Patent Application
20240237227
The present invention relates to a method for a producing circuit board assembly.
Coin-shaped lithium ion secondary batteries are widely used in various devices that require charging, and various coin-shaped lithium ion secondary batteries have been proposed. For example, Patent Literature 1 (JP2012-209178A) discloses a coin-shaped battery in which a positive electrode is disposed on the inner surface of a positive electrode case that also functions as an external terminal, a negative electrode is disposed on the inner surface of a negative electrode sealing plate that also functions as an external terminal, and the positive electrode and the negative electrode are facing via a separator. In such a coin-shaped battery, the positive electrode case and the circumferential edge of the sealing plate are sealed via a gasket so as to retain an electrolytic solution therein. In the aforementioned secondary battery, a powder-dispersed positive electrode (so-called coated electrode) produced by applying a positive electrode mixture containing a positive electrode active material, a conductive agent, a binder, and the like, followed by drying, is employed.
Meanwhile, such powder-dispersed positive electrodes generally contain a relatively large amount (e.g., about 10% by weight) of components (binders and conductive agents) that do not contribute to the capacity of battery, resulting in a low packing density of the positive electrode active material, i.e., lithium complex oxide. Accordingly, the powder-dispersed positive electrode should be greatly improved from the viewpoint of the capacity and charge/discharge efficiency. Some attempts have been made to improve the capacity and charge/discharge efficiency by positive electrodes or layers of positive electrode active material composed of lithium complex oxide sintered plate. In this case, since the positive electrode or the layer of positive electrode active material contains no binder or conductive agent, high capacity and satisfactory charge/discharge efficiency can be expected due to a high packing density of lithium complex oxide. For example, Patent Literature 2 (WO2019/221139A) discloses a coin-shaped lithium ion secondary battery comprising a positive electrode plate that is a lithium complex oxide sintered plate, a negative electrode plate that is a titanium-containing sintered plate, a separator, and an electrolytic solution in an exterior body, wherein excellent heat resistance that enables reflow soldering is obtained by using sintered plates as electrodes.
Patent Literature 1: JP2012-209178A
Patent Literature 2: WO2019/221139
When mounted on a circuit board by reflow soldering, a lithium ion secondary battery is exposed to high temperatures (for example, 260° C.) during reflow heating and the battery performance tends to deteriorate, which has been a problem. In this regard, Patent Literature 2 discloses a lithium ion secondary battery that can be reflow soldered, but there is room for improvement in production conditions since the suitable conditions for reflow soldering are unknown. Accordingly, there is a demand for a production method that prevents the battery performance from deteriorating even when subjected to reflow soldering.
The inventors have recently found that it is possible to effectively suppress the deterioration of the battery performance due to reflow heating by using a lithium ion secondary battery with a state of charge (SOC) of 0 to 29% in reflow soldering.
Accordingly, it is an object of the present invention to provide a method for producing a circuit board assembly, capable of effectively suppressing the deterioration of the battery performance due to heating during reflow soldering.
The present invention provides the following aspects.
A method for producing a circuit board assembly, comprising connecting a lithium ion secondary battery to a circuit board by reflow soldering,
The method for producing a circuit board assembly according to aspect 1, wherein the lithium ion secondary battery has a state of charge (SOC) of 0 to 28%.
The method for producing a circuit board assembly according to aspect 1, wherein the lithium ion secondary battery has a state of charge (SOC) of 0 to 20%.
The method for producing a circuit board assembly according to any one of aspects 1 to 3, wherein reflow heating in the reflow soldering is performed at 180 to 270° C.
The method for producing a circuit board assembly according to any one of aspects 1 to 4, wherein the lithium ion secondary battery comprises:
The method for producing a circuit board assembly according to aspect 5, wherein the exterior body comprises a positive electrode can; a negative electrode can; and a gasket, wherein the positive electrode can and the negative electrode can are crimped with the gasket interposed therebetween to form the closed space.
The method for producing a circuit board assembly according to aspect 5 or 6, further comprising
The method for producing a circuit board assembly according to any one of aspects 5 to 7, wherein the positive electrode layer is a ceramic positive electrode plate.
The method for producing a circuit board assembly according to aspect 8, wherein the ceramic positive electrode plate is a lithium complex oxide sintered plate.
The method for producing a circuit board assembly according to aspect 9, wherein the lithium complex oxide is lithium cobaltate.
The method for producing a circuit board assembly according to any one of aspects 5 to 10, wherein the negative electrode layer is a ceramic negative electrode plate.
The method for producing a circuit board assembly according to aspect 11, wherein the ceramic negative electrode plate is a titanium-containing sintered plate.
The method for producing a circuit board assembly according to aspect 12, wherein the titanium-containing sintered plate comprises lithium titanate or niobium titanium complex oxide.
The method for producing a circuit board assembly according to any one of aspects 5 to 13, wherein the separator is made of cellulose, polyimide, polyester, or ceramics selected from the group consisting of MgO, Al2O3, ZrO2, SiC, Si3N4, AlN, and cordierite.
The method for producing a circuit board assembly according to any one of aspects 5 to 14, wherein the electrolyte is provided in the form of an electrolytic solution, and the electrolytic solution is a solution containing lithium borofluoride (LiBF4) in a non-aqueous solvent consisting of at least one selected from the group consisting of γ-butyrolactone (GBL), ethylene carbonate (EC) and propylene carbonate (PC).
The present invention relates to a method for producing a circuit board assembly. As used herein, the term “circuit board assembly” refers to a product in which a lithium ion secondary battery (and devices, optionally) is mounted on a circuit board. The production method of the present invention includes connecting the lithium ion secondary battery onto the circuit board by reflow soldering. The lithium ion secondary battery has been subjected to at least initial charging and discharging. Then, the lithium ion secondary battery has a state of charge (SOC) of 0 to 29% during reflow soldering. Thus, it is possible to effectively suppress the deterioration of the battery performance due to heating (reflow heating) during reflow soldering by using the lithium ion secondary battery with a SOC of 0 to 29% for reflow soldering.
As mentioned above, there has been a problem that, when mounted on the circuit board by reflow soldering, the lithium ion secondary battery is exposed to high temperatures (for example, 260° C.) during reflow heating, resulting in a problem of easy deterioration of battery performance. However, the present invention can conveniently overcome the problem. The details of the mechanism are not clear but considered to be as follows. When the lithium ion secondary battery is exposed to high temperatures during reflow heating, a gas is generated inside the battery due to the reaction between each electrode and an electrolyte (typically, an electrolytic solution) and/or moisture or due to the volatilization of the electrolytic solution, and the gas causes an increase in battery resistance. In this regard, when the SOC of the battery is 0 to 29%, the amount of gas generated during reflow heating is reduced, as a result of which, the increase in battery resistance due to reflow heating is significantly reduced, and the product yield after reflow heating is considered to be improved.
The SOC of the lithium ion secondary battery during reflow soldering is 0 to 29%, preferably 0 to 28%, more preferably 0 to 20%, further preferably 0 to 15%, particularly preferably 0 to 10%, more particularly preferably 0 to 5%, further particularly preferably 0 to 3%, most preferably 0%. As the SOC is closer to 0%, the gas generation inside the battery during reflow heating can be reduced, as a result of which the deterioration of the battery performance can be suppressed more effectively. The SOC may be measured by a known technique. After the lithium ion secondary battery is initially charged and discharged, and the discharged state is set to SOC 0%, the battery may be charged as necessary so that the SOC falls within the aforementioned ranges. In this sense, it can be said that the lithium ion secondary battery used in the present invention has been subjected to at least initial charging and discharging. However, the initial charging and discharging may be performed by charging and then discharging halfway to adjust the SOC to a desired level.
The lithium ion secondary battery may be connected to the circuit board by a known reflow soldering technique. For example, reflow soldering can be performed by applying or printing solder (for example, solder paste) at a predetermined position of the circuit board, disposing the lithium ion secondary battery on the position, performing reflow heating at a predetermined temperature profile in a reflow furnace to melt the solder, and then cooling and solidifying the molten solder. When the lithium ion secondary battery has a positive electrode terminal and a negative electrode terminal, the positive electrode terminal and/or the negative electrode terminal is preferably connected to the circuit board by reflow soldering.
Reflow heating in reflow soldering is typically performed at 180 to 270° C., more typically 200 to 260° C. This temperature is the temperature measured for the lithium ion secondary battery. Further, it is preferable to employ a heating profile in which the aforementioned temperature range is typically maintained for 5 to 100 seconds, more typically 10 to 60 seconds, and the maximum allowable temperature is 200 to 270° C. The production method of the present invention can effectively suppress the deterioration of the battery performance, even when exposed to such high temperatures.
According to a preferable aspect of the present invention, the lithium ion secondary battery 10 further comprises a positive electrode terminal (not shown) joined to the outer surface of the exterior body 24 closer to the positive electrode layer 12 and a negative electrode terminal (not shown) joined to the outer surface of the exterior body 24 closer to the negative electrode layer 16. In this case, as described above, the positive electrode terminal and/or the negative electrode terminal is preferably used for reflow soldering to mount the lithium ion secondary battery 10 on the circuit board. That is, it is preferable that the positive electrode terminal and/or the negative electrode terminal is connected to the circuit board by reflow soldering. The positive electrode terminal is preferably joined to a positive electrode can 24a of the exterior body 24 by a technique such as resistance welding, diffusion welding, and laser welding. Likewise, the negative electrode terminal is preferably joined to a negative electrode can 24b of the exterior body 24 by a technique such as resistance welding, diffusion welding, and laser welding.
The outer diameter of the lithium ion secondary battery 10 is not specifically limited but is typically 8 to 25 mm, more typically 9.5 to 22 mm, further typically 12.5 to 20 mm.
The positive electrode layer 12 is a layer containing a positive electrode active material. The positive electrode layer 12 may be a powder-dispersed positive electrode (so-called coated electrode) produced by applying a positive electrode mixture containing a positive electrode active material (for example, lithium cobaltate), a conductive agent, a binder, and the like, followed by drying, preferably a ceramic positive electrode plate, more preferably a lithium complex oxide sintered plate. The fact that the positive electrode layer 12 is a ceramic positive electrode plate or a sintered plate means that the positive electrode layer 12 is free from binders or conductive agents. This is because, even if a binder is contained in a green sheet, the binder disappears or burns out during firing. Since the positive electrode layer 12 contains no binder, there is an advantage that deterioration of the positive electrode due to the electrolytic solution 22 can be avoided. The lithium complex oxide constituting the sintered plate is particularly preferably lithium cobaltite (typically, LiCoO2, which may be hereinafter abbreviated as LCO). Various lithium complex oxide sintered plates or LCO sintered plates are known, and one disclosed in Patent Literature 2 (WO2019/221139) can be used, for example.
According to a preferable aspect of the present invention, the lithium complex oxide sintered plate constituting the positive electrode layer 12 is an oriented positive electrode plate comprising a plurality of primary grains composed of lithium complex oxide, the plurality of primary grains being oriented at an average orientation angle of over 0° and 30° or less to the plate face of the positive electrode plate.
The positive electrode layer 12 that is an oriented positive electrode plate is an oriented sintered body composed of the plurality of primary grains 11 bound to each other. The primary grains 11 are each mainly in the form of a plate but may include rectangular, cubic, and spherical grains. The cross-sectional shape of each primary grain 11 is not particularly limited and may be a rectangular shape, a polygonal shape other than the rectangular shape, a circular shape, an elliptical shape, or a complex shape other than above.
The primary grains 11 are composed of a lithium complex oxide. The lithium complex oxide is an oxide represented by LixMO2 (where 0.05<x<1.10 is satisfied, M represents at least one transition metal, and M typically contains one or more of Co, Ni, and Mn). The lithium complex oxide has a layered rock-salt structure. The layered rock-salt structure refers to a crystalline structure in which lithium layers and transition metal layers other than lithium are alternately stacked with oxygen layers interposed therebetween, that is, a crystalline structure in which transition metal ion layers and single lithium layers are alternately stacked with oxide ions therebetween (typically, an α-NaFeO2 structure, i.e., a cubic rock-salt structure in which transition metal and lithium are regularly disposed in the [111] axis direction). Examples of the lithium complex oxide include LixCoO2(lithium cobaltate), LixNiO2 (lithium nickelate), LixMnO2 (lithium manganate), LixNiMnO2(lithium nickel manganate), LixNiCoO2 (lithium nickel cobaltate), LixCoNiMnO2 (lithium cobalt nickel manganate), and LixCoMnO2 (lithium cobalt manganate), particularly preferably LixCoO2 (lithium cobaltate, typically LiCoO2). The lithium complex oxide may contain one or more elements selected from Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba, Bi, and W.
As shown in
The average orientation angle of the primary grains 11 is obtained by the following method. First, three horizontal lines that divide the oriented positive electrode plate into four equal parts in the thickness direction and three vertical lines that divide the oriented positive electrode plate into four equal parts in the plate face direction are drawn in an EBSD image of a rectangular region of 95 μm×125 μm observed at a magnification of 1000 times, as shown in
As shown in
Since the primary grains 11 are each mainly in the form of a plate, the cross section of each primary grain 11 extends in a predetermined direction, typically in a substantially rectangular shape, as shown in
The mean diameter of the plurality of primary grains constituting the oriented sintered body is preferably 5 μm or more. Specifically, the mean diameter of the 30 primary grains 11 used for calculating the average orientation angle is preferably 5 μm or more, more preferably 7 μm or more, further preferably 12 μm or more. Thereby, since the number of grain boundaries between the primary grains 11 in the direction in which lithium ions conduct is reduced, and the lithium ion conductivity as a whole is improved, the rate characteristic can be further improved. The mean diameter of the primary grains 11 is a value obtained by arithmetically averaging the equivalent circle diameters of the primary grains 11. An equivalent circle diameter is the diameter of a circle having the same area as each primary grain 11 on the EBSD image.
The lithium complex oxide sintered plate constituting the positive electrode layer 12 preferably has pores. The electrolytic solution can penetrate into the sintered body by the sintered body including pores, particularly open pores, when the sintered body is integrated into a battery as a positive electrode plate. As a result, the lithium ion conductivity can be improved. This is because there are two types of conduction of lithium ions within the sintered body: conduction through constituent grains of the sintered body; and conduction through the electrolytic solution within the pores, and the conduction through the electrolytic solution within the pores is overwhelmingly faster.
The lithium complex oxide sintered plate constituting the positive electrode layer 12 preferably has a porosity of 20 to 60%, more preferably 25 to 55%, further preferably 30 to 50%, particularly preferably 30 to 45%. The stress relief effect by the pores and the increase in capacity can be expected, and the mutual adhesion between the primary grains 11 can be further improved, so that the rate characteristics can be further improved. The porosity of the sintered body is calculated by polishing a cross section of the positive electrode plate with CP (cross-section polisher) polishing, thereafter observing the cross section at a magnification of 1000 times with SEM, and binarizing the SEM image obtained. The average equivalent circle diameter of pores formed inside the oriented sintered body is not particularly limited but is preferably 8 μm or less. The smaller the average equivalent circle diameter of the pores, the mutual adhesion between the primary grains 11 can be improved more. As a result, the rate characteristic can be improved more. The average equivalent circle diameter of the pores is a value obtained by arithmetically averaging the equivalent circle diameters of 10 pores on the EBSD image. An equivalent circle diameter is the diameter of a circle having the same area as each pore on the EBSD image. Each of the pores formed inside the oriented sintered body is preferably an open pore connected to the outside of the lithium complex oxide sintered plate.
The lithium complex oxide sintered plate constituting the positive electrode layer 12 preferably has a mean pore diameter of 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, further preferably 0.25 to 3.0 μm. Within such a range, stress concentration is suppressed from occurring locally in large pores, and the stress is easily released uniformly in the sintered body.
The lithium complex oxide sintered plate constituting the positive electrode layer 12 preferably has a thickness of 60 to 600 μm, more preferably 70 to 550 μm, further preferably 90 to 500 μm. The thickness within such a range can improve the energy density of the lithium ion secondary battery 10 by increasing the capacity of the active material per unit area together with suppressing the deterioration of the battery characteristics (particularly, the increase of the resistance value) due to repeated charging/discharging.
The negative electrode layer 16 is a layer containing a negative electrode active material. The negative electrode layer 16 may be a powder-dispersed negative electrode (so-called coated electrode) produced by applying a negative electrode mixture containing a negative electrode active material, a conductive agent, a binder, and the like, followed by drying, preferably a ceramic negative electrode plate, more preferably a titanium-containing sintered plate. The titanium-containing sintered plate preferably contains lithium titanate Li4Ti5O12 (which will be hereinafter referred to as LTO) or niobium titanium complex oxide Nb2TiO7, more preferably LTO. LTO is typically known to have a spinel structure but can have other structures during charging and discharging. For example, the reaction of LTO proceeds in the two-phase coexistence of Li4Ti5O12 (spinel structure) and Li7Ti5O12 (rock salt structure) during charging and discharging. Accordingly, the structure of LTO is not limited to the spinel structure.
The fact that the negative electrode layer 16 is a ceramic negative electrode plate or a sintered plate means that the negative electrode layer 16 is free from binders or conductive agents. This is because, even if a binder is contained in a green sheet, the binder disappears or burns out during firing. Since the negative electrode plate is free from binders, high capacity and good charge/discharge efficiency can be achieved by high packing density of the negative electrode active material (for example, LTO or Nb2TiO7). The LTO sintered plate can be produced according to the method described in Patent Literature 2 (WO2019/221139).
The titanium-containing sintered plate constituting the negative electrode layer 16 has a structure that a plurality (namely, a large number) of primary grains are bonded. Accordingly, these primary grains are preferably composed of LTO or Nb2TiO7.
The thickness of the titanium-containing sintered plate constituting the negative electrode layer 16 is preferably 70 to 500 μm, preferably 85 to 400 μm, more preferably 95 to 350 μm. As the LTO sintered plate is thicker, it is easier to achieve a battery with high capacity and high energy density. The thickness of the titanium-containing sintered plate is determined by measuring the distance between substantially parallel faces of the plate, for example, when the cross section of the titanium-containing sintered plate is observed by SEM (scanning electron microscopy).
The primary grain size that is the average grain size of the plurality of primary grains constituting the titanium-containing sintered plate is preferably 1.2 μm or less, more preferably 0.02 to 1.2 μm, further preferably 0.05 to 0.7 μm. Within such a range, the lithium ion conductivity and the electron conductivity are easily compatible with each other, which contributes to improving the rate performance.
The titanium-containing sintered plate constituting the negative electrode layer 16 preferably has pores. The electrolytic solution can penetrate into the sintered plate by the sintered plate including pores, particularly open pores, when the sintered plate is integrated into a battery as a negative electrode plate. As a result, the lithium ion conductivity can be improved. This is because there are two types of conduction of lithium ions within the sintered body: conduction through constituent grains of the sintered body; and conduction through the electrolytic solution within the pores, and the conduction through the electrolytic solution within the pores is overwhelmingly faster.
The titanium-containing sintered plate constituting the negative electrode layer 16 preferably has a porosity of 20 to 60%, more preferably 30 to 55%, further preferably 35 to 50%. Within such a range, the lithium ion conductivity and the electron conductivity are easily compatible with each other, which contributes to improving the rate performance.
The average pore diameter of the titanium-containing sintered plate constituting the negative electrode layer 16 is 0.08 to 5.0 μm, preferably 0.1 to 3.0 μm, more preferably 0.12 to 1.5 μm. Within such a range, the lithium ion conductivity and the electron conductivity are easily compatible with each other, which contributes to improving the rate performance.
The separator 20 is preferably a separator made of cellulose, polyolefin, polyimide, polyester (e.g., polyethylene terephthalate (PET)), or ceramic. A separator made of cellulose is advantageous since it is inexpensive and has excellent heat resistance. Further, being different from widely used polyolefin separators having poor heat resistance, a separator made of polyimide, polyester (e.g., polyethylene terephthalate (PET)), or cellulose has not only excellent heat resistance of itself but also excellent wettability to γ-butyrolactone (GBL), which is an electrolytic solution component having excellent heat resistance. Accordingly, in the case of using an electrolytic solution containing GBL, the electrolytic solution can be sufficiently penetrated into the separator (without repelling). Meanwhile, a separator made of ceramic is advantageous in that it, of course, has excellent heat resistance and can be produced as one integrated sintered body together with the positive electrode layer 12 and the negative electrode layer 16 as a whole. In the case of a ceramic separator, the ceramic constituting the separator is preferably at least one selected from MgO, Al2O3, ZrO2, SiC, Si3N4, AlN, and cordierite, more preferably at least one selected from MgO, Al2O3, and ZrO2.
The electrolytic solution 22 is not specifically limited, and a commercially available electrolytic solution for lithium batteries, such as a solution in which a lithium salt is dissolved in a non-aqueous solvent such as an organic solvent, may be used. In particular, an electrolytic solution with excellent heat resistance is preferable, and the electrolytic solution preferably contains lithium borofluoride (LiBF4) in the non-aqueous solvent. In this case, the non-aqueous solvent is preferably at least one selected from the group consisting of γ-butyrolactone (GBL), ethylene carbonate (EC) and propylene carbonate (PC), more preferably a mixed solvent composed of EC and GBL, a single solvent composed of PC, a mixed solvent composed of PC and GBL, or a single solvent composed of GBL, particularly preferably a mixed solvent composed of EC and GBL or a single solvent composed of GBL. The non-aqueous solvent has an increased boiling point by containing γ-butyrolactone (GBL), which considerably improves the heat resistance. From such a viewpoint, the volume ratio of EC:GBL in the EC and/or GBL containing non-aqueous solvent is preferably 0:1 to 1:1 (GBL ratio: 50 to 100% by volume), more preferably 0:1 to 1:1.5 (GBL ratio: 60 to 100% by volume), further preferably 0:1 to 1:2 (GBL ratio: 66.6 to 100% by volume), particularly preferably 0:1 to 1:3 (GBL ratio: 75 to 100% by volume). The lithium borofluoride (LiBF4) to be dissolved in the non-aqueous solvent is an electrolyte having a high decomposition temperature, which also considerably improves the heat resistance. The LiBF4 concentration in the electrolytic solution 22 is preferably 0.5 to 2 mol/L, more preferably 0.6 to 1.9 mol/L, further preferably 0.7 to 1.7 mol/L, particularly preferably 0.8 to 1.5 mol/L.
The electrolytic solution 22 may further contain vinylene carbonate (VC) and/or fluoroethylene carbonate (FEC) and/or vinyl ethylene carbonate (VEC)) and/or propane sultone (PS) as an additive. Both VC and FEC are excellent in heat resistance. Accordingly, a SEI film having excellent heat resistance can be formed on the surface of the negative electrode layer 16 by the electrolytic solution 22 containing such an additive.
As mentioned above, a solid electrolyte or a polymer electrolyte may be used instead of the electrolytic solution 22 (in other words, a solid electrolyte or a polymer electrolyte can be used as an electrolyte other than the electrolytic solution 22). In such a case, it is preferable that at least the inside of the pores of the separator 20 is impregnated with the electrolyte in the same manner as in the case of the electrolytic solution 22. The impregnation method is not specifically limited, but examples thereof include a method in which the electrolyte is melted and infiltrated into the pores of the separator 20, and a method in which a green compact of the electrolyte is pressed against the separator 20. Alternatively, the separator 20 itself may be constituted by a solid electrolyte.
The exterior body 24 has a closed space, and the closed space accommodates the positive electrode layer 12, the negative electrode layer 16, the separator 20, and the electrolytic solution 22. The exterior body 24 is not specifically limited, as long as it adopts a structure that is generally adopted for coin-shaped batteries (for example, see Patent Literatures 1 and 2). Typically, the exterior body 24 includes the positive electrode can 24a, the negative electrode can 24b, and the gasket 24c, wherein the positive electrode can 24a and the negative electrode can 24b are crimped via the gasket 24c to form the closed space. The positive electrode can 24a and the negative electrode can 24b can be made of metals such as stainless steel and are not specifically limited. The gasket 24c can be an annular member made of an insulating resin such as polypropylene and polytetrafluoroethylene and is not particularly limited. Further, a gel solution may be applied to the gasket 24c to improve the sealability. The type of solution used for the gel solution includes heat-curable olefin-based solutions and synthetic rubber-based solutions but is not limited thereto as long as the solvent has viscosity or adhesiveness after volatilization. Further, the application method is also not limited, and the gasket 24c may be dipped in the solution, or the solution may be applied to the gasket 24c with a dispenser or the like.
The lithium ion secondary battery 10 preferably further includes a positive electrode current collector 14 and/or a negative electrode current collector 18. The positive electrode current collector 14 and the negative electrode current collector 18 are not specifically limited but are preferably metal foils such as copper foils and aluminum foils. The positive electrode current collector 14 is preferably interposed between the positive electrode layer 12 and the positive electrode can 24a, and the negative electrode current collector 18 is preferably interposed between the negative electrode layer 16 and the negative electrode can 24b. Further, a positive side carbon layer 13 is preferably provided between the positive electrode layer 12 and the positive electrode current collector 14 for reducing the contact resistance. Likewise, a negative side carbon layer 17 is preferably provided between the negative electrode layer 16 and the negative electrode current collector 18 for reducing the contact resistance. Both the positive side carbon layer 13 and the negative side carbon layer 17 are preferably composed of a conductive carbon and may be formed, for example, by applying a conductive carbon paste by screen printing or the like.
The battery element may be not only in the form of a unit cell of the positive electrode layer 12/the separator 20/the negative electrode layer 16, as shown in
The lithium complex oxide sintered plate as a preferable embodiment of the positive electrode layer 12 may be produced by any method and is preferably produced through (a) production of a green sheet containing a lithium complex oxide, (b) production of a green sheet containing an excess-lithium source, optionally, and (c) laminating and firing of the green sheets.
First, a raw material powder composed of lithium complex oxide is prepared. The powder preferably comprises pre-synthesized platy particles (e.g., LiCoO2 platy particles) having a composition of LiMO2 (M as described above). The volume-based D50 particle diameter of the raw material powder is preferably 0.3 to 30 μm. For example, the LiCoO2 platy particles can be produced as follows. Co3O4 powder and Li2CO3 powder as raw materials are mixed and fired (500 to 900° C., 1 to 20 hours) to synthesize LiCoO2 powder. The resultant LiCoO2 powder is milled into a volume-based D50 particle diameter of 0.2 μm to 10 μm with a pot mill to yield platy LiCoO2 particles capable of conducting lithium ions along the faces of the plate. Such LiCoO2 particles are also produced by a procedure involving grain growth in a green sheet from LiCoO2 powder slurry and crushing the green sheet, or a procedure involving synthesis of platy crystals, such as a flux process, a hydrothermal synthesis process, a single crystal growth process using a melt, and a sol gel process. The resultant LiCoO2 particles are readily cleaved along cleavage planes. The LiCoO2 particles may be cleaved by crushing to produce LiCoO2 platy particles.
The platy particles may be independently used as raw material powder, or a mixed powder of the platy powder and another raw material powder (for example, Co3O4 particles) may be used as a raw material powder. In the latter case, it is preferred that the platy powder serves as template particles for providing orientation, and another raw material powder (e.g., Co3O4 particles) serves as matrix particles that can grow along the template particle. In this case, the raw powder is preferably composed of a mixed powder in a ratio of template particles to matrix particles of 100:0 to 3:97. When the Co3O4 raw material powder is used as the matrix particles, the volume-based D50 particle diameter of the Co3O4 raw material powder may be any value, for example, 0.1 to 1.0 μm, and is preferably smaller than the volume-based D50 particle diameter of LiCoO2 template particles. The matrix particles may also be produced by heating a Co(OH)2 raw material at 500° C. to 800° C. for 1 to 10 hours. In addition to Co3O4, Co(OH)2 particles may be used, or LiCoO2 particles may be used as the matrix particles.
When the raw material powder is composed of 100% of LiCoO2 template particles, or when LiCoO2 particles are used as matrix particles, a large (e.g., 90 mm×90 mm square) flat LiCoO2 sintered plate can be yielded by firing. Although the mechanism is not clear, since synthesis of LiCoO2 does not proceed in a firing process, a change in volume or local unevenness of the shape probably does not occur.
The raw material powder is mixed with a dispersive medium and any additive (e.g., binder, plasticizer, and dispersant) to form a slurry. A lithium compound (e.g., lithium carbonate) in an excess amount of about 0.5 to 30 mol % other than LiMO2 may be added to the slurry to promote grain growth and compensate for a volatile component in a firing process described later. The slurry preferably contains no pore-forming agent. The slurry is defoamed by stirring under reduced pressure, and the viscosity is preferably adjusted into 4000 to 10000 cP. The resultant slurry is formed into a sheet to give a green sheet containing lithium complex oxide. The resultant green sheet is in the form of an independent sheet. An independent sheet (also referred to as a “self-supported film”) refers to a sheet (including flakes having an aspect ratio of 5 or more) that can be handled in a singular form independently apart from a support that is different therefrom. In other words, the independent sheet does not refer to a sheet that is fixed to a support that is different therefrom (such as a substrate) and integrated with the support (so as to be inseparable or hard to separate). The sheet is preferably formed by a forming procedure capable of applying a shear force to platy particles (for example, template particles) in the raw material powder. Through this process, the primary grains can have a mean tilt angle of over 0° and 30° or less to the plate face. The forming procedure capable of applying a shear force to platy particles suitably includes a doctor blade process. The thickness of the green sheet containing the lithium complex oxide may be appropriately selected so as to give the above desired thickness after firing.
Besides the green sheet containing lithium complex oxide, another green sheet containing an excess-lithium source is then produced, optionally. The excess-lithium source is preferably a lithium compound other than LiMO2. The components other than Li in the compound disappear during firing. A preferable example of such a lithium compound (excess-lithium source) is lithium carbonate. The excess-lithium source is preferably powder and has a volume-based D50 particle diameter of preferably 0.1 to 20 μm, more preferably 0.3 to 10 μm. The lithium source powder is mixed with a dispersive medium and various additives (e.g., a binder, a plasticizer, and a dispersant) to form a slurry. The resultant slurry is defoamed by stirring under reduced pressure, and the viscosity is preferably adjusted into 1000 to 20000 cP. The resultant slurry is formed into a sheet to obtain a green sheet containing an excess-lithium source. The resultant green sheet is also in the form of an independent sheet. The sheet can be formed by any known process and is preferably formed by a doctor blade process. The thickness of the green sheet containing the excess-lithium source is appropriately selected, such that the molar ratio (Li/Co ratio) of the Li content in the green sheet containing the excess-lithium source to the Co content in the green sheet containing the lithium complex oxide is preferably 0.1 or more, more preferably 0.1 to 1.1.
The green sheet containing the lithium complex oxide (e.g., LiCoO2 green sheet) and the green sheet containing the excess-lithium source (e.g., Li2CO3 green sheet), optionally, are sequentially disposed on a bottom setter, and a top setter is disposed on the green sheets. The top and bottom setters are made of ceramic, preferably zirconia or magnesia. If the setters are made of magnesia, the pores tend to get smaller. The top setter may have a porous structure, a honeycomb structure, or a dense structure. If the top setter has a dense structure, the pores in the sintered plate readily get smaller, and the number of pores tends to get larger. As necessary, the green sheet containing the excess-lithium source is preferably cut into a size, such that the molar ratio (Li/Co ratio) of the Li content in the green sheet containing the excess-lithium source to the Co content in the green sheet containing the lithium complex oxide is preferably 0.1 or more, more preferably 0.1 to 1.1.
After the green sheet containing the lithium complex oxide (e.g., a LiCoO2 green sheet) is placed on the bottom setter, the green sheet may be optionally degreased and then calcined at 600 to 850° C. for 1 to 10 hours. In this step, the green sheet containing the excess-lithium source (e.g., a Li2CO3 green sheet) and the top setter may be sequentially disposed on the resultant calcined plate.
The green sheets and/or the calcined plate disposed between the setters are optionally degreased and heated (fired) in a medium temperature range (e.g., 700 to 1000° C.) to give a lithium complex oxide sintered plate. This firing process may be performed in one or two steps. In the case of firing in two separate steps, the temperature in the first firing step is preferably lower than that in the second firing step. The resultant sintered plate is also in the form of an independent sheet.
The titanium-containing sintered plate as a preferable embodiment of the negative electrode layer 16 may be produced by any method. For example, the LTO sintered plate is preferably produced through (a) production of an LTO-containing green sheet and (b) firing of the LTO-containing green sheet.
First, raw material powder (LTO powder) composed of lithium titanate Li4Ti5O12 is prepared. Commercially available or newly synthesized LTO powder may be used as the raw material powder. For example, powder obtained by hydrolyzing a mixture of titanium tetraisopropoxy alcohol and isopropoxy lithium may be used, or a mixture containing lithium carbonate, titania, or the like may be fired. The raw material powder preferably has a volume-based D50 particle size of 0.05 to 5.0 μm, more preferably 0.1 to 2.0 μm. A larger particle size of the raw material powder tends to increase the size of the pores. Further, in the case where the particle size of the raw material is large, milling (such as pot milling, bead milling, and jet milling) may be performed to a desired particle size. The raw material powder is mixed with a dispersive medium and any additive (e.g., binder, plasticizer, and dispersant) to form a slurry. A lithium compound (e.g., lithium carbonate) in an excess amount of about 0.5 to 30 mol % other than LiMO2 may be added to the slurry to promote grain growth and compensate for a volatile component in a firing process described later. The slurry preferably contains no pore-forming agent. The slurry is defoamed by stirring under reduced pressure, and the viscosity is preferably adjusted into 4000 to 10000 cP. The resultant slurry is formed into a LTO-containing green sheet. The resultant green sheet is in the form of an independent sheet. An independent sheet (also referred to as a “self-supported film”) refers to a sheet (including flakes having an aspect ratio of 5 or more) that can be handled in a singular form independently apart from a support that is different therefrom. In other words, the independent sheet does not refer to a sheet that is fixed to a support that is different therefrom (such as a substrate) and integrated with the support (so as to be inseparable or hard to separate). The sheet can be formed by any known process and is preferably formed by a doctor blade process. The thickness of the LTO-containing green sheet may be appropriately selected so as to give the above desired thickness after firing.
The LTO-containing green sheet is placed on the setter. The setter is made of ceramic, preferably zirconia or magnesia. The setter is preferably embossed. The green sheet disposed on the setter is put into a sheath. The sheath is also made of ceramic, preferably alumina. Then, the green sheet in this state is degreased, optionally, and fired to obtain an LTO sintered plate. The firing is preferably performed at 600 to 900° C. for 1 to 50 hours, more preferably at 700 to 800° C. for 3 to 20 hours. The resultant sintered plate is also in the form of an independent sheet. The heating rate during firing is preferably 100 to 1000° C./h, more preferably 100 to 600° C./h. In particular, the heating rate is preferably employed in a temperature rising process from 300° C. to 800° C., more preferably from 400° C. to 800° C.
As described above, an LTO sintered plate can be preferably produced. In this preferable production method, it is effective to 1) adjust the particle size distribution of the LTO powder and/or 2) change the heating rate during firing, and these are considered to contribute to achieving various properties of the LTO sintered plate.
The entire integrated sintered plate with a three-layer structure of the positive electrode layer, the ceramic separator, and the negative electrode layer that is preferably used for the lithium ion secondary battery used in the present invention is preferably coated with a metal oxide layer. Delamination of the integrated sintered plate due to physical impact during battery assembly can be suppressed, and the deterioration in capacity due to storage in a charged state can also be suppressed by coating the entire integrated sintered plate with a metal oxide layer. The integrated sintered plate may be coated with the metal oxide layer by any method, but the metal oxide layer is preferably formed, for example, by i) preparing a coating solution containing a metal compound, ii) immersing the integrated sintered plate in the coating solution to allow the coating solution penetrate therein, iii) taking out the integrated sintered body for drying, and iv) heating the integrated sintered body with the metal compound attached to convert the metal compound into a metal oxide. The coating solution prepared in Procedure i) above is not specifically limited as long as it is a solution containing a metal compound capable of forming a metal oxide layer by heating in a solvent (preferably, an organic solvent), but the metal compound is preferably at least one metal compound selected from the group consisting of Zr, Mg, Al, Nb, and Ti, more preferably metal alkoxides. Preferable examples of such a metal compound include metal alkoxides such as zirconium tetra-n-butoxide, magnesium diethoxide, triisopropoxyaluminum, niobium pentaethoxide, and titanium tetraisopropoxide. In Procedure ii) above, the integrated sintered plate immersed in the coating solution is preferably placed under a vacuum or reduced pressure atmosphere, since the coating solution can penetrate into the integrated sintered plate sufficiently and efficiently. In Procedure iii) above, drying may be performed at room temperature or under heating. In Procedure iv) above, the heating is preferably performed at 300 to 700° C. for 2 to 24 hours, more preferably at 350 to 550° C. for 4 to 6 hours. Thus, the integrated sintered plate entirely coated with a metal oxide layer is obtained.
The invention will be illustrated in more detail by the following examples.
A coin-shaped lithium ion secondary battery for reflow soldering was produced and evaluated as follows.
First, Co3O4 powder (manufactured by CoreMax Corporation) and Li2CO3 powder (manufactured by THE HONJO CHEMICAL CORPORATION) weighed to a molar ratio Li/Co of 1.01 were mixed, and thereafter the mixture was kept at 780° C. for 5 hours. The resultant powder was milled into a volume-based D50 of 0.4 μm with a pot mill to yield powder composed of platy LCO particles. The resultant LCO powder (100 parts by weight), a dispersive medium (toluene:isopropanol=1:1) (100 parts by weight), a binder (polyvinyl butyral: Product No. BM-2, manufactured by SEKISUI CHEMICAL CO., LTD.) (10 parts by weight), a plasticizer (di-2-ethylhexyl phthalate (DOP), manufactured by Kurogane Kasei Co., Ltd.) (4 parts by weight), a dispersant (product name: RHEODOL SP-O30, manufactured by Kao Corporation) (2 parts by weight), and ZrO2 (manufactured by Sigma-Aldrich Corporation) (1 part by weight) were mixed. The resultant mixture was defoamed by stirring under reduced pressure to prepare a LCO slurry with a viscosity of 4000 cP. The viscosity was measured with an LVT viscometer manufactured by Brookfield. The slurry prepared was formed into a LCO green sheet onto a PET film by a doctor blade process. The thickness of the LCO green sheet was adjusted to 200 μm after firing.
First, LTO powder (volume-based D50 particle size: 0.06 μm, manufactured by Sigma-Aldrich Japan) (100 parts by weight), a dispersive medium (toluene:isopropanol=1:1) (100 parts by weight), a binder (polyvinyl butyral: Product No. BM-2, manufactured by SEKISUI CHEMICAL CO., LTD.) (20 parts by weight), a plasticizer (di-2-ethylhexyl phthalate (DOP), manufactured by Kurogane Kasei Co., Ltd.) (4 parts by weight), and a dispersant (product name: RHEODOL SP-O30, manufactured by Kao Corporation) (2 parts by weight) were mixed. The resultant negative electrode raw material mixture was defoamed by stirring under reduced pressure to prepare a LTO slurry with a viscosity of 4000 cP. The viscosity was measured with an LVT viscometer manufactured by Brookfield. The slurry prepared was formed into a LTO green sheet onto a PET film by a doctor blade process. The thickness of the LTO green sheet was adjusted to 100 μm after firing.
Magnesium carbonate powder (manufactured by Konoshima Chemical Co., Ltd.) was heated at 900° C. for 5 hours to obtain MgO powder. The resultant MgO powder and glass frit (CK0199, manufactured by Nippon Frit Co., Ltd.) were mixed at a weight ratio of 4:1. The resultant mixed powder (volume-based D50 particle size: 0.4 μm) (100 parts by weight), a dispersive medium (toluene:isopropanol=1:1) (100 parts by weight), a binder (polyvinyl butyral: Product No. BM-2, manufactured by SEKISUI CHEMICAL CO., LTD.) (20 parts by weight), a plasticizer (di-2-ethylhexyl phthalate (DOP), manufactured by Kurogane Kasei Co., Ltd.) (4 parts by weight), and a dispersant (product name: RHEODOL SP-O30, manufactured by Kao Corporation) (2 parts by weight) were mixed. The resultant raw material mixture was defoamed by stirring under reduced pressure to prepare a slurry with a viscosity of 4000 cP. The viscosity was measured with an LVT viscometer manufactured by Brookfield. The slurry prepared was formed into a separator green sheet onto a PET film by a doctor blade process. The thickness of the separator green sheet was adjusted to 25 μm after firing.
Three LCO green sheets (positive electrode green sheets), the MgO green sheet (separator green sheet), and two LTO green sheets (negative electrode green sheets) were sequentially stacked, and the laminate obtained was pressed at 200 kgf/cm2 by CIP (cold isostatic pressing) to pressure-bond the green sheets together. The laminate thus pressure-bonded was punched into a circular plate with a diameter of 10 mm using a punching die. The resultant laminate in a form of circular plate was degreased at 600° C. for 5 hours, then heated to 800° C. at 1000° C./h, and kept for 10 minutes to fire, followed by cooling. Thus, one integrated sintered plate (integrated electrode) including three layers of the positive electrode layer (LCO sintered layer) 12, the ceramic separator (MgO separator), and the negative electrode layer (LTO sintered layer) was obtained.
(5) Coating with Metal Oxide Layer
First, 10 g of 2-ethoxyethanol, 0.25 g of acetyl acetone, and 1 g of zirconium tetra-n-butoxide were put into a container, followed by stirring, to give a coating solution. The solution was put into a container, and the integrated sintered plate obtained in Procedure (4) above was immersed therein. The container was put into a desiccator, followed by vacuuming to −95 kPa and standing for 3 minutes. Thereafter, the inside of the desiccator was returned to the atmosphere, and the container containing the integrated sintered plate was taken out. The integrated sintered plate was taken out onto a non-woven fabric wiper with tweezers, and the coating solution was lightly wiped off, followed by drying at room temperature for 2 hours. The integrated sintered plate after drying was placed on an alumina setter and heated in a medium-sized super cantal furnace (available from KYOWA KONETSU KOGYO CO., LTD.) at 400° C. for 5 hours. Thus, an integrated sintered plate (integrated electrode) entirely coated with a metal oxide layer (a layer composed of an oxide of Zr or a complex oxide of Zr and Li) was obtained.
Acetylene black and polyimide amide were weighed to a mass ratio of 3:1 and mixed with an appropriate amount of NMP (N-methyl-2-pyrrolidone) as a solvent, to prepare a conductive carbon paste as a conductive adhesive. The conductive carbon paste was screen-printed on an aluminum foil as a negative electrode current collector. The integrated sintered body produced in (5) above was disposed so that the negative electrode layer 16 was located within an undried printing pattern (that is, a region coated with the conductive carbon paste), followed by vacuum drying at 60° C. for 30 minutes, to produce a structure with the negative electrode layer and the negative electrode current collector bonded via the negative side carbon layer. The negative side carbon layer had a thickness of 10 μm.
Acetylene black and polyimide amide were weighed to a mass ratio of 3:1 and mixed with an appropriate amount of NMP (N-methyl-2-pyrrolidone) as a solvent, to prepare a conductive carbon paste. The conductive carbon paste was screen-printed on an aluminum foil as a positive electrode current collector, followed by vacuum drying at 60° C. for 30 minutes, to produce a positive electrode current collector with a positive side carbon layer formed on a surface. The positive side carbon layer had a thickness of 5 μm.
The positive electrode current collector, the positive electrode side carbon layer, the integrated sintered plate (the LCO positive electrode layer, the MgO separator, and the LTO negative electrode layer), the negative electrode side carbon layer, the negative electrode current collector, and a wave washer (manufactured by MISUMI Group Inc.) were accommodated between the positive electrode can and the negative electrode can, which would form a battery case, so as to be stacked in this order from the positive electrode can toward the negative electrode can, and an electrolytic solution was filled therein. Thereafter, the positive electrode can and the negative electrode can were crimped via a gasket to be sealed. Thus, a coin cell-shaped lithium ion secondary battery with a diameter of 12.5 mm and a thickness of 1.0 mm was produced. At this time, a solution obtained by dissolving LiBF4 in a PC organic solvent to a concentration of 1.5 mol/L was used as an electrolytic solution. The positive electrode terminal was joined to the positive electrode can, and the negative electrode terminal was joined to the negative electrode can by resistance welding, respectively. 200 batteries were produced for each example.
The batteries produced were subjected to initial charging and discharging. The initial charging and discharging was performed by charging the battery at a constant current (CC) of a current value of 0.1 C to reach a voltage of 2.7 V, subsequently at a constant voltage (CV) to a current value of 0.01 C, and then discharging the battery at a constant current of a current value of 0.05 C to reach a voltage of 1.5 V. The discharge capacity at this time was defined as the battery capacity, and the state discharged at 0.05 C was defined as SOC 0%. In Examples 2, 3, 4, and 10, this battery with an SOC of 0% was charged at a constant current of 0.1 C to a capacity obtained by multiplying the charging rate (corresponding to SOC) by the battery capacity to adjust the SOC of the battery to the values shown in Table 1. Meanwhile, in Examples 1, 9, and 11, the SOC of the battery with an SOC of 0% was not adjusted.
Using a reflow oven (product name: UNI-5016F, manufactured by ANTOM Co., Ltd.), the battery obtained in (7) above was connected to the circuit board by reflow soldering technique. This connection was made by joining the positive electrode terminals and negative electrode terminals to the circuit board by reflow soldering. The heating (reflow heating) of reflow soldering for connecting to the circuit board was performed with a heating profile in which the maximum temperature was 260° C. (Examples 1 to 4), 240° C. (Example 9), or 280° C. (Examples 10 and 11), and a temperature of 220° C. or more was given for 60 seconds. The reflow heating with this profile was performed twice in total (Examples 1 to 4) or once (Examples 9 to 11).
The resistance of 200 batteries at a SOC of 30% before used for reflow soldering in (7) above was measured in advance, and the average was taken as an initial resistance value. The resistance value was determined at 10 Hz from the AC impedance measurement. The resistance at a SOC of 30% of each battery after mounted on the circuit board in (8) above was measured in the same manner as above, and those with an increase rate from the initial resistance value of 20% or less were determined to be non-defective. The ratio of the number of non-defective batteries out of 200 batteries was calculated and determined as the non-defective product rate.
A battery was produced and evaluated in the same manner as in Example 1, except that uncharged battery obtained in (6) above was used for reflow soldering as it was without the initial charging and discharging and SOC adjustment in (7) above, and the resistance was measured without adjusting the SOC to 30%, while the battery was remained uncharged in the evaluation of the non-defective product rate in (9) above.
A battery was produced and evaluated in the same manner as in Examples 1, 3, and 4, except that i) glass frit was not added in the production of MgO in (3) above (that is, the ratio of MgO powder to glass frit was 100:0), ii) the thickness of the separator green sheet was set to a thickness after firing of 12 μm in (3) above, iii) the lamination, pressure bonding, and firing in (4) above were performed as in (4′) below, iv) the entire positive electrode/separator sintered plate obtained in (4′) below was coated with a metal oxide layer instead of the integrated sintered plate in (5) above, v) a negative electrode sintered plate produced in (4′) below was placed so that the negative electrode layer 16 was fit within an undried printing pattern in (6a) above, and vi) the coin-shaped battery in (6c) above was assembled as in (6c′) below. That is, Examples 6, 7, and 8 respectively correspond to Examples 1, 3, and 4 except for changes i) to vi) above.
Three LCO green sheets (positive electrode green sheets) and an MgO green sheet (separator green sheet) were sequentially stacked, and the laminate obtained was pressed at 200 kgf/cm2 by CIP (cold isostatic pressing) to pressure-bond the green sheets together. The laminate thus pressure-bonded was punched into a circular plate with a diameter of 10 mm using a punching die. The resultant laminate in a form of circular plate was degreased at 600° C. for 5 hours, then heated to 900° C. at 1000° C./h, and kept for 10 minutes to fire, followed by cooling. Thus, a positive electrode/separator sintered plate composed of two layers of a positive electrode layer (LCO sintered layer) 12 and a ceramic separator (MgO separator) was obtained.
Further, two LTO green sheets (negative electrode green sheets) were sequentially stacked, and the laminate obtained was pressed at 200 kgf/cm2 by CIP (cold isostatic pressing) to pressure-bond the green sheets together. The laminate thus pressure-bonded was punched into a circular plate with a diameter of 10 mm using a punching die. The resultant laminate in a form of circular plate was degreased at 600° C. for 5 hours, then heated to 800° C. at 1000° C./h, and kept for 10 minutes to fire, followed by cooling. Thus, a negative electrode sintered plate composed of a negative electrode layer (LTO sintered layer) was obtained.
(6c′) Assembly of Coin-Shaped Battery
The positive electrode current collector, the positive electrode side carbon layer, the positive electrode/separator sintered plate (the LCO positive electrode layer and the MgO separator), the negative electrode sintered plate (the LTO negative electrode layer), the negative electrode side carbon layer, the negative electrode current collector, and a wave washer (manufactured by MISUMI Group Inc.) were accommodated between the positive electrode can and the negative electrode can, where a battery case is to be formed, so as to be stacked in this order from the positive electrode can toward the negative electrode can, and an electrolytic solution was filled therein. Thereafter, the positive electrode can and the negative electrode can were crimped via a gasket to be sealed. Thus, a coin cell-shaped lithium ion secondary battery with a diameter of 12.5 mm and a thickness of 1.0 mm was produced. At this time, a solution obtained by dissolving LiBF4 in a PC organic solvent to a concentration of 1.5 mol/L was used as an electrolytic solution. The positive electrode terminal was joined to the positive electrode can, and the negative electrode terminal was joined to the negative electrode can by resistance welding, respectively. Thus, 200 batteries were produced.
The production conditions and non-defective product rate of the batteries produced in Examples 1 to 11 were as shown in Table 1.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-150652 | Sep 2021 | JP | national |
This application is a continuation application of PCT/JP2022/034077 filed Sep. 12, 2022, which claims priority to Japanese Patent Application No. 2021-150652 filed Sep. 15, 2021, the entire contents all of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2022/034077 | Sep 2022 | WO |
| Child | 18601170 | US |
