
(式2) 0.21≦S3/(S1+S2+S3) ≦0.26
を満たすことを特徴とする負極活物質。 - 1回の充電後に、前記式1および式2の条件を満たすことを特徴とする負極活物質。
- リチウムがプレドープされているケイ素酸化物を含有する負極活物質であって、少なくとも1回充電した後に、前記式1および式2の条件を満たすことを特徴とする請求項1または2に記載の負極活物質。
- (i)熱によるリチウムの拡散を利用する方法、および(ii)電気化学的にリチウムをドープする方法の少なくとも1つ方法を利用して、リチウムをケイ素酸化物にプレドープしたことを特徴とする請求項3記載の負極活物質。
- (i)熱によるリチウムの拡散を利用してプレドープした後、(ii)電気化学的にリチウムをドープする方法を利用してプレドープしたことを特徴とする請求項4記載の負極活物質。
- 請求項1~5の少なくとも1項に記載の負極活物質、結着剤および集電体を有する負極、正極および電解質を有するリチウム二次電池。
- ケイ素酸化物を含有する負極活物質の製造方法であって、
ケイ素酸化物にリチウムをドープする工程を有し、
少なくとも1回充電した後のケイ素酸化物について、ケイ素の固体NMR(29Si-DDMAS)測定を行ったとき、
Si-Si結合を有するSiに帰属される、0~-15ppm、-55ppm、-84ppmおよび-88ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S1と、
Si(OH)4-n(OSi)n(n=3,4)構造を持つSiに帰属される、-100ppmおよび-120ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S2と、
Si(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiに帰属される、-66ppm、-74ppm、-85ppmおよび-96ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S3と
が下記の式1および式2:
(式1) 0.42≦S1/(S1+S2+S3) ≦0.55
(式2) 0.21≦S3/(S1+S2+S3) ≦0.26
を満たすように、前記のケイ素酸化物にリチウムをドープする工程においてリチウムをドープすることを特徴とする負極活物質の製造方法。 - (i)熱によるリチウムの拡散を利用する方法、および(ii)電気化学的にリチウムをドープする方法の少なくとも1つ方法を利用して、ケイ素酸化物にリチウムをドープすることを特徴とする請求項7に記載の負極活物質の製造方法。
- 前記ケイ素酸化物に対して、(i)熱によるリチウムの拡散を利用する方法によりリチウムをドープした後、(ii)電気化学的にリチウムをドープする方法によりリチウムをドープすることを特徴とする請求項8に記載の負極活物質の製造方法。
- ケイ素酸化物を含有する負極活物質の評価方法であって、
少なくとも1回充電した後のケイ素酸化物について、ケイ素の固体NMR(29Si-DDMAS)測定を行ったとき、
Si-Si結合を有するSiに帰属される、0~-15ppm、-55ppm、-84ppmおよび-88ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S1と、
Si(OH)4-n(OSi)n(n=3,4)構造を持つSiに帰属される、-100ppmおよび-120ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S2と、
Si(OLi)4-n(OSi)n(n=0,1,2,3)構造を持つSiに帰属される、-66ppm、-74ppm、-85ppmおよび-96ppmにそれぞれピークを持つ一群のシグナルのピーク面積の和S3と
が下記の式1および式2:
(式1) 0.42≦S1/(S1+S2+S3) ≦0.55
(式2) 0.21≦S3/(S1+S2+S3) ≦0.26
を満たすか否かによって、負極活物質を選別することを特徴とする負極活物質の評価方法。
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CN104781959B (zh) | 2017-07-04 |
JPWO2014077113A1 (ja) | 2017-01-05 |
JP6314831B2 (ja) | 2018-04-25 |
CN104781959A (zh) | 2015-07-15 |
US20160285091A1 (en) | 2016-09-29 |
EP2922120A4 (en) | 2016-11-30 |
US9985286B2 (en) | 2018-05-29 |
EP2922120A1 (en) | 2015-09-23 |
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