WO2012086277A1 - 非水電解質二次電池用正極及びその正極を用いた非水電解質二次電池 - Google Patents
非水電解質二次電池用正極及びその正極を用いた非水電解質二次電池 Download PDFInfo
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- WO2012086277A1 WO2012086277A1 PCT/JP2011/071484 JP2011071484W WO2012086277A1 WO 2012086277 A1 WO2012086277 A1 WO 2012086277A1 JP 2011071484 W JP2011071484 W JP 2011071484W WO 2012086277 A1 WO2012086277 A1 WO 2012086277A1
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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
- 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
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the positive electrode.
- Lithium ion batteries that charge and discharge when lithium ions move between the positive and negative electrodes along with charge and discharge have high energy density and high capacity. Widely used.
- the mobile information terminal has a tendency to further increase power consumption with enhancement of functions such as a video playback function and a game function, and a further increase in capacity is strongly desired.
- a measure to increase the capacity of the non-aqueous electrolyte secondary battery in addition to a measure to increase the capacity of the active material and a measure to increase the filling amount of the active material per unit volume, the charge voltage of the battery is increased.
- the charging voltage of the battery is increased, there is a problem that the electrolytic solution is easily decomposed. In particular, when the battery is stored at a high temperature or a charge / discharge cycle is repeated at a high temperature, the discharge capacity is reduced.
- proposals have been made to use a mixture of lithium cobaltate and nickel cobalt lithium manganate as the positive electrode active material.
- the present invention includes a positive electrode active material composed of a mixture of lithium cobaltate and nickel cobalt lithium manganate having a rare earth compound fixed on a part of the surface, and a binder, and the nickel cobalt relative to the total amount of the positive electrode active material.
- the ratio of lithium manganate is 1 to 50% by mass.
- the present invention even when continuously charged at a high temperature or the like, it is possible to suppress a decrease in discharge capacity and a decrease in discharge voltage. There is an excellent effect that can be suppressed.
- FIG. 2 is a cross-sectional view taken along line AA in FIG. 1.
- Explanatory drawing which shows the surface state of the lithium cobaltate used in embodiment of this invention.
- Explanatory drawing which shows the surface state different from the surface state of the lithium cobaltate used in embodiment of this invention.
- the present invention includes a positive electrode active material composed of a mixture of lithium cobaltate and nickel cobalt lithium manganate having a rare earth compound fixed on a part of the surface, and a binder, and the nickel cobalt relative to the total amount of the positive electrode active material.
- the ratio of lithium manganate is 1 to 50% by mass. If it is the said structure, since it is a case where it exposes to a high temperature state in a charged state etc., since decomposition
- nickel cobalt lithium manganate When lithium cobaltate and nickel cobalt manganate with exposed surfaces are mixed, nickel cobalt lithium manganate is further activated by the high catalytic properties of lithium cobaltate. For this reason, especially when exposed to a high temperature in a charged state (high voltage), cobalt, nickel, and manganese are eluted from the positive electrode active material, or the electrolytic solution is decomposed, and this decomposition product is deposited on the surface of the positive electrode active material. Or stick. As a result, an inactive layer is formed on the surface of the positive electrode active material, and the discharge performance is greatly reduced.
- lithium cobaltate having a rare earth compound fixed on a part of its surface when lithium cobaltate having a rare earth compound fixed on a part of its surface is used, the catalytic properties of cobalt in lithium cobaltate are reduced due to the presence of the rare earth compound. Since it acts, the effect which suppresses elution of nickel, cobalt, and manganese is exhibited. Moreover, since the activation of the lithium nickel cobalt manganate can be suppressed in this way, the activation of the lithium cobalt oxide can be further suppressed, so that the decomposition of the electrolytic solution can be further suppressed. By exhibiting such a synergistic effect, it is possible to suppress the formation of an inactive layer on the surface of the positive electrode active material, and as a result, the discharge performance is dramatically improved.
- the decomposition of the electrolyte and the positive electrode active material are performed. Elution of metals in the substance can be effectively suppressed. Therefore, even after continuous charging at a high temperature, not only the discharge capacity is high, but also a decrease in discharge voltage can be suppressed, and a battery having a high energy density can be obtained even after being exposed to harsh conditions.
- the state in which the rare earth compound is fixed to a part of the surface of the lithium cobaltate means that most of the rare earth compound (peeled off by an external force during the production of the positive electrode) on the surface of the lithium cobaltate particles 21 as shown in FIG. Meaning all the rare earth compounds except the rare earth compounds). That is, in this state, as shown in FIG. 4, lithium cobalt oxide particles 21 and rare earth compound particles 22 are simply mixed, and some rare earth compound particles 22 happen to be in contact with lithium cobalt oxide particles 21. Is not included.
- the rare earth compound means a compound of at least one element selected from the group consisting of rare earth elements.
- the rare earth compound may be an erbium compound (erbium hydroxide or erbium oxyhydroxide) alone. And a mixture of an erbium compound and an yttrium compound (yttrium hydroxide or yttrium oxyhydroxide).
- the reason why the ratio of lithium nickel cobalt manganate to the total amount of the positive electrode active material is regulated to 1% by mass or more and 50% by mass or less is as follows.
- the ratio of lithium nickel cobalt manganate to the total amount of the positive electrode active material is less than 1% by mass, the amount of lithium cobalt oxide becomes excessive, so even if a rare earth compound is fixed to a part of the surface, the electrolyte solution The amount of decomposition increases and the discharge voltage may decrease.
- the proportion of lithium nickel cobalt manganate relative to the total amount of the positive electrode active material exceeds 50% by mass, the proportion of nickel cobalt lithium manganate becomes too high and activation of lithium nickel cobalt manganate cannot be sufficiently suppressed.
- the ratio of lithium nickel cobalt manganate to the total amount of the positive electrode active material is desirably 3% by mass or more and 30% by mass or less, and particularly 5% by mass or more and 20% by mass or less. It is desirable.
- a rare earth compound is fixed to a part of the surface of the lithium nickel cobalt manganate. If the rare earth compound is fixed not only to lithium cobaltate but also to a part of the surface of nickel cobalt lithium manganate, the capacity retention rate after continuous charging at a high temperature is further increased. This is because nickel cobalt lithium manganate also contains cobalt, nickel, etc., so the electrolytic solution may decompose, but if a rare earth compound is fixed to a part of the surface, the nickel cobalt lithium manganate This is because the decomposition reaction of the electrolytic solution on the surface can be suppressed.
- the average particle size of the rare earth compound is desirably 100 nm or less.
- the average particle size of the rare earth compound (including not only the rare earth compound fixed to a part of the surface of the lithium cobaltate but also the rare earth compound fixed to a part of the surface of the nickel cobalt lithium manganate) exceeds 100 nm Even if the rare-earth compound having the same mass is fixed, the fixing part is partially biased, and thus the above-described effect may not be sufficiently exhibited.
- the lower limit of the average particle size of the rare earth compound is preferably 0.1 nm or more, and particularly preferably 1 nm or more. When the average particle size of the rare earth compound is less than 0.1 nm, the rare earth compound is too small and covers the surface of the positive electrode active material excessively.
- the rare earth compound is at least one selected from the group consisting of rare earth hydroxides, rare earth oxyhydroxides, and rare earth carbonate compounds.
- the rare earth element of the rare earth compound is at least one element selected from erbium, neodymium, samarium, and lanthanum.
- the rare earth compound is a hydroxide (for example, erbium hydroxide), an oxyhydroxide (for example, erbium oxyhydroxide) of at least one element selected from erbium, neodymium, samarium, and lanthanum
- the carbonic acid compound is selected from at least one of erbium carbonate (for example, erbium carbonate). When these are used, the effect of suppressing the activity on the lithium cobalt oxide surface is high, and the effect when combined with nickel cobalt lithium manganate is further exhibited.
- a positive electrode for a non-aqueous electrolyte secondary battery (hereinafter, simply referred to as a positive electrode), a negative electrode containing a negative electrode active material, and a separator disposed between the two electrodes and impregnated with an electrolyte.
- an inorganic particle layer containing inorganic particles is formed between the separator and the positive electrode. This is because, when an inorganic particle layer containing inorganic particles is formed between the separator and the positive electrode, contact between the positive electrode active material and the electrolytic solution can be further suppressed, so that decomposition of the electrolytic solution can be further suppressed.
- the inorganic particle layer is formed by directly applying the inorganic particle-containing slurry to the surface of the positive electrode or the surface of the separator on the positive electrode side. Or it can form by sticking the sheet
- the thickness of the inorganic particle layer is preferably regulated to 1 ⁇ m or more and 10 ⁇ m or less. This is due to the following reason. When the thickness is less than 1 ⁇ m, the surface of the positive electrode cannot be sufficiently covered with the inorganic particle layer, and thus the reaction suppressing effect between the positive electrode active material and the electrolytic solution may be insufficient. On the other hand, when the thickness exceeds 10 ⁇ m, the amount of active material of both positive and negative electrodes is reduced by that amount, which may lead to a decrease in battery capacity.
- oxides using single or plural titanium, aluminum, silicon, magnesium and the like conventionally used, phosphoric acid compounds, and those whose surfaces are treated with hydroxides, etc. can be used.
- the inorganic particle layer is desirably formed on the surface of the positive electrode. This is because if the inorganic particle layer is directly formed on the surface of the positive electrode, contact between the positive electrode active material and the electrolytic solution can be further suppressed, so that decomposition of the electrolytic solution can be extremely suppressed.
- an inorganic particle layer containing inorganic particles is formed between the separator and the negative electrode. This is because, when an inorganic particle layer containing inorganic particles is formed between the separator and the negative electrode, contact between the negative electrode active material and the electrolytic solution can be further suppressed, so that decomposition of the electrolytic solution can be further suppressed.
- the inorganic particle layer is formed by directly applying the inorganic particle-containing slurry to the surface of the negative electrode or the surface of the separator on the negative electrode side. Or it can form by sticking the sheet
- the thickness of the inorganic particle layer is preferably regulated to 1 ⁇ m or more and 10 ⁇ m or less. This is due to the following reason. When the thickness is less than 1 ⁇ m, the surface of the positive electrode cannot be sufficiently covered with the inorganic particle layer, and thus the reaction suppressing effect between the negative electrode active material and the electrolytic solution may be insufficient. On the other hand, when the thickness exceeds 10 ⁇ m, the amount of active material of both positive and negative electrodes is reduced by that amount, which may lead to a decrease in battery capacity.
- the inorganic particle the thing similar to the case where an inorganic particle layer is provided between the above-mentioned separator and a positive electrode can be used. Furthermore, the inorganic particle layer can be formed both between the separator and the positive electrode and between the separator and the negative electrode.
- the inorganic particle layer is preferably formed on the surface of the negative electrode. If the inorganic particle layer is directly formed on the surface of the negative electrode, the contact between the negative electrode active material and the electrolytic solution can be further suppressed, so that the decomposition of the electrolytic solution can be extremely suppressed.
- a rare earth hydroxide can be fixed to a part of the surface of lithium cobalt oxide or nickel cobalt lithium manganate. Further, when these lithium cobaltate and the like are heat-treated, the rare earth hydroxide fixed to a part of the surface changes to a rare earth oxyhydroxide or a rare earth oxide. Further, when the hydroxide is fixed, the atmosphere is changed to a carbon dioxide atmosphere or the positive electrode active material powder is dispersed in a solution in which carbon dioxide is dissolved, whereby a rare earth carbonate compound is mainly obtained. Examples of the rare earth compound dissolved in the solution used when fixing the rare earth hydroxide or carbonate compound include rare earth acetates, rare earth nitrates, rare earth sulfates, rare earth oxides, or rare earth chlorides. Can be used.
- the rare earth compound is preferably at least one selected from a rare earth hydroxide, a rare earth oxyhydroxide, or a rare earth carbonate compound. That is, it is preferable not to include rare earth oxides. This is due to the following reason.
- the surface of the surface having a rare earth hydroxide or carbonate compound fixed thereto is heat-treated, it becomes an oxyhydroxide or oxide.
- the temperature at which a rare earth hydroxide or oxyhydroxide is stably converted to an oxide is 500 ° C. or more.
- heat treatment is performed at such a temperature, a part of the rare earth compound fixed on the surface is positive electrode. It diffuses inside the active material. As a result, the effect of inhibiting the decomposition reaction of the electrolytic solution on the surface of the positive electrode active material may be reduced.
- the amount of the rare earth compound fixed to a part of the surface of the lithium cobalt oxide is preferably 0.01% by mass or more and less than 0.5% by mass with respect to lithium cobalt oxide in terms of rare earth elements.
- the amount is less than 0.01% by mass, the amount of the rare earth compound adhering to the surface is too small, so that the effect of fixing the rare earth compound may not be sufficiently exhibited.
- the surface is excessively covered with a compound that is difficult to directly participate in the charge / discharge reaction, and the discharge performance may be deteriorated.
- the amount of the rare earth compound to be fixed is more preferably 0.3% by mass or less. This is because, if regulated in this way, not only the fixing effect of the rare earth compound can be obtained, but also excellent discharge performance can be obtained.
- the amount of the rare earth compound to be fixed to the surface of the lithium nickel cobalt manganate is preferably 0.01% by mass or more and 0.8% by mass or less based on the lithium nickel cobalt manganate in terms of rare earth elements. If it is less than 0.01% by mass, the amount of the rare earth compound adhering to the surface is too small, so that the effect of fixing the rare earth compound may not be sufficiently exhibited.
- the surface of lithium is excessively covered with a compound that is difficult to directly participate in the charge / discharge reaction, and the discharge performance may be deteriorated.
- the amount of the rare earth compound to be fixed is more preferably 0.3% by mass or less. This is because, if regulated in this way, not only the fixing effect of the rare earth compound can be obtained, but also excellent discharge performance can be obtained.
- the lithium cobaltate may be dissolved in a substance such as Al, Mg, Ti, Zr, or may be contained in the grain boundary.
- compounds such as Al, Mg, Ti, and Zr may be fixed to the surface of the lithium cobalt oxide. This is because even if these compounds are fixed, contact between the electrolytic solution and the positive electrode active material can be suppressed.
- nickel cobalt lithium manganate those having a known composition such as a molar ratio of nickel, cobalt, and manganese of 1: 1: 1 or 5: 2: 3 can be used.
- a material having a higher proportion of nickel or cobalt than manganese so that the positive electrode capacity can be increased.
- the solvent of the non-aqueous electrolyte used in the present invention is not limited, and a solvent conventionally used for non-aqueous electrolyte secondary batteries can be used.
- cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid
- esters such as ethyl and ⁇ -butyrolactone
- compounds containing sulfone groups such as propane sultone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,4 -Compounds containing ethers such as dioxane and 2-methyltetrahydrofuran, butyronitrile, valer
- a solvent in which a part of these H is substituted with F is preferably used. Further, these can be used alone or in combination, and a solvent in which a cyclic carbonate and a chain carbonate are combined, and a solvent in which a compound containing a small amount of nitrile or an ether is further combined with these is preferable. .
- the concentration of the solute is not particularly limited, but is preferably 0.8 to 1.5 mol per liter of the electrolyte.
- a conventionally used negative electrode can be used, and in particular, a carbon material capable of occluding and releasing lithium, a metal capable of forming an alloy with lithium, or an alloy containing the metal Compounds.
- the carbon material natural graphite, non-graphitizable carbon, graphite such as artificial graphite, coke, etc. can be used, and examples of the alloy compound include those containing at least one metal that can be alloyed with lithium. .
- silicon or tin is preferable as an element capable of forming an alloy with lithium, and silicon oxide, tin oxide, or the like in which these are combined with oxygen can also be used.
- a mixture of the above carbon material and a compound of silicon or tin can be used.
- a negative electrode material having a higher charge / discharge potential than lithium carbon such as lithium titanate can be used.
- the separator conventionally used can be used. Specifically, not only a separator made of polyethylene, but also a material in which a layer made of polypropylene is formed on the surface of a polyethylene layer, or a material in which a resin such as an aramid resin is applied to the surface of a polyethylene separator is used. Also good.
- the positive electrode for nonaqueous electrolyte secondary batteries and a battery according to the present invention will be described below.
- the positive electrode for nonaqueous electrolyte secondary batteries and a battery in this invention are not limited to what was shown to the following form, In the range which does not change the summary, it can change suitably and can implement.
- Example 1 [Production of positive electrode] First, 1000 g of lithium cobaltate particles in which 1.5 mol% of Mg and Al were each dissolved in lithium cobaltate and 0.05 mol% of Zr were prepared, and this particle was added to 3.0 L of pure water. And a suspension in which lithium cobaltate was dispersed was prepared. Next, a solution in which 1.85 g of erbium nitrate pentahydrate [Er (NO 3 ) 3 .5H 2 O] was dissolved in 200 mL of pure water was added to this suspension. At this time, in order to adjust the pH of the solution in which lithium cobaltate was dispersed to 9, 10% by mass of nitric acid aqueous solution or 10% by mass of sodium hydroxide aqueous solution was appropriately added.
- the obtained powder was dried at 120 ° C., and erbium hydroxide was partially applied to the surface of the lithium cobalt oxide. A compound fixed was obtained. Thereafter, the obtained powder was heat-treated in air at 300 ° C. for 5 hours. When heat treatment is performed at 300 ° C. in this way, all or most of the erbium hydroxide is changed to erbium oxyhydroxide, so that the erbium oxyhydroxide is fixed to a part of the surface of the positive electrode active material particles. However, since some may remain in the state of erbium hydroxide, erbium hydroxide may be fixed to a part of the surface of the positive electrode active material particles.
- lithium cobaltate having an erbium compound fixed to a part of the surface and lithium nickel cobalt manganate (containing nickel, cobalt, and manganese in an equal ratio) have a mass ratio of 50:50.
- a positive electrode active material powder composed of two types of positive electrode active materials.
- the positive electrode active material powder a carbon black (acetylene black) powder having an average particle diameter of 40 nm as a positive electrode conductive agent, and polyvinylidene fluoride (PVdF) as a positive electrode binder in a mass ratio of 95: 2.5. : Kneaded in an NMP solution so as to have a ratio of 2.5 to prepare a positive electrode mixture slurry.
- this positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of aluminum foil, dried, and then rolled with a rolling roller, whereby a positive electrode mixture layer was formed on both surfaces of the positive electrode current collector. A positive electrode was produced.
- a lead terminal is attached to each of the positive and negative electrodes, a separator is disposed between the two electrodes and wound in a spiral shape, and then a spiral electrode body is produced by pulling out the winding core, and the electrode body is further crushed, A flat electrode body was obtained.
- the flat electrode body and the non-aqueous electrolyte are inserted into an aluminum laminate exterior body to produce a flat non-aqueous electrolyte secondary battery having the structure shown in FIGS. did.
- the size of the secondary battery was 3.6 mm ⁇ 35 mm ⁇ 62 mm, and the discharge capacity when the secondary battery was charged to 4.40 V and discharged to 2.75 V was 750 mAh.
- the battery thus produced is hereinafter referred to as battery A1.
- the specific structure of the non-aqueous electrolyte secondary battery 11 is that a positive electrode 1 and a negative electrode 2 are arranged to face each other with a separator 3 therebetween. 2 and the separator 3 are impregnated with a non-aqueous electrolyte.
- the positive electrode 1 and the negative electrode 2 are connected to a positive electrode current collector tab 4 and a negative electrode current collector tab 5, respectively, and have a structure capable of charging and discharging as a secondary battery.
- the electrode body is arrange
- Example 2 As a positive electrode active material, the mass ratio of lithium cobaltate (hereinafter sometimes referred to as surface-modified lithium cobaltate) in which an erbium compound is fixed to a part of the surface and nickel cobalt lithium manganate is 70:30.
- a battery was produced in the same manner as in Example 1 except that the mixture obtained in Example 1 was used. The battery thus produced is hereinafter referred to as battery A2.
- Example 3 A battery was fabricated in the same manner as in Example 1 except that a positive electrode active material was prepared by mixing surface-modified lithium cobaltate and nickel cobalt lithium manganate at a mass ratio of 80:20. The battery thus produced is hereinafter referred to as battery A3.
- Example 4 A battery was fabricated in the same manner as in Example 1 except that the positive electrode active material used was a mixture of surface-modified lithium cobalt oxide and nickel cobalt lithium manganate at a mass ratio of 90:10. The battery thus produced is hereinafter referred to as battery A4.
- Example 5 A battery was fabricated in the same manner as in Example 1 except that a material obtained by mixing surface-modified lithium cobalt oxide and lithium nickel cobalt manganate at a mass ratio of 95: 5 was used as the positive electrode active material. The battery thus produced is hereinafter referred to as battery A5.
- Example 1 A battery was fabricated in the same manner as in Example 1 except that only the surface-modified lithium cobaltate was used as the positive electrode active material. The battery thus produced is hereinafter referred to as battery Z1.
- Example 2 The same as Example 1 except that only lithium cobaltate (the erbium compound is not fixed to a part of the surface; hereinafter may be referred to as surface unmodified lithium cobaltate) was used as the positive electrode active material. Thus, a battery was produced. The battery thus produced is hereinafter referred to as battery Z2.
- Example 3 A battery was fabricated in the same manner as in Example 1 except that only nickel cobalt lithium manganate was used as the positive electrode active material. The battery thus produced is hereinafter referred to as battery Z3.
- Example 4 A battery was fabricated in the same manner as in Example 1 except that a positive electrode active material was prepared by mixing a surface unmodified lithium cobalt oxide and a nickel cobalt lithium manganate in a mass ratio of 50:50. The battery thus produced is hereinafter referred to as battery Z4.
- Example 5 A battery was fabricated in the same manner as in Example 1 except that the positive electrode active material was a mixture of non-surface modified lithium cobalt oxide and nickel cobalt lithium manganate in a mass ratio of 70:30. The battery thus produced is hereinafter referred to as battery Z5.
- Example 6 A battery was fabricated in the same manner as in Example 1 except that a positive electrode active material was prepared by mixing surface unmodified lithium cobalt oxide and nickel cobalt lithium manganate at a mass ratio of 90:10. The battery thus produced is hereinafter referred to as battery Z6.
- a positive electrode active material in which surface-modified lithium cobalt oxide and nickel cobalt lithium manganate were mixed that is, the positive electrode active material of battery Z1 and the positive electrode active material of battery Z3 was used.
- the remaining batteries A1 to A5 had a remaining capacity ratio as compared with the battery Z1 using the surface modified lithium cobaltate alone as the positive electrode active material and the battery Z3 using the nickel cobalt lithium manganate alone as the positive electrode active material. It can be seen that the average discharge voltage becomes equal or higher. That is, it can be seen that both characteristics of the batteries A1 to A5 do not exist within the range of the characteristics of the battery Z1 and the battery Z3 but exist beyond the range of the characteristics (for example, the remaining capacity ratio).
- lithium cobaltate (hereinafter sometimes referred to as surface non-modified lithium cobaltate) in which the erbium compound is not fixed to the surface is mixed with lithium nickelcobaltmanganate (that is, a battery).
- the battery Z2 using the surface-unmodified lithium cobaltate alone as the positive electrode active material is used.
- the residual capacity ratio and the average discharge voltage are high, but the residual capacity ratio and the average discharge voltage are low compared to the battery Z3 using nickel nickel lithium manganate alone as the positive electrode active material. I understand that.
- both characteristics of the batteries Z4 to Z6 are only present within the range of the battery Z2 and the battery Z3. Therefore, it can be seen that in the case of the batteries Z4 to Z6, unlike the case of the batteries A1 to A5, the synergistic effect is not exhibited by mixing the two positive electrode active materials.
- the batteries A2 to A5 have a particularly improved remaining capacity ratio and a higher average discharge voltage than the battery A1. Therefore, the mixing mass ratio of the surface-modified lithium cobalt oxide and the nickel cobalt lithium manganate is particularly preferably regulated to 95: 5 to 70:30.
- Example 1 Example of the first embodiment except that an erbium compound was fixed to a part of the surface of the lithium nickel cobalt manganate (hereinafter, this may be referred to as surface-modified nickel cobalt lithium manganate).
- a battery was produced in the same manner as in Example 1.
- the surface-modified nickel cobalt lithium manganate was produced by the same method as that for producing the surface-modified lithium cobalt oxide.
- the fixed amount of the erbium compound was measured by ICP, it was 0.07 mass% with respect to lithium nickel cobalt manganate in terms of erbium element.
- the battery thus produced is hereinafter referred to as battery B1.
- Example 2 A battery was fabricated in the same manner as in Example 1 above, except that a positive electrode active material in which surface-modified lithium cobalt oxide and surface-modified nickel cobalt lithium manganate were mixed at a mass ratio of 90:10 was used. Produced. The battery thus produced is hereinafter referred to as battery B2.
- the surface unmodified lithium nickel cobalt manganate (nickel cobalt manganese in which the erbium compound is not fixed to a part of the surface) It can be seen that either the remaining capacity ratio or the average discharge voltage is further improved as compared with the batteries A1 and A4 using lithium acid). Therefore, the remaining capacity ratio and the average operating voltage can be further improved by fixing the erbium compound not only to a part of the surface of the lithium cobalt oxide but also to a part of the surface of the nickel cobalt lithium manganate.
- Example 1 Except that the samarium compound was fixed to a part of the surface of the lithium cobaltate instead of the erbium compound, the same as Example 3 of the first example (therefore, cobalt acid surface-modified with the samarium compound)
- the mass ratio of lithium to lithium nickel cobalt manganate was 80:20), and a battery was produced.
- the surface was treated with samarium compound in the same manner as the above method of preparing lithium cobaltate surface-modified with erbium compound. Modified lithium cobaltate was prepared.
- the fixed amount of the samarium compound was measured by ICP, it was 0.07 mass% with respect to lithium cobaltate in terms of samarium element.
- the battery thus produced is hereinafter referred to as battery C1.
- Example 2 Except that a neodymium compound was fixed to a part of the surface of the lithium cobalt oxide instead of the erbium compound, the same procedure as in Example 3 of the first example (therefore, cobalt acid surface-modified with a neodymium compound) The mass ratio of lithium to lithium nickel cobalt manganate was 80:20), and a battery was produced. In addition, it replaced with the erbium nitrate pentahydrate, and except having used the neodymium nitrate hexahydrate, it was the same method as the method of producing the lithium cobaltate surface-modified with the said erbium compound, and a surface is made with a neodymium compound.
- Modified lithium cobaltate was prepared. Moreover, when the adhesion amount of the neodymium compound was measured by ICP, it was 0.07 mass% with respect to lithium cobaltate in terms of neodymium element.
- the battery thus produced is hereinafter referred to as battery C2.
- Example 3 Except that the lanthanum compound was fixed to a part of the surface of the lithium cobaltate in place of the erbium compound, the same as in Example 3 of the first example (therefore, cobalt acid surface-modified with the lanthanum compound)
- the mass ratio of lithium to lithium nickel cobalt manganate was 80:20), and a battery was produced.
- Modified lithium cobaltate was prepared.
- the adhesion amount of the lanthanum compound was measured by ICP, it was 0.07% by mass with respect to lithium cobaltate in terms of lanthanum element.
- the battery thus produced is hereinafter referred to as battery C3.
- Example 1 A battery was fabricated in the same manner as in Example 1 except that only the lithium cobaltate surface-modified with a samarium compound was used as the positive electrode active material.
- the battery thus produced is hereinafter referred to as battery Y1.
- Example 2 A battery was fabricated in the same manner as in Example 2 except that only the lithium cobalt oxide surface-modified with a neodymium compound was used as the positive electrode active material.
- the battery thus produced is hereinafter referred to as battery Y2.
- Example 3 A battery was fabricated in the same manner as in Example 3 except that only the lithium cobalt oxide surface-modified with a lanthanum compound was used as the positive electrode active material. The battery thus produced is hereinafter referred to as battery Y3.
- a positive electrode active in which a surface-modified lithium cobaltate in which a samarium compound, a neodymium compound, or a lanthanum compound is fixed to a part of the surface and nickel cobalt lithium manganate is mixed.
- Batteries C1 to C3 using the materials include batteries Y1 to Y3 each using the same surface-modified lithium cobalt oxide as the positive electrode active material alone as the batteries C1 to C3, and nickel cobalt lithium manganate alone. It can be seen that the remaining capacity ratio is higher and the average discharge voltage is equal to or higher than that of the battery Z3 used as the substance.
- both characteristics of the batteries C1 to C3 are not in the range of the characteristics of the batteries Y1 to Y3 and the battery Z3, as in the case where the erbium compound is fixed to a part of the surface of the lithium cobalt oxide. It turns out that it exists beyond the range of each characteristic. This is considered to be due to the same reason as shown in the experiment in the first embodiment.
- the batteries C1 to C3 and the battery A3 have a remaining capacity ratio and an average discharge voltage that are superior to those of the battery C3, and the battery A3 is the most excellent. It can be seen that it has a residual capacity ratio and an average discharge voltage. This shows that among rare earth elements, a rare earth element having an element number larger than that of neodymium is preferable, and erbium is particularly preferable.
- Example 1 A battery was produced in the same manner as in Example 1 of the first example except that an inorganic particle layer was formed on the surface of the positive electrode (positive electrode mixture layer) by the following method.
- the inorganic particle layer is formed by preparing an aqueous slurry using alumina (AKP3000 [manufactured by Sumitomo Chemical Co., Ltd.]), SBR (styrene butadiene rubber) as an aqueous binder, and CMC (carboxymethylcellulose) as a dispersant (alumina).
- the ratio of the water-based binder to the water-based binder was 100: 3), and this water-based slurry was coated on the surface of the positive electrode using the dipping method and then dried at 90 ° C. for 10 minutes. In addition, it was 4 micrometers when the thickness of the said inorganic particle layer was measured with the micrometer.
- the battery thus produced is hereinafter referred to as battery D1.
- Example 2 A battery was produced in the same manner as in Example 1 of the first example except that the inorganic particle layer was formed on the surface of the negative electrode (negative electrode mixture layer) by the following method.
- the inorganic particle layer is formed by the mass ratio of NMP solution (titania and ethyl acrylate-acrylonitrile copolymer) in which titania (CR-EL [manufactured by Ishihara Sangyo Co., Ltd.]) and ethyl acrylate-acrylonitrile copolymer are dispersed. 100: 3), and the slurry was coated on the surface of the negative electrode using the dipping method, and then dried at 90 ° C. for 10 minutes. In addition, it was 4 micrometers when the thickness of the said inorganic particle layer was measured with the micrometer.
- the battery thus produced is hereinafter referred to as battery D2.
- the inorganic particle layer was not formed on the surface of the positive and negative electrodes. It can be seen that the remaining capacity ratio and the average discharge voltage are further improved as compared with the battery A1. Therefore, in addition to the surface modification of the positive electrode active material, the residual capacity ratio and the average operating voltage can be further improved by forming the inorganic particle layer on the surface of the positive electrode or the negative electrode.
- the inorganic particle layer formed on the surface of the positive electrode or the negative electrode further suppresses the contact between the electrolytic solution and the positive electrode active material, or the electrolytic solution and the negative electrode active material, thereby further suppressing the decomposition of the electrolytic solution. This is thought to be possible.
- the remaining capacity ratio and the average discharge voltage are further improved in the battery D1 in which the inorganic particle layer is formed on the surface of the positive electrode. Therefore, the remaining capacity ratio and the average discharge voltage can be further improved by forming the inorganic particle layer on the surface of the positive electrode rather than forming the inorganic particle layer on the surface of the negative electrode. This is because the surface of the positive electrode active material is more decomposed than the surface of the negative electrode active material, and therefore the formation of an inorganic particle layer on the surface of the positive electrode can effectively suppress the decomposition of the electrolytic solution. it is conceivable that.
- Example 1 A battery was fabricated in the same manner as in Example 1 of the second example, except that an inorganic particle layer was formed on the surface of the positive electrode in the same manner as described in Example 1 of the fourth example. .
- the battery thus produced is hereinafter referred to as battery E1.
- Example 2 A battery was produced in the same manner as in Example 2 of the second example, except that an inorganic particle layer was formed on the surface of the positive electrode by the same method as described in Example 1 of the fourth example. .
- the battery thus produced is hereinafter referred to as battery E2.
- Example 3 A battery was produced in the same manner as in Example 4 of the first example, except that an inorganic particle layer was formed on the surface of the positive electrode by the same method as described in Example 1 of the fourth example. .
- the battery thus produced is hereinafter referred to as battery E3.
- the remaining capacity ratio and the average discharge voltage after continuous charging at 60 ° C. were measured in the same manner as in the experiment of the first example, and the results are shown in Table 5.
- the results of the batteries A1, A4 and B1, B2, D1 described above are also shown.
- the batteries E1 to E3 in which the inorganic particle layer was formed on the surface of the positive electrode were compared with the batteries B1, B2, and A4 in which the inorganic particle layer was not formed on the surface of the positive electrode. It can be seen that the remaining capacity ratio and the average discharge voltage are further improved. Therefore, in addition to the surface modification of the positive electrode active material, the residual capacity ratio and the average operating voltage can be further improved by forming an inorganic particle layer on the surface of the positive electrode. This is presumably because the inorganic particle layer formed on the surface of the positive electrode further suppresses the contact between the electrolytic solution and the positive electrode active material, thereby further suppressing the decomposition of the electrolytic solution.
- the effect of the inorganic particle layer formed on the surface of the positive electrode is uniformly expressed regardless of the mixing ratio of the positive electrode active material and the presence or absence of the fixed element of nickel cobalt lithium manganate. Yes. Therefore, it is considered that the effect of forming the inorganic particle layer is manifested in addition to the effect of the element fixed to the positive electrode active material surface.
- the erbium compound is fixed not only to the batteries A2, A3, A5 and lithium cobaltate, but also to a part of the surface of the nickel cobalt lithium manganate, in which the mixing ratio of the positive electrode active material is different from the batteries A1 and A4.
- the elements fixed on the surface of the lithium cobaltate are samarium compounds, neodymium compounds, and lanthanum compounds, inorganic particles are formed on the positive electrode surface. If a layer is formed, it is thought that the same effect as the above is acquired. Further, it is considered that the same effect can be obtained even when a rare earth compound other than the erbium compound and the samarium compound shown in the third embodiment is used as the element fixed to the surface of the lithium cobalt oxide.
- the present invention can be expected to be developed for a driving power source for mobile information terminals such as mobile phones, notebook computers, and PDAs, and a driving power source for high output such as HEV and electric tools.
- Positive electrode 2 Negative electrode 3: Separator 4: Positive electrode current collector tab 5: Negative electrode current collector tab 6: Aluminum laminate outer package 21: Lithium cobaltate particles 22: Rare earth compound particles
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Abstract
Description
このようなことを考慮して、以下に示すように、コバルト酸リチウムとニッケルコバルトマンガン酸リチウムとを混合したもの等を正極活物質として用いる提案がなされている。
上記構成であれば、充電状態で高温状態に曝した場合等であっても、電解液の分解や正極活物質の劣化を抑制することができるので、放電性能が低下するのを抑制できる。この理由は定かではないが、下記のような理由ではないかと推測される。
正極活物質の総量に対するニッケルコバルトマンガン酸リチウムの割合が1質量%未満になると、コバルト酸リチウムの量が多くなり過ぎるため、表面の一部に希土類化合物が固着されていても、やはり電解液の分解量が多くなって、放電電圧が低下する場合がある。一方、正極活物質の総量に対するニッケルコバルトマンガン酸リチウムの割合が50質量%を超えると、ニッケルコバルトマンガン酸リチウムの割合が高くなり過ぎて、ニッケルコバルトマンガン酸リチウムの活性化を十分に抑制できなくなることがある。
このようなことを考慮すれば、正極活物質の総量に対するニッケルコバルトマンガン酸リチウムの割合は、3質量%以上30質量%以下であることが望ましく、特に、5質量%以上20質量%以下であることが望ましい。
コバルト酸リチウムのみならずニッケルコバルトマンガン酸リチウムの表面の一部にも希土類化合物を固着すれば、高温で連続充電した後における容量維持率が一層高くなる。これは、ニッケルコバルトマンガン酸リチウムにもコバルト、ニッケル等が含まれるため、電解液の分解が生じることがあるが、表面の一部に希土類化合物を固着させておけば、ニッケルコバルトマンガン酸リチウムの表面における電解液の分解反応を抑制できるからである。
希土類化合物(コバルト酸リチウムの表面の一部に固着された希土類化合物のみならず、ニッケルコバルトマンガン酸リチウムの表面の一部に固着された希土類化合物をも含む)の平均粒径が100nmを超えると、同じ質量の希土類化合物を固着させても、固着部位が一部に偏ってしまうため、上述の効果が十分に発揮されないことがある。
尚、希土類化合物の平均粒径の下限は0.1nm以上であることが好ましく、特に1nm以上であることが望ましい。希土類化合物の平均粒径が0.1nm未満となると、希土類化合物が小さ過ぎて、正極活物質表面を過剰に覆うことになる。
これらを用いると、コバルト酸リチウム表面における活性度の抑制効果が高く、ニッケルコバルトマンガン酸リチウムと組み合わせたときの効果が一層発揮される。
セパレータと正極との間に、無機粒子を含む無機粒子層が形成されていると、正極活物質と電解液との接触を一層抑制できるので、電解液の分解をより抑制できるからである。この場合、無機粒子層は、正極の表面或いは正極側のセパレータの表面に無機粒子含有スラリーを直接塗布して形成する。または、無機粒子で形成したシートを、正極の表面或いは正極側のセパレータの表面に貼り付けることにより形成することができる。
尚、無機粒子としては、従来から用いられてきたチタン、アルミニウム、ケイ素、マグネシウム等を単独もしくは複数用いた酸化物や、リン酸化合物、またその表面が水酸化物等で処理されているものを用いることができる。
無機粒子層が正極の表面に直接形成されていれば、正極活物質と電解液との接触をより一層抑制できるので、電解液の分解を極めて抑制できるからである。
セパレータと負極との間に、無機粒子を含む無機粒子層が形成されていると、負極活物質と電解液との接触を一層抑制できるので、電解液の分解がより抑制できるからである。この場合、無機粒子層は、負極の表面或いは負極側のセパレータの表面に無機粒子含有スラリーを直接塗布して形成する。または、無機粒子で形成したシートを、負極の表面或いは負極側のセパレータの表面に貼り付けることにより形成することができる。
尚、無機粒子としては、上述のセパレータと正極との間に無機粒子層を設ける場合と同様のものを用いることができる。更に、無機粒子層は、セパレータと正極との間及びセパレータと負極との間の両方に形成することができる。
無機粒子層が負極の表面に直接形成されていれば、負極活物質と電解液との接触をより一層抑制できるので、電解液の分解を極めて抑制できるからである。
(1)コバルト酸リチウムやニッケルコバルトマンガン酸リチウムの表面の一部に、希土類化合物を固着する方法としては、例えば、これらの正極活物質粉末を分散した溶液に、希土類化合物を溶解した溶液を混合する方法や、正極活物質粉末を混合しながら、希土類化合物を含む溶液を噴霧する方法等によって得ることができる。
上記希土類の水酸化物や炭酸化合物を固着させる際に用いる溶液に溶解させる希土類化合物としては、希土類の酢酸塩、希土類の硝酸塩、希土類の硫酸塩、希土類の酸化物、又は、希土類の塩化物等を用いることができる。
表面に希土類の水酸化物や炭酸化合物が固着したものを熱処理すると、オキシ水酸化物や酸化物となる。しかし、一般に、希土類水酸化物やオキシ水酸化物が安定的に酸化物となる温度は500℃以上であるが、このような温度で熱処理すると、表面に固着した希土類化合物の一部は、正極活物質の内部に拡散してしまう。この結果、正極活物質表面での電解液の分解反応抑制効果が低下する恐れがあるという理由による。
一方、非水電解液の溶質としては、従来から用いられてきた溶質を用いることができ、LiPF6、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiPF6-x(CnF2n-1)x[但し、1<x<6、n=1又は2]等が例示され、更に、これらの1種もしくは2種以上を混合して用いても良い。溶質の濃度は特に限定されないが、電解液1リットル当り0.8~1.5モルであることが望ましい。
炭素材料としては、天然黒鉛や難黒鉛化性炭素、人造黒鉛等のグラファイト類、コークス類等を用いることができ、合金化合物としては、リチウムと合金可能な金属を少なくとも1種類含むものが挙げられる。特に、リチウムと合金形成可能な元素としてはケイ素やスズであることが好ましく、これらが酸素と結合した、酸化ケイ素や酸化スズ等も用いることもできる。また、上記炭素材料とケイ素やスズの化合物とを混合したものを用いることができる。
上記の他、エネルギー密度は低下するものの、負極材料としてはチタン酸リチウム等の金属リチウムに対する充放電の電位が、炭素材料等より高いものも用いることができる。
以下、この発明に係る非水電解質二次電池用正極及び電池を、以下に説明する。尚、この発明における非水電解質二次電池用正極及び電池は、下記の形態に示したものに限定されず、その要旨を変更しない範囲において適宜変更して実施できるものである。
〔正極の作製〕
先ず、コバルト酸リチウムに対してMg及びAlを各1.5モル%固溶し、且つZrを0.05モル%含有したコバルト酸リチウム粒子1000gを用意し、この粒子を3.0Lの純水に添加し攪拌して、コバルト酸リチウムが分散した懸濁液を調製した。次に、この懸濁液に、硝酸エルビウム5水和物[Er(NO3)3・5H2O]1.85gが200mLの純水に溶解された溶液を加えた。この際、コバルト酸リチウムを分散した溶液のpHを9に調整するために、10質量%の硝酸水溶液、或いは、10質量%の水酸化ナトリウム水溶液を適宜加えた。
先ず、負極活物質の人造黒鉛と、CMC(カルボキシメチルセルロースナトリウム)と、結着剤のSBR(スチレン-ブタジエンゴム)とを98:1:1の質量比で水溶液中において混合し、負極合剤スラリーを調製した。次に、この負極合剤スラリーを銅箔から成る負極集電体の両面に均一に塗布、乾燥した後、圧延ローラにより圧延することにより、負極集電体の両面に負極合剤層が形成された負極を得た。尚、この負極における負極活物質の充填密度は1.70g/cm3であった。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)とを、3:7の体積比で混合した混合溶媒に対し、六フッ化リン酸リチウム(LiPF6)を1.0モル/リットルの濃度になるように溶解させて、非水電解液を調製した。
上記正負極それぞれにリード端子を取り付け、これら両極間にセパレータを配置して渦巻き状に巻回した後、巻き芯を引き抜いて渦巻状の電極体を作製し、更にこの電極体を押し潰して、扁平型の電極体を得た。次に、この扁平型の電極体と上記非水電解液とを、アルミニウムラミネート製の外装体内に挿入し、図1及び図2に示される構造を有する扁平型の非水電解質二次電池を作製した。尚、当該二次電池のサイズは、3.6mm×35mm×62mmであり、また、当該二次電池を4.40Vまで充電し、2.75Vまで放電したときの放電容量は750mAhであった。
このようにして作製した電池を、以下、電池A1と称する。
正極活物質として、表面の一部にエルビウム化合物を固着させたコバルト酸リチウム(以下、表面改質コバルト酸リチウムと称することがある)と、ニッケルコバルトマンガン酸リチウムとを、70:30の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池A2と称する。
正極活物質として、表面改質コバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとを、80:20の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池A3と称する。
正極活物質として、表面改質コバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとを、90:10の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池A4と称する。
正極活物質として、表面改質コバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとを、95:5の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池A5と称する。
正極活物質として、表面改質コバルト酸リチウムのみを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z1と称する。
正極活物質として、コバルト酸リチウム(表面の一部にエルビウム化合物は固着されていない。以下、表面非改質コバルト酸リチウムと称することがある)のみを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z2と称する。
正極活物質として、ニッケルコバルトマンガン酸リチウムのみを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z3と称する。
正極活物質として、表面非改質コバルト酸リチウムとニッケルコバルトマンガン酸リチウムとを、50:50の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z4と称する。
正極活物質として、表面非改質コバルト酸リチウムとニッケルコバルトマンガン酸リチウムとを、70:30の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z5と称する。
正極活物質として、表面非改質コバルト酸リチウムとニッケルコバルトマンガン酸リチウムとを、90:10の質量比で混合したものを用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Z6と称する。
上記の電池A1~A5、Z1~Z6について、下記条件にて充放電し、60℃連続充電後の残存容量率と平均放電電圧とを調べたので、それらの結果を表1に示す。
・1サイクル目の充電条件
1.0It(750mA)の電流で電池電圧が4.40Vとなるまで定電流充電を行い、更に、4.40Vの電圧で電流値が37.5mAとなるまで定電圧充電を行った。
・1サイクル目の放電条件
1.0It(750mA)の電流で電池電圧が2.75Vとなるまで定電流放電を行った。
・休止
上記充電と放電との間の休止間隔は10分間とした。
上記の条件で充放電サイクル試験を1回行って、放電容量Q1(連続充電試験前の放電容量Q1)を測定した後、60℃の恒温槽に1時間放置した。そして、60℃の環境のまま、1.0It(750mA)の定電流で電池電圧が4.40Vとなるまで充電し、さらに4.40Vの定電圧で64時間充電した。
室温にまで冷却してから、室温にて上記1サイクル目の放電条件と同様の条件で、連続充電試験後の1回目の放電容量Q2を測定し、下記(1)式から残存容量率を求めた。
残存容量率=(連続充電試験後の1回目の放電容量Q2/連続充電試験前の放電容量Q1)×100(%)・・・(1)
連続充電保存後の放電容量Q2を測定した後、室温状態での上記1サイクル目の充放電条件と同様の条件で充放電サイクルを1回行って、平均放電電圧を測定した。尚、上記残存容量率測定時の放電容量Q2/2の時の放電電圧を平均放電電圧とした。
第2実施例では、コバルト酸リチウムのみならず、ニッケルコバルトマンガン酸リチウムの表面の一部にもエルビウム化合物を固着させた場合について検討した。
ニッケルコバルトマンガン酸リチウムの表面の一部にもエルビウム化合物を固着させた(以下、これを、表面改質ニッケルコバルトマンガン酸リチウムと称することがある)こと以外は、上記第1実施例の実施例1と同様にして電池を作製した。尚、表面改質ニッケルコバルトマンガン酸リチウムは、上記表面改質コバルト酸リチウムを作製する方法と同様の方法で作製した。また、エルビウム化合物の固着量をICPにより測定したところ、エルビウム元素換算で、ニッケルコバルトマンガン酸リチウムに対し0.07質量%であった。
このようにして作製した電池を、以下、電池B1と称する。
表面改質コバルト酸リチウムと、表面改質ニッケルコバルトマンガン酸リチウムとを、質量比で90:10となるように混合した正極活物質を用いた以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池B2と称する。
上記の電池B1及びB2について、上記第1実施例の実験と同様にして、60℃連続充電後の残存容量率と平均放電電圧とを測定したので、それらの結果を表2に示す。尚、上述した電池A1、A4の結果についても、併せて示す。
第3実施例では、コバルト酸リチウムの表面の一部に固着させる希土類元素の種類について検討した。
コバルト酸リチウムの表面の一部に、エルビウム化合物に代えてサマリウム化合物を固着させたこと以外は、上記第1実施例の実施例3と同様にして(したがって、サマリウム化合物で表面改質したコバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとの質量比は80:20)、電池を作製した。尚、硝酸エルビウム5水和物に代えて、硝酸サマリウム6水和物を用いたこと以外は、上記エルビウム化合物で表面改質したコバルト酸リチウムを作製する方法と同様の方法で、サマリウム化合物で表面改質したコバルト酸リチウムを作製した。また、サマリウム化合物の固着量をICPにより測定したところ、サマリウム元素換算で、コバルト酸リチウムに対し0.07質量%であった。
このようにして作製した電池を、以下、電池C1と称する。
コバルト酸リチウムの表面の一部に、エルビウム化合物に代えてネオジム化合物を固着させたこと以外は、上記第1実施例の実施例3と同様にして(したがって、ネオジム化合物で表面改質したコバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとの質量比は80:20)、電池を作製した。尚、硝酸エルビウム5水和物に代えて、硝酸ネオジム6水和物を用いたこと以外は、上記エルビウム化合物で表面改質したコバルト酸リチウムを作製する方法と同様の方法で、ネオジム化合物で表面改質したコバルト酸リチウムを作製した。また、ネオジム化合物の固着量をICPにより測定したところ、ネオジム元素換算で、コバルト酸リチウムに対し0.07質量%であった。
このようにして作製した電池を、以下、電池C2と称する。
コバルト酸リチウムの表面の一部に、エルビウム化合物に代えてランタン化合物を固着させたこと以外は、上記第1実施例の実施例3と同様にして(したがって、ランタン化合物で表面改質したコバルト酸リチウムと、ニッケルコバルトマンガン酸リチウムとの質量比は80:20)、電池を作製した。尚、硝酸エルビウム5水和物に代えて、硝酸ランタン6水和物を用いたこと以外は、上記エルビウム化合物で表面改質したコバルト酸リチウムを作製する方法と同様の方法で、ランタン化合物で表面改質したコバルト酸リチウムを作製した。また、ランタン化合物の固着量をICPにより測定したところ、ランタン元素換算で、コバルト酸リチウムに対し0.07質量%であった。
このようにして作製した電池を、以下、電池C3と称する。
正極活物質として、サマリウム化合物で表面改質したコバルト酸リチウムのみを用いたこと以外は、上記実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Y1と称する。
正極活物質として、ネオジム化合物で表面改質したコバルト酸リチウムのみを用いたこと以外は、上記実施例2と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Y2と称する。
正極活物質として、ランタン化合物で表面改質したコバルト酸リチウムのみを用いたこと以外は、上記実施例3と同様にして電池を作製した。
このようにして作製した電池を、以下、電池Y3と称する。
上記の電池C1~C3、Y1~Y3について、上記第1実施例の実験と同様にして、60℃連続充電後の残存容量率と平均放電電圧とを測定したので、それらの結果を表3に示す。尚、上述した電池A3、Z1~Z3の結果についても、併せて示す。
尚、電池C1~C3と電池A3との結果を比較すると、電池C1~C2及び電池A3が電池C3よりも優れた残存容量率と平均放電電圧を有しており、中でも電池A3が最も優れた残存容量率と平均放電電圧を有していることが認められる。このことから、希土類元素の中でもネオジムより元素番号の大きい希土類元素が好ましく、その中でも特にエルビウムが好ましいことがわかる。
第4実施例では、正極の表面又は負極の表面に、無機粒子を含む無機粒子層を形成した場合について検討した。
正極(正極合剤層)の表面に、下記の方法で無機粒子層を形成した以外は、上記第1実施例の実施例1と同様の方法で電池を作製した。無機粒子層の形成は、アルミナ(AKP3000〔住友化学株式会社製〕)と、水系バインダーとしてSBR(スチレンブタジエンゴム)と、分散剤としてCMC(カルボキシメチルセルロース)とを用いて水系スラリーを調製し(アルミナと水系バインダーとの割合は質量比で100:3)、この水系スラリーを、ディップ法を用いて正極の表面にコーティングした後、90℃で10分間乾燥することにより作製した。尚、上記無機粒子層の厚みをマイクロメーターで測定したところ、4μmであった。
このように作製した電池を以下、電池D1と称する。
負極(負極合剤層)の表面に、下記の方法で無機粒子層を形成した以外は、上記第1実施例の実施例1と同様の方法で電池を作製した。無機粒子層の形成は、チタニア(CR-EL〔石原産業株式会社製〕)とアクリル酸エチル-アクリロニトリルコポリマーとを分散したNMP溶液(チタニアとアクリル酸エチル-アクリロニトリルコポリマーとの割合は、質量比で100:3)とを用いてスラリーを調製し、このスラリーを、ディップ法を用いて負極の表面にコーティングした後、90℃で10分間乾燥することにより作製した。尚、上記無機粒子層の厚みをマイクロメーターで測定したところ、4μmであった。
このように作製した電池を以下、電池D2と称する。
これは、正極又は負極の表面に形成した無機粒子層により、電解液と正極活物質、又は、電解液と負極活物質との接触が一層抑制されるため、電解液の分解を更に抑制することができるためと考えられる。
第5実施例では、第4実施例で用いた以外の正極活物質を用いて、正極の表面に無機粒子層を形成した場合について検討した。
上記第4実施例の実施例1に記載した方法と同様の方法で、正極の表面に無機粒子層を形成した以外は、上記第2実施例の実施例1と同様の方法で電池を作製した。
このように作製した電池を以下、電池E1と称する。
上記第4実施例の実施例1に記載した方法と同様の方法で、正極の表面に無機粒子層を形成した以外は、上記第2実施例の実施例2と同様の方法で電池を作製した。
このように作製した電池を以下、電池E2と称する。
上記第4実施例の実施例1に記載した方法と同様の方法で、正極の表面に無機粒子層を形成した以外は、上記第1実施例の実施例4と同様の方法で電池を作製した。
このように作製した電池を以下、電池E3と称する。
これは、正極の表面に形成した無機粒子層により、電解液と正極活物質との接触が一層抑制されるため、電解液の分解をさらに抑制することができるためと考えられる。
また、表5から明らかなように、正極活物質の混合割合や、ニッケルコバルトマンガン酸リチウムの固着元素の有無に関係なく、正極の表面に形成した無機粒子層の効果が一様に発現している。したがって、正極活物質表面への固着元素の効果に加えて、無機粒子層を形成することによる効果が発現していることは明らかであると考えられる。
2:負極
3:セパレータ
4:正極集電タブ
5:負極集電タブ
6:アルミラミネート外装体
21:コバルト酸リチウム粒子
22:希土類化合物粒子
Claims (12)
- 表面の一部に希土類化合物が固着されたコバルト酸リチウムとニッケルコバルトマンガン酸リチウムとの混合物から成る正極活物質、及び結着剤を含み、上記正極活物質の総量に対する上記ニッケルコバルトマンガン酸リチウムの割合が、1質量%以上50質量%以下であることを特徴とする非水電解質二次電池用正極。
- 上記正極活物質の総量に対する上記ニッケルコバルトマンガン酸リチウムの割合が、3質量%以上30質量%以下である、請求項1に記載の非水電解質二次電池用正極。
- 上記正極活物質の総量に対する上記ニッケルコバルトマンガン酸リチウムの割合が、5質量%以上20質量%以下である、請求項1に記載の非水電解質二次電池用正極。
- 上記ニッケルコバルトマンガン酸リチウムの表面の一部に希土類化合物が固着されている、請求項1~3の何れか1項に記載の非水電解質二次電池用正極。
- 上記希土類化合物の平均粒径が100nm以下である、請求項1~4の何れか1項に記載の非水電解質二次電池用正極。
- 上記希土類化合物が、希土類の水酸化物、希土類のオキシ水酸化物、希土類の炭酸化合物から成る群から選択された少なくとも1種である、請求項1~5の何れか1項に記載の非水電解質二次電池用正極。
- 上記希土類化合物の希土類元素がエルビウム、ネオジム、サマリウム、ランタンの中から選ばれる少なくとも1種の元素である、請求項1~6の何れか1項に記載の非水電解質二次電池用正極。
- 請求項1~7の何れか1項に記載の非水電解質二次電池用正極と、負極活物質を含む負極と、これら両極間に配置され電解液が含浸されたセパレータとを備えることを特徴とする非水電解質二次電池。
- 上記セパレータと上記非水電解質二次電池用正極との間に、無機粒子を含む無機粒子層が形成されている、請求項8に記載の非水電解質二次電池。
- 上記無機粒子層は上記非水電解質二次電池用正極の表面に形成されている、請求項9に記載の非水電解質二次電池。
- 上記セパレータと上記負極との間に、無機粒子を含む無機粒子層が形成されている、請求項8~10の何れか1項に記載の非水電解質二次電池。
- 上記無機粒子層は上記負極の表面に形成されている、請求項11に記載の非水電解質二次電池。
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US10128495B2 (en) | 2013-02-28 | 2018-11-13 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery that uses the positive electrode |
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EP2658013A1 (en) | 2013-10-30 |
JP2013179095A (ja) | 2013-09-09 |
JPWO2012086277A1 (ja) | 2014-05-22 |
US20130302689A1 (en) | 2013-11-14 |
JP5910576B2 (ja) | 2016-04-27 |
CN103270627A (zh) | 2013-08-28 |
JP5349700B2 (ja) | 2013-11-20 |
US9437869B2 (en) | 2016-09-06 |
CN103270627B (zh) | 2016-02-17 |
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