WO2015045400A1 - 偏平形非水電解質二次電池及びそれを用いた組電池 - Google Patents
偏平形非水電解質二次電池及びそれを用いた組電池 Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- 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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- 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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- 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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- 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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- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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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- 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 flat non-aqueous electrolyte secondary battery and an assembled battery using the same.
- 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.
- it is indispensable to achieve high capacity while maintaining output characteristics with large current charge / discharge.
- Patent Document 1 discloses a lithium-containing composite oxide containing Li element and at least one transition metal element selected from Ni, Co, and Mn (provided that the molar amount of Li element is the total of the transition metal elements). It is suggested that the capacity retention rate after the cycle is improved by using a positive electrode active material calcined at a low temperature after adding Zr or Ta oxide. Has been.
- Patent Document 2 in an automobile battery, an insulating particle layer made of an alumina layer is provided on the negative electrode surface, and the constituent pressure of the battery is changed from 4 kgf / cm 2 (0.39 MPa) to 50 kgf / cm 2 (4.91 MPa). It is shown that when the insulating particle layer is provided on the negative electrode surface, it is possible to suppress a decrease in battery output during cycling.
- a positive electrode plate on which a positive electrode mixture layer including a positive electrode active material capable of reversibly inserting and extracting lithium is formed;
- the positive electrode mixture there is a compound containing at least one selected from the group consisting of the element M belonging to Group 5 of the periodic table, and the battery is positively connected from the outside. Pressure is applied in the stacking direction of the plate, the negative electrode plate, and the separator.
- the plurality of flat non-aqueous electrolyte secondary batteries are assembled batteries connected in series, parallel, or series-parallel, and reversibly occluded lithium.
- a compound containing at least one selected from the group is present, and the plurality of flat nonaqueous electrolyte secondary batteries constituting the assembled battery are arranged in the stacking direction of the positive electrode plate, the negative electrode plate, and the separator In addition, the flat non-aqueous electrolyte secondary batteries are arranged in the arrangement direction. Being constrained, the polarized flat non-aqueous electrolyte secondary battery, the positive electrode plate from the outside, is confining pressure in the stacking direction of the negative electrode plate and a separator have been added.
- a battery having a small positive electrode resistance after cycling can be obtained even when a high-capacity active material is used for the positive electrode. It becomes like this.
- FIG. 1 is a perspective view of a flat electrode body.
- 2A is a schematic front view of a laminated nonaqueous electrolyte secondary battery
- FIG. 2B is a cross-sectional view taken along the line IIB-IIB in FIG. 2A.
- FIG. 3A is a schematic diagram before charging the secondary particle portion of the positive electrode active material in Experimental Example 4, and
- FIG. 3B is a schematic diagram after charging.
- FIG. 4 is a diagram showing a Nyquist plot.
- lithium nickel cobalt manganese composite oxide represented by the above Li 1.06 [Ni 0.33 Co 0.33 Mn 0.28 ] O 2 and Ta 2 O 5 having an average particle size of 0.2 ⁇ m.
- a positive electrode active material in which Ta 2 O 5 was partially attached to the surface of the lithium nickel cobalt manganese composite oxide.
- the amount of Ta 2 O 5 in the positive electrode active material thus produced was 0.3 mol%.
- the positive electrode active material thus obtained was mixed with carbon black as the positive electrode conductive agent and polyvinylidene fluoride (PVdF) as the binder, and the mass ratio of the positive electrode active material, the positive electrode conductive agent and the binder.
- VdF polyvinylidene fluoride
- the positive electrode mixture slurry is uniformly applied to both surfaces of a positive electrode current collector made of aluminum foil, dried, and then rolled by a rolling roller to form a positive electrode mixture layer formed on both surfaces of the positive electrode current collector.
- the packing density was 2.6 g / cm 3 .
- a positive electrode plate having a positive electrode mixture layer formed on both surfaces of the positive electrode current collector was prepared by attaching a positive electrode current collector tab to the surface of the positive electrode current collector.
- LiPF 6 Lithium hexafluorophosphate
- EC ethylene carbonate
- MEC methyl ethyl carbonate
- DMC dimethyl carbonate
- VC vinylene carbonate
- the flat wound body For producing the flat wound body, one positive electrode plate, one negative electrode plate, and two separators made of polyethylene microporous film were used. First, the positive electrode plate 16 and the negative electrode plate 17 are opposed to each other through a separator 18 (see FIG. 2B) while being insulated from each other, and as shown in FIG. 1, both the positive electrode tab 11 and the negative electrode tab 12 are on the outermost peripheral side. Thus, after winding in a spiral shape with a cylindrical winding core, the winding core was pulled out to produce a wound electrode body, and then crushed to obtain a flat wound body 13.
- the flat wound body 13 has a structure in which a positive electrode plate 16 and a negative electrode plate 17 are laminated via a separator 18.
- the flat wound body 13 and the non-aqueous electrolyte prepared as described above are inserted into an aluminum laminate exterior body 14 in a glow box under an argon atmosphere, and FIGS. 2A and 2B.
- the laminated nonaqueous electrolyte secondary battery 10 includes a positive electrode plate 16, a positive electrode tab 11, a negative electrode plate 17, a negative electrode tab 12, an exterior body 14 of an aluminum laminate material, and a closed portion 15 in which the ends of the aluminum laminate material are heat sealed.
- the non-aqueous electrolyte and the flat wound body 13 are enclosed in an outer package 14 made of an aluminum laminate material.
- the laminate-type nonaqueous electrolyte secondary battery 10 is placed in the direction of the thickness d shown in FIG. 2B, that is, the stacking direction of the positive electrode plate 16, the negative electrode plate 17, and the separator 18 using a pressing jig (not shown).
- the flat non-aqueous electrolyte secondary of Experimental Example 1 is configured such that a pressure (constitutive pressure) of 0.0883 MPa (0.9 kgf / cm 2 ) is applied to the flat winding body 13 with respect to the arrow direction in FIG. A battery was obtained.
- Example 4 As the positive electrode active material, a lithium nickel cobalt manganese composite oxide represented by Li 1.06 [Ni 0.33 Co 0.33 Mn 0.28 ] O 2 not mixed with Ta 2 O 5 was used. A flat nonaqueous electrolyte secondary battery of Experimental Example 4 was produced in the same manner as in Experimental Example 1 except that the above was not applied.
- the charging / discharging under the above conditions was defined as one cycle, and this charging / discharging cycle was performed 40 times. After 40 cycles, a resistance value was measured by an alternating current impedance method using a battery charged until the battery voltage reached 4.4 V under the charge condition of the first cycle. A method for measuring the resistance value will be described below.
- a Nyquist plot shown in FIG. 4 is obtained by using a frequency response analyzer and a potentiogalvanostat (manufactured by Solartron). The Nyquist plot represents the sum of the current collecting resistance, the solution resistance, the negative electrode resistance, and the positive electrode resistance, and the positive electrode resistance is indicated by an arc 2 in FIG.
- the positive electrode resistance after 40 cycles of the batteries of Experimental Examples 1 to 4 was measured by using the above measuring method. Then, relative values of the positive electrode resistances of the batteries of Experimental Examples 1 to 3 with respect to the case where the positive electrode resistance value of the battery of Experimental Example 4 was set to 100 were obtained, and the positive electrode resistance ratio after 40 cycles was obtained. The results are summarized in Table 1 below.
- the additive compound present in the vicinity of the surface of the positive electrode active material particles causes the nonaqueous electrolyte solution on the surface of the secondary particles to Although the decomposition reaction can be suppressed, since there is no constituent pressure, the positive electrode active material expands and contracts during the charge / discharge cycle, thereby preventing cracks 23 from being generated inside the secondary particles and preventing primary particles from forming.
- the presence of the insulating additive compound also becomes a resistance, and the positive electrode resistance after the cycle increases.
- the positive electrode mixture layer contains Ta 2 O 5 and has a constituent pressure exceeding 0.0883 MPa (0.9 kgf / cm 2 ). It can be seen that the battery has excellent cycle characteristics as compared with the battery of Experimental Example 3 in which these constituent pressures are not applied.
- the batteries of Experimental Examples 5 and 6 have a small positive electrode resistance ratio similar to the battery of Experimental Example 1 in which a constituent pressure of 0.0883 MPa is applied. From this, it is considered that when the constituent pressure is set to 0.13 MPa and 0.22 MPa, the same effect is exhibited as in the case where the constituent pressure is set to 0.0883 MPa.
- the positive electrode plate 16 and the negative electrode plate 17 are opposed to each other while being insulated from each other via a separator 18 (see FIG. 2B), wound in a spiral shape, and then crushed.
- An example using the flat wound body 13 (see FIG. 1 and FIG. 2B) was shown.
- the same effect can be obtained by using a laminated electrode body (not shown) produced by laminating a positive electrode plate and a negative electrode plate in a state of being insulated from each other via a separator. There is an effect.
- an example in which an aluminum laminate material was used as the exterior body 14 that accommodates the flat wound body 13 was shown.
- a conventional unit cell is used as the exterior body used in the present invention.
- the pressure applied from the outside of the flat non-aqueous electrolyte secondary battery is not particularly limited as long as the pressure applied from the outside of the flat non-aqueous electrolyte secondary battery is transmitted to the flat winding body in the outer package.
- Examples of such an exterior body include a metal can and an aluminum laminate.
- the target pressure can be applied to the flat wound body by appropriately adjusting the pressure applied from the outside of the flat nonaqueous electrolyte secondary battery. it can.
- the target pressure can be applied to each flat winding body by appropriately adjusting the restraining pressure.
- an aluminum laminate material is used as the exterior body 14, and as shown in FIG. 2B, the inner wall of the exterior body 14 and the flat wound body 13 are arranged in close contact with each other. I'm taking it. According to this configuration, it is considered that a pressure substantially equal to the pressure applied from the outside of the flat type nonaqueous electrolyte secondary battery is transmitted to the flat winding body 13 in the exterior body 14.
- the additive compound present in the positive electrode mixture is an oxide
- examples of the additive compound include hydroxide, oxide, oxyhydroxide, and carbonic acid. It is preferably at least one selected from a compound, a phosphoric acid compound and a fluorine-containing compound, and the same effect can be obtained when these compounds are used.
- the positive electrode active material is preferably a positive electrode active material composed of secondary particles formed by agglomerating positive electrode active materials composed of a plurality of primary particles. This is because the output performance is improved because the non-aqueous electrolyte enters the inside as compared with the case where the positive electrode active material is formed of only primary particles.
- the positive electrode active material has an average crystallite size of 450 mm or more obtained by using the Halder-Wagner method from the integral width obtained by the Pawley method.
- Lithium carbonate Li 2 CO 3 , nickel cobalt manganese composite hydroxide represented by [Ni 0.55 Co 0.10 Mn 0.35 ] (OH) 2 obtained by coprecipitation, Li and transition metal The mixture was mixed in an Ishikawa type mortar so that the molar ratio with respect to the whole was 1.10: 1. Next, this mixture was pulverized after heat treatment at 960 ° C. for 20 hours in an air atmosphere, whereby Li 1.07 [Ni 0.51 Co 0.10 Mn 0.32 ] having an average secondary particle diameter of about 15 ⁇ m was obtained. A lithium nickel cobalt manganese composite oxide represented by O 2 was obtained.
- a positive electrode plate was produced in the same manner as in Experimental Example 1 except that the positive electrode active material thus obtained was used.
- a three-electrode test cell was prepared using the positive electrode plate as a working electrode and metallic lithium as a counter electrode and a reference electrode.
- a non-aqueous electrolyte lithium hexafluorophosphate is mixed with a mixed solvent in which ethylene carbonate (EC), methyl ethyl carbonate (MEC), and dimethyl carbonate (DMC) are mixed at a volume ratio of 3: 3: 4.
- EC ethylene carbonate
- MEC methyl ethyl carbonate
- DMC dimethyl carbonate
- LiPF 6 was dissolved to a concentration of 1.0 mol / liter.
- a nonaqueous electrolytic solution in which 1% by mass of vinylene carbonate (VC) was added and dissolved with respect to the total amount of the electrolytic solution was used.
- the three-electrode test cell thus produced is hereinafter referred to as the battery of Reference Experimental Example 1.
- the charge / discharge at the first cycle under the above conditions was defined as one cycle, and this charge / discharge cycle was performed once. Thereafter, charge / discharge after the second cycle under the above conditions was defined as one cycle, and this charge / discharge cycle was repeated 49 times. After 50 cycles, each battery was disassembled and the positive electrode plate was taken out. Using the extracted positive electrode plate, a cross section of secondary particles was prepared with a cross section polisher or the like, and this cross section was observed with SEM or TEM to confirm the presence or absence of cracks in the secondary particles.
- the X-ray diffraction pattern was measured using an X-ray diffractometer (RINT-TTR2 manufactured by Rigaku Co., Ltd.) using a Cu-K ⁇ ray filled with a lithium transition metal complex oxide in a sample holder. The test was performed under the condition of a current of 300 mA.
- the positive electrode active material has a high capacity because the average crystallite size of the positive electrode active material obtained by using the Halder-Wagner method is 470 mm or more from the integral width obtained by the Pawley method. It is preferable when it becomes. However, when the crystallite size is increased, cracks in the secondary particles are likely to occur due to expansion and contraction of the positive electrode active material during charge and discharge, and the positive electrode resistance increases due to poor contact due to cracks in the positive electrode active material after cycling. It is suggested that it becomes easy to become. However, as in the present invention, a compound containing at least one selected from the group consisting of the element M belonging to Group 5 of the periodic table is present in the positive electrode plate mixture, and is not flat. By applying pressure in the stacking direction of the positive electrode plate, the negative electrode plate and the separator from the outside in the water electrolyte secondary battery, the positive electrode resistance after the cycle can be reduced even if the above-described high capacity positive electrode active material is used.
- the compound present in the positive electrode mixture is partially attached to the surface of the secondary particles of the active material. This is because if the surface of the secondary particles is covered with a compound too much, the rate characteristics and the discharge capacity are reduced. Further, after mixing the positive electrode active material particles with a compound containing at least one selected from the group consisting of the element M belonging to Group 5 of the periodic table, for example, when heat treatment is performed at a temperature of 450 ° C. or lower, It can adhere firmly. This is because deterioration at the surface of the secondary particles or at the primary particle interface is suppressed.
- the compound present in the positive electrode mixture is a compound containing at least one selected from the group consisting of the element M belonging to Group 5 of the periodic table. It is preferable. This is because in the case of a compound of the element M belonging to Group 5, the decomposition reaction of the electrolytic solution due to the catalytic properties of transition metals such as Co and Ni can be efficiently suppressed. Of these, tantalum is preferred because of its high stability in the electrolyte solution.
- the total mass of the above elements in the total mass of the positive electrode active material particles and the compound containing the above elements is preferably about 0.01 to 5% by mass, and is 0.02% to 1% by mass. It is more preferable. If it is less than 0.01% by mass, the effect of improving the characteristics is small, and if it exceeds 5% by mass, the discharge rate characteristics deteriorate.
- cracks due to deterioration may occur not only from the primary particle bonding interface near the surface of the secondary particles but also from the crystallite bonding interface. Even in this case, by using the configuration of the present invention, it is possible to similarly suppress cracking from the crystallite bonding interface.
- the packing density of the positive electrode mixture layer is preferably 2.2 g / cm 3 or more and 3.4 g / cm 3 or less. This is because if the packing density of the positive electrode mixture layer is less than 2.2 g / cm 3 , the packing density is too low and the resistance may rather increase. If it exceeds 3.4 g / cm 3 , the secondary particles in which the primary particles are aggregated are pulverized and become primary particles, and the positive electrode active material that is not in contact with the conductive agent tends to be isolated and the output may be reduced. Because there is.
- a plurality of flat non-aqueous electrolyte secondary batteries having an adhesion compound as described above are assembled batteries connected in series, parallel, or series-parallel, and constitute the assembled battery.
- the flat non-aqueous electrolyte secondary batteries are arranged in the stacking direction of the positive electrode plate, the negative electrode plate and the separator, and the flat non-aqueous electrolyte secondary batteries are bound to each other in the arrangement direction.
- a plurality of flat non-aqueous electrolyte secondary batteries are provided in which a binding pressure is applied from the outside in the stacking direction of the positive electrode plate, the negative electrode plate, and the separator.
- arrangement pressure is preferably at 9.81 ⁇ 10 -3 MPa or more, and more preferably less 9.81 ⁇ 10 -3 MPa over 10 MPa.
- a lithium-containing transition metal composite oxide can be used as the positive electrode active material.
- Ni—Co—Mn lithium composite oxide and Ni—Co—Al lithium composite oxide are preferable because of high capacity and high input / output performance.
- Other examples include lithium-cobalt composite oxide, Ni—Mn—Al-based lithium composite oxide, olivine-type transition metal oxide containing iron, manganese, etc. (expressed as LiMPO 4 , where M is Fe, Mn , Co, and Ni). These may be used alone or in combination.
- substances such as Al, Mg, Ti, Zr, and W may be dissolved in the lithium-containing transition metal composite oxide.
- the molar ratio of Ni, Co, and Mn is 1: 1: 1, or 5: 2: 3, 4: 4: 2.
- those having a known composition can be used.
- the difference is preferably 0.04% or more.
- the particle size of the positive electrode active material may be the same or different.
- Nonaqueous electrolytes used in the nonaqueous electrolyte secondary battery of the present invention are conventionally used cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate.
- a chain carbonate can be used.
- 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
- the lithium salt used in the battery using the positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention is a fluorine-containing lithium salt conventionally used, such as LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (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 , And LiAsF 6 can be used.
- fluorine-containing lithium salt a fluorine-containing lithium salt other than the lithium salt [P, B, O, S, N, lithium salt containing one or more elements in Cl (e.g., LiClO 4, etc.)] was added A thing 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.
- separators used in the nonaqueous electrolyte secondary battery of the present invention include conventionally used resins such as polypropylene and polyethylene separators, polypropylene-polyethylene multilayer separators, and aramid resins on the separator surface. The coated one can be used.
- separator conventionally used separators 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 negative electrode active material used in the negative electrode of the present invention a conventionally used negative electrode active material 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 a metal thereof
- the alloy compound containing is mentioned.
- 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.
- the element capable of forming an alloy with lithium is preferably silicon or tin, and an alloy of silicon or tin can also be used.
- the negative electrode active material it is preferable to mainly use a carbon material, and it is particularly preferable to mainly use graphite. Thereby, in the combination with the lithium transition metal composite oxide used as the positive electrode active material in the present invention, output regeneration characteristics can be maintained in a wide range of charge / discharge depths.
- the negative electrode mixture layer containing the negative electrode active material may contain a known carbon conductive agent such as graphite, and a known binder such as CMC (carboxymethylcellulose sodium) and SBR (styrene butadiene rubber). .
- a known carbon conductive agent such as graphite
- a known binder such as CMC (carboxymethylcellulose sodium) and SBR (styrene butadiene rubber).
- a layer made of an inorganic filler that has been 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.
- the flat type non-aqueous electrolyte secondary battery of one aspect of the present invention does not increase the resistance of the positive electrode after cycling, and therefore, for example, high output at a wide temperature, particularly at a low temperature, can be expected over a long period of time.
- high output at a wide temperature, particularly at a low temperature can be expected over a long period of time.
- a high output at a wide temperature, particularly at a low temperature can be obtained over a long period.
- the flat non-aqueous electrolyte secondary battery according to one aspect of the present invention is applied to, for example, a driving power source of a mobile information terminal such as a mobile phone, a notebook computer, a smartphone, and a tablet terminal, and particularly used for a high energy density. can do. 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.
- a mobile information terminal such as a mobile phone, a notebook computer, a smartphone, and a tablet terminal
- EV electric vehicles
- HEV hybrid electric vehicles
- PHEV PHEV
Abstract
Description
[実験例1]
まず、実験例1の偏平形非水電解質二次電池の構成を説明する。
炭酸リチウムLi2CO3と、共沈により得られた[Ni0.35Co0.35Mn0.30](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とを、Liと遷移金属全体とのモル比が1.10:1になるように、石川式らいかい乳鉢にて混合した。次に、この混合物を空気雰囲気中にて1000℃で20時間熱処理後に粉砕することにより、平均二次粒子径が約15μmのLi1.06[Ni0.33Co0.33Mn0.28]O2で表されるリチウムニッケルコバルトマンガン複合酸化物を得た。
増粘剤であるCMC(カルボキシメチルセルロースナトリウム)を水に溶かした水溶液中に、負極活物質としての人造黒鉛と、結着剤としてのSBR(スチレン-ブタジエンゴム)とを、負極活物質と結着剤と増粘剤の質量比が98:1:1の比率になるようにして加えた後に混練し、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からなる負極集電体の両面に均一に塗布し、乾燥した後、圧延ローラにより圧延し、負極集電体の表面に負極集電タブを取り付けることにより、負極集電体の両面に負極合剤層が形成された負極板を作製した。
エチレンカーボネート(EC)とメチルエチルカーボネート(MEC)とジメチルカーボネート(DMC)を、25℃で3:3:4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1.2モル/リットルの濃度になるように溶解した。さらにビニレンカーボネート(VC)を電解液全量に対して1質量%添加し溶解させて、非水電解液を調製した。
偏平状の巻取り体の作製には、上記正極板を1枚、上記負極板を1枚、ポリエチレン製微多孔膜からなるセパレータを2枚用いた。まず、正極板16と負極板17とをセパレータ18(図2B参照)を介して互いに絶縁した状態で対向させ、図1に示したように、正極タブ11、負極タブ12共に最外周側となるようにして、円柱型の巻き芯で渦巻き状に巻回した後、巻き芯を引き抜いて巻回電極体を作製した後、押し潰して、偏平状の巻取り体13を得た。この偏平状の巻取り体13は、正極板16と負極板17とがセパレータ18を介して積層された構造を有している。
正極活物質として、Ta2O5を混合させていないLi1.06[Ni0.33Co0.33Mn0.28]O2で表されるリチウムニッケルコバルトマンガン複合酸化物を用いた以外は、上記実験例1と同様にして、実験例2の偏平形非水電解質二次電池を作製した。
構成圧をかけないこと以外は、上記実験例1と同様にして、実験例3の偏平形非水電解質二次電池を作製した。
正極活物質として、Ta2O5を混合させていないLi1.06[Ni0.33Co0.33Mn0.28]O2で表されるリチウムニッケルコバルトマンガン複合酸化物を用い、構成圧をかけないこと以外は上記実験例1と同様にして、実験例4の偏平形非水電解質二次電池を作製した。
上述のようにして作製された実験例1~4の偏平形非水電解質二次電池について、それぞれ以下の条件で充放電を繰り返し、40サイクル後の正極の抵抗を測定した。
・1サイクル目の充電条件
700mAの定電流で電池電圧が4.4V(正極電位はリチウム基準で4.5V)となるまで定電流充電を行い、電池電圧が4.4Vに達した後は、4.4Vの定電圧で電流値が35mA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
700mAの定電流で電池電圧が3.0V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。
[実験例5]
電池にかける構成圧を、0.0883MPa(0.9kgf/cm2)に代えて0.13MPaにした以外は、上記実験例1と同様にして実験例5の偏平形非水電解質二次電池を作製した。
電池にかける構成圧を、0.0883MPa(0.9kgf/cm2)に代えて0.22MPaにした以外は、上記実験例1と同様にして実験例6の偏平形非水電解質二次電池を作製した。
[参考実験例1]
まず、参考実験例1で用いた三電極式試験用セルの構成を説明する。
炭酸リチウムLi2CO3と、共沈により得られた[Ni0.55Co0.10Mn0.35](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とを、Liと遷移金属全体とのモル比が1.10:1になるように、石川式らいかい乳鉢にて混合した。次に、この混合物を空気雰囲気中にて960℃で20時間熱処理後に粉砕することにより、平均二次粒子径が約15μmのLi1.07[Ni0.51Co0.10Mn0.32]O2で表されるリチウムニッケルコバルトマンガン複合酸化物を得た。
正極活物質を作製する際に、熱処理温度を930℃にしたこと以外は、上記参考実験例1と同様にして三電極式試験用セルを作製した。このようにして作製した三電極式試験用セルを、以下、参考実験例2の電池と称する。
正極活物質を作製する際に、熱処理温度を900℃にしたこと以外は、上記参考実験例1と同様にして三電極式試験用セルを作製した。このようにして作製した三電極式試験用セルを、以下、参考実験例3の電池と称する。
正極活物質を作製する際に、熱処理温度を870℃にしたこと以外は、上記参考実験例1と同様にして三電極式試験用セルを作製した。このようにして作製した三電極式試験用セルを、以下、参考実験例4の電池と称する。
まず、上述のようにして作製された参考実験例1~4の電池について、それぞれ以下の条件で充放電し、初回放電容量及び50サイクル後の正極活物質の二次粒子内部の割れの有無を評価した。
・1サイクル目の充電条件
0.2mA/cm2の電流密度で正極電位が4.3V(vs.Li/Li+)となるまで定電流充電を行い、正極電位が4.3V(vs.Li/Li+)に達した後は、4.3V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。
・1サイクル目の放電条件
0.2mA/cm2の電流密度で電池電圧が2.5V(vs.Li/Li+)となるまで定電流放電を行った。このときの放電容量を測定し、初回放電容量とした。
・休止
上記充電と放電との間の休止間隔は10分間とした。
2.0mA/cm2の電流密度で正極電位が4.3V(vs.Li/Li+)となるまで定電流充電を行い、正極電位が4.3V(vs.Li/Li+)に達した後は、4.3V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。
・2サイクル目以降の放電条件
2.0mA/cm2の電流密度で電池電圧が2.5V(vs.Li/Li+)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。
上記とは別に、参考実験例1~4で得られた正極活物質を用い、正極活物質の平均結晶子サイズを、Pawley法で求めた積分幅よりHalder-wagner法を用いて評価した。正極活物質の平均結晶子サイズは、以下の方法で求めた。
1)X線回折用標準資料(National Institute of Standards and Technology(NIST) Standard Reference Materials(SRM) 660b(LaB6))のX線回折パターンから、ミラー指数(100)、(110)、(111)、(200)、(210)、(211)、(220)、(221)、(310)、(311)の10本のピークを用いてPawley法で分割型擬voigt関数を用いて、積分強度、ピーク高さから積分幅β1を算出。
測定サンプルに由来する積分幅β=β2-β1・・・(a)
4)Halder-wagner法を用いて、β2/tan2θをβ/(tanθsinθ)に対してプロットして近似する直線の傾きから測定サンプルに由来する平均結晶子サイズLを算出。
・2θ=37.9°付近にあるミラー指数(006)で指数付けされるピーク
・2θ=38.4°付近にあるミラー指数(012)で指数付けされるピーク
・2θ=44.5°付近にあるミラー指数(104)で指数付けされるピーク
・2θ=48.6°付近にあるミラー指数(015)で指数付けされるピーク
・2θ=58.6°付近にあるミラー指数(107)で指数付けされるピーク
・2θ=64.4°付近にあるミラー指数(018)で指数付けされるピーク
・2θ=65.0°付近にあるミラー指数(110)で指数付けされるピーク
・2θ=68.3°付近にあるミラー指数(113)で指数付けされるピーク
上記した正極活物質の平均結晶子サイズ、初回放電容量、サイクル後の粒子割れの有無を表3に纏めて示す。
11 正極タブ
12 負極タブ
13 偏平状の巻取り体
14 外装体
15 閉口部
16 正極板
17 負極板
18 セパレータ
21 二次粒子
22 一次粒子
23 割れ
24 割れ
Claims (10)
- リチウムを可逆的に吸蔵・放出可能な正極活物質を含む正極合剤層が形成された正極板と、リチウムを可逆的に吸蔵・放出可能な負極活物質を含む負極合剤層が形成された負極板と、前記正極板と前記負極板とがセパレータを介して積層された構造を有する電極体と、非水電解液と、を備えた偏平形非水電解質二次電池であって、
前記正極合剤層中には、周期律表の第5族に帰属される元素Mよりなる群から選択される少なくとも1種を含む化合物が存在しており、
前記電池は、外部より正極板、負極板及びセパレータの積層方向に圧力が加えられている、偏平形非水電解質二次電池。 - 前記正極活物質は、複数の一次粒子からなる正極活物質が凝集して形成された二次粒子を含む、請求項1に記載の偏平形非水電解質二次電池。
- 前記正極活物質は、Pawley法で求めた積分幅よりHalder-wagner法を用いて求めた平均結晶子サイズが450Å以上である、請求項1又は2に記載の偏平形非水電解質二次電池。
- 前記正極合剤層の充填密度は、2.2g/cm3以上3.4g/cm3以下である、請求項1~3のいずれか1項に記載の偏平形非水電解質二次電池。
- 前記圧力は、9.81×10-3MPa以上である、請求項1~4のいずれか1項に記載の偏平形非水電解質二次電池。
- 前記正極合剤層中に存在している化合物は、前記正極活物質の二次粒子の表面に部分的に付着している、請求項1~5のいずれか1項に記載の偏平形非水電解質二次電池。
- 前記正極合剤層中に存在している化合物は、Taを含む化合物である、請求項1~6のいずれか1項に記載の偏平形非水電解質二次電池。
- 前記正極合剤層中に存在している化合物は、水酸化物、酸化物、オキシ水酸化物、炭酸化合物、燐酸化合物及びフッ素含有化合物から選ばれた少なくとも1種である、請求項1~7のいずれか1項に記載の偏平形非水電解質二次電池。
- 複数の偏平形非水電解質二次電池が、直列、並列又は直並列に接続された組電池であって、
リチウムを可逆的に吸蔵・放出可能な正極活物質を含む正極合剤層が形成された正極板と、リチウムを可逆的に吸蔵・放出可能な負極活物質を含む負極合剤層が形成された負極板と、前記正極板と前記負極板とがセパレータを介して積層された構造を有する電極体と、非水電解液と、を備え、
前記正極合剤層中には、周期律表の第5族に帰属される元素Mよりなる群から選択される少なくとも1種を含む化合物が存在しており、
前記組電池を構成する前記複数の偏平形非水電解質二次電池は、正極板、負極板及びセパレータの積層方向に配列されるとともに、前記配列方向に偏平形非水電解質二次電池が互いに拘束されており、前記偏平形非水電解質二次電池は、外部より正極板、負極板及びセパレータの積層方向に拘束圧が加えられている、組電池。 - 前記拘束圧は、9.81×10-3MPa以上である、請求項9に記載の組電池。
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- 2014-09-26 JP JP2015538911A patent/JP6288098B2/ja active Active
- 2014-09-26 CN CN201480048084.4A patent/CN105493334B/zh active Active
- 2014-09-26 WO PCT/JP2014/004931 patent/WO2015045400A1/ja active Application Filing
- 2014-09-26 US US14/910,745 patent/US20160197350A1/en not_active Abandoned
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JP2001093577A (ja) * | 1999-09-20 | 2001-04-06 | Toyota Central Res & Dev Lab Inc | リチウム二次電池 |
JP2003068298A (ja) * | 2001-08-24 | 2003-03-07 | Seimi Chem Co Ltd | リチウム含有遷移金属複合酸化物およびその製造方法 |
JP2011070789A (ja) * | 2008-09-26 | 2011-04-07 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
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JP2013171646A (ja) * | 2012-02-20 | 2013-09-02 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
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JP2019140054A (ja) * | 2018-02-15 | 2019-08-22 | Tdk株式会社 | 正極及び非水電解液二次電池 |
Also Published As
Publication number | Publication date |
---|---|
CN105493334B (zh) | 2018-07-31 |
JP6288098B2 (ja) | 2018-03-07 |
JPWO2015045400A1 (ja) | 2017-03-09 |
US20160197350A1 (en) | 2016-07-07 |
CN105493334A (zh) | 2016-04-13 |
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