WO2013129032A1 - 非水電解質二次電池用正極、その製造方法、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、その製造方法、及び非水電解質二次電池 Download PDFInfo
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- WO2013129032A1 WO2013129032A1 PCT/JP2013/052460 JP2013052460W WO2013129032A1 WO 2013129032 A1 WO2013129032 A1 WO 2013129032A1 JP 2013052460 W JP2013052460 W JP 2013052460W WO 2013129032 A1 WO2013129032 A1 WO 2013129032A1
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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
- H01M4/364—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
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
Definitions
- the present invention relates to a positive electrode for a non-aqueous electrolyte secondary battery, a manufacturing method thereof, and a non-aqueous electrolyte secondary battery.
- non-aqueous electrolyte secondary batteries such as lithium secondary batteries have been widely used as power sources for electronic devices and the like.
- Examples of a method for increasing the capacity of the nonaqueous electrolyte secondary battery include a method for increasing the charging voltage.
- a method for increasing the charging voltage For example, when lithium cobaltate is used as the positive electrode active material of a non-aqueous electrolyte secondary battery, if the non-aqueous electrolyte secondary battery is charged to 4.3 V with respect to metallic lithium, the capacity of the non-aqueous electrolyte secondary battery is It becomes about 160 mAh / g. On the other hand, when the non-aqueous electrolyte secondary battery is charged to 4.5 V with respect to metallic lithium, the capacity of the non-aqueous electrolyte secondary battery is about 190 mAh / g.
- the nonaqueous electrolyte secondary battery When the charging voltage of the nonaqueous electrolyte secondary battery is increased, there is a problem that the nonaqueous electrolyte is easily decomposed by the positive electrode active material. In particular, when a nonaqueous electrolyte secondary battery is charged at a high charge voltage at a high temperature, the nonaqueous electrolyte is more easily decomposed.
- Patent Document 1 includes an adhesion step of depositing a phosphate compound on composite oxide particles containing lithium and nickel, and a heating step of heat-treating the composite oxide particles deposited with the phosphate compound.
- a method for producing a positive electrode active material is disclosed.
- Patent Document 1 it is proposed to increase the charging current capacity of a secondary battery by using a positive electrode active material obtained by such a manufacturing method.
- the main object is to provide a positive electrode for a water electrolyte secondary battery.
- the positive electrode for nonaqueous electrolyte secondary batteries includes a positive electrode active material layer.
- the positive electrode active material layer includes a positive electrode active material and a compound represented by the general formula (1): MH 2 PO 2 .
- M is a monovalent cation.
- a non-aqueous electrolyte secondary battery of the present invention includes the positive electrode, the negative electrode, a non-aqueous electrolyte, and a separator.
- the method for producing a positive electrode for a non-aqueous electrolyte secondary battery according to the present invention is for forming a positive electrode active material layer by mixing a compound represented by the general formula (1): MH 2 PO 2 , a positive electrode active material, and a solvent.
- M is a monovalent cation.
- a positive electrode for a non-aqueous electrolyte secondary battery can be provided.
- FIG. 1 is a schematic cross-sectional view of a nonaqueous electrolyte secondary battery in an embodiment of the present invention. It is a schematic sectional drawing of the positive electrode for nonaqueous electrolyte secondary batteries in one Embodiment of this invention.
- 3 is a graph showing AC impedance characteristics of a battery A and batteries C to E.
- the nonaqueous electrolyte secondary battery 1 includes a battery container 17.
- the battery container 17 has a flat shape.
- the shape of the battery container is not limited to a flat shape.
- the shape of the battery container may be, for example, a cylindrical shape or a square shape.
- an electrode body 10 impregnated with a nonaqueous electrolyte is accommodated.
- non-aqueous electrolyte for example, a known non-aqueous electrolyte can be used.
- the non-aqueous electrolyte includes a solute, a non-aqueous solvent, and the like.
- the solute of the non-aqueous electrolyte for example, LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiC (SO 2 CF 3) 3, LiC (SO 2 C 2 F 5) 3, LiClO 4 or the like can be mentioned.
- the non-aqueous electrolyte may contain one type of solute or may contain a plurality of types of solutes.
- non-aqueous solvent for the non-aqueous electrolyte examples include cyclic carbonates, chain carbonates, mixed solvents of cyclic carbonates and chain carbonates, and the like.
- cyclic carbonate examples include ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, and the like.
- chain carbonate examples include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.
- a mixed solvent of a cyclic carbonate and a chain carbonate is preferably used as a non-aqueous solvent having a low viscosity and a low melting point and a high lithium ion conductivity.
- the mixing ratio of cyclic carbonate to chain carbonate may be in the range of 1: 9 to 5: 5 by volume ratio. preferable.
- the nonaqueous electrolyte may be a gel polymer electrolyte in which a polymer electrolyte such as polyethylene oxide or polyacrylonitrile is impregnated with an electrolytic solution.
- the electrode body 10 is formed by winding a negative electrode 11, a positive electrode 12, and a separator 13 disposed between the negative electrode 11 and the positive electrode 12.
- the separator 13 can suppress a short circuit due to contact between the negative electrode 11 and the positive electrode 12, and is impregnated with a nonaqueous electrolyte.
- Separator 13 can be constituted by a porous film made of resin, for example.
- the resin porous membrane include a polypropylene porous membrane and a polyethylene porous membrane, and a laminate of a polypropylene porous membrane and a polyethylene porous membrane.
- the negative electrode 11 has a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
- the negative electrode current collector can be formed of a foil made of a metal such as Cu or an alloy containing a metal such as Cu, for example.
- the negative electrode active material layer contains a negative electrode active material.
- the negative electrode active material is not particularly limited as long as it can reversibly store and release lithium.
- Examples of the negative electrode active material include carbon materials such as graphite and coke, metal oxides such as tin oxide, metals that can be alloyed with lithium such as silicon and tin, and lithium, metal lithium, and the like.
- a carbon material is preferable as a negative electrode active material because it has little volume change associated with insertion and extraction of lithium and is excellent in reversibility.
- the negative electrode active material layer may contain a carbon conductive agent such as graphite, a binder such as sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR).
- a carbon conductive agent such as graphite
- a binder such as sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR).
- the positive electrode 12 has a positive electrode current collector 12a and a positive electrode active material layer 12b disposed on the positive electrode current collector 12a.
- the positive electrode current collector 12a can be formed of a foil made of a metal such as Al or an alloy containing a metal such as Al, for example.
- the positive electrode active material layer 12b contains a positive electrode active material.
- the positive electrode active material layer 12b may contain a binder, a conductive agent, and the like in addition to the positive electrode active material.
- the binder include polytetrafluoroethylene and polyvinylidene fluoride (PVDF).
- PVDF polyvinylidene fluoride
- the conductive agent include carbon materials such as graphite, acetylene black, and carbon black.
- the positive electrode active material may be in the form of particles.
- the kind of positive electrode active material is not particularly limited.
- the positive electrode active material is composed of, for example, a lithium-containing transition metal oxide.
- the lithium-containing transition metal oxide preferably has a layered structure.
- Examples of lithium-containing transition metal oxides include lithium-nickel composite oxides, lithium-nickel-cobalt-aluminum composite oxides, lithium-nickel-cobalt-manganese composite oxides, and lithium-cobalt composite oxides.
- Etc. Lithium cobaltate in which at least one of Al and Mg is solid-solved inside the crystal and Zr is fixed to the surface is preferable as a lithium-containing transition metal oxide because of its high crystal structure stability.
- the proportion of nickel in the lithium-containing transition metal oxide is preferably 40 mol% or more from the viewpoint of reducing the amount of cobalt used.
- the positive electrode active material may be composed of only one type or may be composed of two or more types.
- the positive electrode active material layer 12b has the following general formula (1): MH 2 PO 2 (1) [Wherein M is a monovalent cation. ]
- M is a monovalent cation.
- M is preferably at least one selected from the group consisting of NH 4 , Na, Li and K, and more preferably at least one of NH 4 and Na.
- Compound (1) is considered to act as a reducing agent in the positive electrode active material layer 12b of the nonaqueous electrolyte secondary battery 1. That is, it is considered that the oxidation and decomposition of the nonaqueous electrolyte are suppressed by oxidizing the compound (1) in the positive electrode active material layer 12b.
- the decomposition of the nonaqueous electrolyte is suppressed, the amount of gas generated in the nonaqueous electrolyte secondary battery 1 is reduced, and characteristics such as capacity retention rate and charge / discharge efficiency are hardly deteriorated.
- a part of the compound (1) is a transition metal in the positive electrode active material. It is thought that it reduces. For this reason, the electroconductivity of the positive electrode active material surface is improved, and the discharge capacity maintenance rate of the nonaqueous electrolyte secondary battery 1 is increased.
- the positive electrode 12 can be manufactured, for example, as follows. First, the positive electrode active material, the compound (1), and a solvent are mixed to obtain a positive electrode active material layer forming slurry.
- a solvent N-methyl-2-pyrrolidone (NMP) or the like is preferably used.
- NMP N-methyl-2-pyrrolidone
- the positive electrode active material layer forming slurry may be mixed with a conductive agent, a binder, and the like.
- the order of mixing the positive electrode active material, the compound (1), the solvent, the conductive agent, the binder and the like is not particularly limited.
- compound (1) may be mixed as a solid or as an aqueous solution. An aqueous solution containing the compound (1) may be sprayed on the positive electrode active material.
- the positive electrode active material layer forming slurry is applied onto the positive electrode current collector 12a and dried to form the positive electrode active material layer 12b. Through the above steps, the positive electrode 12 can be completed.
- the phosphate compound is decomposed by heat-treating the composite oxide particles to which the phosphate compound is deposited.
- Compound (1) decomposes when heated at a temperature of about 200 ° C. or higher.
- the nonaqueous electrolyte secondary battery 1 when the compound (1) is decomposed, the effect of the compound (1) as a reducing agent is lost, and the battery thickness may increase.
- the positive electrode active material layer forming slurry to which the compound (1) is added is preferably dried at a temperature of 150 ° C. or lower, and is dried at a temperature of 130 ° C. or lower. More preferred.
- the compound (1) is preferably contained in an amount of 0.001 part by mass or more, more preferably 0.02 part by mass or more, relative to 100 parts by mass of the positive electrode active material. More preferably, the content is 04 parts by mass or more. This is because if the content of the compound (1) is too small, the effect of improving the charge / discharge efficiency of the nonaqueous electrolyte secondary battery 1 may not be sufficiently obtained.
- the compound (1) is preferably contained in an amount of 1.0 part by mass or less, more preferably 0.5 part by mass or less, relative to 100 parts by mass of the positive electrode active material. More preferably, 2 parts by mass or less is included.
- the gas generation amount in the nonaqueous electrolyte secondary battery 1 will increase easily, and the thickness of the nonaqueous electrolyte secondary battery 1 may become large easily.
- Example 1 A positive electrode active material, acetylene black, and polyvinylidene fluoride (PVDF) were kneaded together with NMP to prepare a slurry.
- a positive electrode active material LiCoO 2 (Al and Mg are each dissolved in 1.0 mol% and 0.05 mol% of Zr adheres to the surface), LiNi 1/3 Co 1/3 A mixture of Mn 1/3 O 2 at a mass ratio of 9: 1 was used. The mass ratio of the positive electrode active material, acetylene black, and PVDF was set to 95: 2.5: 2.5.
- NaH 2 PO 2 .H 2 O powder pulverized in a mortar and passed through a mesh having an opening of 20 ⁇ m was prepared.
- 0.1 parts by weight of this additive was added to 100 parts by weight of the positive electrode active material and stirred to prepare a slurry for forming a positive electrode active material layer.
- a slurry for forming a positive electrode active material layer was applied to both surfaces of an aluminum foil, dried at 120 ° C. for 3 minutes, and then rolled to obtain a positive electrode.
- the packing density of the positive electrode was 3.8 g / ml.
- Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed at a volume ratio of 3: 6: 1. Then, a mixture was obtained by adding LiPF 6 so that the amount of LiPF 6 is 1.0 mol / l. With respect to 100 parts by mass of this mixture, vinylene carbonate was added at a ratio of 2 parts by mass to obtain a nonaqueous electrolyte.
- Electrode terminals were attached to the positive electrode and the negative electrode obtained above, respectively.
- the positive electrode and the negative electrode facing each other through a separator were wound up in a spiral shape.
- the obtained wound body was crushed to obtain a flat electrode body.
- the electrode body and the non-aqueous electrolyte were put in a battery container made of an aluminum laminate, and the battery container was sealed to prepare a battery A.
- the design capacity of the battery A was 800 mAh.
- the design capacity of the battery A was designed based on the end-of-charge voltage when the battery A was charged to a voltage of 4.4V.
- the size of the battery A was 3.6 mm ⁇ 35 mm ⁇ 62 mm.
- the battery A was charged with a constant current at 0.5 It (400 mA) until the voltage reached 4.4V. Next, the battery A was charged to a current of 40 mA at a constant voltage of 4.4 V, and then left for 10 minutes. Next, constant current discharge was performed on the battery A at 0.5 It (400 mA) until the voltage reached 2.75 V.
- Capacity retention ratio (%) Q 1 / Q 0 ⁇ 100 (A)
- the battery A was charged with a constant current at 0.5 It (400 mA) until the voltage reached 4.4V.
- the battery A was charged to a current of 40 mA at a constant voltage of 4.4 V, and then left for 10 minutes.
- constant current discharge was performed on the battery A at 3 It (2400 mA) until the voltage reached 2.75 V, and the discharge capacity Q 3C at 3 It was measured.
- the discharge capacity retention rate (%) was calculated by the following formula (C) to evaluate the discharge performance.
- Discharge capacity maintenance rate (%) Q 3C / Q 1C ⁇ 100 (C)
- Example 2 In the preparation of the positive electrode in place of NaH 2 PO 2 ⁇ H 2 O , except for using NH 4 H 2 PO 2 as an additive, to prepare a battery B in the same manner as the battery A, the characteristics of the battery B evaluated. The results are shown in Table 1.
- Batteries A and B had higher capacity retention rates than batteries C to G. This is considered due to the fact that the gas generation amounts of the battery A and the battery B are suppressed as compared with those of the batteries C to G.
- the charge / discharge efficiency of the battery A and the battery B was almost 100%.
- the transition metal is eluted from the positive electrode, and is deposited on the negative electrode to cause a micro short circuit. As a result, the charge / discharge efficiency is considered to be lowered.
- AC impedance measurement conditions The AC impedance of the battery was measured by changing the frequency from 1 MHz to 30 MHz with an amplitude of 10 mV.
- Example 3 In the preparation of the positive electrode, except that the added 0.02 parts by weight of NaH 2 PO 2 ⁇ H 2 O powder with respect to the positive electrode active material 100 parts by weight, to prepare a battery H in the same manner as the battery A, a battery H The characteristics were evaluated. The results are shown in Table 2.
- Example 4 In the preparation of the positive electrode, except that the added 0.05 parts by mass of NaH 2 PO 2 ⁇ H 2 O powder with respect to the positive electrode active material 100 parts by weight, to prepare a battery I in the same manner as the battery A, a battery I The characteristics were evaluated. The results are shown in Table 2.
- Example 5 In the preparation of the positive electrode, except that the added 0.2 parts by mass of NaH 2 PO 2 ⁇ H 2 O powder with respect to the positive electrode active material 100 parts by weight, to prepare a battery J in the same manner as the battery A, a battery J The characteristics were evaluated. The results are shown in Table 2.
- Example 6 In the preparation of the positive electrode, and the NaH 2 PO 2 ⁇ H 2 O and an aqueous solution dissolved in water. Next, this aqueous solution was added dropwise to the positive electrode active material while stirring the positive electrode active material used in Battery A. NaH 2 PO 2 was adjusted so as to have a mixed amount of 0.1 parts by mass with respect to 100 parts by mass of the positive electrode active material. Then, what was dried at 120 degreeC for 2 hours was kneaded with acetylene black, polyvinylidene fluoride, and NMP, and it was set as the slurry for positive electrode active material layer formation. A battery K was produced in the same manner as the battery A, except that the positive electrode active material layer forming slurry thus obtained was used, and the characteristics of the battery K were evaluated. The results are shown in Table 3.
- Nonaqueous electrolyte secondary battery 10 Electrode body 11 ... Negative electrode 12 ... Positive electrode 12a ... Positive electrode collector 12b ... Positive electrode active material layer 13 ... Separator 17 ... Battery container
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Abstract
Description
として好ましい。また、リチウム含有遷移金属酸化物がニッケルを含む場合、コバルトの使用量を減らす観点からは、リチウム含有遷移金属酸化物に占めるニッケルの割合は、40モル%以上であることが好ましい。正極活物質は、1種類のみから構成されていてもよいし、2種類以上により構成されていてもよい。
MH2PO2 (1)
[式中、Mは一価のカチオンである。]
で表される化合物(1)を含む。化合物(1)において、Mは、NH4、Na、Li及びKからなる群から選ばれる少なくとも1種であることが好ましく、NH4及びNaの少なくとも一方であることがより好ましい。
(II)7(NH4)H2PO2→H2P2O7+2HPO3+H2O+7NH3+2H2
(III)5LiH2PO2→Li4P2O7+LiPO3+2PH3+2H2
(IV)5KH2PO2→K4P2O7+KPO3+2PH3+2H2
正極活物質と、アセチレンブラックと、ポリフッ化ビニリデン(PVDF)とを、NMPと共に混錬して、スラリーを調製した。正極活物質としては、LiCoO2(Al及びMgがそれぞれ1.0モル%固溶されており、かつ0.05モル%のZrが表面に付着したもの)と、LiNi1/3Co1/3Mn1/3O2とを9:1の質量比で混合したものを用いた。正極活物質、アセチレンブラック、及びPVDFの質量比は、95:2.5:2.5となるようにした。次に、添加剤として、乳鉢で粉砕し、目開き20μmのメッシュを通過させたNaH2PO2・H2O粉末を用意した。正極活物質100質量部に対して、この添加剤を0.1質量部加えて攪拌し、正極活物質層形成用スラリーを作製した。正極活物質層形成用スラリーをアルミニウム箔の両面に塗布し、120℃で3分間乾燥した後、圧延して正極を得た。正極の充填密度は3.8g/mlとした。
黒鉛と、スチレン・ブタジエンゴムと、カルボキシメチルセルロースとを質量比で98:1:1となるようにして、水と共に混練して負極合剤スラリーを作製した。この負極合剤スラリーを銅箔の両面に塗布し、乾燥した後、圧延して負極を得た。
エチレンカーボネート(EC)とエチルメチルカーボネート(EMC)とジエチルカーボネート(DEC)とを体積比で3:6:1となるようにして混合した。次に、LiPF6の量が1.0モル/lとなるようにLiPF6を加えて混合物を得た。この混合物100質量部に対して、ビニレンカーボネートを2質量部の割合で添加して、非水電解質を得た。
上記で得られた正極及び負極に、それぞれリード端子を取り付けた。次に、セパレータを介して正極及び負極を対向させたものを渦巻状に巻き取った。得られた巻回体を押し潰して、扁平形状の電極体を得た。次に、電極体と非水電解質を、アルミニウムのラミネート体からなる電池容器に入れ、電池容器を封止し、電池Aを作製した。なお、電池Aの設計容量は、800mAhとした。電池Aの設計容量は、電池Aを電圧4.4Vになるまで充電したときの充電終止電圧を基準にして設計した。電池Aのサイズは、3.6mm×35mm×62mmとした。
電池Aに対して1It(800mA)で充電と放電を1回行い、放電容量Q0を測定した。次に、電池Aの厚みを測定した。次に、電池Aを、60℃の恒温槽内において、電圧4.4Vの定電圧で65時間充電した。次に、電池Aの厚みを測定して、電池厚みの増加量を求めた。次に、電池Aを室温になるまで冷却した後、室温下で1It(800mA)で放電し、放電容量Q1を測定した。容量維持率(%)を以下の式(A)により算出した。
電池Aに対して0.5It(400mA)で、電圧4.4Vになるまで定電流充電を行った。次に、電圧4.4Vの定電圧で電流40mAになるまで電池Aを充電した後、10分間放置した。次に、電池Aに対して1It(800mA)で電圧2.75Vになるまで定電流放電を行い、1Itにおける放電容量Q1Cを測定した。
正極の作製において、NaH2PO2・H2Oの代わりに、NH4H2PO2を添加剤として用いたこと以外は、電池Aと同様にして電池Bを作製し、電池Bの特性を評価した。結果を表1に示す。
正極の作製において、NaH2PO2・H2Oを用いなかったこと以外は、電池Aと同様にして電池Cを作製し、電池Cの特性を評価した。結果を表1に示す。
正極の作製において、NaH2PO2・H2Oの代わりに、NaH2PO3・5H2Oを添加剤として用いたこと以外は、電池Aと同様にして電池Dを作製し、電池Dの特性を評価した。結果を表1に示す。
正極の作製において、NaH2PO2・H2Oの代わりに、NaH2PO4を添加剤として用いたこと以外は、電池Aと同様にして電池Eを作製し、電池Eの特性を評価した。結果を表1に示す。
正極の作製において、NaH2PO2・H2Oの代わりに、NH4H2PO4を添加剤として用いたこと以外は、電池Aと同様にして電池Fを作製し、電池Fの特性を評価した。結果を表1に示す。
正極の作製において、NaH2PO2・H2Oの代わりに、Li3PO4を添加剤として用いたこと以外は、電池Aと同様にして電池Gを作製し、電池Gの特性を評価した。結果を表1に示す。
上記の60℃連続充電保存試験を行う前に、電池A及び電池C~電池Eの交流インピーダンスを以下の条件で測定した。結果を図3に示す。なお、図3のグラフにおいて、横軸は、交流インピーダンスの実数部であり、縦軸は、交流インピーダンスの虚数部である。
電池に対して1.0It(800mA)で、電圧4.4Vになるまで定電流充電を行った。次に、電圧4.4Vの定電圧で、1/20It(40mA)になるまで電池を充電した。
振幅を10mVとし、周波数を1MHzから30MHzまで変化させて、電池の交流インピーダンスを測定した。
正極の作製において、正極活物質100質量部に対してNaH2PO2・H2O粉末を0.02質量部加えたこと以外は、電池Aと同様にして電池Hを作製し、電池Hの特性を評価した。結果を表2に示す。
正極の作製において、正極活物質100質量部に対してNaH2PO2・H2O粉末を0.05質量部加えたこと以外は、電池Aと同様にして電池Iを作製し、電池Iの特性を評価した。結果を表2に示す。
正極の作製において、正極活物質100質量部に対してNaH2PO2・H2O粉末を0.2質量部加えたこと以外は、電池Aと同様にして電池Jを作製し、電池Jの特性を評価した。結果を表2に示す。
正極の作製において、NaH2PO2・H2Oを水に溶解させて水溶液とした。次に、電池Aで用いた正極活物質を攪拌しながら、正極活物質に対してこの水溶液を滴下し、添加した。NaH2PO2は、正極活物質100質量部に対して0.1質量部の混合量となるように調整した。その後、120℃で2時間乾燥させたものを、アセチレンブラック、ポリフッ化ビニリデン、及びNMPと共に混錬して、正極活物質層形成用スラリーとした。このようにして得られた正極活物質層形成用スラリーを用いたこと以外は、電池Aと同様にして電池Kを作製し、電池Kの特性を評価した。結果を表3に示す。
10…電極体
11…負極
12…正極
12a…正極集電体
12b…正極活物質層
13…セパレータ
17…電池容器
Claims (6)
- 正極活物質と、
下記一般式(1):
MH2PO2 (1)
[式中、Mは一価のカチオンである。]
で表される化合物と、
を含む正極活物質層を備える、非水電解質二次電池用正極。 - 一般式(1)で表される化合物において、MがNH4、Na、Li及びKからなる群から選ばれる少なくとも1種である、請求項1に記載の非水電解質二次電池用正極。
- 一般式(1)で表される化合物が、正極活物質100質量部に対して、0.001質量部以上、1.0質量部以下含まれる、請求項1または2に記載の非水電解質二次電池用正極。
- 請求項1~3のいずれか一項に記載の非水電解質二次電池用正極と、負極と、非水電解質と、セパレータとを備える、非水電解質二次電池。
- 下記一般式(1):
MH2PO2 (1)
[式中、Mは一価のカチオンである。]
で表される化合物、正極活物質、及び溶媒を混合して、正極活物質層形成用スラリーを得る工程と、
前記正極活物質層形成用スラリーを正極集電体の上に塗布し、乾燥させて、正極活物質層を形成する工程と、
を備える、非水電解質二次電池用正極の製造方法。 - 下記一般式(1):
MH2PO2 (1)
[式中、Mは一価のカチオンである。]
で表される化合物を溶媒に溶解させる工程と、
前記一般式(1)で表される化合物が溶解された溶液を、正極活物質に添加する工程と、
前記一般式(1)で表される化合物が溶解された溶液が添加された正極活物質及び溶媒を混合して、正極活物質層形成用スラリーを得る工程と、
前記正極活物質層形成用スラリーを正極集電体の上に塗布し、乾燥させて、正極活物質層を形成する工程と、
を備える、非水電解質二次電池用正極の製造方法。
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JPH11273674A (ja) * | 1998-03-19 | 1999-10-08 | Shin Kobe Electric Mach Co Ltd | 有機電解液二次電池 |
JP2008027778A (ja) * | 2006-07-21 | 2008-02-07 | Sony Corp | 非水電解質電池用正極及び非水電解質電池 |
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JPH11273674A (ja) * | 1998-03-19 | 1999-10-08 | Shin Kobe Electric Mach Co Ltd | 有機電解液二次電池 |
JP2008027778A (ja) * | 2006-07-21 | 2008-02-07 | Sony Corp | 非水電解質電池用正極及び非水電解質電池 |
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