WO2022172750A1 - 非水電解質電池 - Google Patents
非水電解質電池 Download PDFInfo
- Publication number
- WO2022172750A1 WO2022172750A1 PCT/JP2022/002789 JP2022002789W WO2022172750A1 WO 2022172750 A1 WO2022172750 A1 WO 2022172750A1 JP 2022002789 W JP2022002789 W JP 2022002789W WO 2022172750 A1 WO2022172750 A1 WO 2022172750A1
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- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- expanded metal
- aqueous electrolyte
- battery
- electrolyte battery
- Prior art date
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to non-aqueous electrolyte batteries.
- a sheet formed of a positive electrode mixture is prepared by forming a stainless steel plate with a thickness of 0.1 mm into a mesh having a center-to-center dimension SW in the short direction of the mesh of 1.5 mm and a center-to-center dimension LW in the long direction of 3 mm. 0 mm and a three-dimensional thickness of 0.2 mm.
- Patent Document 2 in a lead-acid battery using an aqueous electrolyte, when a lead-tin alloy is expanded to obtain a positive electrode grid, the shape of the grid is set to a maximum point and a minimum point of a plurality of continuous curves. By forming a network structure in which points overlap each other to form intersections, uneven distribution of strain during expansion processing is eliminated, microcracks that induce corrosion do not occur inside the lattice, and local corrosion does not occur. It is disclosed that the lead-acid battery is inhibited from deteriorating thereby.
- an electrode e.g., positive electrode
- an electrode is usually produced by filling an expanded metal such as that disclosed in Patent Document 1 with a mixture containing an active material, a binder, and the like, followed by rolling. be done.
- Expanded metal is a metal plate formed by making a large number of cuts and stretching it to form a large number of openings in a net shape (for example, a rhombic pattern).
- the direction of filling and rolling of the mixture is the same as the short direction (SW direction) of the expanded metal.
- stress such as tensile stress and compression is applied to the expanded metal, so that the distance in the short direction of the expanded metal becomes longer, and the distance between the long directions (LW direction) becomes shorter, so that the entire bone part deforms.
- the elongation of expanded metal is basically derived from the physical properties of the base material that makes up the expanded metal. If the stress during filling and rolling is applied more than the elongation of the base material, the gap between SW may be excessively stretched and broken. As a result, the current collecting property of the electrode is lowered, and battery performance such as discharge performance may be lowered.
- Non-aqueous electrolyte battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte
- the positive electrode is a positive electrode active material and expanded metal
- the expanded metal includes bones forming a mesh
- the bones include four or more crosspieces surrounding openings of the mesh, and a connecting portion connecting the crosspieces.
- the number of crosspieces per opening is four or more, and at least one crosspiece per opening has a bent shape or a curved shape.
- a non-aqueous electrolyte battery with high energy density and excellent discharge performance can be realized.
- FIG. 2 is a schematic diagram showing an example of a current collector made of expanded metal
- FIG. 2 is a schematic diagram showing a schematic configuration of an apparatus used to manufacture the expanded metal of FIG. 1; It is a schematic diagram which shows the example of the curved shape or bending shape of a crosspiece. It is a schematic diagram which shows the example of the curved shape or bending shape of a crosspiece. It is a schematic diagram which shows the example of the curved shape or bending shape of a crosspiece. It is a schematic diagram which shows the example of the curved shape or bending shape of a crosspiece.
- BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a front view of a partial cross-section of a non-aqueous electrolyte battery according to an embodiment of the present disclosure;
- a nonaqueous electrolyte battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte.
- the positive electrode includes a positive electrode active material and expanded metal.
- Expanded metal is a metal plate that is stretched with a large number of cuts to form a large number of openings in a mesh shape (for example, a rhombic pattern).
- the mesh of expanded metal is a mesh.
- the center-to-center distance of the expanded metal means the distance between mesh center positions.
- the expanded metal contains bones that make up the mesh.
- the bone portion includes crosspieces surrounding openings in the mesh and connecting portions that connect the crosspieces.
- the number of crosspieces per opening is four or more, and at least one crosspiece per opening has a bent or curved shape.
- the crosspiece In the expanded metal, the crosspiece is usually formed in a straight line extending from one connecting portion to the other connecting portion.
- at least one of the crosspieces has a bent or curved shape instead of a straight line.
- the crosspiece has extensibility. Therefore, in the manufacturing process of the battery, the folded or curved portion extends (or bends) against the tensile stress or compressive stress applied to the expanded metal in the process of filling the expanded metal with the mixture and then rolling it to fabricate the electrode. ), it is possible to prevent the expanded metal from stretching more than the amount of elongation derived from the material. This suppresses deformation and breakage of the entire bone portion of the expanded metal. As a result, even when the mixture is densely filled, the deterioration of the current collecting property of the electrode is suppressed, and a non-aqueous electrolyte battery with high energy density and excellent discharge performance can be realized.
- Patent Document 2 by making the shape of the expanded metal curvilinear in the vicinity of the intersection of the lattice, uneven distribution of strain during the expansion process is suppressed, and the generation of microcracks that cause local corrosion is prevented. It does not consider the lattice elongation that occurs during rolling. Therefore, the invention described in Patent Document 2 is completely different from the present invention, which aims to suppress breakage due to excessive deformation of the expanded metal during rolling. Suppression of grid corrosion, which is a problem of the invention described in Patent Document 2, is a problem specific to lead-acid batteries using a lead-tin alloy for the grid, and does not exist in the non-aqueous electrolyte battery according to the present invention.
- the bent or curved shape of the crosspiece may be convex or concave.
- the contour line has a convex shape (concave shape) due to the bent shape or the curved shape
- the bent shape or the curved shape has a convex shape (concave shape) ).
- a bent shape is formed by at least two straight lines.
- the bent shape may be formed by three or more straight lines.
- a curved shape may be formed by a plurality of curved lines.
- the bent or curvilinear shape may have convex and concave shapes, for example, undulating curves and zigzag shapes.
- FIG. 1 shows an example of a current collector made of expanded metal.
- FIG. 1(A) is a top view
- FIG. 1(B) is a cross-sectional view seen from the X 1 -X 2 direction.
- T, SW, LW, and W in (A) of FIG. 1 are called the thickness T of the expanded metal, the center-to-center distance SW in the short direction, the center-to-center distance LW in the long direction, and the feed width W, respectively.
- the expanded metal 100 shown in FIG. 1 can be produced, for example, by processing a metal plate using the production apparatus shown in FIG.
- the expanded metal 100 has four crosspieces 101a to 101d surrounding the openings of the mesh and a connecting part 102 connecting the crosspieces.
- the crosspieces 101a to 101d are processed into a curved shape (a circular arc shape in the example of FIG. 1).
- the mesh shape approximates a rhombus.
- the shape of the mesh is not a rhombus, but a curved line surrounded by four arcs.
- the radius of curvature of the four arcs is not particularly limited, but can be, for example, 1-4 mm.
- the crosspiece Since the crosspiece has a bent shape or a curved shape, the stress applied to the expanded metal during the manufacturing process of the battery is caused by the extension of the bent shape or the curved shape and/or the bending of the bent shape or the curved shape. It is relieved by applying stress and bending the bent or curved portion. As a result, excessive elongation and breakage of the core material are suppressed, and a non-aqueous electrolyte battery having high energy density and excellent discharge performance can be realized.
- the crosspieces 101a and 101c generally extend along the first direction, although the direction of extension changes at the portion having the curved shape.
- the crosspieces 101b and 101d generally extend along the second direction intersecting the first direction, although the direction of extension changes at the portion having the curved shape.
- the first direction and the second direction are directions parallel to the straight line connecting the connecting portions 102 .
- the crosspieces 101a and 101c have the same curved shape, and when the crosspiece 101a is translated in the second direction, it overlaps with the crosspiece 101c.
- the crosspieces 101b and 101d have the same curved shape, and when the crosspiece 101b is translated in the first direction, it overlaps with the crosspiece 101d.
- the expanded metal manufacturing apparatus 200 shown in FIG. 2 includes a lower blade 201 and an upper blade 202 extending in a first direction D1 parallel to the main surface of a metal plate 204.
- the upper blade 202 is movable in the vertical direction (the direction perpendicular to the metal plate 204), and forms a cut in the metal plate 204 by moving downward from the state shown in FIG. can be formed.
- the upper blade 202 is also capable of reciprocating with a predetermined width in the first direction D1.
- the metal plate 204 is intermittently sent in a second direction D2 parallel to the main surface of the metal plate 204 and perpendicular to the first direction in conjunction with the vertical movement of the upper blade 202 .
- the upper blade 202 moves in the first direction D1 in conjunction with the transport of the metal plate 204 in the second direction D2.
- the metal plate 204 is alternately cut at regular intervals, and the cut portions are spread out via the upper blade 202 to form a diamond-shaped mesh.
- the upper blade 202 has a curved shape. As a result, the crosspiece is processed into a shape having a corresponding curved shape.
- the thickness T of the expanded metal corresponds to the thickness of the metal plate 204 before processing in FIG.
- the feed width W approximately matches the interval between the cuts.
- the center-to-center distance SW in the short direction corresponds to the length of the shorter diagonal line of the rhombic mesh.
- the longitudinal center-to-center distance LW corresponds to the length of the longer diagonal of the rhombic mesh.
- the crosspiece has a curved shape (arc shape).
- the curved shape is not limited to a circular arc, and may be any curved shape. Due to the curved portion, the contour of the mesh (apertures) has convex or concave portions.
- the curved shape may be formed by a plurality of curves with different curvatures.
- the curvilinear shape may be, for example, a wavy shape or an S-shaped shape having a convex portion and a concave portion.
- the crosspiece may have a bent shape.
- a bent shape is formed by at least two straight lines.
- the bent shape may be formed by three or more straight lines.
- the bent shape may also be a shape having a convex shape and a concave shape, such as a zigzag shape, similar to the curved shape.
- FIG. 3 shows another example of the curved or bent shape of the crosspiece.
- FIGS. 3A to 3D each show an example in which the crosspiece 101a in FIG. 1 is provided with a portion having a bent shape.
- the bent shape may be a convex shape with three straight lines, as shown in FIG. 3A, or a concave shape with three straight lines, as shown in FIG. 3B. Also, as shown in FIG. 3C, it may have a zigzag shape with a plurality of straight lines. As shown in FIG. 3D, two straight lines may form a convex shape on the crosspiece.
- the center-to-center distance SW in the short direction and the center-to-center distance LW in the long direction of the expanded metal preferably satisfy 2 mm 2 ⁇ LW ⁇ SW ⁇ 20 mm 2 and 6 mm 2 ⁇ LW ⁇ SW ⁇ 20 mm 2 . more preferred.
- LW ⁇ SW the layer of the positive electrode active material can be formed by pressure bonding without gaps, and variations in the density of the positive electrode active material can be reduced. Therefore, non-uniformity of the battery reaction (for example, discharge reaction) within the electrode plate is suppressed, and the discharge performance of the battery is improved.
- LW ⁇ SW is preferably 20 mm 2 or less in order to suppress deterioration in current collection.
- SW and LW can be selected so that LW ⁇ SW is 2 mm 2 or more and 20 mm 2 or less (more preferably 6 mm 2 or more and 20 mm 2 or less).
- the thickness of the positive electrode is 0.3 mm or more and preferably 3 mm or less. More preferably, the thickness of the positive electrode is 0.8 mm or more and 3 mm or less. As the thickness of the positive electrode increases, more pressure is applied to the expanded metal during filling, so that the expanding effect of the expanded metal of the present invention is exhibited. Further, when the thickness of the positive electrode is 3 mm or less, the distance from the expanded metal to the outermost surface of the electrode does not become too long, and deterioration of the current collecting property can be suppressed.
- the thickness T or feed width W of the expanded metal is small, the core material portion (bone) is likely to break when the positive electrode mixture is crimped. Moreover, the electrical resistance is increased, and the current collecting property is lowered. On the other hand, by increasing the thickness T or the feed width W, breakage of the core material portion (bone) during crimping of the positive electrode mixture can be suppressed. However, if the thickness T or the feed width W is increased, the rigidity of the expanded metal increases, and it may become difficult to wind the electrodes to produce an electrode group.
- the thickness T is preferably 0.1 mm or more so that the bones of the expanded metal do not become too thin, the expanded metal does not break when the positive electrode mixture is crimped, and the electrical resistance is kept low. More preferably, it is 0.15 mm or more. On the other hand, if the thickness T is too large, the rigidity becomes high, making it difficult to process the expanded metal, and it may be difficult to wind the electrode plate to produce an electrode group (wound body). .
- the thickness T is preferably 0.3 mm or less in order to facilitate processing of the expanded metal and fabrication of the wound body.
- the feed width W should be 0.13 mm or more so that the bones of the expanded metal do not become too thin, the expanded metal does not break when the positive electrode mixture is crimped, and the electrical resistance is kept low. is preferable, and 0.15 mm or more is more preferable.
- the feed width W is too large, the rigidity increases, and it may become difficult to wind the electrode plate to produce an electrode group (wound body).
- the height H of the expanded metal increases, and it may become difficult to uniformly fill the expanded metal with the positive electrode mixture.
- the feed width W is preferably 0.3 mm or less in order to facilitate the production of the wound body and to suppress the density difference of the positive electrode mixture in the electrode plate.
- the ratio T/W of the thickness T to the feed width W is preferably 0.3 or more and 2.4 or less, more preferably 0.5 or more and 2 or less, and even more preferably 0.7 or more and 1.5 or less. If the ratio T/W is less than 0.3, the joint portion of the expanded metal becomes bulky, making it difficult to adhere the positive electrode mixture to the joint portion, and the positive electrode mixture tends to have a density difference. In addition, the expanded metal is likely to be elongated in the longitudinal direction during crimping, which may deform the lattice shape and reduce the current collection efficiency.
- the ratio T/W is greater than 2.4, the line becomes thicker, making it difficult to fill the positive electrode mixture, and the density difference of the positive electrode mixture tends to occur.
- the ratio T/W in the range of 0.3 or more and 2.4 or less, it is easy to uniformly fill the expanded metal with the positive electrode mixture, and non-uniformity of the battery reaction is suppressed.
- the height H of the expanded metal may be 0.5 mm or less. By setting the height H to 0.5 mm or less, it is possible to suppress the exposure of the expanded metal when the positive electrode mixture is pressure-bonded.
- the height H may be reduced by rolling or stretching the expanded metal after processing.
- the height H of the expanded metal refers to the maximum distance from the outer surface of the expanded metal to the flat surface when the expanded metal is placed on the flat surface. In general, the height H is the distance between two parallel planes tangent to the expanded metal seam from the outside. In the example of FIG. 1, the length H in (B) of FIG. 1 corresponds to the height H of the expanded metal.
- the height H can be obtained by cutting the expanded metal or the electrode plate and analyzing the contour shape of the expanded metal on the cut surface.
- the thickness T of the expanded metal satisfies 0.1 mm ⁇ T ⁇ 0.3 mm, SW and LW satisfy 2 mm 2 ⁇ LW ⁇ SW ⁇ 20 mm 2 , and the feed width of the expanded metal is W may satisfy 0.13 mm ⁇ W ⁇ 0.3 mm.
- high battery performance for example, discharge performance
- high energy density can be achieved.
- Expanded metal can be produced by processing a metal plate as described above, using the apparatus of FIG. 2, for example.
- metal plates include stainless steel, aluminum, nickel, and titanium.
- stainless steels such as SUS444, SUS430, SUS304, and SUS316 are preferable.
- the tensile strength of the metal plate is not particularly limited, but may be in the range of 400-550 N/mm 2 , for example.
- the tensile strength of the metal plate is greater than 550 N/mm 2 , it tends to partially break against the elongation of the expanded metal. In addition, the difference in density of the positive electrode mixture tends to increase. On the other hand, if it is less than 400 N/mm 2 , the expanded metal tends to stretch and is difficult to break, but it becomes difficult to control the density and thickness of the positive electrode mixture. On the other hand, when the tensile strength is in the range of 400 to 550 N/mm 2 , the expanded metal is moderately stretched to suppress breakage, and the density and thickness of the positive electrode mixture can be easily controlled.
- the expanded metal after processing may be heat treated (annealed). Annealing can reduce the Young's modulus of the expanded metal, making it easier to wind the electrode plate group and fabricate the electrode assembly.
- the Vickers hardness of the metal plate is preferably 230 HV or less, more preferably 160 HV or less.
- the electrode plate can be wound to obtain an electrode group with a high roundness, and non-uniformity in charge/discharge reaction can be suppressed.
- the uniformity of the charge/discharge reaction (especially the discharge reaction) is improved, and high discharge characteristics can be maintained even at a deep discharge depth exceeding 90%.
- the material of the metal plate may be stainless steel in that the Vickers hardness can be easily lowered.
- austenitic stainless steel SUS304, SUS316, etc.
- ferritic stainless steel SUS430, SUS444, etc.
- Expanded metal produced by processing austenitic stainless steel can easily have its Vickers hardness reduced to 160 HV or less by heat treatment (annealing).
- the mesh shape of the expanded metal can be approximated to a diamond shape in the example of Fig. 1, but it may be a polygonal shape having more than four crosspieces.
- a hexagonal expanded metal having six crosspieces per opening can be produced. At least one of the six crosspieces should have a bent shape or a curved shape.
- the mesh shape of the expanded metal after the completion of the battery may be a bent shape or a curved shape that is deformed by stretching of the crosspiece.
- the crosspiece may be extended to have a substantially linear shape.
- the shape of the crosspiece of the expanded metal can be approximated to a rhombus as it is stretched, but it may be approximated to a polygonal shape (for example, a hexagon).
- the shape of the expanded metal can be obtained from an image obtained by photographing the bones and crosspieces of the expanded metal by passing through the battery with an X-ray transmission device. Also, the values of SW and LW can be obtained by measuring the dimensions from the image.
- the positive electrode active material may be contained in the positive electrode material mixture layer together with the conductive aid and/or the binder.
- the density of the positive electrode mixture layer is preferably 2.4 g/cm 3 or more and 3.2 g/cm 3 or less.
- the density of the positive electrode mixture layer is preferably 2.8 g/cm 3 or more and 3.2 g/cm 3 or less, and in this case the effect of the present invention is remarkable.
- the average particle size of the positive electrode active material filled in the expanded metal may be 15 ⁇ m to 80 ⁇ m, or may be 30 ⁇ m to 60 ⁇ m.
- the average particle diameter of the positive electrode active material is 15 ⁇ m or more, a large amount of the conductive aid adheres to the positive electrode active material particles, and electrical connection with the expanded metal can be improved through the conductive aid. Therefore, the current collecting property is improved, and the charging/discharging performance can be improved. For example, voltage drop during pulse discharge can be suppressed.
- the average particle size is too large, the particles become bulky, the mixture density tends to decrease, and the conductive additive tends to be unevenly distributed in the gaps between the particles. By setting the average particle size within 80 ⁇ m, it is possible to suppress the decrease in the mixture density and the current collecting property.
- the average particle size of the positive electrode active material is calculated by measuring in the state of particles or the state of electrodes.
- the positive electrode active material alone or the positive electrode active material extracted from the mixture is measured by a quantitative laser diffraction/scattering method. (D50) is determined and taken as the average particle diameter. Or, for a plurality of (for example, 100 or more) active material particles with an optical microscope, the median value is obtained by particle size distribution measurement using the circle equivalent diameter, major axis diameter, minor axis diameter, biaxial average diameter, and circumscribed rectangle equivalent diameter. may be asked for.
- the state of the electrode may be calculated by taking out the positive electrode from the battery, cutting it to prepare a cross section of the positive electrode mixture layer, and observing it with a scanning electron microscope.
- the magnification is set so that 10 or more active material particles are included in one field of view, the grain boundaries of the positive electrode active material are obtained by image analysis of the cross-sectional photograph, and the particle size is determined by the diameter of a circle (equivalent circle) equal to the area of the particles in the cross section.
- the median value is determined by distribution measurement and taken as the average particle size. It is preferable to measure a total of 100 particles or more in multiple fields of view.
- the present disclosure can be applied to any non-aqueous electrolyte battery using expanded metal as a current collector, regardless of whether the battery is a primary battery or a secondary battery, and regardless of the configuration of the positive electrode and the negative electrode.
- a battery with high capacity and excellent discharge characteristics can be realized.
- the structure of the non-aqueous electrolyte battery may be a cylindrical battery comprising a wound electrode group configured by spirally winding a strip-shaped positive electrode and a strip-shaped negative electrode with a separator interposed therebetween. It may be a flat plate type battery or a coin type battery having a single-layer or laminated electrode structure in which a strip-shaped negative electrode and a separator are laminated.
- the battery of the present disclosure is not particularly limited as long as it is a non-aqueous electrolyte battery.
- the non-aqueous electrolyte battery according to the present embodiment will be described more specifically by taking a cylindrical lithium primary battery as an example.
- the positive electrode may include a positive electrode mixture layer and a positive electrode current collector holding the positive electrode mixture layer.
- the positive electrode current collector contains expanded metal.
- the positive electrode mixture layer is formed by, for example, pressing a wet positive electrode mixture prepared by adding an appropriate amount of water to a positive electrode active material and an additive in the thickness direction so as to fill the expanded metal mesh, and then drying. obtained by
- Manganese dioxide is mentioned as a positive electrode active material contained in the positive electrode.
- a positive electrode containing manganese dioxide develops a relatively high voltage and has excellent pulse discharge characteristics.
- Manganese dioxide may be in a mixed crystal state containing a plurality of crystal states.
- the positive electrode may contain manganese oxides other than manganese dioxide.
- Manganese oxides other than manganese dioxide include MnO, Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 7 . It is preferable that the main component of the manganese oxide contained in the positive electrode is manganese dioxide.
- Part of the manganese dioxide contained in the positive electrode may be doped with lithium. If the doping amount of lithium is small, a high capacity can be secured.
- Manganese dioxide and manganese dioxide doped with a small amount of lithium can be represented by Li x MnO 2 (0 ⁇ x ⁇ 0.05).
- the average composition of all manganese oxides contained in the positive electrode should be Li x MnO 2 (0 ⁇ x ⁇ 0.05).
- the ratio x of Li should be 0.05 or less in the initial state of discharge of the lithium primary battery.
- the ratio x of Li generally increases as the discharge of the lithium primary battery progresses.
- the oxidation number of manganese contained in manganese dioxide is theoretically tetravalent.
- the oxidation number of manganese may decrease from 4. Therefore, in Li x MnO 2 , the average oxidation number of manganese is allowed to be slightly smaller than tetravalent.
- the positive electrode can contain other positive electrode active materials used in lithium primary batteries. Fluorinated graphite etc. are mentioned as another positive electrode active material.
- the proportion of Li x MnO 2 in the entire positive electrode active material may be 90% by mass or more.
- Electrolytic manganese dioxide is preferably used as manganese dioxide. If necessary, electrolytic manganese dioxide that has been subjected to at least one of neutralization treatment, washing treatment, and calcination treatment may be used. Electrolytic manganese dioxide is generally obtained by electrolysis of an aqueous manganese sulfate solution.
- the BET specific surface area of Li x MnO 2 may be 10 m 2 /g or more and 50 m 2 /g or less.
- the BET specific surface area of Li x MnO 2 is within such a range, in a lithium primary battery, it is possible to suppress voltage drop during pulse discharge, obtain a higher effect of suppressing self-discharge, and suppress gas generation. .
- the positive electrode mixture layer can be easily formed.
- the BET specific surface area of Li x MnO 2 may be measured by a known method. For example, it is measured based on the BET method using a specific surface area measuring device (manufactured by Mountec Co., Ltd.). For example, LixMnO 2 separated from the positive electrode taken out of the battery may be used as the measurement sample.
- the median particle size of Li x MnO 2 may be 15 ⁇ m or more and 80 ⁇ m or less.
- the positive electrode active material Li x MnO 2 is connected to the current collector (expanded metal) via a large number of conductive aids, and current collection You can enhance your sexuality.
- the median particle size of Li x MnO 2 is, for example, the median particle size distribution determined by a quantitative laser diffraction/scattering method (qLD method).
- qLD method quantitative laser diffraction/scattering method
- Li x MnO 2 separated from the positive electrode taken out of the battery may be used as the measurement sample.
- SALD-7500nano manufactured by Shimadzu Corporation is used.
- the positive electrode mixture may contain a binder in addition to the positive electrode active material.
- the positive electrode mixture may contain a conductive agent.
- binders examples include fluororesins, rubber particles, and acrylic resins.
- Examples of conductive agents include conductive carbon materials.
- Examples of conductive carbon materials include natural graphite, artificial graphite, carbon black, and carbon fiber.
- the negative electrode may contain metallic lithium, a lithium alloy, or both metallic lithium and a lithium alloy.
- a composite containing metallic lithium and a lithium alloy may be used for the negative electrode.
- Lithium alloys include Li--Al alloys, Li--Sn alloys, Li--Ni--Si alloys, and Li--Pb alloys.
- the content of metal elements other than lithium contained in the lithium alloy is preferably 0.05 to 15% by mass from the viewpoint of securing discharge capacity and stabilizing internal resistance.
- Metallic lithium, lithium alloys, or composites thereof can be molded into any shape and thickness according to the shape, dimensions, standard performance, etc. of the lithium primary battery.
- a sheet of metallic lithium, a lithium alloy, or a composite thereof may be used for the negative electrode. Sheets are obtained, for example, by extrusion. More specifically, a cylindrical battery uses a metallic lithium or lithium alloy foil or the like having a shape with a longitudinal direction and a lateral direction.
- a long tape having a resin base material and an adhesive layer may be attached along the longitudinal direction to at least one main surface of the negative electrode.
- the main surface means the surface facing the positive electrode.
- the width of this tape is preferably 0.5 mm or more and 3 mm or less, for example. This tape has the role of preventing current collection failure due to tearing of the negative electrode when the lithium component of the negative electrode is consumed by a reaction at the end of discharge.
- resin substrate for example, fluorine resin, polyimide, polyphenylene sulfide, polyethersulfone, polyethylene, polyolefin such as polypropylene, polyethylene terephthalate, and the like can be used. Among them, polyolefin is preferred, and polypropylene is more preferred.
- the adhesive layer contains, for example, at least one component selected from the group consisting of rubber components, silicone components and acrylic resin components.
- synthetic rubber, natural rubber, or the like can be used as the rubber component.
- Synthetic rubbers include butyl rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, neoprene, polyisobutylene, acrylonitrile-butadiene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butadiene block A copolymer etc. are mentioned.
- silicone component an organic compound having a polysiloxane structure, a silicone-based polymer, or the like can be used.
- silicone-based polymers include peroxide-curable silicones and addition-reactive silicones.
- acrylic resin component polymers containing acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters can be used.
- Acrylic monomers such as ethyl, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate alone or in combination A polymer etc. are mentioned.
- the adhesive layer may contain a cross-linking agent, a plasticizer, and a tackifier.
- non-aqueous electrolyte for example, a non-aqueous electrolytic solution in which lithium salt or lithium ion is dissolved in a non-aqueous solvent can be used.
- Non-aqueous solvent examples include organic solvents that can be generally used in non-aqueous electrolytes for lithium primary batteries.
- Non-aqueous solvents include ethers, esters, carbonate esters and the like.
- dimethyl ether, ⁇ -butyl lactone, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane and the like can be used.
- the non-aqueous electrolyte may contain one non-aqueous solvent, or may contain two or more non-aqueous solvents.
- the non-aqueous solvent preferably contains a cyclic carbonate with a high boiling point and a chain ether with low viscosity even at low temperatures.
- the cyclic carbonate preferably contains at least one selected from the group consisting of propylene carbonate (PC) and ethylene carbonate (EC), with PC being particularly preferred.
- the chain ether preferably has a viscosity of 1 mPa ⁇ s or less at 25° C., and particularly preferably contains dimethoxyethane (DME).
- the viscosity of the non-aqueous solvent can be obtained by measurement using a trace sample viscometer m-VROC manufactured by Leosence Corporation at a temperature of 25° C. and a shear rate of 10000 (1/s).
- the non-aqueous electrolyte may contain a lithium salt other than the cyclic imide component.
- Lithium salts include, for example, lithium salts used as solutes in lithium primary batteries. Examples of such lithium salts include LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiClO 4 , LiBF 4 , LiPF 6 , LiR a SO 3 (R a is an alkyl fluoride having 1 to 4 carbon atoms).
- the non-aqueous electrolyte may contain one kind of these lithium salts, or two or more kinds thereof.
- the concentration of lithium ions contained in the electrolytic solution is, for example, 0.2 to 2.0 mol/L, and may be 0.3 to 1.5 mol/L.
- the electrolyte may contain additives as necessary.
- additives include propane sultone, vinylene carbonate, and the like.
- the total concentration of such additives contained in the non-aqueous electrolyte is, for example, 0.003-5 mol/L.
- Lithium primary batteries usually have a separator interposed between a positive electrode and a negative electrode.
- a porous sheet made of an insulating material that is resistant to the internal environment of the lithium primary battery may be used.
- synthetic resin nonwoven fabrics, synthetic resin microporous membranes, laminates thereof, and the like can be mentioned.
- Synthetic resins used for nonwoven fabrics include polypropylene, polyphenylene sulfide, and polybutylene terephthalate.
- Synthetic resins used for the microporous membrane include, for example, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers.
- the microporous membrane may contain inorganic particles, if necessary.
- the thickness of the separator is, for example, 5 ⁇ m or more and 100 ⁇ m or less.
- FIG. 4 shows a front view with a partial cross section of a cylindrical lithium primary battery according to an embodiment of the present disclosure.
- a lithium primary battery 10 an electrode group in which a positive electrode 1 and a negative electrode 2 are wound with a separator 3 interposed therebetween is housed in a battery case 9 together with a non-aqueous electrolyte (not shown).
- a sealing plate 8 is attached to the opening of the battery case 9 .
- a positive electrode lead 4 connected to the current collector 1 a of the positive electrode 1 is connected to the sealing plate 8 .
- a negative electrode lead 5 connected to the negative electrode 2 is connected to the case 9 .
- An upper insulating plate 6 and a lower insulating plate 7 are arranged above and below the electrode group, respectively, to prevent an internal short circuit.
- ⁇ Batteries A1 to A3>> (1) Preparation of positive electrode 100 parts by mass of electrolytic manganese dioxide and 5 parts by mass of Ketjenblack, which is a conductive agent, are mixed, and 5 parts by mass of polytetrafluoroethylene, which is a binder, and an appropriate amount of pure water. , were added and kneaded to prepare a positive electrode mixture in a wet state.
- An expanded metal was prepared as a positive electrode current collector.
- the expanded metal was made of stainless steel (SUS316), and after working into the expanded metal, heat treatment (annealing) was performed at 1000° C. for 10 minutes in a reducing atmosphere.
- the expanded metal used has a center-to-center distance SW in the short direction of 2 mm, a center-to-center distance LW in the long direction of 4 mm, and has substantially rhomboid mesh openings formed by four connecting portions.
- the sides of the rhombus (crosspieces) were formed not as straight lines but as arcuate curves, similar to the shape shown in FIG. 1(A).
- the maximum separation distance (the dimension Y in FIG. 1(A)) from the curve represented by the center line of the arc-shaped crosspiece to the straight line connecting the connecting portions was 0.2 mm.
- the positive electrode mixture was put between a pair of rolls to obtain a positive electrode mixture sheet.
- the obtained two positive electrode mixture sheets were press-bonded from both sides with an expanded metal interposed therebetween and dried to obtain a positive electrode precursor.
- the positive electrode precursor was rolled using another pair of rolls to obtain a positive electrode having a predetermined positive electrode mixture density.
- the thickness of the positive electrode after rolling was 0.8 mm.
- the positive electrode was cut into strips having a width of 42 mm and the longitudinal direction being the short direction of the expanded metal.
- a tab lead made of SUS316 was resistance-welded to the portion.
- Negative Electrode A negative electrode was obtained by cutting a metallic lithium foil into strips (40 mm wide) of a predetermined size. A tab lead made of nickel was connected to a predetermined portion of the negative electrode by pressure welding.
- Electrode Group A positive electrode and a negative electrode were layered with a separator interposed therebetween, and wound along a winding core with a diameter of 4 mm with the direction parallel to the longitudinal direction of the expanded metal as an axis to fabricate an electrode group.
- a bottomed cylindrical battery case made of a nickel-plated steel sheet of a predetermined size was prepared.
- the electrode group was inserted into the battery case with a ring-shaped lower insulating plate disposed on the bottom of the electrode group. After that, the tab lead of the positive electrode was connected to the inner surface of the sealing plate, and the tab lead of the negative electrode was connected to the inner bottom surface of the battery case.
- a non-aqueous electrolyte was injected into the battery case, an upper insulating plate was placed on the electrode group, and then the opening of the battery case was sealed with a sealing plate. After that, each battery was pre-discharged so that the battery voltage became 3.2V. In this way, a test lithium primary battery (diameter 17 mm, height 50 mm) with a design capacity of 3 Ah, as shown in FIG. 3, was completed.
- the average particle size (median value D50) of MnO 2 contained in the positive electrode was 25 ⁇ m.
- Batteries A1 to A3 having different positive electrode mixture densities were produced by changing the thickness of the positive electrode precursor and the pressure during rolling in the production of the positive electrode.
- the positive electrode mixture density was set to 2.6 g/cm 3 .
- the positive electrode mixture density was set to 2.8 g/cm 3 .
- the positive electrode mixture density was set to 3.0 g/cm 3 .
- test lithium primary batteries A1 to A3 were produced and evaluated by the following method.
- Lithium primary batteries B1 to B3 for testing were produced in the same manner as batteries A1 to A3 except for the above, and evaluated in the same manner.
- the positive electrode mixture density was set to 2.6 g/cm 3 .
- the positive electrode mixture density was set to 2.8 g/cm 3 .
- the positive electrode mixture density was set to 3.0 g/cm 3 .
- Table 1 shows the evaluation results of the voltage V1 after pulse discharge for the lithium primary batteries A1 to A3 and B1 to B3. Batteries A1 to A3 are examples, and batteries B1 to B3 are comparative examples. Table 1 also shows the density of the positive electrode mixture in each battery. In the batteries A1-3 and B1-B3, the longitudinal lengths of the positive electrode and the negative electrode after cutting were adjusted according to the density of the positive electrode mixture so as to have a constant design capacity. In addition, the thickness of the negative electrode was adjusted so that the capacity was more sufficient than the designed capacity of the positive electrode.
- the non-aqueous electrolyte battery of the present disclosure has high energy density and excellent discharge characteristics, so it can be suitably used, for example, as the main power source and memory backup power source for various meters.
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Abstract
Description
図1に、エキスパンドメタルで構成された集電体の一例を示す。図1の(A)は上面図であり、図1の(B)はX1-X2方向から見た断面図である。図1の(A)におけるT、SW、LW、Wは、それぞれ、エキスパンドメタルの肉厚T、短目方向の中心間距離SW、長目方向の中心間距離LW、および、送り幅Wと呼ばれる。図1に示すエキスパンドメタル100は、例えば、図2に示す製造装置を用いて金属板を加工することにより作製され得る。
正極活物質は、導電助剤および/または結着剤とともに、正極合剤層に含まれ得る。正極合剤層の密度は、2.4g/cm3以上3.2g/cm3以下が好ましい。正極合剤層の密度を2.4g/cm3以上とすることで、正極合剤層の結着性が強まり、充放電に伴う極板の膨張が抑制され、容量を高く維持できる。一方で、正極合剤層の密度を高めるほど、正極合剤をエキスパンドメタルに圧着するのに高い圧力が必要であり、エキスパンドメタルが破断し易くなる。しかしながら、正極合剤層の密度を3.2g/cm3以下とすることで、圧着時のエキスパンドメタルの破断を抑制できる。電池の容量の観点からは、正極合剤層の密度は2.8g/cm3以上3.2g/cm3以下が好ましく、この場合により本発明の効果が顕著である。
(正極)
正極は、正極合剤層と、正極合剤層を保持する正極集電体を含み得る。正極集電体は、エキスパンドメタルを含む。正極合剤層は、例えば、正極活物質および添加剤に適量の水を加えて調製した湿潤状態の正極合剤を、エキスパンドメタルのメッシュを充填するように、厚み方向に加圧し、乾燥することにより得られる。
負極は、金属リチウムまたはリチウム合金を含んでいてもよく、金属リチウムおよびリチウム合金の双方を含んでいてもよい。例えば、金属リチウムとリチウム合金とを含む複合物を負極に用いてもよい。
電解質(非水電解質)には、例えば、リチウム塩またはリチウムイオンを、非水溶媒に溶解させた非水電解液を用いることができる。
非水溶媒としては、リチウム一次電池の非水電解液に一般的に用いられ得る有機溶媒が挙げられる。非水溶媒としては、エーテル、エステル、炭酸エステルなどが挙げられる。非水溶媒としては、ジメチルエーテル、γ-ブチルラクトン、プロピレンカーボネート、エチレンカーボネート、1,2-ジメトキシエタンなどを用いることができる。非水電解液は、一種の非水溶媒を含んでいてもよく、二種以上の非水溶媒を含んでいてもよい。
非水電解液は、環状イミド成分以外のリチウム塩を含んでいてもよい。リチウム塩としては、例えば、リチウム一次電池で溶質として用いられるリチウム塩が挙げられる。このようなリチウム塩としては、例えば、LiCF3SO3、LiN(CF3SO2)2、LiClO4、LiBF4、LiPF6、LiRaSO3(Raは炭素数1~4のフッ化アルキル基)、LiFSO3、LiN(SO2Rb)(SO2Rc)(RbおよびRcはそれぞれ独立に炭素数1~4のフッ化アルキル基)、LiN(FSO2)2、LiPO2F2、LiB(C2O4)2、LiBF2(C2O4)が挙げられる。非水電解液は、これらのリチウム塩を一種含んでいてもよく、二種以上含んでいてもよい。
電解液に含まれるリチウムイオンの濃度(リチウム塩の合計濃度)は、例えば、0.2~2.0mol/Lであり、0.3~1.5mol/Lであってもよい。
リチウム一次電池は、通常、正極と負極との間に介在するセパレータを備えている。セパレータとしては、リチウム一次電池の内部環境に対して耐性を有する絶縁性材料で形成された多孔質シートを使用すればよい。具体的には、合成樹脂製の不織布、合成樹脂製の微多孔膜、またはこれらの積層体などが挙げられる。
以下、本開示を実施例および比較例に基づいて具体的に説明するが、本開示は以下の実施例に限定されるものではない。
(1)正極の作製
電解二酸化マンガン100質量部と、導電剤であるケッチェンブラック5質量部と、を混合し、さらに結着剤であるポリテトラフルオロエチレン5質量部と、適量の純水と、を加えて混錬し、湿潤状態の正極合剤を調製した。
金属リチウム箔を所定のサイズの帯状(幅40mm)に裁断することにより、負極を得た。負極の所定箇所にニッケル製のタブリードを圧接により接続した。
正極と負極とをセパレータを介して重ね、直径4mmの巻き芯に沿って、エキスパンドメタルの長目方向に平行な方向を軸として巻回し、電極群を作製した。セパレータには厚み25μmのポリエチレン製の微多孔膜を用いた。
PCとDMEとを体積比4:6で混合した。得られる混合物に、LiCF3SO3を0.5mol/Lの濃度となるように溶解させ、非水電解質を調製した。
所定サイズのニッケルめっき鋼板製の有底円筒形の電池ケースを準備した。電極群を、その底部にリング状の下部絶縁板を配した状態で、電池ケースの内部に挿入した。その後、正極のタブリードを封口板の内面に接続し、負極のタブリードを電池ケースの内底面に接続した。
組み立て直後のリチウム一次電池を、500mA、1秒のパルス電流で放電させ、パルス放電後の電池電圧V1を測定した。なお、放電は25℃の環境で行った。
正極の作製において、エキスパンドメタルとして4つの接続部により略菱形状の網目の開口を有するものを用い、菱形の辺の部分を略直線に形成した。エキスパンドメタルは、短目方向の中心間距離SWを2mm、長目方向の中心間距離LWを4mmとした。これ以外については、電池A1~A3と同様にして、試験用のリチウム一次電池B1~B3を作製し、同様に評価した。電池B1では、正極合剤密度を2.6g/cm3とした。電池B2では、正極合剤密度を2.8g/cm3とした。電池B3では、正極合剤密度を3.0g/cm3とした。
1a 正極集電体
2 負極
3 セパレータ
4 正極リード
5 負極リード
6 上部絶縁板
7 下部絶縁板
8 封口板
9 電池ケース
10 リチウム一次電池
100 エキスパンドメタル
101a~101d 桟部
102 接続部
200 エキスパンドメタルの製造装置
201 下刃
202 上刃
204 金属板
Claims (7)
- 正極と、負極と、前記正極と前記負極との間に介在するセパレータと、非水電解質と、を備えた非水電解質電池であって、
前記正極は、正極活物質およびエキスパンドメタルを含み、
前記エキスパンドメタルは、網目を構成する骨部を含み、
前記骨部は、前記網目の開口を囲む桟部と、前記桟部同士を繋ぐ接続部と、を含み、
前記開口1つ当たりの前記桟部の数が4本以上であり、
前記開口1つ当たり少なくとも1本の前記桟部が、折れ曲がり形状または曲線形状を有する、非水電解質電池。 - 前記エキスパンドメタルの短目方向の中心間距離SWおよび長目方向の中心間距離LWが、2mm2≦LW・SW≦20mm2を満たす、請求項1に記載の非水電解質電池。
- 前記エキスパンドメタルの肉厚Tが、0.1mm≦T≦0.3mmを満たし、
前記エキスパンドメタルの送り幅Wが、0.13mm≦W≦0.3mmを満たす、請求項1または2に記載の非水電解質電池。 - 前記正極の厚みが0.3mm以上3mm以下である、請求項1~3のいずれか1項に記載の非水電解質電池。
- 前記SWが1mm以上であり、1.5≦LW/SW≦3を満たす、請求項1~4のいずれか1項に記載の非水電解質電池。
- 前記正極活物質は二酸化マンガンを含む、請求項1~5のいずれか1項に記載の非水電解質電池。
- 前記正極の合剤密度は2.4g/cm3以上3.2g/cm3以下である、請求項6に記載の非水電解質電池。
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JPH07240199A (ja) * | 1994-02-28 | 1995-09-12 | Matsushita Electric Ind Co Ltd | 電池用極板の製造法およびその極板を用いた円筒形電池 |
JPH1050319A (ja) * | 1996-07-31 | 1998-02-20 | Sony Corp | 非水電解質二次電池 |
JPH11260418A (ja) * | 1998-03-13 | 1999-09-24 | Matsushita Electric Ind Co Ltd | 非水電解質電池 |
JP2004335381A (ja) * | 2003-05-09 | 2004-11-25 | Hitachi Maxell Ltd | 非水電解液電池 |
JP2006164668A (ja) * | 2004-12-06 | 2006-06-22 | Matsushita Electric Ind Co Ltd | 有機電解液電池用エキスパンド格子体 |
WO2011039924A1 (ja) * | 2009-09-29 | 2011-04-07 | パナソニック株式会社 | 二硫化鉄・リチウム一次電池 |
JP2017188342A (ja) * | 2016-04-07 | 2017-10-12 | 日産自動車株式会社 | 燃料電池単セル及び燃料電池スタック |
JP2018190679A (ja) * | 2017-05-11 | 2018-11-29 | 古河電池株式会社 | リチウム二次電池の充放電方法 |
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- 2022-01-26 WO PCT/JP2022/002789 patent/WO2022172750A1/ja active Application Filing
- 2022-01-26 US US18/263,767 patent/US20240204207A1/en active Pending
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JPH07240199A (ja) * | 1994-02-28 | 1995-09-12 | Matsushita Electric Ind Co Ltd | 電池用極板の製造法およびその極板を用いた円筒形電池 |
JPH1050319A (ja) * | 1996-07-31 | 1998-02-20 | Sony Corp | 非水電解質二次電池 |
JPH11260418A (ja) * | 1998-03-13 | 1999-09-24 | Matsushita Electric Ind Co Ltd | 非水電解質電池 |
JP2004335381A (ja) * | 2003-05-09 | 2004-11-25 | Hitachi Maxell Ltd | 非水電解液電池 |
JP2006164668A (ja) * | 2004-12-06 | 2006-06-22 | Matsushita Electric Ind Co Ltd | 有機電解液電池用エキスパンド格子体 |
WO2011039924A1 (ja) * | 2009-09-29 | 2011-04-07 | パナソニック株式会社 | 二硫化鉄・リチウム一次電池 |
JP2017188342A (ja) * | 2016-04-07 | 2017-10-12 | 日産自動車株式会社 | 燃料電池単セル及び燃料電池スタック |
JP2018190679A (ja) * | 2017-05-11 | 2018-11-29 | 古河電池株式会社 | リチウム二次電池の充放電方法 |
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