WO2015056385A1 - 電池、電池パック、電子機器、電動車両、蓄電装置および電力システム - Google Patents
電池、電池パック、電子機器、電動車両、蓄電装置および電力システム Download PDFInfo
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- WO2015056385A1 WO2015056385A1 PCT/JP2014/004280 JP2014004280W WO2015056385A1 WO 2015056385 A1 WO2015056385 A1 WO 2015056385A1 JP 2014004280 W JP2014004280 W JP 2014004280W WO 2015056385 A1 WO2015056385 A1 WO 2015056385A1
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- battery
- positive electrode
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- active material
- separator
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- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
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- B60L58/12—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries responding to state of charge [SoC]
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Definitions
- This technology relates to a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.
- a lithium ion secondary battery having a large energy density is most suitable as a battery that satisfies such requirements.
- a lithium ion secondary battery for example, a battery using a laminate film as an exterior member has been put into practical use because it is lightweight and has high energy density, and can be manufactured in a very thin shape. .
- Patent Documents 1 to 3 describe techniques related to separators used in gel electrolyte batteries.
- Batteries are required to suppress capacity deterioration due to repeated charge and discharge.
- an object of the present technology is to provide a battery capable of suppressing capacity deterioration due to repeated charge / discharge, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system using the battery.
- the present technology provides a positive electrode including a positive electrode current collector and a positive electrode active material and having a positive electrode active material layer provided on both surfaces of the positive electrode current collector, a negative electrode, and at least a porous film
- the porous film is a battery that satisfies the following (formula).
- the battery pack, electronic device, electric vehicle, power storage device, and power system of the present technology include the above-described battery.
- FIG. 1 is an exploded perspective view showing a configuration of a laminated film type nonaqueous electrolyte battery according to a first embodiment of the present technology.
- FIG. 2 is a cross-sectional view showing a cross-sectional configuration along the II line of the spirally wound electrode body shown in FIG.
- FIG. 3A is a schematic cross-sectional view illustrating a configuration example of a first separator of the present technology.
- FIG. 3B is a schematic cross-sectional view illustrating a configuration example of a second separator of the present technology.
- FIG. 4 is an exploded perspective view showing a configuration example of a simplified battery pack.
- FIG. 5A is a schematic perspective view showing an appearance of a simple battery pack.
- FIG. 5B is a schematic perspective view showing an appearance of a simple battery pack.
- FIG. 6 is a block diagram illustrating a configuration example of a battery pack according to the third embodiment of the present technology.
- FIG. 7 is a schematic diagram illustrating an example applied to a residential power storage system using the battery of the present technology.
- FIG. 8 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- S area density
- Patent Document 1 Patent No. 4075259 cited in the “Background Art” column, a separator having a film thickness of 5 to 16 ⁇ m and a porosity of 25 to 60% is used. A battery having a gel electrolyte is described.
- the relationship between the area density of a positive electrode active material layer and the thickness of a separator is not considered. For this reason, for example, when the area density of the positive electrode active material layer is set to 27 mg / cm 2 or more, the electrode length is shortened compared to the case where the separator of the present technology is used with the same size battery, and the amount of active material May reduce the energy density of the battery.
- Patent Document 2 Japanese Patent Laid-Open No. 2007-280749 describes a technology that can provide a battery having excellent cycle characteristics by using a separator having an air permeability of 80 to 300 sec / 100 cc.
- Patent Document 2 when the technique described in Patent Document 2 is applied to a separator having a large film thickness, the ion permeability of the separator is lowered, so that the local overvoltage on the electrode surface during charge / discharge tends to increase. In particular, when the area density of the electrode increases beyond a certain range, clogging of the separator occurs due to electrolyte decomposition due to overvoltage, resulting in deterioration of cycle characteristics.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2012-48918 discloses a battery having a cycle characteristic when a separator having a film thickness of 5 to 25 ⁇ m and having a pore number per unit area of 200 or more is used. It is described that it can be provided.
- the inventors of the present application have made extensive studies and can obtain the following effects by using a separator having a predetermined structure when the area density of the positive electrode active material layer is set to 27 mg / cm 2 or more. I found out.
- the energy density can be improved by increasing the amount of active material per volume.
- By increasing the amount of active material per unit area of the electrode it is possible to relieve overvoltage that increases due to an increase in current density and improve cycle characteristics.
- the electrolytic solution is more likely to be decomposed. Therefore, the cycle characteristics can be improved by suppressing the excessive overvoltage.
- FIG. 1 illustrates an exploded perspective configuration of the nonaqueous electrolyte battery according to the first embodiment of the present technology
- FIG. 2 is an enlarged cross-sectional view taken along line II of the spirally wound electrode body 30 illustrated in FIG. It shows.
- This non-aqueous electrolyte battery is mainly one in which a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is housed in a film-shaped exterior member 40.
- the battery structure using the film-shaped exterior member 40 is called a laminate film type.
- This nonaqueous electrolyte battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged, and is, for example, a lithium ion secondary battery.
- the positive electrode lead 31 and the negative electrode lead 32 are led out in the same direction from the inside of the exterior member 40 to the outside, for example.
- the positive electrode lead 31 is made of, for example, a metal material such as aluminum
- the negative electrode lead 32 is made of, for example, a metal material such as copper, nickel, or stainless steel. These metal materials are, for example, in a thin plate shape or a mesh shape.
- the exterior member 40 has a configuration in which resin layers are provided on both surfaces of a metal layer made of metal foil, such as an aluminum laminate film in which a nylon film, an aluminum foil, and a polyethylene film are bonded in this order.
- the general structure of the exterior member 40 has, for example, a laminated structure of an outer resin layer / a metal layer / an inner resin layer.
- the exterior member 40 has a structure in which the outer edges of two rectangular aluminum laminate films are bonded to each other by fusion or an adhesive so that the inner resin layer faces the wound electrode body 30. Have.
- Each of the outer resin layer and the inner resin layer may be composed of a plurality of layers.
- the metal material constituting the metal layer only needs to have a function as a moisture-permeable barrier film, and includes aluminum (Al) foil, stainless steel (SUS) foil, nickel (Ni) foil, and plated iron ( Fe) foil or the like can be used.
- Al aluminum
- SUS stainless steel
- Ni nickel
- Fe plated iron
- the aluminum foil which is thin and lightweight and excellent in workability.
- annealed aluminum JIS A8021P-O
- JIS A8079P-O JIS A8079P-O
- JIS A1N30-O JIS A1N30-O
- the thickness of the metal layer is typically preferably 30 ⁇ m or more and 150 ⁇ m or less, for example.
- the thickness is less than 30 ⁇ m, the material strength tends to decrease.
- the thickness exceeds 150 ⁇ m, processing becomes extremely difficult and the thickness of the laminate film 52 increases, and the volume efficiency of the nonaqueous electrolyte battery tends to be reduced.
- the inner resin layer is a part that is melted by heat and fused to each other, such as polyethylene (PE), non-axially oriented polypropylene (CPP), polyethylene terephthalate (PET), low density polyethylene (LDPE), high density polyethylene (HDPE), Linear low density polyethylene (LLDPE) or the like can be used, and a plurality of these can be selected and used.
- PE polyethylene
- CPP non-axially oriented polypropylene
- PET polyethylene terephthalate
- LDPE low density polyethylene
- HDPE high density polyethylene
- LLDPE Linear low density polyethylene
- polyolefin resin polyamide resin, polyimide resin, polyester, or the like is used because of its beautiful appearance, toughness, flexibility, and the like.
- nylon polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polybutylene naphthalate (PBN) are used. Is also possible.
- the adhesion film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air.
- the adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32. Examples of such a material include polyolefin resins such as polyethylene, polypropylene, modified polyethylene, and modified polypropylene.
- the exterior member 40 may be constituted by a laminated film having another laminated structure instead of the aluminum laminated film having the laminated structure described above, or may be constituted by a polymer film such as polypropylene or a metal film. It may be.
- FIG. 2 shows a cross-sectional configuration along the II line of the spirally wound electrode body 30 shown in FIG.
- This wound electrode body 30 is formed by laminating and winding a belt-like positive electrode 33 and a belt-like negative electrode 34 via a belt-like separator 35 and an electrolyte 36, and the outermost periphery is protected by a protective tape 37. Has been.
- the positive electrode 33 has, for example, a double-sided formation part in which a positive electrode active material layer 33B is provided on both surfaces of a positive electrode current collector 33A having one main surface and another main surface. Although not shown, the single-sided formation portion in which the positive electrode active material layer 33B is provided only on one side of the positive electrode current collector 33A may be provided.
- the positive electrode current collector 33A is made of, for example, a metal foil such as an aluminum foil.
- the positive electrode active material layer 33B contains one or more positive electrode materials capable of inserting and extracting lithium as a positive electrode active material.
- the positive electrode active material layer 33B may include other materials such as a binder and a conductive agent as necessary.
- the positive electrode material it is preferable to use a lithium-cobalt composite oxide containing at least layered lithium and cobalt capable of inserting and extracting lithium.
- this lithium cobalt composite oxide is used, the discharge curve is flat (the plateau region is large), the average voltage is high, the energy density is high, and the cut-off voltage is high.
- the lithium cobalt composite oxide having such characteristics is particularly suitable for a gel electrolyte battery such as a laminate film type of the present technology used for cellular (cell phone equipment, smart phone) and the like that are required to be lightweight and have a high capacity. Yes.
- the thermal stability in the state of charge is poor (battery safety) that sag at the end of the discharge curve (short plateau region). Is relatively poor), the cut-off voltage is low, and there is much gas generation during high-temperature storage. For this reason, the nickel-based positive electrode active material is not suitable for the gel electrolyte battery such as the laminate film type according to the first embodiment of the present technology.
- positive electrode material other positive electrode active materials capable of inserting and extracting lithium other than the lithium cobalt composite oxide may be used together with the lithium cobalt composite oxide.
- lithium cobalt composite oxide it is preferable to use a lithium cobalt composite oxide having a composition represented by the following general formula (Formula 1).
- lithium-cobalt composite oxide represented by Formula 1 more specifically, for example, Li p CoO 2 (p is as defined above), Li p Co 0.98 Al 0.01 Mg 0.01 O 2 (p is as defined above ) And the like.
- Coated particles As the positive electrode material capable of inserting and extracting lithium, the lithium cobalt composite oxide particles described above and a coating layer provided on at least a part of the surface of the lithium cobalt composite oxide particles serving as the base material Coated particles having the following may be used. By using such coated particles, battery characteristics can be further improved.
- the coating layer is provided on at least a part of the surface of the particles of the lithium cobalt composite oxide serving as the base material, and has a composition element or composition ratio different from that of the particles of the lithium cobalt composite oxide serving as the base material. Is.
- the presence of the coating layer can be confirmed by examining the concentration change of the constituent elements from the surface of the positive electrode material toward the inside.
- the concentration change can be obtained by scraping lithium composite oxide particles provided with a coating layer by sputtering, etc., and then analyzing the composition by Auger Electron Spectroscopy (AES) or SIMS (Secondary Ion Mass Mass Spectrometry; secondary ion mass spectrometry ). It is also possible to slowly dissolve lithium composite oxide particles provided with a coating layer in an acidic solution, etc., and measure the time change of the elution by inductively coupled plasma (ICP) spectroscopy. is there.
- ICP inductively coupled plasma
- the coating layer examples include those containing an oxide or a transition metal compound.
- the coating layer may contain a halide such as lithium fluoride or a chalcogenide other than oxygen.
- the coating layer is provided on at least a part of the particles of the lithium cobalt composite oxide, and differs from the main transition metal that substantially constitutes the transition metal contained in the particles of the lithium cobalt composite oxide. It may contain at least one element M selected and at least one element X selected from phosphorus (P), silicon (Si), germanium (Ge), and a halogen element. In this coating layer, the element M and the element X may exhibit different distributions.
- the main transition metal constituting the particles of the lithium cobalt composite oxide means the transition metal having the largest ratio among the transition metals constituting the particles of the lithium cobalt composite oxide.
- the main transition metal represents cobalt (Co).
- This coating layer is a layer formed by the element M and / or the element X being distributed on the surface of the transition metal composite oxide particle, and the composition ratio of the element M and / or the element X in the coating layer is the transition metal composite oxidation. This is a region higher than the composition ratio of element M and / or element X in the physical particles.
- the element M and the element X contained in the coating layer may exhibit different distributions in the coating layer.
- the element M and the element X have a difference in distribution uniformity, and the element M is preferably distributed more uniformly on the surface of the transition metal composite oxide particle than the element X. Further, it is preferable that the element M is distributed more on the surface of the transition metal composite oxide particle than the element X.
- the distribution form of such elements M and X is, for example, a scanning electron microscope (SEM) (hereinafter referred to as SEM) equipped with an energy dispersive X-ray analyzer (EDX: Energy Dispersive X-ray). / Referred to as EDX) can be confirmed by observing the composite oxide particles having a coating layer.
- the surface and cross-section of the complex oxide particles are analyzed by TOF-SIMS (Time-of-Flight-secondary-Ion-Mass-Spectrometry) to measure ions containing element M and element X. But it can be confirmed.
- TOF-SIMS Time-of-Flight-secondary-Ion-Mass-Spectrometry
- the element M is preferably distributed almost uniformly on the surface of the lithium cobalt composite oxide particles to form a coating layer.
- the covering layer containing the element M covers the surface of the lithium cobalt composite oxide particles, thereby suppressing the elution of main transition metal elements contained in the lithium cobalt composite oxide particles and suppressing the reaction with the electrolytic solution. This is because deterioration of battery characteristics can be suppressed.
- an element M for example, a group 2 to group 16 element that has been conventionally substituted, added, coated, etc., to lithium cobaltate (LiCoO 2 ) used for the positive electrode active material is used. be able to.
- the element X is preferably distributed so as to be scattered on the particle surface of the lithium cobalt composite oxide to form a coating layer. This is because the inhibition of the occlusion / release of lithium by the coating layer containing the element X can be suppressed.
- the element X may be unevenly distributed on the surface of the composite oxide particle, for example, or may be scattered at a plurality of points on the entire surface. Further, the element X may be distributed on the coating layer containing the element M.
- the element X is at least one element selected from phosphorus (P), silicon (Si), germanium (Ge), and a halogen element, but these elements are difficult to dissolve in the composite oxide particles on the surface. It is an element that can be scattered and can suppress gas generation by forming a stable compound with lithium.
- the element ratio of cobalt (Co), element X, and element M on the surface of the positive electrode active material can be measured using a scanning X-ray photoelectron spectrometer (ESCA: Quantara SXM manufactured by ULVAC-PHI). Specifically, the measurement is performed by embedding a particle sample to be measured in a metal indium piece and fixing the sample piece to a sample stage with a leaf spring.
- the X-ray source monochromatic Al—K ⁇ ray (1486.6 eV) can be used, and measurement can be performed while charging the surface of the measurement sample in an automatic mode using an argon ion gun and an electron neutralization gun.
- the method for forming the coating layer is not particularly limited.
- the raw material of the coating layer is deposited on the lithium cobalt composite oxide particles serving as core particles by an apparatus that applies compressive shear stress such as mechano-fusation.
- a method of forming by performing heat treatment, a method of forming by performing a heat treatment after depositing a hydroxide serving as a precursor of the coating layer on the particles of lithium cobalt composite oxide by a neutralization titration method, etc. be able to.
- the coating layer is not limited to those described above, and has a composition element or composition ratio different from that of the lithium cobalt composite oxide particles, and covers at least a part of the surface of the lithium cobalt composite oxide particles. If it is what.
- conductive agent for example, a carbon material such as carbon black or graphite is used.
- binder examples include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resin materials. At least one selected from a copolymer or the like mainly composed of is used.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PAN polyacrylonitrile
- SBR styrene butadiene rubber
- CMC carboxymethyl cellulose
- the area density S (mg / cm 2 ) of the positive electrode active material layer 33B is set to, for example, 27 mg / cm 2 or more from the viewpoint of increasing the capacity.
- the separator having a predetermined structure according to the present technology it is possible to reduce an overvoltage that is increased by increasing the area density S (mg / cm 2 ) of the positive electrode active material layer 33B and to improve cycle characteristics.
- the area density S (mg / cm 2 ) of the positive electrode active material layer 33B is the area of the positive electrode 33 (both side forming portions) where the positive electrode active material layer 33B is provided on both sides of the positive electrode current collector 33A ( 1 cm 2 ) is the total mass of the positive electrode active material layer 33B on one side and the positive electrode active material layer 33B on the other side.
- the area density S (mg / cm 2 ) of the positive electrode active material layer 33B can be measured, for example, as follows.
- the negative electrode 34 has, for example, a structure having a double-sided formation part in which a negative electrode active material layer 34B is provided on both sides of a negative electrode current collector 34A having one main surface and another main surface.
- a negative electrode current collector 34A is made of, for example, a metal foil such as a copper foil.
- the negative electrode active material layer 34B includes one or more negative electrode materials capable of occluding and releasing lithium as the negative electrode active material, and the positive electrode active material layer 33B as necessary. Other materials such as a conductive agent and a binder similar to those described above may be included.
- the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 33.
- the metal is not deposited.
- Examples of the negative electrode material capable of inserting and extracting lithium include non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber or activated carbon.
- examples of the coke include pitch coke, needle coke, and petroleum coke.
- An organic polymer compound fired body is a carbonized material obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon.
- These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained.
- graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density.
- non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.
- those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.
- Examples of the negative electrode material capable of inserting and extracting lithium include materials capable of inserting and extracting lithium and containing at least one of a metal element and a metalloid element as a constituent element. This is because a high energy density can be obtained by using such a material. In particular, the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained.
- the negative electrode material may be a single element, alloy, or compound of a metal element or a metalloid element, or may have at least a part of one or more of these phases.
- the alloy includes an alloy including one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements.
- the nonmetallic element may be included. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture of two or more of them.
- Examples of the metal element or metalloid element constituting the anode material include a metal element or metalloid element capable of forming an alloy with lithium.
- a metal element or metalloid element capable of forming an alloy with lithium is referred to as an alloy-based negative electrode material.
- Specific examples of metal elements or metalloid elements capable of forming an alloy with lithium include magnesium (Mg), boron (B), aluminum (Al), titanium (Ti), gallium (Ga), and indium.
- In silicon (Si), germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), or platinum (Pt). These may be crystalline or amorphous.
- a material containing a 4B group metal element or metalloid element in the short-period type periodic table as a constituent element is preferable, and more preferably, at least one of silicon (Si) and tin (Sn) is included as a constituent element. And particularly preferably those containing at least silicon. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium, and a high energy density can be obtained.
- the negative electrode material having at least one of silicon and tin include at least a part of a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or one or more phases thereof. The material which has in is mentioned.
- tin alloys include silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), and manganese (Mn) as second constituent elements other than tin (Sn).
- tin (Sn) compound or silicon (Si) compound examples include those containing oxygen (O) or carbon (C), and in addition to tin (Sn) or silicon (Si), Two constituent elements may be included.
- cobalt (Co), tin (Sn), and carbon (C) are included as constituent elements, and the carbon content is 9.9 mass% or more and 29.7 mass% or less.
- SnCoC containing material whose ratio of cobalt (Co) with respect to the sum total of tin (Sn) and cobalt (Co) is 30 mass% or more and 70 mass% or less is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.
- This SnCoC-containing material may further contain other constituent elements as necessary.
- other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum.
- Mo silicon
- Al aluminum
- phosphorus (P) gallium
- Ga bismuth
- This SnCoC-containing material has a phase containing tin (Sn), cobalt (Co), and carbon (C), and this phase has a low crystallinity or an amorphous structure. It is preferable.
- this SnCoC-containing material it is preferable that at least a part of carbon (C) as a constituent element is bonded to a metal element or a metalloid element as another constituent element.
- the decrease in cycle characteristics is thought to be due to the aggregation or crystallization of tin (Sn) or the like.
- the combination of carbon (C) with other elements suppresses such aggregation or crystallization. Because it can.
- XPS X-ray photoelectron spectroscopy
- the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. .
- Au4f gold atom 4f orbital
- it will appear at 284.8 eV.
- the charge density of the carbon element increases, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV.
- the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV
- at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.
- the C1s peak is used to correct the energy axis of the spectrum.
- the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard.
- the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
- Examples of the negative electrode material capable of inserting and extracting lithium include metal oxides or polymer compounds capable of inserting and extracting lithium.
- Examples of the metal oxide include lithium titanate (Li 4 Ti 5 O 12 ), iron oxide, ruthenium oxide, and molybdenum oxide.
- Examples of the polymer compound include polyacetylene, polyaniline, and polypyrrole. .
- the negative electrode material capable of inserting and extracting lithium may be other than the above.
- 2 or more types of said negative electrode materials may be mixed by arbitrary combinations.
- the negative electrode active material layer 34B may be formed by any of, for example, a gas phase method, a liquid phase method, a thermal spray method, a firing method, or a coating method, or a combination of two or more thereof.
- the negative electrode active material layer 34B is formed using a vapor phase method, a liquid phase method, a thermal spraying method or a firing method, or two or more of these methods
- the negative electrode active material layer 34B and the negative electrode current collector 34A include It is preferable to alloy at least a part of the interface.
- the constituent elements of the negative electrode current collector 34A are diffused into the negative electrode active material layer 34B at the interface, the constituent elements of the negative electrode active material layer 34B are diffused into the negative electrode current collector 34A, or these constituent elements are It is preferable that they diffuse to each other. This is because breakage due to expansion and contraction of the negative electrode active material layer 34B due to charging / discharging can be suppressed, and electronic conductivity between the negative electrode active material layer 34B and the negative electrode current collector 34A can be improved. .
- vapor phase method for example, physical deposition method or chemical deposition method, specifically, vacuum vapor deposition method, sputtering method, ion plating method, laser ablation method, thermal chemical vapor deposition (CVD; Chemical Vapor Deposition) Or plasma chemical vapor deposition.
- liquid phase method a known method such as electroplating or electroless plating can be used.
- the firing method is, for example, a method in which a particulate negative electrode active material is mixed with a binder or the like and dispersed in a solvent, followed by heat treatment at a temperature higher than the melting point of the binder or the like.
- a known method can also be used for the firing method, for example, an atmospheric firing method, a reactive firing method, or a hot press firing method.
- the separator 35 is configured to include at least a porous film 35a. As such a separator 35, the 1st separator 35 or the 2nd separator 35 etc. are mentioned, for example.
- FIG. 3A shows a configuration example of the first separator 35.
- FIG. 3B shows a configuration example of the second separator 35.
- the 1st separator 35 is comprised only with the porous film 35a.
- the area density S (mg / cm 2 ) of the positive electrode active material layer 33B is 27 mg / cm 2 or more. In consideration of the range in which the above (formula) is established, the area density S (mg / cm 2 ) of the positive electrode active material layer 33B is preferably 51 mg / cm 2 or less.
- the pore diameter d (nm) is an average pore diameter measured using a non-mercury palm porometer (product name: IEP-200-A) manufactured by Seika Sangyo Co., Ltd.
- the maximum height Rz ( ⁇ m) of the surface roughness can be measured using a nanoscale hybrid microscope (product name: VN-8000) manufactured by Keyence Corporation according to JIS B0601.
- the maximum height Rz ( ⁇ m) of the surface roughness is a total value of values measured for each of the two main surfaces (front surface and back surface) of the porous film 35a.
- ⁇ is the density of the material of the porous film 35a.
- the air permeability T (sec / 100 cc) is the Gurley air permeability.
- the Gurley air permeability can be measured according to JIS P8117.
- the Gurley air permeability indicates the number of seconds that 100 cc of air passes through the membrane at a pressure of 1.22 kPa.
- the film thickness L was measured by measuring the thickness of five layers of two porous films 35a with a load of 1N using a probe type film thickness meter (Sony DIGITAL GUAGE STAND DZ-501) with a load of 1 N, and the average of the measured values. The average film thickness obtained by calculating / 2.
- a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin
- a polyolefin resin polyolefin film
- the porous film 35a may have a structure in which two or more resin layers made of a resin material are stacked.
- the porous film 35a may be a resin film formed by melting and kneading two or more kinds of resin materials.
- the porous film 35a may contain additives such as an antioxidant.
- the porous film 35a can be produced as follows, for example. For example, a uniform solution prepared by mixing a polymer such as polyolefin resin and a solvent (plasticizer) at a high temperature is formed into a film by T-die method, inflation method, etc., and then stretched, and then the solvent is replaced with another volatile solvent. By extracting and removing, the porous film 35a is formed.
- a solvent a non-volatile organic solvent that dissolves the polymer at high temperature is used alone or in combination. The form of phase separation differs depending on the combination of the polymer and solvent, and the porous structure also changes.
- the stretching method sequential biaxial stretching by roll stretching and tenter stretching, simultaneous biaxial stretching by simultaneous biaxial tenter, and the like are applicable.
- the porous film 35a having a desired structure that satisfies the above (formula) can be obtained.
- the manufacturing method of the porous film 35a is not limited to the said example.
- the thickness Ltotal of the first separator 35 (Thickness of separator) can be arbitrarily set as long as it is equal to or greater than the thickness that can maintain the required strength.
- the thickness Ltotal of the first separator 35 is, for example, an ion permeable property for ensuring insulation between the positive electrode 33 and the negative electrode 34 to prevent a short circuit and the like and for favorably performing a battery reaction via the first separator 35. It is preferable that the thickness of the active material layer that contributes to the battery reaction in the battery is set to a thickness that can make the volume efficiency as high as possible.
- the thickness Ltotal of the first separator 35 is preferably, for example, 3 ⁇ m or more and 17 ⁇ m or less.
- the thickness Ltotal of the first separator 35 exceeds ⁇ 0.0873S 2 + 6.9788S ⁇ 122.66 [S: area density of positive electrode active material layer (mg / cm 2 )] ⁇ m, the first separator 35 As the thickness Ltotal increases, the electrode length is shortened, and the influence of the capacity reduction due to the decrease in the amount of active material of the entire battery tends to increase. For this reason, the thickness Ltotal of the first separator is ⁇ 0.0873S 2 + 6.9788S ⁇ 122.66 [S: from the viewpoint that the volume energy density can be further increased (for example, 300 Wh / L or more).
- the area density (mg / cm 2 ) of the positive electrode active material layer] is more preferably ⁇ m or less.
- the porosity ⁇ of the porous film 35a is, for example, preferably 20% or more from the viewpoint of ensuring good ionic conductivity, and is 57% or less from the viewpoint of maintaining physical strength and suppressing the occurrence of short circuits. It is preferable that it is 25% or more and 46% or less.
- the air permeability T of the porous film 35a is preferably 50 sec / 100 cc or more from the viewpoint of maintaining physical strength and suppressing the occurrence of short circuits, and 1000 sec / 100 cc from the viewpoint of ensuring good ionic conductivity. Or less, more preferably 50 sec / 100 cc or more and 500 sec / 100 cc or less.
- the second separator 35 includes a porous film 35a and a surface layer 35b provided on at least one surface of the porous film 35a.
- 3B is an example in which the surface layer 35b is provided on one surface of the porous film 35a. Although illustration is omitted, the surface layer 35b may be provided on both surfaces of the porous film 35a.
- porous film 35a The porous film 35a has the same configuration as described above.
- the surface layer 35b includes a resin material.
- the resin material may have, for example, a three-dimensional network structure in which the fibers are fibrillated and the fibrils are continuously connected to each other.
- Examples of the resin material contained in the surface layer 35b include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, Styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid Cellulose such as ester copolymer, acrylonitrile-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose Melting point and glass transition
- the surface layer 35b may further contain particles such as inorganic particles and organic particles.
- the resin material is contained in the surface layer 35b in order to bind the particles to the surface of the porous film 35a or to bind the particles.
- the particles may be supported on a resin material having a three-dimensional network structure. In this case, the particles can be kept in a dispersed state without being connected to each other.
- the resin material which is not fibrillated may bind the surface and particle
- inorganic particles examples include metal oxides, metal oxide hydrates, metal hydroxides, metal nitrides, metal carbides, and metal sulfides that are electrically insulating inorganic particles.
- metal oxide or metal oxide hydrate examples include aluminum oxide (alumina, Al 2 O 3 ), boehmite (Al 2 O 3 H 2 O or AlOOH), magnesium oxide (magnesia, MgO), titanium oxide (titania, TiO 2 ), zirconium oxide (zirconia, ZrO 2 ), silicon oxide (silica, SiO 2 ), yttrium oxide (yttria, Y 2 O 3 ), zinc oxide (ZnO), or the like can be suitably used.
- silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN), titanium nitride (TiN), or the like can be preferably used.
- metal carbide silicon carbide (SiC) or boron carbide (B 4 C) can be suitably used.
- metal sulfide barium sulfate (BaSO 4 ) or the like can be suitably used.
- metal hydroxide aluminum hydroxide (Al (OH) 3 ) or the like can be used.
- zeolite M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M represents a metal element, x ⁇ 2, y ⁇ 0 ) porous aluminosilicates such as, talc (Mg 3 Si 4 O Silicates such as layered silicates such as 10 (OH) 2 ) and minerals such as barium titanate (BaTiO 3 ) or strontium titanate (SrTiO 3 ) may be used. It may also be used Li 2 O 4, Li 3 PO 4, lithium compound such as LiF. Carbon materials such as graphite, carbon nanotubes, and diamond may be used. Among these, alumina, boehmite, talc, titania (particularly those having a rutile structure), silica or magnesia are preferably used, and alumina or boehmite is more preferably used.
- inorganic particles may be used alone or in combination of two or more.
- the shape of the inorganic particles is not particularly limited, and any of a spherical shape, a fiber shape, a needle shape, a scale shape, a plate shape, a random shape, and the like can be used.
- Organic particles Materials constituting the organic particles include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, styrene Butadiene copolymer or its hydride, acrylonitrile-butadiene copolymer or its hydride, acrylonitrile-butadiene-styrene copolymer or its hydride, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer Polymers, acrylonitrile-acrylic acid ester copolymers, ethylene propylene rubber, polyvinyl acetate, etc., cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose
- thermosetting resin such as a phenol resin, an epoxy resin, and the like. These materials may be used alone or in combination of two or more.
- the shape of the organic particles is not particularly limited, and any of a spherical shape, a fiber shape, a needle shape, a scale shape, a plate shape, a random shape, and the like can be used.
- a resin material is added to a dispersion solvent such as N-methyl-2-pyrrolidone, and the resin material is dissolved to obtain a resin solution.
- This resin solution is added to at least one of the porous films 35a. It can be obtained by applying to the surface and drying.
- the surface layer 34b contains particles together with the resin material
- the surface layer 35b is prepared by mixing the resin material and particles and adding them to a dispersion solvent such as N-methyl-2-pyrrolidone to dissolve the resin material.
- a resin solution can be obtained, and this resin solution can be applied to at least one surface of the porous film 35a and dried.
- the thickness Ltotal of the second separator 35 (Thickness of separator)
- the thickness Ltotal of the second separator 35 (the total value of the thickness L of the porous film 35a and the thickness of the surface layer 35b) can be arbitrarily set as long as the thickness can maintain the necessary strength. is there.
- the thickness Ltotal of the second separator 35 is, for example, an ion permeable property for achieving insulation between the positive electrode 33 and the negative electrode 34 to prevent a short circuit or the like and to suitably perform a battery reaction via the second separator 35. It is preferable that the thickness of the active material layer that contributes to the battery reaction in the battery is set to a thickness that can make the volume efficiency as high as possible.
- the thickness Ltotal of the second separator 35 is preferably, for example, 3 ⁇ m or more and 17 ⁇ m or less.
- the thickness Ltotal of the second separator 35 exceeds ⁇ 0.0873S 2 + 6.9788S ⁇ 122.66 [S: area density of positive electrode active material layer (mg / cm 2 )] ⁇ m, the second separator 35 As the thickness Ltotal increases, the electrode length is shortened, and the influence of the capacity reduction due to the decrease in the amount of active material of the entire battery tends to increase. For this reason, the thickness Ltotal of the second separator 35 is ⁇ 0.0873S 2 + 6.9788S ⁇ 122.66 [S from the viewpoint that the volume energy density can be further increased (for example, 300 Wh / L or more). : Area density of positive electrode active material layer (mg / cm 2 )] ⁇ m or less is more preferable.
- the electrolyte 36 includes a nonaqueous electrolytic solution (electrolytic solution) and a polymer compound (matrix polymer compound) that holds the nonaqueous electrolytic solution.
- the electrolyte 36 is, for example, a so-called gel electrolyte.
- a gel electrolyte is preferable because high ion conductivity (for example, 1 mS / cm or more at room temperature) is obtained and liquid leakage is prevented.
- the electrolyte 36 may further contain particles such as inorganic particles and organic particles. The details of the inorganic particles and the organic particles are the same as described above.
- Nonaqueous electrolyte The nonaqueous electrolytic solution includes an electrolyte salt and a nonaqueous solvent that dissolves the electrolyte salt.
- the electrolyte salt contains, for example, one or more light metal compounds such as lithium salts.
- the lithium salt include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium tetraphenylborate (LiB (C 6 H 5) 4), methanesulfonic acid lithium (LiCH 3 SO 3), lithium trifluoromethanesulfonate (LiCF 3 SO 3), tetrachloroaluminate lithium (LiAlCl 4), six Examples thereof include dilithium fluorosilicate (Li 2 SiF 6 ), lithium chloride (LiCl), and lithium bromide (LiBr).
- At least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable.
- non-aqueous solvent examples include lactone solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, Carbonate ester solvents such as diethyl carbonate, ether solvents such as 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran, and nitriles such as acetonitrile
- Nonaqueous solvents such as solvents, sulfolane-based solvents, phosphoric acids, phosphate ester solvents, and pyrrolidones are exemplified. Any one of the non-aqueous solvents may be used alone, or two or more thereof may be mixed and used.
- a mixture of a cyclic carbonate and a chain carbonate as the non-aqueous solvent, and it may contain a compound in which a part or all of the hydrogen of the cyclic carbonate or the chain carbonate includes a fluorination.
- the fluorinated compound include fluoroethylene carbonate (4-fluoro-1,3-dioxolan-2-one: FEC) or difluoroethylene carbonate (4,5-difluoro-1,3-dioxolan-2-one: DFEC) is preferably used.
- Polymer compound As the polymer compound, those having a property compatible with a solvent can be used. Examples of such a polymer compound include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, and polyphosphazene.
- Polysiloxane polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, or polycarbonate. These may be single and multiple types may be mixed. Among these, polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable. This is because it is electrochemically stable.
- This nonaqueous electrolyte battery is manufactured, for example, by the following three types of manufacturing methods (first to third manufacturing methods).
- the area density of the positive electrode active material layer 33B can be adjusted by compression molding with a roll press or the like while adjusting the thickness and density while heating as necessary. In this case, compression molding may be repeated a plurality of times.
- a negative electrode material and a binder are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry.
- the negative electrode mixture slurry is applied to both surfaces of the negative electrode current collector 34A, the solvent is dried, and the negative electrode active material layer 34B is formed by compression molding with a roll press machine or the like, thereby producing the negative electrode 34.
- a precursor solution containing an electrolytic solution, a polymer compound, and a solvent is prepared and applied to at least one of both surfaces of the positive electrode 33 and the negative electrode 34, and then the solvent is volatilized to form a gel electrolyte 36.
- the positive electrode lead 31 is attached to the positive electrode current collector 33A
- the negative electrode lead 32 is attached to the negative electrode current collector 34A.
- the gel electrolyte 36 may be formed on at least one surface of both surfaces of the separator.
- the positive electrode 33 and the negative electrode 34 on which the electrolyte 36 is formed are stacked via the separator 35 and then wound in the longitudinal direction, and a protective tape 37 is adhered to the outermost peripheral portion to produce the wound electrode body 30.
- a protective tape 37 is adhered to the outermost peripheral portion to produce the wound electrode body 30.
- the outer edge portions of the exterior member 40 are bonded to each other by heat fusion or the like, so that the wound electrode body 30 is Encapsulate.
- the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40.
- the nonaqueous electrolyte battery shown in FIGS. 1 and 2 is completed.
- the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34.
- the positive electrode 33 and the negative electrode 34 are laminated and wound through a separator 35 coated with a polymer compound on both sides, and then a protective tape 37 is adhered to the outermost periphery thereof to form a wound electrode body.
- a wound body that is a precursor of 30 is prepared.
- the remaining outer peripheral edge except for the outer peripheral edge on one side is bonded by thermal fusion or the like, so that the bag-shaped exterior is obtained.
- the wound body is accommodated in the member 40.
- Examples of the polymer compound applied to the separator 35 include a polymer containing vinylidene fluoride as a component, that is, a homopolymer, a copolymer, a multi-component copolymer, and the like. Specifically, polyvinylidene fluoride, binary copolymers containing vinylidene fluoride and hexafluoropropylene as components, and ternary copolymers containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. A coalescence or the like is preferred.
- the polymer compound may contain one or more other polymer compounds together with the polymer containing vinylidene fluoride as a component.
- the polymer compound on the separator 35 may form a porous polymer compound as follows, for example. That is, first, a solution in which a polymer compound is dissolved in a first solvent composed of a polar organic solvent such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, etc. And this solution is applied onto the separator 35. Next, the separator 35 coated with the above solution is compatible with the above polar organic solvent such as water, ethyl alcohol, propyl alcohol, etc., and in the second solvent which is a poor solvent for the above polymer compound. Immerse. At this time, solvent exchange occurs, phase separation accompanied by spinodal decomposition occurs, and the polymer compound forms a porous structure. Thereafter, by drying, a porous polymer compound having a porous structure can be obtained.
- a polar organic solvent such as N-methyl-2-pyrrolidone, ⁇
- an electrolytic solution is prepared and injected into the bag-shaped exterior member 40, and then the opening of the exterior member 40 is sealed by heat fusion or the like. Finally, the exterior member 40 is heated while applying a load, and the separator 35 is brought into close contact with the positive electrode 33 and the negative electrode 34 through the polymer compound. Thereby, the electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form a gel electrolyte 36, thereby completing the nonaqueous electrolyte battery shown in FIGS. In addition, it is good also as an electrode body by lamination
- the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34. Subsequently, after the positive electrode 33 and the negative electrode 34 are laminated and wound via the separator 35, a protective tape 37 is adhered to the outermost peripheral portion thereof, and a wound body that is a precursor of the wound electrode body 30. Is made.
- the open circuit voltage (that is, the battery voltage) in a fully charged state per pair of positive electrode and negative electrode is, for example, 4.20V, 4.25V, or 4.35V, for example. It may be designed to be 4.65V, 4.80V, or 6.00V or less.
- the energy density can be increased by increasing the battery voltage. Even when the battery voltage is increased, in the embodiment of the present technology, the separator having a predetermined structure is used, so that deterioration of cycle characteristics can be suppressed. For example, when the open circuit voltage at full charge is 4.25 V or more, the amount of lithium released per unit mass increases even with the same positive electrode active material, compared to a 4.20 V battery. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. Thereby, a higher energy density can be obtained.
- Second Embodiment an example of a battery pack of a laminate film type battery (nonaqueous electrolyte battery) provided with the same gel electrolyte layer as in the first embodiment will be described.
- This battery pack is a simple battery pack (also referred to as a soft pack).
- a simple battery pack is built in an electronic device such as a smartphone.
- the battery cell, protection circuit, etc. are fixed with insulating tape, and a part of the battery cell is exposed.
- An output of a connector or the like connected to is provided.
- FIG. 4 is an exploded perspective view showing a configuration example of a simple battery pack.
- FIG. 5A is a schematic perspective view showing an external appearance of a simple battery pack, and
- FIG. 5B is a schematic perspective view showing an external appearance of the simple battery pack.
- the simplified battery pack includes a battery cell 101, leads 102a and 102b derived from the battery cell 101, insulating tapes 103a to 103c, an insulating plate 104, A circuit board 105 on which a protection circuit (PCM (Protection Circuit Module)) is formed and a connector 106 are provided.
- the battery cell 101 is the same as the nonaqueous electrolyte battery according to the first embodiment, for example.
- the insulating plate 104 and the circuit board 105 are disposed on the terrace portion 101 a at the front end of the battery cell 101, and the leads 102 a and the leads 102 b led out from the battery cell 101 are connected to the circuit board 105.
- a connector 106 for output is connected to the circuit board 105.
- Members such as the battery cell 101, the insulating plate 104, and the circuit board 105 are fixed by applying insulating tapes 103a to 103c to predetermined positions.
- FIG. 6 is a block diagram illustrating a circuit configuration example when the battery according to the first embodiment of the present technology (hereinafter appropriately referred to as a secondary battery) is applied to a battery pack.
- the battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.
- the battery pack also includes a positive electrode terminal 321 and a negative electrode terminal 322.
- the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.
- the assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel.
- the secondary battery 301a is a secondary battery of the present technology.
- FIG. 6 a case where six secondary batteries 301a are connected in two parallel three series (2P3S) is shown as an example, but in addition, n parallel m series (n and m are integers) Any connection method may be used.
- the switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310.
- the diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301.
- the diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current.
- the switch unit 304 is provided on the + side, but may be provided on the-side.
- the charge control switch 302a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charging control switch 302a is turned off, only discharging is possible via the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.
- the discharge control switch 303 a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow in the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.
- the temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the assembled battery 301, and supplies the measured temperature to the control unit 310.
- the voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies it to the control unit 310.
- the current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.
- the switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313.
- the switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.
- the overcharge detection voltage is determined to be 4.20 V ⁇ 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ⁇ 0.1 V, for example. .
- the charge / discharge switch for example, a semiconductor switch such as a MOSFET can be used.
- the parasitic diode of the MOSFET functions as the diodes 302b and 303b.
- the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively.
- the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.
- control signals CO and DO are set to the high level, and the charge control switch 302a and the discharge control switch 303a are turned off.
- the memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory.
- EPROM Erasable Programmable Read Only Memory
- the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.
- the temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control at the time of abnormal heat generation, and performs correction in the calculation of the remaining capacity.
- the battery according to the first embodiment of the present technology described above, and the battery pack according to the second embodiment and the third embodiment using the battery include, for example, an electronic device, an electric vehicle, It can be used for mounting or supplying power to a device such as a power storage device.
- Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory card, pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.
- examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.
- Examples of power storage devices include power storage power supplies for buildings such as houses or power generation facilities.
- the first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy.
- the second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device.
- the third power storage system is an electronic device that receives power supply from the power storage device.
- the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is.
- the fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit.
- the sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device.
- the power storage system will be described.
- a power storage device using a battery of the present technology is applied to a residential power storage system
- a power storage system 400 for a house 401 power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like.
- a power storage device 403 Supplied to the device 403.
- power is supplied to the power storage device 403 from an independent power source such as the power generation device 404 in the home.
- the electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403.
- the same power storage system can be used not only for the house 401 but also for buildings.
- the house 401 is provided with a power generation device 404, a power consumption device 405, a power storage device 403, a control device 410 that controls each device, a smart meter 407, and a sensor 411 that acquires various types of information.
- Each device is connected by a power network 409 and an information network 412.
- a solar cell, a fuel cell, or the like is used as the power generation device 404, and the generated power is supplied to the power consumption device 405 and / or the power storage device 403.
- the power consuming device 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d, and the like.
- the electric power consumption device 405 includes an electric vehicle 406.
- the electric vehicle 406 is an electric vehicle 406a, a hybrid car 406b, and an electric motorcycle 406c.
- the battery of the present technology is applied to the power storage device 403.
- the battery of the present technology may be configured by, for example, the above-described lithium ion secondary battery.
- the smart meter 407 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company.
- the power network 409 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.
- the various sensors 411 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 411 is transmitted to the control device 410. Based on the information from the sensor 411, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 405 can be automatically controlled to minimize the energy consumption. Furthermore, the control apparatus 410 can transmit the information regarding the house 401 to an external electric power company etc. via the internet.
- the power hub 408 performs processing such as branching of the power line and DC / AC conversion.
- Communication methods of the information network 412 connected to the control device 410 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, Wi-Fi, etc. There is a method using a sensor network according to the standard.
- the Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication.
- ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4.
- IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
- the control device 410 is connected to an external server 413.
- the server 413 may be managed by any one of the house 401, the power company, and the service provider.
- the information transmitted and received by the server 413 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.
- the control device 410 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 403 in this example.
- the control device 410 is connected to the power storage device 403, the domestic power generation device 404, the power consumption device 405, various sensors 411, the server 413 and the information network 412, and adjusts, for example, the amount of commercial power used and the amount of power generation It has a function to do. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
- the power generation device 404 (solar power generation, wind power generation) in the home is used as the power storage device 403. Can be stored. Therefore, even if the generated power of the power generation device 404 in the home fluctuates, it is possible to perform control such that the amount of power transmitted to the outside is constant or discharge is performed as necessary. For example, the power obtained by solar power generation is stored in the power storage device 403, and the nighttime power at a low charge is stored in the power storage device 403 at night, and the power stored by the power storage device 403 is discharged during a high daytime charge. You can also use it.
- control device 410 is stored in the power storage device 403 .
- control device 410 may be stored in the smart meter 407 or may be configured independently.
- the power storage system 400 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
- FIG. 8 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied.
- a series hybrid system is a vehicle that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power that is temporarily stored in a battery.
- the hybrid vehicle 500 includes an engine 501, a generator 502, a power driving force conversion device 503, driving wheels 504 a, driving wheels 504 b, wheels 505 a, wheels 505 b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511. Is installed.
- the battery of the present technology described above is applied to the battery 508.
- Hybrid vehicle 500 travels using power driving force conversion device 503 as a power source.
- An example of the power / driving force conversion device 503 is a motor.
- the electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the driving wheels 504a and 504b.
- DC-AC DC-AC
- AC-DC conversion AC-DC conversion
- the power driving force conversion device 503 can be applied to either an AC motor or a DC motor.
- the various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown).
- Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
- the rotational force of the engine 501 is transmitted to the generator 502, and the electric power generated by the generator 502 by the rotational force can be stored in the battery 508.
- the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 503, and the regenerative electric power generated by the electric power driving force conversion device 503 by this rotational force becomes the battery 508. Accumulated in.
- the battery 508 is connected to an external power source of the hybrid vehicle 500, so that it can receive power from the external power source using the charging port 511 as an input port and store the received power.
- an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided.
- an information processing apparatus for example, there is an information processing apparatus that displays a battery remaining amount based on information on the remaining amount of the battery.
- the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.
- a positive electrode was produced as follows. 91 parts by mass of a positive electrode active material (LiCo 0.98 Al 0.01 Mg 0.01 O 2 ), 6 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder are mixed, did. Further, this positive electrode mixture was dispersed in N-methyl-2-pyrrolidone as a solvent to make a paste. Next, the obtained positive electrode mixture paste was uniformly applied to both surfaces of a 12 ⁇ m-thick strip-shaped aluminum foil serving as a positive electrode current collector, and then subjected to a drying treatment.
- a positive electrode active material LiCo 0.98 Al 0.01 Mg 0.01 O 2
- graphite as a conductive agent
- polyvinylidene fluoride as a binder
- the positive electrode active material layer was formed by compression molding with a roller press.
- adjustment of the area density of a positive electrode active material layer was performed by adjusting thickness and density, heating as needed in a compression molding process.
- the area density of the positive electrode active material layer was adjusted to 31.1 mg / cm 2 .
- an aluminum lead was welded to a portion where the positive electrode active material layer of the positive electrode current collector was not formed to obtain a positive electrode terminal, thereby obtaining a positive electrode.
- a negative electrode was produced as follows. 90 parts by mass of graphite as a negative electrode active material and 10 parts by mass of polyvinylidene fluoride as a binder were mixed to obtain a negative electrode mixture. Further, this negative electrode mixture was dispersed in N-methyl-2-pyrrolidone as a solvent to make a paste. Next, the obtained negative electrode mixture paste was uniformly applied to both surfaces of a strip-shaped copper foil having a thickness of 8 ⁇ m serving as a negative electrode current collector, and then a drying treatment was performed. After drying, the negative electrode active material layer was formed by compression molding with a roller press. Furthermore, a lead made of nickel was welded to a portion where the negative electrode active material layer of the negative electrode current collector was not formed to obtain a negative electrode terminal, thereby obtaining a negative electrode.
- this polyethylene composition solution 100 parts by mass of this polyethylene composition solution was mixed with 0.125 parts by mass of 2,5-di-t-butyl-p-cresol and tetrakis [(methylene) -3- (3,5-di-t -Butyl-4-hydroxylphenyl) -propionate)] 0.25 part by weight of methane was added as an antioxidant.
- This mixed solution was filled in an autoclave equipped with a stirrer and stirred at 200 ° C. for 90 minutes to obtain a uniform solution.
- This solution was extruded from a T-die with an extruder having a diameter of 45 mm, and a gel-like sheet was formed while being taken up by a cooling roll.
- the obtained sheet was set in a biaxial stretching machine, and simultaneous biaxial stretching was performed at a stretching temperature and a stretching ratio according to a desired structure.
- the obtained stretched membrane is washed with methylene chloride to remove residual liquid paraffin, and then dried to obtain a desired structure (film thickness 7 ⁇ m, maximum height of surface roughness 2 ⁇ m, porosity before correction 30%
- a gel electrolyte layer was formed on the positive electrode and the negative electrode as follows. First, a solution (by mixing 80 g of dimethyl carbonate (DMC), 40 g of ethylene carbonate (EC), 40 g of propylene carbonate (PC), 9.2 g of LiPF 6 and 0.8 g of vinylene carbonate (VC) ( Electrolyte solution) was prepared.
- DMC dimethyl carbonate
- EC ethylene carbonate
- PC propylene carbonate
- VC vinylene carbonate
- PVdF polyvinylidene fluoride
- HFP hexafluoropropylene
- the obtained electrolyte solution was uniformly applied to both surfaces of the positive electrode and the negative electrode by a doctor blade method. Thereafter, the electrolyte solution is gelled by placing the positive electrode and the negative electrode coated with the electrolyte solution in a drier whose internal temperature is kept at 40 ° C. for 1 minute, and the thickness of each of the positive electrode and the negative electrode is increased. A gel electrolyte layer of about 8 ⁇ m was formed.
- the battery was assembled as follows. A belt-like positive electrode having a gel electrolyte layer formed on both sides and a belt-like negative electrode having a gel electrolyte layer formed on both sides, which are produced as described above, are laminated via a separator to form a laminate. The laminated body was wound in the longitudinal direction to obtain an electrode winding body (winding electrode body).
- the electrode winding body is sandwiched between a moisture-proof exterior film (laminate film) in which 25 ⁇ m-thick nylon, 40 ⁇ m-thick aluminum, and 30 ⁇ m-thick polypropylene are laminated in order from the outermost layer.
- the periphery was sealed by heat-sealing under reduced pressure, and the electrode winding body was sealed in the exterior film.
- the positive electrode terminal and the negative electrode terminal were sandwiched between the sealing portions of the exterior film, and a polyolefin film was disposed at a contact portion between the exterior film, the positive electrode terminal, and the negative electrode terminal.
- the electrode element was subjected to a heat treatment while being sealed with the exterior film.
- a laminated film type gel electrolyte battery (battery size thickness 4.4 mm, width 65 mm, height 71 mm, battery volume 2.03 ⁇ 10 ⁇ 5 L) was completed.
- Example 1-2 to Example 1-6 Comparative Example 1-1>
- a separator having the film thickness, the maximum height of surface roughness, the porosity before correction, the corrected porosity, the air permeability, the pore diameter, the curvature, and the membrane resistance shown in Table 1 below
- a laminate film type gel electrolyte battery was completed.
- Example 2-1 to Example 2-11 Comparative Example 2-1 to Comparative Example 2-3> The area density of the positive electrode active material layer was adjusted to 34.3 mg / cm 2 .
- Example 3-1 to Example 3-3 Example 3-5 to Example 3-10, Comparative Example 3-1 to Comparative Example 3-3>
- the area density of the positive electrode active material layer was adjusted to 36.3 mg / cm 2 .
- Example 3-4> The area density of the positive electrode active material layer was adjusted to 36.3 mg / cm 2 .
- PVdF polyvinylidene fluoride
- a positive electrode and a negative electrode produced in the same manner as in the first embodiment are closely attached via a separator having a porous polymer compound formed on both sides, and then wound in the longitudinal direction to provide a protective tape on the outermost periphery.
- a wound electrode body was prepared by pasting.
- the wound electrode body was sandwiched between exterior members and three sides were heat-sealed.
- As the exterior member a moisture-proof aluminum laminate film having a structure in which a 25 ⁇ m-thick nylon film, a 40 ⁇ m-thick aluminum foil, and a 30 ⁇ m-thick polypropylene film were laminated in order from the outermost layer was used.
- the electrolyte solution is a mixture of 17 g of ethyl methyl carbonate (EMC), 34 g of ethylene carbonate (EC), 34 g of diethyl carbonate (DEC), 14 g of LiPF 6, and 0.8 g of vinylene carbonate (VC). What was prepared by (1) was used. Then, the porous polymer compound was swollen by heating with being sandwiched between iron plates to obtain a gel electrolyte. Thus, a laminate film type gel electrolyte battery having the same size as that of Example 1-1 was completed.
- EMC ethyl methyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- VC vinylene carbonate
- Example 4-1 to Example 4-4, Example 4-7, Comparative Example 4-1> The area density of the positive electrode active material layer was adjusted to 38.5 mg / cm 2 .
- Example 4-5 to Example 4-6 Comparative Example 4-2> The area density of the positive electrode active material layer was adjusted to 38.5 mg / cm 2 .
- Example 5-1 and Comparative Example 5-1> The area density of the positive electrode active material layer was adjusted to 42.0 mg / cm 2 .
- Example 1-1 to Example 5-1 and Comparative Example 1-1 to Comparative Example 5-1 the pore diameter d (nm) of the separator, the maximum height Rz ( ⁇ m) of the surface roughness, and the film thickness L ( ⁇ m), porosity ⁇ (%), air permeability T (sec / 100 cc), corrected porosity ⁇ ′ (%), curvature ⁇ , area density S of positive electrode active material layer (mg / cm 2 ) and membrane resistance Ri ( ⁇ m) are measured as follows.
- the pore diameter d (nm) is an average pore diameter measured using a non-mercury palm porometer (product name: IEP-200-A) manufactured by Seika Sangyo Co., Ltd.
- the maximum height Rz ( ⁇ m) of the surface roughness was measured using a nanoscale hybrid microscope (product name: VN-8000) manufactured by Keyence Corporation according to JIS B0601. It is the total value of the values measured for each of the two main surfaces of the porous film (polyethylene film (separator)).
- ⁇ is the density of the separator material.
- the air permeability T (sec / 100 cc) of the separator is the Gurley air permeability.
- the Gurley air permeability can be measured according to JIS P8117.
- the Gurley air permeability indicates the number of seconds that 100 cc of air passes through the membrane at a pressure of 1.22 kPa.
- Film thickness L Using a probe-type film thickness meter (DIYGITAL GUAGE STAND DZ-501 made by Sony), measure the thickness of 5 layers of two porous films (polyethylene film (separator)) with a load of 1 N with a ⁇ 5 mm probe. The average film thickness obtained by calculating the average / 2.
- DIYGITAL GUAGE STAND DZ-501 made by Sony
- Corrected porosity ⁇ ′ (%) [ ⁇ (L ⁇ ⁇ / 100) ⁇ Rz ⁇ 0.46 / 3 ⁇ / L] ⁇ 100 (%)
- Formula (A) [L: film thickness ( ⁇ m), ⁇ : porosity (%), Rz: maximum height of surface roughness (total value of front and back surfaces) ( ⁇ m)]
- the energy density (Wh / L) was determined by multiplying the initial discharge capacity (mAh) determined in the cycle test by the average discharge voltage (V) and dividing by the battery volume.
- Table 1 shows the measurement results of Example 1-1 to Example 5-1, and Comparative Example 1-1 to Comparative Example 5-1.
- the area density (S) is a predetermined value (31.1 mg / cm) in FIGS. 2, 34.3mg / cm 2, 36.3mg / cm 2, a 38.5mg / cm 2, 42mg / cm 2) coordinate plane of L-Ri in the case of (L-Ri plane) shown.
- the regions S1 to S5, Ri min and Ri max shown in FIGS. 9 to 13 are derived according to the above (formula). The relational expressions of the areas S1 to S5, Ri min and Ri max will be described below.
- the volume energy density of the battery is 300 Wh / L or more. From the above, it was found that when the thickness L of the separator is ⁇ 0.0873S 2 + 6.9788S ⁇ 122.66 ⁇ m or less, the volume energy density of the battery is 300 Wh / L or more.
- the battery according to the above-described embodiment is not limited to a secondary battery, and may be a primary battery.
- a battery having a laminate film type battery structure using a laminate film as an exterior and a battery having a wound structure in which an electrode is wound have been described.
- the present invention is not limited thereto. is not.
- the present technology is similarly applied to batteries having other battery structures such as a cylindrical battery, a stack type having a structure in which electrodes are stacked, a square type, a coin type, a flat type, or a button type battery. Can do.
- a battery structure in which a positive electrode and a negative electrode are stacked via a sheet separator for example, a battery structure in which a positive electrode and a negative electrode are stacked via a sheet separator, a battery structure in which a positive electrode and a negative electrode are stacked through a single strip-shaped separator folded, and a negative electrode are sandwiched
- Examples thereof include a battery structure in which a positive electrode and a negative electrode are stacked through a pair of separators folded by spelling in a state.
- the surface layer 35a constituting the second separator 35 may have a configuration in which particles are omitted.
- the electrolyte 36 may contain an ionic liquid (room temperature molten salt).
- the electrolyte 36 may be a liquid electrolyte.
- a positive electrode including a positive electrode current collector and a positive electrode active material, and having a positive electrode active material layer provided on both surfaces of the positive electrode current collector; A negative electrode, A separator including at least a porous film;
- the positive electrode active material has a layered structure, and has a positive electrode material containing a lithium-cobalt composite oxide containing at least lithium and cobalt.
- the area density S (mg / cm 2 ) of the positive electrode active material layer is 27 mg / cm 2 or more
- the porous film is a battery that satisfies the following (formula).
- the positive electrode active material layer has an area density S (mg / cm 2 ) of 51 mg / cm 2 or less.
- the separator has a thickness of 3 ⁇ m to 17 ⁇ m.
- the positive electrode material is a coated particle further including a coating layer provided on at least a part of the surface of the lithium cobalt composite oxide particle.
- the lithium cobalt composite oxide is at least one lithium cobalt composite oxide represented by the general formula (Formula 1).
- (Chemical formula 1) Li p Co (1-q) M1 q O (2-y) X z
- M1 represents at least one element selected from Groups 2 to 15 excluding cobalt (Co)
- X represents at least one element selected from Group 16 elements and Group 17 elements other than oxygen (O).
- P, q, y, and z are within the range of 0.9 ⁇ p ⁇ 1.1, 0 ⁇ q ⁇ 0.5, ⁇ 0.10 ⁇ y ⁇ 0.20, and 0 ⁇ z ⁇ 0.1.
- [12] The battery according to any one of [1] to [11], wherein an open circuit voltage in a fully charged state per pair of the positive electrode and the negative electrode is 4.25 V or more.
- [14] [1] An electronic device comprising the battery according to any one of [12] and receiving power supply from the battery.
- a power storage device that includes the battery according to any one of [12] and supplies electric power to an electronic device connected to the battery.
- a power information control device that transmits and receives signals to and from other devices via a network, The power storage device according to [16], wherein charge / discharge control of the battery is performed based on information received by the power information control device.
- a power system that receives power from the battery according to any one of [11], or that supplies power to the battery from a power generation device or a power network.
- Assembly battery 301a ... Secondary battery, 302a ... Charge control switch, 302b ... Diode, 303a ... Discharge control switch H, 303b ... Diode, 304 ... Switch unit, 307 ... Current detection resistor, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement unit, 314 ... switch control unit, 317 ... memory, 318 ... temperature detection unit, 321 ... positive electrode terminal, 322 ... negative electrode terminal, 400 ... electric storage system, 401 ...
- sensor 412 ... information network, 413 ... Server, 500 ... Hybrid vehicle, 501 ... Engine, 502 ... Generator, 503 ... Electric power driving force converter, 504a ... Driving wheel, 504b ... Driving wheel, 505a ... wheel, 505b ... wheel, 508 ... battery, 509 ... vehicle controller, 510 ... sensor, 511 ... charge port
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Abstract
Description
(式)
0.04≦Ri≦-0.07L-0.09×S+4.99
Ri=τ2L/ε’
ε’=[{(L×ε/100)-Rz×0.46/3}/L]×100
τ={(1.216×ε’Td×10-4)/L}0.5
[Ri:膜抵抗(μm)、L:膜厚(μm)、τ:曲路率、T:透気度(sec/100cc)、d:細孔径(nm)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)、ε:空孔率(%)、ε’:補正空孔率(%)、S:正極活物質層の面積密度(mg/cm2)]
まず、本技術の理解を容易にするため、本技術の技術的背景について説明する。[背景技術]の欄で挙げた特許文献1(特許第4075259号公報)には、膜厚5~16μm、空孔率25~60%のセパレータを用い、コバルト酸リチウム等を有するCo系正極とゲル電解質とを有する電池が記されている。
1.第1の実施の形態(電池)
2.第2の実施の形態(電池パックの例)
3.第3の実施の形態(電池パックの例)
4.第4の実施の形態(蓄電システム等の例)
5.他の実施の形態(変形例)
なお、以下に説明する実施の形態等は本技術の好適な具体例であり、本技術の内容がこれらの実施の形態等に限定されるものではない。また、本明細書に記載された効果はあくまで例示であって限定されるものではなく、また例示した効果と異なる効果が存在することを否定するものではない。
(電池の構成)
本技術の第1の実施の形態による非水電解質電池(電池)について説明する。図1は本技術の第1の実施の形態による非水電解質電池の分解斜視構成を表しており、図2は図1に示す巻回電極体30のI-I線に沿った断面を拡大して示している。
正極33は、例えば、一主面および他主面を有する正極集電体33Aの両面に正極活物質層33Bが設けられた両面形成部を有している。なお、図示はしないが、正極集電体33Aの片面のみに正極活物質層33Bが設けられた片面形成部を有していてもよい。正極集電体33Aは、例えば、アルミニウム箔等の金属箔により構成されている。
LipCo(1-q)M1qO(2-y)Xz
(式中、M1はコバルト(Co)を除く2族~15族から選ばれる元素のうち少なくとも一種を示し、Xは酸素(O)以外の16族元素および17族元素のうち少なくとも1種を示す。p、q、y、zは、0.9≦p≦1.1、0≦q<0.5、-0.10≦y≦0.20、0≦z≦0.1の範囲内の値である。)
リチウムを吸蔵および放出することが可能な正極材料としては、上述したリチウムコバルト複合酸化物の粒子と、この母材となるリチウムコバルト複合酸化物の粒子の表面の少なくとも一部に設けられた被覆層とを有する被覆粒子を用いてもよい。このような被覆粒子を用いることで、電池特性をより向上できる。
導電剤としては、例えばカーボンブラックまたはグラファイト等の炭素材料等が用いられる。
結着剤としては、例えば、ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン(PTFE)、ポリアクリロニトリル(PAN)、スチレンブタジエンゴム(SBR)およびカルボキシメチルセルロース(CMC)等の樹脂材料、ならびにこれら樹脂材料を主体とする共重合体等から選択される少なくとも1種が用いられる。
正極活物質層33Bの面積密度S(mg/cm2)は、高容量化の観点から、例えば、27mg/cm2以上に設定されている。なお、本技術の所定構造のセパレータを用いることによって、正極活物質層33Bの面積密度S(mg/cm2)を大きくすることで大きくなる過電圧を緩和し、サイクル特性を改善できる。
電池を完全放電させてから解体して正極板(正極33)を取り出し、溶剤(例えばDMC(ジメチルカーボネート)等)で洗浄した後、充分に乾燥させる。正極集電体33Aの両面に正極活物質層33Bが形成されている部分(両面形成部)を所定の面積(cm2)(打ち抜き面積と称する)で打ち抜き、質量(mg)(質量Aと称する)を測定し、両面ともに合剤層が塗布されていない部分を同様にして打ち抜き、質量(mg)(質量Bと称する)を測定する。そして、下記計算式により算出する。
計算式:面積密度S(mg/cm2)=(質量A-質量B)÷打ち抜き面積
負極34は、例えば、一主面および他主面を有する負極集電体34Aの両面に負極活物質層34Bが設けられた両面形成部を有する構造を有している。なお、図示はしないが、負極集電体34Aの片面のみに負極活物質層34Bが設けられた片面形成部を有しいてもよい。負極集電体34Aは、例えば、銅箔等の金属箔により構成されている。
セパレータ35は、少なくとも多孔性フィルム35aを含む構成とされる。このようなセパレータ35としては、例えば、第1のセパレータ35または第2のセパレータ35等が挙げられる。図3Aに、第1のセパレータ35の構成例を示す。図3Bに第2のセパレータ35の構成例を示す。
図3Aに示すように、第1のセパレータ35は、多孔性フィルム35aのみで構成されたものである。
多孔性フィルム35aは、下記(式)を満たす構造を有するものである。
(式)
0.04≦Ri≦-0.07L-0.09×S+4.99
Ri=τ2L/ε’
ε’=[{(L×ε/100)-Rz×0.46/3}/L]×100
τ={(1.216×ε’Td×10-4)/L}0.5
[Ri:膜抵抗(μm)、L:膜厚(μm)、τ:曲路率、T:透気度(sec/100cc)、d:細孔径(nm)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)、ε:空孔率(%)、ε’:補正空孔率(%)、S:正極活物質層の面積密度(mg/cm2)]
細孔径d(nm)は、西華産業株式会社製の非水銀パームポロメータ(製品名:IEP-200-A)を用いて測定した平均細孔径である。
表面粗さの最大高さRz(μm)は、JIS B0601に準じて、株式会社キーエンス製のナノスケールハイブリット顕微鏡(製品名:VN-8000)を用いて測定できる。なお、表面粗さの最大高さRz(μm)は、多孔性フィルム35aの2つの主面(表面および裏面)それぞれについて測定した値の合計値である。
多孔性フィルム35aの空孔率ε(%)は、重量法を用いて測定することができる。この方法では、多孔性フィルム35aの10箇所を、多孔性フィルム35aの厚さ方向に向けて直径2cmの円形に打ち抜き、打ち抜いた円形フィルムの中心部の厚さhと、フィルムの質量wとをそれぞれ測定する。さらに、上記厚さhおよび質量wを用いて10枚分のフィルムの体積Vと、10枚分のフィルムの質量Wとを求め、以下の式から空孔率ε(%)を算出することができる。
空孔率ε(%)={(ρV-W)/(ρV)}×100
ここで、ρは多孔性フィルム35aの材料の密度である。
透気度T(sec/100cc)は、ガーレー透気度である。ガーレー透気度は、JIS P8117に準拠して測定できる。ガーレー透気度は、1.22kPa圧で100ccの空気が膜を透過する秒数を示す。
膜厚Lは、プローブ式膜厚計(Sony製DIGITAL GUAGE STAND DZ-501)でΦ5mmのプローブで1Nの荷重で多孔性フィルム35aを2枚重ねた膜厚を5箇所測定し、測定値の平均/2を算出することにより得た平均膜厚である。
膜厚L、空孔率ε、細孔径d、表面粗さの最大高さRzの測定値から式(A)により、補正空孔率ε’を算出することができる。
補正空孔率ε’(%)=[{(L×ε/100)-Rz×0.46/3}/L]×100・・・式(A)
[L:膜厚(μm)、ε:空孔率(%)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)]
透気度T、補正空孔率ε’、細孔径d、膜厚Lの測定値から式(B)により、曲路率τを算出することができる。
曲路率τ={(1.216×ε’Td×10-4)/L}0.5・・・式(B)
[L:膜厚(μm)、ε’:補正空孔率(%)、T:透気度(sec/100cc)]
補正空孔率ε’、膜厚Lおよび曲路率τの測定値から式(C)により、膜抵抗Ri(μm)を算出することができる。
Ri=τ2L/ε’・・・式(C)
[L:膜厚(μm)、ε’:補正空孔率(%)、τ:曲路率]
多孔性フィルム35aは、例えば、以下のように作製できる。例えば、ポリオレフィン樹脂等のポリマーと溶剤(可塑剤)とを高温で混合して調製した均一溶液を、Tダイ法、インフレーション法等でフィルム化したのち、延伸した後、溶剤を別の揮発溶剤で抽出除去することにより、多孔性フィルム35aが形成される。溶剤としては高温でポリマーを溶解する不揮発性の有機溶剤を単独または混合して用いる。ポリマーと溶剤との組み合わせにより相分離の形態が異なり、多孔構造も変化する。延伸の方法は、ロール延伸とテンター延伸による逐次二軸延伸、同時二軸テンターによる同時二軸延伸等が適用可能である。製造工程において、例えば、可塑剤の量、延伸倍率および延伸温度の少なくとも何れかを調整することにより、上記(式)を満たす所望の構造の多孔性フィルム35aを得ることができる。なお、多孔性フィルム35aの製造方法は、上記例に限定されるものではない。
第1のセパレータ35の厚さLtotal(=多孔性フィルムの厚さL)は、必要な強度を保つことができる厚さ以上であれば任意に設定可能である。第1のセパレータ35の厚さLtotalは、例えば、正極33および負極34間の絶縁を図り、短絡等を防止するとともに、第1のセパレータ35を介した電池反応を好適に行うためのイオン透過性を有し、かつ電池内において電池反応に寄与する活物質層の体積効率をできるだけ高くできる厚さに設定されることが好ましい。具体的には、第1のセパレータ35の厚さLtotalは、例えば3μm以上17μm以下が好ましい。
多孔性フィルム35aの空孔率εは、良好なイオン導電性を確保する観点から、例えば、20%以上であることが好ましく、物理的な強度を維持しショート発生を抑制する観点から57%以下であることが好ましく、25%以上46%以下であることがより好ましい。
多孔性フィルム35aの透気度Tは、物理的な強度を維持しショート発生を抑制する観点から、50sec/100cc以上であることが好ましく、良好なイオン導電性を確保する観点から、1000sec/100cc以下であることが好ましく、50sec/100cc以上500sec/100cc以下であることがより好ましい。
図3Bに示すように、第2のセパレータ35は、多孔性フィルム35aおよび該多孔性フィルム35aの少なくとも一方の表面に設けられた表面層35bで構成されたものである。なお、図3Bに示すものは、表面層35bが多孔性フィルム35aの一方の表面に設けられた例である。図示は省略するが、表面層35bが多孔性フィルム35aの両方の表面に設けられていてもよい。
多孔性フィルム35aは、上述したものと同様の構成である。
表面層35bは、樹脂材料を含む。
樹脂材料は、例えば、フィブリル化し、フィブリルが相互連続的に繋がった三次元的なネットワーク構造を有していてもよい。
無機粒子としては、電気絶縁性の無機粒子である金属酸化物、金属酸化物水和物、金属水酸化物、金属窒化物、金属炭化物、金属硫化物等を挙げることができる。金属酸化物または金属酸化物水和物としては、酸化アルミニウム(アルミナ、Al2O3)、ベーマイト(Al2O3H2OまたはAlOOH)、酸化マグネシウム(マグネシア、MgO)、酸化チタン(チタニア、TiO2)、酸化ジルコニウム(ジルコニア、ZrO2)、酸化ケイ素(シリカ、SiO2)または酸化イットリウム(イットリア、Y2O3)、酸化亜鉛(ZnO)等を好適に用いることができる。金属窒化物としては、窒化ケイ素(Si3N4)、窒化アルミニウム(AlN)、窒化ホウ素(BN)または窒化チタン(TiN)等を好適に用いることができる。金属炭化物としては、炭化ケイ素(SiC)または炭化ホウ素(B4C)等を好適に用いることができる。金属硫化物としては、硫酸バリウム(BaSO4)等を好適に用いることができる。金属水酸化物としては水酸化アルミニウム(Al(OH)3)等を用いることができる。また、ゼオライト(M2/nO・Al2O3・xSiO2・yH2O、Mは金属元素、x≧2、y≧0)等の多孔質アルミノケイ酸塩、タルク(Mg3Si4O10(OH)2)等の層状ケイ酸塩等のケイ酸塩、チタン酸バリウム(BaTiO3)またはチタン酸ストロンチウム(SrTiO3)等の鉱物を用いてもよい。また、Li2O4、Li3PO4、LiF等のリチウム化合物を用いてもよい。黒鉛、カーボンナノチューブ、ダイヤモンド等の炭素材料を用いてもよい。中でも、アルミナ、ベーマイト、タルク、チタニア(特にルチル型構造を有するもの)、シリカまたはマグネシアを用いることが好ましく、アルミナまたはベーマイトを用いることがより好ましい。
有機粒子を構成する材料としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等の含フッ素樹脂、フッ化ビニリデン-テトラフルオロエチレン共重合体、エチレン-テトラフルオロエチレン共重合体等の含フッ素ゴム、スチレン-ブタジエン共重合体またはその水素化物、アクリロニトリル-ブタジエン共重合体またはその水素化物、アクリロニトリル-ブタジエン-スチレン共重合体またはその水素化物、メタクリル酸エステル-アクリル酸エステル共重合体、スチレン-アクリル酸エステル共重合体、アクリロニトリル-アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリ酢酸ビニル等、エチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース等のセルロース誘導体、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリイミド、全芳香族ポリアミド(アラミド)等のポリアミド、ポリアミドイミド、ポリアクリロニトリル、ポリビニルアルコール、ポリエーテル、アクリル酸樹脂またはポリエステル等の融点およびガラス転移温度の少なくとも一方が180℃以上の高い耐熱性を有する樹脂、フェノール樹脂、エポキシ樹脂等の熱硬化性樹脂等が挙げられる。これら材料は、単独で用いてもよいし、2種以上を混合して用いてもよい。有機粒子の形状は特に限定されるものではなく、球状、繊維状、針状、鱗片状、板状およびランダム形状等のいずれも用いることができる。
第2のセパレータ35の厚さLtotal(多孔性フィルム35aの厚さLおよび表面層35bの厚さの合計値)は、必要な強度を保つことができる厚さ以上であれば任意に設定可能である。第2のセパレータ35の厚さLtotalは、例えば、正極33および負極34間の絶縁を図り、短絡等を防止するとともに、第2のセパレータ35を介した電池反応を好適に行うためのイオン透過性を有し、かつ電池内において電池反応に寄与する活物質層の体積効率をできるだけ高くできる厚さに設定されることが好ましい。具体的には、第2のセパレータ35の厚さLtotalは、例えば3μm以上17μm以下が好ましい。
電解質36は、非水電解液(電解液)と、それを保持する高分子化合物(マトリックス高分子化合物)とを含んでいる。電解質36は、例えば、いわゆるゲル状の電解質である。ゲル状の電解質は、高いイオン伝導率(例えば、室温で1mS/cm以上)が得られると共に漏液が防止されるので好ましい。なお、電解質36はさらに無機粒子、有機粒子等の粒子を含んでいてもよい。無機粒子および有機粒子の詳細は、上記と同様である。
非水電解液は、電解質塩と、この電解質塩を溶解する非水溶媒とを含む。
高分子化合物としては、溶媒に相溶可能な性質を有するもの等を用いることができる。このような高分子化合物としては、例えば、ポリアクリロニトリル、ポリフッ化ビニリデン、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリフォスファゼン、ポリシロキサン、ポリ酢酸ビニル、ポリビニルアルコール、ポリメタクリル酸メチル、ポリアクリル酸、ポリメタクリル酸、スチレン-ブタジエンゴム、ニトリル-ブタジエンゴム、ポリスチレン、またはポリカーボネート等が挙げられる。これらは単独でもよいし、複数種が混合されてもよい。中でも、ポリアクリロニトリル、ポリフッ化ビニリデン、ポリヘキサフルオロプロピレンまたはポリエチレンオキサイドが好ましい。電気化学的に安定だからである。
この非水電解質電池は、例えば、以下の3種類の製造方法(第1~第3の製造方法)によって製造される。
第1の製造方法では、最初に、例えば、正極材料と、導電剤と、結着剤とを混合して正極合剤を調製し、この正極合剤をN-メチル-2-ピロリドン等の溶剤に分散させてペースト状の正極合剤スラリーを作製する。次に、この正極合剤スラリーを正極集電体33Aの両面に塗布し溶剤を乾燥させ、ロールプレス機等により圧縮成型することにより正極活物質層33Bを形成し、正極33を作製する。なお、圧縮成型工程において、必要に応じて加熱しながら、ロールプレス機等により圧縮成型し、厚みおよび密度を調整することで正極活物質層33Bの面積密度を調整できる。この場合には圧縮成型を複数回繰り返してもよい。
第2の製造方法では、最初に、正極33に正極リード31を取り付けると共に、負極34に負極リード32を取り付ける。続いて、高分子化合物が両面に塗布されたセパレータ35を介して正極33と負極34とを積層して巻回させたのち、その最外周部に保護テープ37を接着させて、巻回電極体30の前駆体である巻回体を作製する。
第3の製造方法では、最初に、正極33に正極リード31を取り付けると共に、負極34に負極リード32を取り付ける。続いて、セパレータ35を介して正極33と負極34とを積層して巻回させたのち、その最外周部に保護テープ37を接着させて、巻回電極体30の前駆体である巻回体を作製する。
第2の実施の形態では、第1の実施の形態と同様のゲル電解質層を備えたラミネートフィルム型の電池(非水電解質電池)の電池パックの例について説明する。
(電池パックの例)
図6は、本技術の第1の実施の形態による電池(以下、二次電池と適宜称する)を電池パックに適用した場合の回路構成例を示すブロック図である。電池パックは、組電池301、外装、充電制御スイッチ302aと、放電制御スイッチ303a、を備えるスイッチ部304、電流検出抵抗307、温度検出素子308、制御部310を備えている。
上述した本技術の第1の実施の形態による電池、並びにこれを用いた第2の実施の形態および第3の実施の形態による電池パックは、例えば電子機器や電動車両、蓄電装置等の機器に搭載または電力を供給するために使用することができる。
本技術の電池を用いた蓄電装置を住宅用の蓄電システムに適用した例について、図7を参照して説明する。例えば住宅401用の蓄電システム400においては、火力発電402a、原子力発電402b、水力発電402c等の集中型電力系統402から電力網409、情報網412、スマートメータ407、パワーハブ408等を介し、電力が蓄電装置403に供給される。これと共に、家庭内の発電装置404等の独立電源から電力が蓄電装置403に供給される。蓄電装置403に供給された電力が蓄電される。蓄電装置403を使用して、住宅401で使用する電力が給電される。住宅401に限らずビルに関しても同様の蓄電システムを使用できる。
パワーハブ408によって、電力線の分岐、直流交流変換等の処理がなされる。制御装置410と接続される情報網412の通信方式としては、UART(Universal Asynchronous Receiver-Transceiver:非同期シリアル通信用送受信回路)等の通信インターフェースを使う方法、Bluetooth、ZigBee、Wi-Fi等の無線通信規格によるセンサーネットワークを利用する方法がある。Bluetooth方式は、マルチメディア通信に適用され、一対多接続の通信を行うことができる。ZigBeeは、IEEE(Institute of Electrical and Electronics Engineers)802.15.4の物理層を使用するものである。IEEE802.15.4は、PAN(Personal Area Network)またはW(Wireless)PANと呼ばれる短距離無線ネットワーク規格の名称である。
本技術を車両用の蓄電システムに適用した例について、図8を参照して説明する。図8に、本技術が適用されるシリーズハイブリッドシステムを採用するハイブリッド車両の構成の一例を概略的に示す。シリーズハイブリッドシステムはエンジンで動かす発電機で発電された電力、またはそれをバッテリーに一旦貯めておいた電力を用いて、電力駆動力変換装置で走行する車である。
[正極の作製]
以下のようにして正極を作製した。正極活物質(LiCo0.98Al0.01Mg0.01O2)を91質量部と、導電剤として黒鉛を6質量部と、結着剤としてポリフッ化ビニリデンを3質量部とを混合して、正極合剤とした。さらに、この正極合剤を、溶媒となるN-メチル-2-ピロリドンに分散させてペースト状にした。次に、得られた正極合剤ペーストを、正極集電体となる厚さ12μmの帯状アルミニウム箔の両面に均一に塗布した後、乾燥処理を行った。乾燥後に、ローラープレス機により圧縮成型することにより、正極活物質層を形成した。なお、正極活物質層の面積密度の調整は、圧縮成型工程において、必要に応じて加熱しながら、厚みおよび密度を調整することで行った。実施例1では、正極活物質層の面積密度が、31.1mg/cm2になるように調整した。さらに、正極集電体の正極活物質層非形成部分に、アルミニウム製のリードを溶接して正極端子とし、正極を得た。
以下のようにして負極を作製した。負極活物質として黒鉛を90質量部と、結着剤としてポリフッ化ビニリデンを10質量部とを混合して負極合剤とした。さらに、この負極合剤を、溶媒となるN-メチル-2-ピロリドンに分散させてペースト状にした。次に、得られた負極合剤ペーストを、負極集電体となる厚さ8μmの帯状銅箔の両面に均一に塗布した後、乾燥処理を行った。乾燥後に、ローラープレス機により圧縮成型することにより、負極活物質層を形成した。さらに、負極集電体の負極活物質層非形成部分に、ニッケル製のリードを溶接して負極端子とし、負極を得た。
セパレータとして、以下のポリエチレンフィルムを作製した。重量平均分子量(Mw)が2.5×106の超高分子量ポリエチレン2質量部と、重量平均分子量(Mw)が2.4×105のポリエチレン13質量部とを混合した原料樹脂と、所望の構造に応じた量で、流動パラフィンとを混合し、ポリエチレン組成物の溶液を調製した。
以下のようにして正極および負極上にゲル電解質層を形成した。
まず、ジメチルカーボネート(DMC)80gと、エチレンカーボネート(EC)を40gと、プロピレンカーボネート(PC)40gと、LiPF69.2gと、ビニレンカーボネート(VC)0.8gとを混合することにより溶液(電解液)を調製した。
以下のようにして電池を組み立てた。上述のようにして作製された、両面にゲル電解質層が形成された帯状の正極と、両面にゲル電解質層が形成された帯状の負極とをセパレータを介して積層して積層体とし、さらにこの積層体をその長手方向に巻回することにより電極巻回体(巻回電極体)を得た。
下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製したこと以外は、実施例1-1と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
正極活物質層の面積密度を34.3mg/cm2に調整した。下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。以上のこと以外は、実施例1-1と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
正極活物質層の面積密度を36.3mg/cm2に調整した。下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。以上のこと以外は、実施例1-1と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
正極活物質層の面積密度を36.3mg/cm2に調整した。下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。
正極活物質層の面積密度を38.5mg/cm2に調整した。下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。以上のこと以外は、実施例1-1と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
正極活物質層の面積密度を38.5mg/cm2に調整した。下掲の表1に示す表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。以上のこと以外は、実施例3-4と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
正極活物質層の面積密度を42.0mg/cm2に調整した。下掲の表1に示す膜厚、表面粗さの最大高さ、補正前空孔率、補正空孔率、透気度、細孔径、曲路率、膜抵抗を備えるセパレータを作製した。以上のこと以外は、実施例3-4と同様にして、ラミネートフィルム型のゲル電解質電池を完成した。
細孔径d(nm)は、西華産業株式会社製の非水銀パームポロメータ(製品名:IEP-200-A)を用いて測定した平均細孔径である。
表面粗さの最大高さRz(μm)は、JIS B0601に準じて、株式会社キーエンス製のナノスケールハイブリット顕微鏡(製品名:VN-8000)を用いて測定した。多孔性フィルム(ポリエチレンフィルム(セパレータ))の2つの主面それぞれについて測定した値の合計値である。
セパレータの空孔率ε(%)は、重量法を用いて測定することができる。この方法では、セパレータの10箇所を、セパレータの厚さ方向に向けて直径2cmの円形に打ち抜き、打ち抜いた円形フィルムの中心部の厚さhと、フィルムの質量wとをそれぞれ測定する。さらに、上記厚さhおよび質量wを用いて10枚分のフィルムの体積Vと、10枚分のフィルムの質量Wとを求め、以下の式から空孔率ε(%)を算出することができる。
空孔率ε[%]={(ρV-W)/(ρV)}×100
ここで、ρはセパレータの材料の密度である。
セパレータの透気度T(sec/100cc)は、ガーレー透気度である。ガーレー透気度は、JIS P8117に準拠して測定できる。ガーレー透気度は、1.22kPa圧で100ccの空気が膜を透過する秒数を示す。
プローブ式膜厚計(Sony製DIGITAL GUAGE STAND DZ-501)でΦ5mmのプローブで1Nの荷重で多孔性フィルム(ポリエチレンフィルム(セパレータ))を2枚重ねた膜厚を5箇所測定し、測定値の平均/2を算出することにより得た平均膜厚である。
膜厚、空孔率、細孔径、表面粗さの最大高さの測定値から式(A)により、補正空孔率ε’(%)を算出した。
補正空孔率ε’(%)=[{(L×ε/100)-Rz×0.46/3}/L]×100(%)・・・式(A)
[L:膜厚(μm)、ε:空孔率(%)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)]
透気度、補正空孔率、細孔径、膜厚の測定値から式(B)により、曲路率τを算出した。
曲路率τ={(1.216×ε’Td×10-4)/L}0.5・・・式(B)
[L:膜厚(μm)、ε’:補正空孔率(%)、T:透気度(sec/100cc)]
電池を完全放電させてから解体して正極板を取り出し、溶剤(DMC:ジメチルカーボネート)で洗浄した後、充分に乾燥させた。正極集電体の両面に正極活物質層が形成されている部分(両面形成部)を所定の面積(打ち抜き面積)で打ち抜き、質量(mg)(質量Aと称する)を測定し、両面ともに合剤層が塗布されていない部分を同様にして打ち抜き、質量(mg)(質量Bと称する)を測定した。そして、下記計算式により算出した。
計算式:面積密度(mg/cm2)=(質量A-質量B)÷打ち抜き面積
補正空孔率ε’(%)、膜厚L(μm)および曲路率τの測定値から式(C)により、膜抵抗Ri(μm)を算出した。
Ri=τ2L/ε’・・・式(C)
[L:膜厚(μm)、ε’:補正空孔率(%)、τ:曲路率]
作製した電池について、以下のサイクル試験を行い容量維持率(サイクル維持率)を求めた。23℃にて所定の充電電圧(下掲の表1に示す電圧)で0.5Cの電流でCC-CV充電(定電流定電圧充電)を5時間行い、3時間休止した後、0.5Cの放電電流で3.0Vの電圧まで放電した。この操作を2回繰り返した。2回目の放電を1サイクル目として、このときの放電容量をこの電池の初期放電容量とした。同様の条件にて充放電を繰り返し行い、[500サイクル後の容量/初期放電容量]×100(%)をサイクル維持率とした。なお、1Cは、理論容量を1時間で放電(または充電)しきる電流値である。0.5は、理論容量を2時間で放電(または充電)しきる電流値である。
サイクル試験で求めた初期放電容量(mAh)に平均放電電圧(V)を乗じて電池体積で割ることにより、エネルギー密度(Wh/L)を求めた。
0.04≦Ri≦-0.07L-0.09×S+4.99
Ri=τ2L/ε’
ε’=[{(L×ε/100)-Rz×0.46/3}/L]×100
τ={(1.216×ε’Td×10-4)/L}0.5
[Ri:膜抵抗(μm)、L:膜厚(μm)、τ:曲路率、T:透気度(sec/100cc)、d:細孔径(nm)、Rz:表面の最大高さ、表裏の合計(μm)、ε:空孔率(%)、ε’:補正空孔率(%)、S:正極活物質層の面積密度(mg/cm2)]
領域S1:Rimin≦Ri≦Rimax
Rimin=0.40
Rimax=-0.07L-0.09×S+4.99(S=31.1)
領域S2:Rimin≦Ri≦Rimax
Rimin=0.40
Rimax=-0.07L-0.09×S+4.99(S=34.3)
領域S3:Rimin≦Ri≦Rimax
Rimin=0.40
Rimax=-0.07L-0.09×S+4.99(S=36.3)
領域S4:Rimin≦Ri≦Rimax
Rimin=0.40
Rimax=-0.07L-0.09×S+4.99(S=38.5)
領域S5:Rimin≦Ri≦Rimax
Rimin=0.40
Rimax=-0.07L-0.09×S+4.99(S=42.0)
本技術は、上述した本技術の実施の形態に限定されるものでは無く、本技術の要旨を逸脱しない範囲内で様々な変形や応用が可能である。
[1]
正極集電体および正極活物質を含み且つ上記正極集電体の両面に設けられた正極活物質層を有する正極と、
負極と、
少なくとも多孔性フィルムを含むセパレータと、
電解質と
を備え、
上記正極活物質は、層状構造を有し、且つ、リチウムとコバルトとを少なくとも含むリチウムコバルト複合酸化物を含む正極材料を有し、
上記正極活物質層の面積密度S(mg/cm2)は、27mg/cm2以上であり、
上記多孔性フィルムは、下記(式)を満たす電池。
(式)
0.04≦Ri≦-0.07L-0.09×S+4.99
Ri=τ2L/ε’
ε’=[{(L×ε/100)-Rz×0.46/3}/L]×100
τ={(1.216×ε’Td×10-4)/L}0.5
[Ri:膜抵抗(μm)、L:膜厚(μm)、τ:曲路率、T:透気度(sec/100cc)、d:細孔径(nm)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)、ε:空孔率(%)、ε’:補正空孔率(%)、S:正極活物質層の面積密度(mg/cm2)]
[2]
上記電解質は、電解液および高分子化合物を含み、且つ、上記電解液が上記高分子化合物により保持されたゲル状の電解質である[1]に記載の電池。
[3]
上記電解質は、粒子をさらに含む[1]~[2]の何れかに記載の電池。
[4]
上記正極活物質層の面積密度S(mg/cm2)は、51mg/cm2以下である[1]~[3]の何れかに記載の電池。
[5]
上記セパレータの厚さは、3μm以上17μm以下である[1]~[4]の何れかに記載の電池。
[6]
上記正極材料は、上記リチウムコバルト複合酸化物の粒子の表面の少なくとも一部に設けられた被覆層をさらに含む被覆粒子である[1]~[5]の何れかに記載の電池。
[7]
上記リチウムコバルト複合酸化物は、一般式(化1)で表されるリチウムコバルト複合酸化物の少なくとも1種である[1]~[6]の何れかに記載の電池。
(化1)
LipCo(1-q)M1qO(2-y)Xz
(式中、M1はコバルト(Co)を除く2族~15族から選ばれる元素のうち少なくとも一種を示し、Xは酸素(O)以外の16族元素および17族元素のうち少なくとも1種を示す。p、q、y、zは、0.9≦p≦1.1、0≦q<0.5、-0.10≦y≦0.20、0≦z≦0.1の範囲内の値である。)
[8]
上記セパレータは、上記多孔性フィルムの少なくとも一方の主面に設けられた、粒子および樹脂を含む表面層をさらに含む[1]~[7]の何れかに記載の電池。
[9]
上記多孔性フィルムは、ポリオレフィン樹脂フィルムである[1]~[8]の何れかに記載の電池。
[10]
上記セパレータの厚さは、-0.0873S2+6.9788S-122.66μm以下である[1]~[9]の何れかに記載の電池。
[11]
上記正極、上記負極、上記セパレータおよび上記電解質が、フィルム状の外装部材に収容された[1]~[10]の何れかに記載の電池。
[12]
一対の上記正極および上記負極当たりの完全充電状態における開回路電圧が4.25V以上である[1]~[11]の何れかに記載の電池。
[13]
[1]~[12]の何れかに記載の電池と、
上記電池を制御する制御部と、
上記電池を内包する外装と
を有する電池パック。
[14]
[1]~[12]の何れかに記載の電池を有し、上記電池から電力の供給を受ける電子機器。
[15]
[1]~[12]の何れかに記載の電池と、
上記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
上記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。
[16]
[1]~[12]の何れかに記載の電池を有し、上記電池に接続される電子機器に電力を供給する蓄電装置。
[17]
他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
上記電力情報制御装置が受信した情報に基づき、上記電池の充放電制御を行う[16]に記載の蓄電装置。
[18]
[1]~[11]の何れかに記載の電池から電力の供給を受け、または、発電装置もしくは電力網から上記電池に電力が供給される電力システム。
Claims (18)
- 正極集電体および正極活物質を含み且つ上記正極集電体の両面に設けられた正極活物質層を有する正極と、
負極と、
少なくとも多孔性フィルムを含むセパレータと、
電解質と
を備え、
上記正極活物質は、層状構造を有し、且つ、リチウムとコバルトとを少なくとも含むリチウムコバルト複合酸化物を含む正極材料を有し、
上記正極活物質層の面積密度S(mg/cm2)は、27mg/cm2以上であり、
上記多孔性フィルムは、下記(式)を満たす電池。
(式)
0.04≦Ri≦-0.07L-0.09×S+4.99
Ri=τ2L/ε’
ε’=[{(L×ε/100)-Rz×0.46/3}/L]×100
τ={(1.216×ε’Td×10-4)/L}0.5
[Ri:膜抵抗(μm)、L:膜厚(μm)、τ:曲路率、T:透気度(sec/100cc)、d:細孔径(nm)、Rz:表面粗さの最大高さ(表面および裏面の合計値)(μm)、ε:空孔率(%)、ε’:補正空孔率(%)、S:正極活物質層の面積密度(mg/cm2)] - 上記電解質は、電解液および高分子化合物を含み、且つ、上記電解液が上記高分子化合物により保持されたゲル状の電解質である請求項1に記載の電池。
- 上記電解質は、粒子をさらに含む請求項2に記載の電池。
- 上記正極活物質層の面積密度S(mg/cm2)は、51mg/cm2以下である請求項1に記載の電池。
- 上記セパレータの厚さは、3μm以上17μm以下である請求項1に記載の電池。
- 上記正極材料は、上記リチウムコバルト複合酸化物の粒子の表面の少なくとも一部に設けられた被覆層をさらに含む被覆粒子である請求項1に記載の電池。
- 上記リチウムコバルト複合酸化物は、一般式(化1)で表されるリチウムコバルト複合酸化物の少なくとも1種である請求項1に記載の電池。
(化1)
LipCo(1-q)M1qO(2-y)Xz
(式中、M1はコバルト(Co)を除く2族~15族から選ばれる元素のうち少なくとも一種を示し、Xは酸素(O)以外の16族元素および17族元素のうち少なくとも1種を示す。p、q、y、zは、0.9≦p≦1.1、0≦q<0.5、-0.10≦y≦0.20、0≦z≦0.1の範囲内の値である。) - 上記セパレータは、上記多孔性フィルムの少なくとも一方の主面に設けられた、粒子および樹脂を含む表面層をさらに含む請求項1に記載の電池。
- 上記多孔性フィルムは、ポリオレフィン樹脂フィルムである請求項1に記載の電池。
- 上記セパレータの厚さは、-0.0873S2+6.9788S-122.66μm以下である請求項1に記載の電池。
- 上記正極、上記負極、上記セパレータおよび上記電解質が、フィルム状の外装部材に収容された請求項1に記載の電池。
- 一対の上記正極および上記負極当たりの完全充電状態における開回路電圧が4.25V以上である請求項1に記載の電池。
- 請求項1に記載の電池と、
上記電池を制御する制御部と、
上記電池を内包する外装と
を有する電池パック。 - 請求項1に記載の電池を有し、上記電池から電力の供給を受ける電子機器。
- 請求項1に記載の電池と、
上記電池から電力の供給を受けて車両の駆動力に変換する変換装置と、
上記電池に関する情報に基づいて車両制御に関する情報処理を行う制御装置と
を有する電動車両。 - 請求項1に記載の電池を有し、上記電池に接続される電子機器に電力を供給する蓄電装置。
- 他の機器とネットワークを介して信号を送受信する電力情報制御装置を備え、
上記電力情報制御装置が受信した情報に基づき、上記電池の充放電制御を行う請求項16に記載の蓄電装置。 - 請求項1に記載の電池から電力の供給を受け、または、発電装置もしくは電力網から上記電池に電力が供給される電力システム。
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CN201480003392.5A CN105027344B (zh) | 2013-10-15 | 2014-08-21 | 电池、电池组、电子装置、电动车辆、蓄电设备及电力系统 |
CA2894233A CA2894233C (en) | 2013-10-15 | 2014-08-21 | Battery with improved cycle characteristics, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and power system |
US14/650,441 US9647256B2 (en) | 2013-10-15 | 2014-08-21 | Battery, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and power system |
EP14853251.8A EP3059793B1 (en) | 2013-10-15 | 2014-08-21 | Battery, battery pack, electronic device, electric vehicle and electric storage device |
KR1020157014829A KR102035375B1 (ko) | 2013-10-15 | 2014-08-21 | 전지, 전지 팩, 전자 기기, 전동 차량, 축전 장치 및 전력 시스템 |
JP2015521897A JP6428612B2 (ja) | 2013-10-15 | 2014-08-21 | 電池、電池パック、電子機器、電動車両、蓄電装置および電力システム |
US15/585,541 US10096812B2 (en) | 2013-10-15 | 2017-05-03 | Battery, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and power system |
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US15/585,541 Continuation US10096812B2 (en) | 2013-10-15 | 2017-05-03 | Battery, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and power system |
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WO2021033413A1 (ja) * | 2019-08-21 | 2021-02-25 | 東レ株式会社 | ポリオレフィン微多孔膜、またその捲回体および製造方法 |
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CA2894233C (en) | 2020-03-24 |
CA2894233A1 (en) | 2015-04-23 |
JP6428612B2 (ja) | 2018-11-28 |
JPWO2015056385A1 (ja) | 2017-03-09 |
EP3059793B1 (en) | 2019-10-02 |
CN105027344B (zh) | 2019-02-22 |
EP3059793A1 (en) | 2016-08-24 |
KR20160072070A (ko) | 2016-06-22 |
KR102035375B1 (ko) | 2019-10-22 |
CN105027344A (zh) | 2015-11-04 |
EP3059793A4 (en) | 2017-06-28 |
US9647256B2 (en) | 2017-05-09 |
US20170250391A1 (en) | 2017-08-31 |
US20150311493A1 (en) | 2015-10-29 |
US10096812B2 (en) | 2018-10-09 |
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