WO2016017073A1 - 非水電解質二次電池用正極及び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非水電解質二次電池 Download PDFInfo
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- WO2016017073A1 WO2016017073A1 PCT/JP2015/003401 JP2015003401W WO2016017073A1 WO 2016017073 A1 WO2016017073 A1 WO 2016017073A1 JP 2015003401 W JP2015003401 W JP 2015003401W WO 2016017073 A1 WO2016017073 A1 WO 2016017073A1
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/366—Composites as layered products
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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
- 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
- H01M2004/028—Positive 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 positive electrode for a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte secondary battery.
- a non-aqueous electrolyte secondary battery that performs charge / discharge by moving lithium ions between the positive and negative electrodes along with charge / discharge has a high energy density and a high capacity. Widely used as a drive power source.
- non-aqueous electrolyte secondary batteries have attracted attention as power sources for power tools, electric vehicles (EV), hybrid electric vehicles (HEV, PHEV), etc., and further expansion of applications is expected.
- a power source is required to have a high capacity so that it can be used for a long time and to improve output characteristics when a large current is repeatedly charged and discharged in a relatively short time.
- Patent Document 1 gas generation inside the battery during storage can be suppressed by attaching a tungstic acid compound and a phosphoric acid compound to a composite oxide mainly composed of lithium nickelate and performing a heat treatment. It is shown.
- the object is to provide a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary in which a decrease in initial charge capacity is suppressed even when a positive electrode active material or a positive electrode exposed to the atmosphere is used. It is to provide a positive electrode active material for a battery.
- a positive electrode for a non-aqueous electrolyte secondary battery comprising a lithium-containing transition metal composite oxide represented by at least one element selected from the group comprising a tungsten oxide and a phosphoric acid compound It is.
- a positive electrode for a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte secondary battery in which a decrease in initial charge is suppressed even when a positive electrode active material or a positive electrode exposed to the atmosphere is used.
- a positive electrode for a non-aqueous electrolyte secondary battery comprising a lithium-containing transition metal composite oxide represented by at least one element selected from the group consisting of group 13 elements and group 14 elements, and a non-aqueous electrolyte
- the positive electrode for a secondary battery contains tungsten oxide and a phosphoric acid compound.
- the positive electrode is preferably composed of a positive electrode current collector and a positive electrode mixture layer formed on the positive electrode current collector.
- a positive electrode current collector for example, a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the positive electrode such as aluminum, or a film having a metal surface layer such as aluminum is used.
- the positive electrode mixture layer preferably contains a binder and a conductive agent in addition to the positive electrode active material particles.
- the cause of the characteristic deterioration due to atmospheric exposure is LiOH generation reaction.
- the moisture present on the surface of the lithium-containing transition metal composite oxide reacts with the lithium-containing transition metal composite oxide, resulting in a lithium-containing transition metal.
- This is a reaction in which Li is extracted from the lithium-containing transition metal composite oxide by generating a substitution reaction between Li and hydrogen in the surface layer of the composite oxide, thereby generating LiOH.
- the amount of water used for the LiOH generation reaction is reduced due to the suppression of moisture adsorption on the lithium-containing transition metal composite oxide, the LiOH that is the cause of characteristic deterioration due to atmospheric exposure.
- the production reaction can be further suppressed, whereby the deterioration of the initial charging characteristics due to atmospheric exposure can be further reduced.
- the lithium-containing transition metal composite oxide represented by at least one element selected from the group consisting of group elements) is not particularly limited, but Li is monovalent and O is -2 M preferably contains an element having a valence of 2 so that the formal valence of Mn is 4 in that case, and preferably contains Ni from the viewpoint of structural stability.
- nickel cobalt lithium manganate containing cobalt in addition to nickel is more preferable because the structure is stable. More preferably, the molar ratio of nickel, cobalt, and manganese is 5: 2: 3, 5: 3: 2. 6: 2: 2, 7: 1: 2, 7: 2: 1, 8: 1: 1, and the like.
- lithium-containing transition metal composite oxide it is preferable to use a lithium-containing transition metal composite oxide that satisfies the condition of 0 ⁇ x ⁇ 0.2 in the composition ratio (1 + x) of Li.
- the lithium-containing transition metal composite oxide may further contain other additive elements.
- the additive element examples include transition metal elements other than Mn, Ni, and Co, alkali metal elements, alkaline earth metal elements, Group 12 elements, Group 13 elements, and Group 14 elements.
- transition metal elements other than Mn, Ni, and Co, alkali metal elements, alkaline earth metal elements, Group 12 elements, Group 13 elements, and Group 14 elements.
- B Magnesium (Mg), aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tungsten ( W), tantalum (Ta), tin (Sn), sodium (Na), potassium (K), barium (Ba), strontium (Sr), calcium (Ca) and the like.
- lithium-containing transition metal composite oxide examples include particles having an average particle diameter of 2 to 30 ⁇ m, and the particles may be in the form of secondary particles in which primary particles of 100 nm to 10 ⁇ m are bonded.
- tungsten oxide and a phosphoric acid compound are attached to the surface of the lithium-containing transition metal composite oxide.
- the synergistic effect by the said tungsten oxide and a phosphoric acid compound is exhibited further, and the fall of the initial stage charge characteristic by atmospheric exposure is improved further.
- the tungsten oxide contained in the positive electrode is not particularly limited, but WO 3 that is hexavalent in which the oxidation number of tungsten is most stable is preferable.
- the state in which the positive electrode contains tungsten oxide is a state in which tungsten oxide is present in the vicinity of the surface of the positive electrode active material particles made of a lithium-containing transition metal composite oxide, and is preferably scattered and adhered to the surface. More preferably, it is a state where the surface is uniformly scattered and adhered.
- the amount of tungsten mixed is small, the above-described effects of tungsten cannot be sufficiently obtained.
- the amount of tungsten is too large, the surface of the lithium-containing transition metal composite oxide is caused by tungsten oxide. Is widely covered (there are too many covered parts), and the charge / discharge characteristics of the battery are reduced.
- the amount of tungsten in the positive electrode active material is preferably 0.05 mol% or more and 10 mol% or less with respect to the total amount of transition metals of the lithium-containing transition metal composite oxide. More preferably, they are 0.1 mol% or more and 5 mol% or less, More preferably, they are 0.2 mol% or more and 3 mol% or less.
- tungsten oxide is mixed in a step of kneading a conductive agent and a binder. The method of adding is mentioned.
- the particle size of the tungsten oxide particles is preferably smaller than the particle size of the lithium-containing transition metal composite oxide, and particularly preferably smaller than 1 ⁇ 4. If tungsten oxide is larger than the lithium-containing transition metal composite oxide, the contact area with the lithium-containing transition metal composite oxide becomes small, and the effect may not be sufficiently exhibited.
- the phosphate compound contained in the positive electrode is not particularly limited, but is lithium phosphate, lithium dihydrogen phosphate, cobalt phosphate, nickel phosphate, manganese phosphate, potassium phosphate, ammonium dihydrogen phosphate. Of these, lithium phosphate is particularly preferable. When these phosphoric acid compounds are used, the effect of suppressing the decrease in the initial charge capacity due to atmospheric exposure is further exhibited.
- the ratio of the phosphoric acid compound to the total mass of the lithium-containing transition metal composite oxide is preferably 0.01% by mass or more and 1.5% by mass or less, and 0.02% by mass or more and 1. 2 mass% or less is more preferable, 0.1 mass% or more and 1.0 mass% or less are still more preferable.
- the ratio is less than 0.01% by mass, the effect of tungsten oxide and the phosphoric acid compound cannot be sufficiently obtained, and the deterioration of characteristics due to exposure of the electrode plate to the atmosphere may not be suppressed.
- the ratio exceeds 1.5% by mass, the amount of the positive electrode active material is reduced by that amount, so that the positive electrode capacity is reduced.
- a method for producing a positive electrode containing a phosphoric acid compound in addition to a method in which a lithium-containing transition metal composite oxide and a phosphoric acid compound are mixed and adhered in advance, a conductive agent and a binder are kneaded. The method of adding an acid compound is mentioned.
- the particle size of the phosphoric acid compound particles is preferably smaller than the particle size of the lithium-containing transition metal composite oxide, and particularly preferably smaller than 1 ⁇ 4. If the phosphoric acid compound is larger than the lithium-containing transition metal composite oxide, the contact area with the lithium-containing transition metal composite oxide becomes small, and the effect may not be sufficiently exhibited.
- the phosphoric acid compound exists in the vicinity of tungsten oxide, and in this case also, the effect of the phosphoric acid compound and tungsten oxide can be obtained. That is, the phosphoric acid compound may adhere to the particle surface of the lithium-containing transition metal composite oxide, or may exist in the vicinity of tungsten oxide in the positive electrode without adhering to the surface. If the phosphoric acid compound is preliminarily mixed with the lithium-containing transition metal composite oxide, for example, to adhere more selectively to the particle surface of the lithium-containing transition metal composite oxide, the synergistic effect of the phosphoric acid compound and tungsten oxide is obtained. This is particularly preferable because it becomes large.
- the above-described positive electrode active material can be further mixed with another positive electrode active material.
- the other positive electrode active material to be mixed is not particularly limited as long as it is a compound that can reversibly insert and desorb lithium.
- lithium ions can be inserted and desorbed while maintaining a stable crystal structure.
- a layered structure, a spinel structure, a olivine structure, or the like can be used.
- the positive electrode active materials may be of the same particle size or of different particle sizes. Also good.
- binder examples include fluorine-based polymers and rubber-based polymers.
- PTFE polytetrafluoroethylene
- PVdF polyvinylidene fluoride
- examples include coalescence. These may be used alone or in combination of two or more.
- the binder may be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).
- Examples of the conductive agent include carbon materials such as carbon black, acetylene black, ketjen black, and graphite as carbon materials. These may be used alone or in combination of two or more.
- a positive electrode active material for a non-aqueous electrolyte secondary battery which is an example of an embodiment of the present invention, includes a lithium-containing transition metal composite oxide, tungsten oxide attached to the surface of the lithium-containing transition metal composite oxide, and the above And a phosphate compound adhering to the surface of the lithium-containing transition metal composite oxide.
- a conventionally used negative electrode can be used.
- a negative electrode active material and a binder are mixed with water or an appropriate solvent, applied to the negative electrode current collector, dried, and rolled. Can be obtained.
- the negative electrode current collector it is preferable to use a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the negative electrode such as copper, a film having a metal surface layer such as copper, or the like.
- the binder PTFE or the like can be used as in the case of the positive electrode, but it is preferable to use a styrene-butadiene copolymer (SBR) or a modified body thereof.
- SBR styrene-butadiene copolymer
- the binder may be used in combination with a thickener such as CMC.
- the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium ions.
- a carbon material, a metal or alloy material alloyed with lithium such as Si or Sn, or a metal composite An oxide or the like can be used. These may be used alone or in admixture of two or more, and are a combination of a negative electrode active material selected from a carbon material, a metal alloyed with lithium, an alloy material, or a metal composite oxide. May be.
- Nonaqueous electrolyte As the nonaqueous electrolyte solvent, conventionally used cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, and chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate may be used. it can. In particular, it is preferable to use a mixed solvent of a cyclic carbonate and a chain carbonate as a non-aqueous solvent having a high lithium ion conductivity in terms of high dielectric constant, low viscosity, and low melting point. Further, the volume ratio of the cyclic carbonate to the chain carbonate in the mixed solvent is preferably regulated in the range of 2: 8 to 5: 5.
- esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and ⁇ -butyrolactone; compounds containing sulfone groups such as propane sultone; 1,2-dimethoxyethane, 1,2- Compounds containing ethers such as diethoxyethane, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 2-methyltetrahydrofuran; butyronitrile, valeronitrile, n-heptanenitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile , 1,2,3-propanetricarbonitrile, compounds containing nitriles such as 1,3,5-pentanetricarbonitrile; compounds containing amides such as dimethylformamide, etc. can be used together with the above-mentioned solvents, These
- solutes can be used as the solute of the non-aqueous electrolyte, for example, LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN which are fluorine-containing lithium salts.
- (CF 3 SO 2 ) 2 LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6, etc.
- LiPF 6 LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN which are fluorine-containing lithium salts.
- (CF 3 SO 2 ) 2 LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6, etc.
- lithium salt other than fluorine-containing lithium salt [lithium salt containing one or more elements among P, B, O, S, N, Cl (for example, LiClO 4 etc.)] is added to fluorine-containing lithium salt. May be used.
- lithium salts having the oxalato complex as an anion include LiBOB [lithium-bisoxalate borate], Li [B (C 2 O 4 ) F 2 ], Li [P (C 2 O 4 ) F 4 ], li [P (C 2 O 4 ) 2 F 2] and the like.
- LiBOB lithium-bisoxalate borate
- Li [B (C 2 O 4 ) F 2 ] Li [P (C 2 O 4 ) F 4 ]
- li [P (C 2 O 4 ) 2 F 2] and the like.
- the said solute may be used independently and may be used in mixture of 2 or more types.
- separator As a separator, the separator conventionally used can be used. For example, a polypropylene or polyethylene separator, a polypropylene-polyethylene multilayer separator, or a separator whose surface is coated with a resin such as an aramid resin can be used.
- a layer made of an inorganic filler conventionally used can be formed at the interface between the positive electrode and the separator or the interface between the negative electrode and the separator.
- the filler it is possible to use oxides or phosphate compounds using titanium, aluminum, silicon, magnesium, etc., which have been used conventionally, or those whose surfaces are treated with hydroxide or the like. .
- the filler layer may be formed by directly applying a filler-containing slurry to the positive electrode, negative electrode, or separator, or by attaching a filler-formed sheet to the positive electrode, negative electrode, or separator. Can do.
- positive electrode active material particles made of the above Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2 , tungsten oxide (WO 3 ), and lithium phosphate are mixed at a predetermined ratio to obtain a positive electrode.
- An active material was prepared.
- the amount of tungsten in the positive electrode active material thus produced was 1.0 mol% with respect to the total amount of transition metals in the lithium-containing transition metal composite oxide. Further, the amount of lithium phosphate in the positive electrode active material was 0.5 wt%.
- the positive electrode mixture slurry is applied to both surfaces of a positive electrode current collector made of an aluminum foil, dried, and then rolled with a rolling roller, and a current collector tab made of aluminum is further attached.
- a positive electrode plate having a positive electrode mixture layer formed on both sides of the electric body was produced.
- the obtained positive electrode plate was observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- particles of tungsten oxide having an average particle diameter of 150 nm and lithium phosphate having an average particle diameter of 100 nm were obtained from the lithium-containing transition metal composite oxide. It was confirmed that it adhered to the surface. However, some of them are included in the positive electrode without adhering to the positive electrode active material particles because tungsten oxide and lithium phosphate may be peeled off from the surface of the positive electrode active material particles in the step of mixing the conductive agent and the binder. Sometimes it is. Further, it was confirmed that lithium phosphate is attached to tungsten oxide or exists in the vicinity of tungsten oxide.
- the positive electrode produced as described above is used as the working electrode 11, while metallic lithium is used for the counter electrode 12 and the reference electrode 13 serving as the negative electrode, and ethylene is used as the non-aqueous electrolyte 14.
- LiPF 6 was dissolved to a concentration of 1 mol / l in a mixed solvent in which carbonate, methyl ethyl carbonate, and dimethyl carbonate were mixed at a volume ratio of 3: 3: 4, and 1% by mass of vinylene carbonate was further dissolved.
- a three-electrode test cell was prepared using this.
- the battery thus produced is hereinafter referred to as battery A1.
- Example 2 In the preparation of the positive electrode active material in Experimental Example 1, except that the amount of tungsten oxide was increased with respect to the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2. Produced the three-electrode test cell of Experimental Example 2 in the same manner as in Experimental Example 1 above. The battery thus produced is hereinafter referred to as battery A2. The amount of tungsten in the positive electrode active material thus produced was 3.0 mol% with respect to the total amount of transition metals in the lithium-containing transition metal composite oxide.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A2, except that after the rolling with a rolling roller and the air exposure was performed under the above-described conditions. B2) was produced.
- Example 3 In preparation of the positive electrode active material in Experimental Example 1, the amount of lithium phosphate was increased with respect to the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2 .
- a three-electrode test cell of Experimental Example 3 was produced in the same manner as in Experimental Example 1 except for the above.
- the battery thus produced is hereinafter referred to as battery A3.
- the amount of lithium phosphate in the positive electrode active material thus produced was 3 wt%.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A3, except that after being rolled by a rolling roller and exposed to the air under the above-described conditions. B3) was produced.
- Example 4 In preparation of the positive electrode active material in Experimental Example 1, tungsten oxide and lithium phosphate were mixed with the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2. A three-electrode test cell of Experimental Example 4 was produced in the same manner as in Experimental Example 1 except that it was not. The battery thus produced is hereinafter referred to as battery A4.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A4, except that after being rolled by a rolling roller and exposed to the air under the above-described conditions. B4) was produced.
- Example 5 In preparation of the positive electrode active material in Example 1, except that a mixture of only tungsten oxide for positive electrode active material particles composed of the above Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279] O 2 is In the same manner as in Experimental Example 1, the three-electrode test cell of Experimental Example 5 was produced. The battery thus produced is hereinafter referred to as battery A5.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A5, except that after being rolled by a rolling roller and exposed to the air under the above-described conditions. B5) was produced.
- Example 6 In the production of the positive electrode active material in Experimental Example 5, except that the amount of tungsten oxide was increased with respect to the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2. Produced the three-electrode test cell of Experimental Example 6 in the same manner as in Experimental Example 5 above. The battery thus produced is hereinafter referred to as battery A6.
- the amount of tungsten in the positive electrode active material thus produced was 3.0 mol% with respect to the total amount of transition metals in the lithium-containing transition metal composite oxide.
- XRD X-ray diffraction
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A6, except that after being rolled by a rolling roller and exposed to the atmosphere under the above-described conditions. B6) was produced.
- Example 7 In preparation of the positive electrode active material in Experimental Example 1, only lithium phosphate was mixed with the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2. Produced the three-electrode test cell of Experimental Example 7 in the same manner as in Experimental Example 1 above. The battery thus produced is hereinafter referred to as battery A7.
- Example 8 In preparation of the positive electrode active material in Experimental Example 7, the amount of lithium phosphate was increased with respect to the positive electrode active material particles made of Li 1.07 [Ni 0.465 Co 0.186 Mn 0.279 ] O 2 .
- a three-electrode test cell of Experimental Example 8 was produced in the same manner as in Experimental Example 7 except for the above. The battery thus produced is hereinafter referred to as battery A8.
- the amount of lithium phosphate in the positive electrode active material thus produced was 3 wt%.
- the initial charge capacity without exposure to the atmosphere is defined as the “initial charge capacity without exposure”, and there is exposure to the atmosphere (using the positive electrode plate exposed to the atmosphere)
- the initial charge capacity with exposure is defined as “initial charge capacity with exposure”.
- the batteries of Experimental Examples 1 to 3 in which tungsten oxide and lithium phosphate are adhered to the particle surfaces of the lithium-containing transition metal composite oxide are the batteries of Experimental Examples 4 to 8. Compared with, the deterioration rate of charging capacity due to atmospheric exposure is greatly reduced.
- Example 9 The nickel-cobalt-manganese composite, lithium hydroxide, nickel-cobalt-manganese composite oxide, zirconium oxide (ZrO 2 ) used in Example 1, lithium, nickel-cobalt-manganese as a transition metal as a whole, and moles of zirconium
- the three-electrode test of Experimental Example 9 is performed in the same manner as in Experimental Example 1 except that the ratio is 1.15: 1: 0.005, which is mixed and baked in an Ishikawa-type rough mortar. A cell was produced.
- the battery thus produced is hereinafter referred to as battery A9.
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A10, except that after being rolled by a rolling roller and exposed to the atmosphere under the above-described conditions. B10) was produced.
- the battery of Experimental Example 9 in which zirconium oxide was mixed together with lithium hydroxide and a transition metal composite oxide to produce a lithium-containing transition metal composite oxide was obtained by using tungsten oxide and lithium phosphate.
- the battery of Experimental Example 10 in which both are not attached to the surface of the lithium-containing transition metal compound it was found that the deterioration of the initial charging characteristics due to atmospheric exposure was greatly suppressed.
- the effect of the zirconium is not clear, the adsorption of moisture in the atmosphere to the lithium-containing transition metal compound is suppressed, and as a result, the progress of the LiOH generation reaction that causes the characteristic deterioration due to atmospheric exposure is further suppressed. It is considered that the deterioration of the initial charging characteristics due to atmospheric exposure could be further reduced.
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A11, except that after being rolled by a rolling roller and exposed to the atmosphere under the above-described conditions. B11) was produced.
- Example 12 In preparation of the positive electrode active material in Experimental Example 11, tungsten oxide and lithium phosphate were mixed with the positive electrode active material particles made of Li 1.024 [Ni 0.683 Co 0.195 Mn 0.098 ] O 2. A three-electrode test cell of Experimental Example 12 was produced in the same manner as in Experimental Example 11 except that it was not. The battery thus produced is hereinafter referred to as battery A12.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A12, except that the positive electrode plate was rolled with a rolling roller and then exposed to the air under the above-described conditions. B12) was produced.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A13, except that the positive electrode plate was rolled by a rolling roller and then exposed to the air under the above-described conditions. B13) was produced.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A14, except that the positive electrode plate was rolled with a rolling roller and then exposed to the air under the above-described conditions. B14) was produced.
- a battery (battery) using a positive electrode plate exposed to the air in the same manner as the battery A15, except that after being rolled by a rolling roller and exposed to the air under the above-described conditions. B15) was produced.
- Example 16 In preparation of the positive electrode active material in Experimental Example 15, tungsten oxide and lithium phosphate were mixed with the positive electrode active material particles made of the above Li 1.015 [Ni 0.808 Co 0.148 Al 0.029 ] O 2. A three-electrode test cell of Experimental Example 16 was produced in the same manner as in Experimental Example 15 except that it was not. The battery thus produced is hereinafter referred to as battery A16.
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A16 except that it was exposed to the atmosphere under the above-mentioned conditions after being rolled by a rolling roller. B16) was produced.
- Example 17 In preparation of the positive electrode active material in Experimental Example 15, except that only tungsten oxide was mixed with the positive electrode active material particles made of Li 1.015 [Ni 0.808 Co 0.148 Al 0.029 ] O 2 described above. In the same manner as in Experimental Example 15, the three-electrode test cell of Experimental Example 17 was produced. The battery thus produced is hereinafter referred to as battery A17.
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A17, except that the positive electrode plate was rolled with a rolling roller and then exposed to the air under the above-described conditions. B17) was produced.
- a lithium nickel acid composite oxide represented by O 2 was obtained.
- Example 20 In preparation of the positive electrode active material in Experimental Example 19, tungsten oxide and lithium phosphate were not mixed with the positive electrode active material particles made of Li 1.024 [Ni 0.781 Co 0.146 Mn 0.049 ]. A three-electrode test cell of Experimental Example 20 was produced in the same manner as in Experimental Example 19 except for the above. The battery thus produced is hereinafter referred to as battery A20.
- a battery (battery) using a positive electrode plate exposed to the atmosphere in the same manner as the battery A20, except that after being rolled by a rolling roller and exposed to the atmosphere under the above-described conditions. B20) was produced.
- a positive electrode for a non-aqueous electrolyte secondary battery according to one aspect of the present invention and a non-aqueous electrolyte secondary battery using the same are, for example, driving power sources for mobile information terminals such as mobile phones, notebook computers, smartphones, tablet terminals, and the like. It can be applied to applications where high energy density is required. Furthermore, it can be expected to be used for high-power applications such as electric vehicles (EV), hybrid electric vehicles (HEV, PHEV) and electric tools.
- EV electric vehicles
- HEV hybrid electric vehicles
- PHEV PHEV
Abstract
Description
本発明の実施形態の一例である非水電解質二次電池用正極は、一般式Li1+xMnaMbO2+c(式中、x、a、bおよびcは、x+a+b=1、0<x≦0.2、0.09≦a、-0.1≦c≦0.1の条件を満たし、MはMn以外の遷移金属元素、アルカリ金属元素、アルカリ土類金属元素、第12族元素、第13族元素および第14族元素からなる群より選択される少なくとも1種の元素)で表されるリチウム含有遷移金属複合酸化物を含む非水電解質二次電池用正極であって、かつ非水電解質二次電池用正極に酸化タングステン及びリン酸化合物を含んでいるものである。
負極としては、従来から用いられてきた負極を用いることができ、例えば、負極活物質と、結着剤とを水あるいは適当な溶媒で混合し、負極集電体に塗布し、乾燥し、圧延することにより得られる。負極集電体には、導電性を有する薄膜体、特に銅などの負極の電位範囲で安定な金属箔や合金箔、銅などの金属表層を有するフィルム等を用いることが好適である。結着剤としては、正極の場合と同様にPTFE等を用いることもできるが、スチレンーブタジエン共重合体(SBR)又はこの変性体等を用いることが好ましい。結着剤は、CMC等の増粘剤と併用されてもよい。
非水電解質の溶媒としては、従来から使用されている、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネート等の環状カーボネートや、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート等の鎖状カーボネートを用いることができる。特に、高誘電率、低粘度、低融点の観点でリチウムイオン伝導度の高い非水系溶媒として、環状カーボネートと鎖状カーボネートとの混合溶媒を用いることが好ましい。また、この混合溶媒における環状カーボネートと鎖状カーボネートとの体積比は、2:8~5:5の範囲に規制することが好ましい。
セパレータとしては、従来から用いられてきたセパレータを用いることができる。例えば、ポリプロピレン製やポリエチレン製のセパレータ、ポリプロピレン-ポリエチレンの多層セパレータや、セパレータの表面にアラミド系樹脂等の樹脂が塗布されたものを用いることができる。
(実験例1)
[正極活物質の作製]
まず、共沈により得られた[Ni0.5Co0.20Mn0.30](OH)2で表されるニッケルコバルトマンガン複合水酸化物を500℃で焼成して、ニッケルコバルトマンガン複合酸化物を得た。次に、水酸化リチウムと、上記で得たニッケルコバルトマンガン複合酸化物とを、リチウムと、遷移金属全体とのモル比が1.15:1になるように、石川式らいかい乳鉢にて混合した。その後、この混合物を空気雰囲気中にて900℃で10時間焼成し、粉砕することにより、平均二次粒子径が約8μmのLi1.07[Ni0.465Co0.186Mn0.279]O2で表されるリチウムニッケルマンガンコバルト複合酸化物を得た。
上記正極活物質と導電剤としてのカーボンブラックと、結着剤としてのポリフッ化ビニリデンを溶解させたN-メチル-2-ピロリドン溶液とを、正極活物質と導電剤と結着剤との質量比が92:5:3となるように秤量し、これらを混練して正極合剤スラリーを調製した。
正極極板を作製する際に、圧延ローラーにより圧延した後、以下の条件で大気曝露を行ったこと以外は、上記電池A1と同様にして大気曝露した正極極板を用いた電池(電池B1)を作製した。
・大気曝露条件
温度60℃、湿度30%の恒温恒湿槽に3日静置した。
実験例1における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対して酸化タングステンの量を増やした以外は、上記の実験例1の場合と同様にして、実験例2の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A2と称する。なお、このようにして作製した正極活物質中におけるタングステンの量はリチウム含有遷移金属複合酸化物の遷移金属の総量に対して3.0mol%だった。
実験例1における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対してリン酸リチウムの量を増やした以外は、上記の実験例1の場合と同様にして、実験例3の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A3と称する。なお、このようにして作製した正極活物質中におけるリン酸リチウムの量は3wt%であった。
実験例1における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対して酸化タングステン、リン酸リチウムを混合させなかった以外は、上記の実験例1の場合と同様にして、実験例4の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A4と称する。
実験例1における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対して酸化タングステンのみを混合した以外は、上記の実験例1の場合と同様にして、実験例5の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A5と称する。
実験例5における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対して酸化タングステンの量を増やした以外は、上記の実験例5の場合と同様にして、実験例6の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A6と称する。
実験例1における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対してリン酸リチウムのみを混合した以外は、上記の実験例1の場合と同様にして、実験例7の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A7と称する。
実験例7における正極活物質の作製において、上記のLi1.07[Ni0.465Co0.186Mn0.279]O2からなる正極活物質粒子に対してリン酸リチウムの量を増やした以外は、上記の実験例7の場合と同様にして、実験例8の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A8と称する。なお、このようにして作製した正極活物質中におけるリン酸リチウムの量は3wt%だった。
25℃の温度条件下において、0.2mA/cm2の電流密度で4.3V(vs.Li/Li+)まで定電流充電を行い、4.3V(vs.Li/Li+)の定電圧で電流密度が0.04mA/cm2になるまで定電圧充電を行った。
上記で求めた初期充電容量のうち、大気曝露なし(大気曝露していない正極極板使用時)の初期充電容量を「曝露なし初期充電容量」とし、大気曝露あり(大気曝露した正極極板使用時)の初期充電容量を「曝露あり初期充電容量」とし、下記に示す式(1)に基づき、対応する電池の曝露なし初期充電容量と曝露あり初期充電容量の差から大気曝露による劣化充電容量を算出した。
劣化充電容量=(曝露なし初期充電容量)-(曝露あり初期充電容量) (1)
(実験例9)
実験例1で用いたニッケルコバルトマンガン複合物と水酸化リチウムとニッケルコバルトマンガン複合酸化物と、酸化ジルコニウム(ZrO2)とを、リチウムと、遷移金属全体としてのニッケルコバルトマンガンと、ジルコニウムとのモル比が1.15:1:0.005になるように、石川式らいかい乳鉢にて混合し焼成した以外は、上記の実験例1の場合と同様にして、実験例9の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A9と称する。
実験例9における正極活物質の作製において、酸化タングステン、リン酸リチウムを混合させなかった以外は、上記の実験例9の場合と同様にして、実験例10の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A10と称する。
(実験例11)
まず、共沈により得られた[Ni0.70Co0.20Mn0.10](OH)2で表されるニッケルコバルトマンガン複合水酸化物を500℃で焼成して、ニッケルコバルトマンガン複合酸化物を得た。次に、水酸化リチウムと、上記で得たニッケルコバルトマンガン複合酸化物とを、リチウムと、遷移金属全体とのモル比が1.05:1になるように、石川式らいかい乳鉢にて混合した。
実験例11における正極活物質の作製において、上記のLi1.024[Ni0.683Co0.195Mn0.098]O2からなる正極活物質粒子に対して酸化タングステン、リン酸リチウムを混合させなかった以外は、上記の実験例11の場合と同様にして、実験例12の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A12と称する。
実験例11における正極活物質の作製において、上記のLi1.024[Ni0.683Co0.195Mn0.098]O2からなる正極活物質粒子に対して酸化タングステンのみを混合した以外は、上記の実験例11の場合と同様にして、実験例13の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A13と称する。
実験例11における正極活物質の作製において、上記のLi1.024[Ni0.683Co0.195Mn0.098]O2からなる正極活物質粒子に対してリン酸リチウムのみを混合した以外は、上記の実験例11の場合と同様にして、実験例14の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A14と称する。
まず、共沈により得られた[Ni0.82Co0.15Al0.03](OH)2で表されるニッケルコバルトアルミ複合水酸化物を500℃で焼成して、ニッケルコバルトアルミ複合酸化物を得た。次に、水酸化リチウムと、上記で得たニッケルコバルトアルミ複合酸化物とを、リチウムと、遷移金属全体とのモル比が1.03:1になるように、石川式らいかい乳鉢にて混合した。
実験例15における正極活物質の作製において、上記のLi1.015[Ni0.808Co0.148Al0.029]O2からなる正極活物質粒子に対して酸化タングステン、リン酸リチウムを混合させなかった以外は、上記の実験例15の場合と同様にして、実験例16の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A16と称する。
実験例15における正極活物質の作製において、上記のLi1.015[Ni0.808Co0.148Al0.029]O2からなる正極活物質粒子に対して酸化タングステンのみを混合した以外は、上記の実験例15の場合と同様にして、実験例17の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A17と称する。
実験例15における正極活物質の作製において、上記のLi1.015[Ni0.808Co0.148Al0.029]O2からなる正極活物質粒子に対してリン酸リチウムのみを混合した以外は、上記の実験例15の場合と同様にして、実験例18の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A18と称する。
まず、共沈により得られた[Ni0.80Co0.15Mn0.05](OH)2で表されるニッケルコバルトマンガン複合水酸化物を500℃で焼成して、ニッケルコバルトマンガン複合酸化物を得た。次に、水酸化リチウムと、上記で得たニッケルコバルトマンガン複合酸化物とを、リチウムと、遷移金属全体とのモル比が1.05:1になるように、石川式らいかい乳鉢にて混合した。
実験例19における正極活物質の作製において、上記のLi1.024[Ni0.781Co0.146Mn0.049]からなる正極活物質粒子に対して酸化タングステン、リン酸リチウムを混合させなかった以外は、上記の実験例19の場合と同様にして、実験例20の三電極式試験セルを作製した。このようにして作製した電池を、以下、電池A20と称する。
12 対極(負極)
13 参照極
14 非水電解液
20 三電極式試験セル
Claims (7)
- 一般式Li1+xMnaMbO2+c(式中、x、a、bおよびcは、x+a+b=1、0<x≦0.2、0.09≦a、-0.1≦c≦0.1の条件を満たし、MはMn以外の遷移金属元素、アルカリ金属元素、アルカリ土類金属元素、第12族元素、第13族元素および第14族元素からなる群より選択される少なくとも1種の元素)で表されるリチウム含有遷移金属複合酸化物を含む非水電解質二次電池用正極であって、
酸化タングステン及びリン酸化合物を含む非水電解質二次電池用正極。 - 前記酸化タングステン及びリン酸化合物が、前記リチウム含有遷移金属複合酸化物の表面の少なくとも一部に付着している、請求項1に記載の非水電解質二次電池用正極。
- 前記酸化タングステンがWO3である請求項1または2に記載の非水電解質二次電池用正極。
- 前記リン酸化合物が、リン酸リチウムである請求項1~3のいずれかに記載の非水電解質二次電池用正極。
- 前記MがNiを含む請求項1~4のいずれかに記載の非水電解質二次電池用正極。
- 前記MがZrを含む請求項1~5のいずれかに記載の非水電解質二次電池用正極。
- 請求項1~6のいずれかに記載の非水電解質二次電池用正極を用いた非水電解質二次電池。
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US10522877B2 (en) | 2019-12-31 |
JPWO2016017073A1 (ja) | 2017-04-27 |
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CN106663780B (zh) | 2020-03-10 |
US20170141441A1 (en) | 2017-05-18 |
JP6614149B2 (ja) | 2019-12-04 |
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