Patent Application
20090166192
1. Field of the Invention
The present invention relates to an electrode for electrochemical devices, and to an electrochemical device.
2. Related Background Art
Spirally wound electrochemical devices are formed by winding electrodes in the longitudinal direction, the electrodes being obtained by forming active material layers on an elongated collector. When the length of the collector in the longitudinal direction is substantial, the collector is provided with a plurality of leads, spaced apart from each other, in the longitudinal direction of the collector, in order to suppress heat generation, polarization and the like that result from concentration of large currents (see, for instance, Japanese Patent Application Laid-open Nos. H7-192717, H11-283882, H11-283883, H11-317218, 2000-106167, 2000-182656, 2000-110453, 2006-260892 and 2006-286404).
During winding, same-polarity leads have conventionally been disposed on the collector overlapping substantially with each other, without paying special attention to the arrangement spacing between leads or to the number of leads thus arranged. To be used with greater efficiency, the electrochemical device must exhibit lower impedance. In terms of lowering the impedance of the electrochemical device, it may presumably suffice to reduce the contribution of the collector to resistance, by simply increasing the number of leads and narrowing the lead arrangement spacing.
However, the inventors have found that leakage current increases when the lead arrangement spacing is too narrow. An increase in leakage current is accompanied by energy loss, and is thus undesirable. That is, the inventors have found that there is a suitable range for the lead arrangement spacing.
On the basis of the above finding, it is an object of the present invention to provide an electrode for electrochemical devices that allows reducing both impedance and leakage current, and to provide an electrochemical device using the electrode for electrochemical devices.
The electrode for an electrochemical device according to the present invention comprises an elongated collector, a lead provided halfway along a longitudinal direction of the collector, and an active material layer provided on the collector.
When La (m) is a distance from one end of the collector, in the longitudinal direction, up to said lead, Lb (m) is a distance from the other end of the collector, in the longitudinal direction, up to the lead, and ρ (Ωm) is a resistivity of the collector at 25° C., where Lopt (m) being 1.9×106ρ, the La (m) and Lb (m) are from 0.95 Lopt to 1.05 Lopt respectively.
Another electrode for an electrochemical device according to the present invention comprises an elongated collector, n leads (n being an integer equal to 2 or greater) provided spaced apart from each other in the collector, in a longitudinal direction of the collector, and an active material layer provided on the collector.
When La (m) is a distance from one end of the collector, in tie longitudinal direction, up to a lead closest to the one end, Lb (m) is a distance from the other end of tie collector, in the longitudinal direction, up to a lead closest to the other end, L1, L2, . . . , Ln−1 (m) are distances between adjacent leads, and ρ (Ωm) is a resistivity of the collector at 25° C., where Lopt (m) being 1.9×106ρ, the La and Lb are from 0.95 Lopt to 1.05 Lopt respectively, and (L1/2), (L2/2), . . . , (Ln−1/2) respectively range from 0.95 Lopt to 1.05 Lopt.
The electrochemical device according to the present invention comprises a pair of electrodes, both electrodes being the above-described electrode for electrochemical devices.
Such an electrode for electrochemical devices affords an electrochemical device having low impedance and low leakage current.
Preferred embodiments of the present invention are explained in detail below with reference to accompanying drawings. In the drawings, identical or equivalent elements are denoted with identical reference numerals, and recurrent explanations thereof are omitted. The dimensional ratios in the drawings do not necessarily match actual dimensional ratios.
An electrode for electrochemical devices 10 according to a first embodiment will be explained with reference to
The collector 12 is a conductive member in the form of a rectangular elongated plate. Although not particularly limited thereto, the material of the collector is preferably a metallic material, such as copper, aluminum or nickel. For instance, the electric resistivity ρ of copper, aluminum and nickel are 1.68×10−8 Ωm, 2.65×10−8 Ωm, 6.99×10−8 Ωm, respectively. The thickness of the collector is not particularly limited, and may range from 10 to 50 μm. Also, the length L0 in the longitudinal direction and the length W0 in the direction (width direction) perpendicular to the longitudinal direction are not particularly limited. The length L0 in the longitudinal direction may range, for instance, from 80 to 150 mm, while the length W0 in the width direction may range, for instance, from 12 to 16 mm. The aspect ratio (L0/W0) of the collector is preferably 5 to 10, more preferably about 7.0
The lead 15 is a conductive member that plays the role of current input terminal in the collector 12. The lead 15 is shaped as a rectangular plate, the longitudinal direction of the lead 15 being perpendicular to the longitudinal direction of the collector 12. In the present embodiment, one end face 15d of the lead 15 in the longitudinal direction extends up to one side face 12d of the collector 12 in the direction (width direction) perpendicular to the longitudinal direction of the collector 12, while the other end face 15c of the lead 15, in the longitudinal direction, extends beyond the other side face 12c of the collector 12 in a direction (width direction) that is perpendicular to the longitudinal direction of the collector 12. The thickness of the lead 15 is not particularly limited, and may be for instance similar to that of the collector 12. The length of the lead 15 in the longitudinal direction can be arbitrarily set in accordance with the way in which the lead is to be used, provided that the other end face 15c of the lead 15 protrudes beyond the side face 12c of the collector 12. The length A of the lead 15, in a direction perpendicular to the longitudinal direction of the lead 15, is best sufficiently shorter than the length L0 of the collector 12 in the longitudinal direction of the latter. For instance, the lead 15 may protrude about 10 to 25 mm beyond the side face 12c of the collector 12, and the width A of the lead 15 may range, for instance, from 2 to 10 mm.
The lead 15 and the collector 12 are fixed together and electrically connected by way of, for instance, a conductive adhesive, soldering or welding. Side faces 15a and 15b of the lead 15 extending in the longitudinal direction thereof are respectively parallel to end faces (one end, other end) 12a, 12b that are perpendicular to the longitudinal direction of the collector 12.
The active material layers 13A, 13C, which are layers containing an active material, are provided on the front and rear faces, respectively, of the collector 12. Specifically, the active material layer 13C is provided over substantially the entire surface of the collector 12 where the lead 15 is not provided. Meanwhile, the active material layers 13A, 13A are dividedly provided on the surface of the collector 12 on which the lead 15 is provided, at portions other than the portion at which the lead 15 is provided.
The active material layers 13A, 13C comprise preferably an active material and a binder. More preferably, the active material layers 13A, 13C comprise a conduction enhancer.
Various active materials, not particularly limited, can be used as active materials for positive electrodes of lithium-ion secondary batteries, so long as the active material is capable of storing and releasing lithium ions, desorbing and intercalating lithium ions, and allows reversible doping and dedoping of lithium ions and counter anions of lithium ions (for instance, ClO4−). The active material may be, for instance, a lithium-containing metal oxide. Examples of lithium-containing metal oxides include, for instance, a lithium oxide comprising at least one metal selected from the group consisting of Co, Ni and Mn, such as LiMO2 (wherein M denotes Co, Ni or Mn) or LiCoxNi1-xO2, LiMn2O4 and LiCoxNiyMn1-x-yO2 (wherein x and y are greater than 0 and smaller than 1), lithium vanadium compound (LiV2O5) or olivine-like LiMPO4 (wherein M denotes Co, Ni, Mn or Fe).
Various active materials, not particularly limited, can be used as active materials for negative electrodes of lithium-ion secondary batteries, so long as the active material is capable of storing and releasing lithium ion, desorbing and intercalating lithium ions, and allows reversible doping and dedoping of lithium ions and counter anions of lithium ions (for instance, ClO4−). Examples include, for instance, natural graphite, artificial graphite, mesocarbon microbeads, mesocarbon fibers (MCF), coke, glass-like carbon, carbonaceous materials such as fired product of organic compounds or the like, metals that can combine with lithium, such as Al, Si or Sn, or amorphous compounds having, as a main component, an oxide such as SiO2 or SnO2.
The electrodes for electric double-layer capacitors may be, for instance, various porous materials having electron conductivity. Suitable examples include, for instance, natural graphite, artificial graphite, mesocarbon microbeads, mesocarbon fibers (MCF), coke, glass-like carbon or carbonaceous materials such as fired products of organic compounds or the like.
As the binder there may be used various bonding agents, not particularly limited, provided that they can fix the above active material and, preferably also the conduction enhancer, to the collector. Examples thereof include, for instance, a fluororesin such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE), or a mixture of styrene-butadiene rubber (SBR) with a water-soluble polymer (carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, dextrin, gluten and the like).
Examples of the conduction enhancer include, for instance, carbon black, metal micropowders of copper, nickel, stainless steel, iron or the like, mixtures of carbon materials and metal micropowders, or conductive oxides such as ITO. The conduction enhancer is a material added with a view to increasing the electron conductivity of the active material layers 13A, 13C. Acetylene black or carbon black can be suitably used as the conduction enhancer.
Conventional methods may be used for forming the active material layers 13A, 13C. Although the active material layers 13A, 13C cover preferably most of the regions on the front and rear faces of the collector 12, the active material layers 13A, 13C need not necessarily cover all the regions, so that, for instance, the edges of the collector may remain uncovered.
In the present embodiment, the distance La between the lead 15 and an end face (one end) 12a of the collector 12 in the longitudinal direction, and the distance Lb between the lead 15 and an end face (other end) 12b of the collector 12 in the longitudinal direction range both from 0.95 Lopt to 1.05 L opt.
Herein, Lopt (m)=1.9×106ρ, with ρ denoting the electric resistivity (Ωm) of the collector 12 at 25° C.
The distance La and the distance Lb can be thought of as the maximum distance covered by current in the collector 12 when current is supplied to, and discharged from, the active material layers 13A, 13C via the collector 12. Also, Lopt is the optimal value of this maximum distance, and is determined by the electric resistivity of the collector 12. In the present embodiment, therefore, the distance La and the distance Lb range from 95 to 105% of the optimal value Lopt.
An electrochemical device using such an electrode has enhanced characteristics, with extremely low impedance and leakage current values. Leakage current tends to increase when the distances La and Lb are smaller than 0.95 Lopt, while the impedance of the electrochemical device tends to increase when the distances La and Lb exceed 1.05 Lopt.
An electrode for electrochemical devices 10 according to a second embodiment is explained next with reference to
An electrode for electrochemical devices 10 according to a embodiment is explained next with reference to
An electrode for electrochemical devices 10 according to a fourth embodiment is explained next with reference to
Here, L1 denotes the distance between adjacent leads 151, 152, L2 the distance between adjacent leads 152, 153, . . . and Ln−1 the distance between adjacent leads lead 15n−1, 15n. In the present embodiment, the distances L1,L2, . . . , Ln−1 are set so as to satisfy the condition that (L1/2),(L2/2), . . . , (Ln−1/2) range all from 0.95 Lopt to 1.05 Lopt.
As is the case with La and Lb in the first embodiment, (L1/2),(L2/2), . . . , (Ln−1/2) can be thought of as the maximum distances covered by the current in the collector 12 when current is supplied to, and charging is carried out in, the electrode 10. Also, Lopt is the optimal value of the largest distance. In the present embodiment not only the distance L1 and the distance L2 but also (L1/2),(L2/2), . . . , (Ln−1/2) range all from 95% to 105% of the optimal value.
Such an electrode for electrochemical devices 10 elicits the same effect as that of the first embodiment. Needless to say, the electrode of the second embodiment and the third embodiment may be provided as a plurality of electrodes, as in the fourth embodiment.
Electrochemical Device
An electrochemical device using the above-described electrode 10 is explained next with reference to
An electrochemical device 100 illustrated in
The case 50 seals the wound body 30 and prevents intrusion of air and moisture into the interior of the case. The material used in the case 50 may be, for instance, a synthetic resin such as an epoxy resin, a laminate film in which a metal sheet of aluminum or the like is coated with a resin. The lead 15 of the wound body 30 protrudes out of the case 50.
The electrolyte solution (not shown) fills the inner space of the case 50. Part of the electrolyte solution is contained in the interior of an electrode 10, an electrode 10 and a separator 20.
In the case of a lithium-ion secondary battery, for instance, the electrolyte solution used may be, for instance, a nonaqueous electrolyte solution in which a lithium salt is dissolved in an organic solvent. Examples of the lithium salt include, for instance, LiPF6, LiClO4, LiBF4, LiAsF6, LiCF3SO3, LiCF3CF2SO3, LiC(CF3SO2)3, LiN(CF3SO2)2, LiN(CF3CF2SO2)2, LiN(CF3SO2)(C4F9SO2) and LiN(CF3CF2CO)2.
In the case of an electric double-layer capacitor, for instance, there can be used an electrolyte solution obtained by dissolving a quaternary ammonium salt such as tetraethylammonium tetrafluoroborate (TEA+BF4−) or triethylmonomethylammonium tetrafluoroborate (TEMA+BF4−) in an organic solvent.
These salts may be used singly or in combinations of two or more. The electrolyte solution may form a gel through addition of a polymer or the like.
Known solvents used in electrochemical devices may be employed as the organic solvent. Preferred examples thereof include, for instance, propylene carbonate, ethylene carbonate and diethyl carbonate. These organic solvents may be used singly or in mixtures of two or more at arbitrary mixing ratios.
The wound body 30 is obtained by winding, in the longitudinal direction, a pair of the above-described electrodes for electrochemical devices 10, 10, in such a manner that a separator 20 is interposed between the electrodes for electrochemical devices 10, 10.
Specifically, for instance, a stack resulting from stacking an electrode 10/separator 20/electrode 10/separator 20 is wound into a tubular form, starting form one end of the stack, to yield the wound body 30 illustrated in
The position at which the leads 15 protrude may lie in the same direction between electrodes, as illustrated in
The separator 20, which provides electric insulation between the electrodes for electrochemical devices 10, 10, is an electrically insulating porous member. The material of the separator is not particularly limited, and there may be used various separator materials. Examples of electrically insulating porous members include, for instance, a stretched film of a single-layer or a multilayer film comprising polyethylene, polypropylene or a polyolefin, or of a mixture of the foregoing resins, or, alternatively, a fibrous nonwoven fabric comprising at least one constituent material selected from the group consisting of cellulose, polyester and polypropylene.
In such an electrochemical device there must be used an electrode for electrochemical devices in which La and Lb, or La, Lb, (L1/2), (L2/2), . . . and (Ln−1/2) are as prescribed above. Both impedance and leakage current are small in such an electrochemical device.
The present invention is not limited to the above embodiments, and may accommodate various modifications. In the above embodiments, for instance, the collector is shaped as an elongated plate, but the collector need only be a thin a long member, i.e. need only have a longitudinal direction. The collector may thus be shaped, for instance, as an elongated wire.
The electrochemical device is not limited to batteries such as lithium-ion secondary batteries, or to electric double-layer capacitors, and may also be realized in, for instance, electrolytic capacitors or the like.
A coating material was prepared by mixing activated carbon particles, as the active material, and PVDF as the binder, to a ratio active material: binder=70:30; then N-methyl pyrrolidone was added to the obtained mixture, and the whole was kneaded. The coating material was coated, using a doctor blade, onto both faces of 30 μm aluminum foil, except at the portion intended for lead placing. The resulting coating films were then dried. The aluminum foil having formed thereon the coating films was then punched into a rectangle, and then a lead having a width A of 2 mm, a length of 25 mm and a thickness of 0.1 mm was ultrasonically welded to the uncoated portion of the collector, as illustrated in
Both faces of one of the obtained electrodes were covered with a nonwoven fabric of regenerated cellulose (thickness 30 μm), after which the electrode was disposed opposite the other electrode, and the resulting stack was wound into a tubular shape, from one end of the stack. The wound stack was fitted into a case made of aluminum laminate film, the lead was drawn out through the opening of the laminate film, and the opening was thermocompression-bonded, flanking the lead portion. An electrolyte solution for electric double-layer capacitors was poured onto the stack through the last remaining opening of the outer bag of aluminum laminate in which the stack was placed. The remaining opening was then sealed through vacuum thermocompression bonding, followed by aging, to yield the various electric double-layer capacitors. The electrolyte solution was a solution of tetraethylammonium tetrafluoroborate (TEA+BF4−) as the electrolyte, dissolved in propylene carbonate (PC), as an organic solvent. The electrolyte concentration in the electrolyte solution was 1.0 mol/L.
Electric double-layer capacitors were obtained in the same way as in Example 1, but using herein 17 μm-thickness copper foil instead of aluminum foil, with L0, La and Lb set as in
Cathode electrodes were manufactured in accordance with the procedure below. Firstly there were prepared LiCoO2 as a positive electrode active material, acetylene black as a conduction enhancer and polyvinylidene fluoride (PVdF) as a binding agent. These were mixed and dispersed in a planetary mixer to relative weights of positive electrode active material: conduction enhancer: binding agent=90:6:4. Thereafter, the viscosity of the resulting dispersion was adjusted through addition of a suitable amount of NMP, as a solvent, to yield a slurry-like cathode coating liquid (slurry).
Aluminum foil (thickness 20 μm) was prepared next as the collector, and the cathode coating liquid was coated to an active material carrying amount of 1.0 mg/cm2, onto both faces of the aluminum foil, except at the portion planned for lead welding, using a doctor blade. This was followed by pressing using a calender roll, to a porosity of 28% of the coated active material layers. The pressed product was punched into a rectangle, to yield the cathode electrode. The distances L0, La, Lb were set as in
Anode electrodes were manufactured next in accordance with the procedure below. Firstly there were prepared natural graphite as a negative electrode active material and polyvinylidene fluoride (PVdF) as a binding agent. These were blended, mixed and dispersed in a planetary mixer to relative weights of negative electrode active material: binding agent=95:5). Thereafter, the viscosity of the resulting dispersion was adjusted through addition of a suitable amount of NMP, as a solvent, to yield a slurry-like anode coating liquid. Copper foil (thickness 17 μm) was prepared next, and the anode coating liquid was coated to an active material carrying amount, on the anode electrode, of 3.0 mg/cm2, onto both faces of the copper foil, except at the portion planned for lead welding, using a doctor blade. This was followed by pressing using a calender roll, to a porosity of 30% of the active material layers of the anode electrode. The pressed product was punched into a rectangle, to yield the anode electrode. The distances L0, La, Lb were set as in
Both faces of one of the obtained electrodes were covered with a single-layer polyethylene porous film (thickness 12 μm), as a separator, after which the electrode was disposed opposite the other electrode, and the resulting stack was wound into a tubular shape, from one end of the stack. The wound stack was fitted into a case made of aluminum laminate film, the lead was drawn out through the opening of the laminate film, and the opening was thermocompression-bonded, flanking the lead portion. An electrolyte solution for lithium-ion secondary batteries was poured onto the stack through the last remaining opening of the outer bag of aluminum laminate in which the stack was placed. The remaining opening was then sealed through vacuum thermocompression bonding, followed by aging, to yield the various lithium-ion secondary batteries.
As the electrolyte for lithium-ion secondary batteries there was used an electrolyte obtained by dissolving LiPF6, to a concentration of 1.5 mol/dm3, in a solvent resulting from mixing propylene carbonate (PC), ethylene carbonate (EC) and diethyl carbonate (DEC), to a volume ratio of 2:1:7, respectively. To 100 parts by weight of the resulting solution there were further added 3 parts by weight of 1,3-propane sultone.
Evaluation of the electric double-layer capacitors and lithium-ion secondary batteries
The electric double-layer capacitors and lithium-ion secondary batteries of the examples and comparative examples were measured for impedance and leakage current. The values are illustrated in
In Examples A1 to A3, relating to electric double-layer capacitors using collectors made of aluminum, there was achieved an impedance of less than 100 mΩ. In Examples A4 and A5, relating to electric double-layer capacitors using collectors made of copper, there was achieved an impedance of less than 60 mΩ. In Examples B1 to B3, relating to lithium-ion secondary batteries, there was achieved an impedance of less than 130 mΩ. A leakage current no greater than 20 mA/h was achieved in all the examples.
| Number | Date | Country | Kind |
|---|---|---|---|
| P2007-340307 | Dec 2007 | JP | national |
