Patent Application
20230238573
The present invention relates to a secondary battery.
In recent years, in order to fight global warming, there is a strong need for reduction of the amount of carbon dioxide. In the automobile industry, there are increasing expectations for a reduction of carbon dioxide emissions by introduction of electric vehicles (EV) and hybrid electric vehicles (HEV), and development of non-aqueous electrolyte secondary batteries such as secondary batteries for motor driving, which are key to practical application of such vehicles, has been actively conducted.
A secondary battery for motor driving is required to have extremely high output characteristics and high energy as compared with a lithium-ion secondary battery for consumer use used in a mobile phone, a notebook computer, and the like. Therefore, a lithium-ion secondary battery having the highest theoretical energy among all practical batteries has attracted attention, and is currently being rapidly developed.
Here, lithium-ion secondary batteries that are currently widespread use a combustible organic electrolyte solution as an electrolyte. In such liquid-based lithium-ion secondary batteries, safety measures against liquid leakage, short circuit, overcharge, and the like are more strictly required than other batteries.
Therefore, in recent years, research and development on an all-solid battery such as an all-solid lithium-ion secondary battery using an oxide-based or sulfide-based solid electrolyte as an electrolyte have been actively conducted. The solid electrolyte is a material mainly made of an ion conductor that enables ion conduction in a solid. For this reason, in an all-solid lithium-ion secondary battery, in principle, various problems caused by combustible organic electrolyte solution do not occur unlike the conventional liquid-based lithium-ion secondary battery. In general, use of a high-potential and large-capacity positive electrode material and a large-capacity negative electrode material can achieve significant improvement in output density and energy density of a battery. An all-solid lithium-ion secondary battery using a sulfur simple substance (S) or a sulfide-based material as a positive electrode active material is a promising candidate.
Meanwhile, in the lithium-ion secondary battery, the negative electrode potential decreases with the progress of charging. When the negative electrode potential decreases to be lower than 0 V (vs. Li/Li+), metal lithium is precipitated at the negative electrode, and dendrite (tree-like) crystals are precipitated (this phenomenon is also referred to as “electrodeposition of metal lithium”). Particularly, in an all-solid battery using metal lithium or a lithium-containing alloy as a negative electrode active material, the electrodeposition of metal lithium is a charge reaction itself. Here, if the electrodeposition of metal lithium excessively occurs in the all-solid battery, the precipitated dendrite may penetrate the solid electrolyte layer to cause an internal short-circuit of the battery.
In order to prevent such electrodeposition of metal lithium in the all-solid battery, for example, US 2018/0342768 discloses a technique of coating solid electrolyte particles constituting a solid electrolyte layer with a polymer film containing a thermoplastic resin. According to US 2018/0342768, with such a configuration, the mechanical strength and porosity of the solid electrolyte layer are improved, thereby suppressing the growth of dendrite in the solid electrolyte layer.
According to US 2018/0342768, with such a configuration, the mechanical strength and porosity of the solid electrolyte layer are improved, thereby suppressing the growth of dendrite.
However, according to the study by the present inventors, it has been found that sufficient battery performance may not be obtained in some cases even when the technique described in US 2018/0342768 is adopted. That is, it has been found that, depending on the physical properties of the polymer to be adopted, the ion conductivity in the solid electrolyte layer may decrease, leading to deterioration of input/output characteristics of the battery.
Therefore, an object of the present invention is to provide a means for inhibiting the growth of dendrite in a solid electrolyte layer while suppressing the decrease in ion conductivity in the solid electrolyte layer as much as possible, in a secondary battery which includes a solid electrolyte layer.
According to one aspect of the present invention, there is provided a secondary battery which includes a power-generating element formed by laminating a positive electrode which contains a positive electrode active material, a solid electrolyte layer which contains a solid electrolyte, and a negative electrode which contains a negative electrode active material in this order. In the secondary battery, the solid electrolyte layer further contains a binder having a Young’s modulus of 200 [MPa] or lower.
One aspect of the present invention is a secondary battery including a power-generating element formed by laminating a positive electrode which contains a positive electrode active material, a solid electrolyte layer which contains a solid electrolyte, and a negative electrode which contains a negative electrode active material in this order, in which the solid electrolyte layer further contains a binder having a Young’s modulus of 200 [MPa] or lower. According to the secondary battery of the present invention, it is possible to inhibit the growth of dendrite in a solid electrolyte layer while suppressing the decrease in ion conductivity in the solid electrolyte layer as much as possible.
Hereinafter, the embodiments of the positive electrode for a secondary battery according to the present aspect will be described with reference to the drawings, but the technical scope of the present invention should be determined based on the description of the claims, and is not limited to the following embodiments. The dimensional ratios of the drawings are exaggerated for convenience of description and may differ from the actual ratios.
As illustrated in
The lithium-ion secondary battery according to the present aspect is not limited to a laminate type flat shape. A wound type lithium ion secondary battery is not particularly limited, and may have a cylindrical shape, or may have a rectangular flat shape obtained by deforming such a cylindrical shape. As for the lithium-ion secondary battery having the cylindrical shape, a laminate film may be used or a conventional cylindrical can (metal can) may be used as an outer casing material thereof, and the outer casing material is not particularly limited. Preferably, a power-generating element is housed in a laminate film including aluminum. According to this form, weight reduction can be achieved.
In addition, the extending of the current collecting plates (25 and 27) illustrated in
As illustrated in
As illustrated in
The negative electrode current collector 11′ and the positive electrode current collector 11″ have a structure in which a negative electrode current collecting plate (tab) 25 and a positive electrode current collecting plate (tab) 27 which are electrically connected to the respective electrodes (the positive electrode and the negative electrode) are respectively attached to the negative electrode current collector 11′ and the positive electrode current collector 11″ and are led to an outside of the laminate film 29 so as to be sandwiched between ends of the laminate film 29 as the outer casing material. The positive electrode current collecting plate 27 and the negative electrode current collecting plate 25 may be attached to the positive electrode current collector 11″ and the negative electrode current collector 11′ of the respective electrodes with a positive electrode lead and a negative electrode lead (not illustrated) interposed therebetween, respectively by ultrasonic welding, resistance welding, or the like as necessary.
Hereinafter, main constituent members of the lithium-ion secondary battery according to the present aspect is applied will be described.
A current collector has a function of mediating transfer of electrons from electrode active material layers. A material constituting the current collector is not particularly limited. As the material constituting the current collector, for example, a metal or a resin having conductivity can be adopted.
Specific examples of the metal include aluminum, nickel, iron, stainless steel, titanium, copper, and the like. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or the like may be used. Further, a foil in which a metal surface is coated with aluminum may be used. Above all, aluminum, stainless steel, copper, and nickel are preferred from the viewpoint of the electron conductivity, the battery operating potential, the adhesion of the negative electrode active material by sputtering to the current collector, and the like.
Examples of the latter resin having conductivity include a resin obtained by adding a conductive filler to a non-conductive polymer material as necessary.
Examples of the non-conductive polymer material include polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), and the like), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamide imide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), polystyrene (PS), and the like. Such a non-conductive polymer material can have excellent potential resistance or solvent resistance.
A conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary. Particularly, in a case where a resin serving as a base material of the current collector is composed only of a non-conductive polymer, a conductive filler is essential to impart conductivity to the resin.
The conductive filler can be used without particular limitation as long as the conductive filler is a substance having conductivity. Examples of materials excellent in conductivity, potential resistance, or lithium-ion blocking property include metals and conductive carbon. Examples of the metals are not particularly limited, but preferably include at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, and Sb, or an alloy or a metal oxide containing these metals. The conductive carbon is not particularly limited. Preferably, examples of the conductive carbon include at least one selected from the group consisting of acetylene black, Vulcan (registered trademark), Black Pearl (registered trademark), carbon nanofiber, Ketjen black (registered trademark), carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
The addition amount of the conductive filler is not particularly limited as long as sufficient conductivity can be imparted to the current collector, and is generally 5 to 80 mass% with respect to a total mass of 100 mass% of the current collector.
The current collector may have a single-layer structure made of a single material, or may have a laminated structure in which layers made of these materials are appropriately combined. From the viewpoint of weight reduction of the current collector, it is preferable that the current collector includes at least a conductive resin layer made of a resin having conductivity. From the viewpoint of blocking the movement of lithium ions between single battery layers, a metal layer may be provided in a part of the current collector. Further, as long as a negative electrode active material layer and a positive electrode active material layer to be described later have conductivity by themselves and can have a current collecting function, a current collector as a member different from these electrode active material layers is not necessarily used. In such an embodiment, the negative electrode active material layer described later as it is constitutes a negative electrode, and the positive electrode active material layer described later as it is constitutes a positive electrode.
In the secondary battery according to the present aspect, the solid electrolyte layer is a layer that is interposed between the positive electrode active material layer and the negative electrode active material layer and essentially contains a solid electrolyte. The specific form of the solid electrolyte contained in the solid electrolyte layer is not particularly limited.
Examples of the solid electrolyte include a sulfide solid electrolyte and an oxide solid electrolyte, and a sulfide solid electrolyte is preferred from the viewpoint of obtaining higher ion conductivity.
Examples of the sulfide solid electrolyte include LiI—Li2S—SiS2, LiI—Li2S—P2O5, LiI—Li3PO4—P2S5, Li2S—P2S5, LiI—Li3PS4, LiI—LiBr—Li3PS4, Li3PS4, Li2S—P2S5, Li2S—P2S5—LiI, Li2S—P2S5—Li2O, Li2S—P2S5—Li2O—LiI, Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—LiBr, Li2S—SiS2—LiCl, Li2S—SiS2—B2S3—LiI, Li2S—SiS2—P2S5—LiI, Li2S—B2S3, Li2S—P2S5—ZmSn (where m and n are positive numbers, and Z is any of Ge, Zn, and Ga), Li2S—GeS2, Li2S—SiS2—Li3PO4, Li2S—SiS2—LixMOy (where x and y are positive numbers, and M is any of P, Si, Ge, B, Al, Ga, and In), and the like. The description of “Li2S—P2S5” means a sulfide solid electrolyte obtained by using a raw material composition containing Li2S and P2S5, and the same applies to other descriptions.
The sulfide solid electrolyte may have, for example, a Li3PS4 skeleton, a Li4P2S7 skeleton, or a Li4P2S6 skeleton. Examples of the sulfide solid electrolyte having a Li3PS4 skeleton include LiI—Li3PS4, LiI—LiBr—Li3PS4, and Li3PS4. Examples of the sulfide solid electrolyte having a Li4P2S7 skeleton include a Li—P—S—based solid electrolyte called LPS (e.g., Li7P3S11). As the sulfide solid electrolyte, for example, LGPS expressed by Li(4-x)Ge(1-x)PxS4 (x satisfies 0 < x < 1) or the like may be used. Above all, the sulfide solid electrolyte is preferably a sulfide solid electrolyte containing a P element, and the sulfide solid electrolyte is more preferably a material containing Li2S—P2S5 as a main component. Furthermore, the sulfide solid electrolyte may contain halogen (F, Cl, Br, I). Examples of the halogen-containing sulfide solid electrolyte include argyrodite type solid electrolytes (Li6PS5Cl and Li6PS5Br), and these electrolytes are also materials that can be preferably used.
In a case where the sulfide solid electrolyte is Li2S—P2S5 based, a molar ratio of Li2S and P2S5 is preferably within a range of Li2S — P2S5 = 50 : 50 to 100 : 0, and particularly preferably within a range of Li2S — P2S5 = 70 : 30 to 80 : 20.
In addition, the sulfide solid electrolyte may be sulfide glass, may be crystallized sulfide glass, or may be a crystalline material obtained by a solid phase method. The sulfide glass can be obtained, for example, by performing mechanical milling (ball milling or the like) on a raw material composition. The crystallized sulfide glass can be obtained, for example, by heat-treating sulfide glass at a temperature equal to or higher than a crystallization temperature. In addition, ion conductivity (e.g., Li ion conductivity) of the sulfide solid electrolyte at a normal temperature (25° C.) is, for example, preferably 1 × 10-5 S/cm or more, and more preferably 1×10-4 S/cm or more. A value of the ion conductivity of the solid electrolyte can be measured by an AC impedance method.
Examples of the oxide solid electrolyte include a compound having a NASICON-type structure, and the like. Examples of the compound having a NASICON-type structure include a compound (LAGP) expressed by general formula: Li1+xAlxGe2-x(PO4)3 (0 ≤ x ≤ 2), a compound (LATP) expressed by general formula: Li1+xAlxTi2-x(PO4)3 (0 ≤ x ≤ 2), and the like. Other examples of the oxide solid electrolyte include LiLaTiO (e.g., Li0.34La0.51TiO3), LiPON (e.g., Li2.9PO3.3N0.46), LiLaZrO (e.g., Li7La3Zr2O12), and the like.
Examples of the shape of the solid electrolyte include particle shapes such as a perfectly spherical shape and an elliptically spherical shape, a thin film shape, and the like. When the solid electrolyte has a particle shape, the average particle diameter (D50) is not particularly limited, but is preferably 40 µm or less, more preferably 20 µm or less, and still more preferably 10 µm or less. Meanwhile, the average particle diameter (D50) is preferably 0.01 µm or more, and more preferably 0.1 µm or more.
In the secondary battery according to the present aspect, the solid electrolyte layer further contains a binder in addition to the solid electrolyte described above. The binder is characterized in that it essentially contains a binder having a Young’s modulus of 200 [MPa] or lower. The “Young’s modulus” is a parameter, also referred to as “longitudinal elastic modulus”, and is a proportionality constant of strain and stress in a coaxial direction in an elastic range in which Hooke’s law holds. In the present specification, as the value of the Young’s modulus of the binder, a value measured by a nanoindentation method described in the section of Examples to be described later is adopted. In a case where the binder contained in the solid electrolyte layer has a Young’s modulus of 200 [MPa] or lower, the decrease in ion conductivity in the solid electrolyte layer can be sufficiently suppressed even after adding the binder to the solid electrolyte layer. This is presumed to be because, as illustrated in
Here, the specific chemical structure of the binder having a Young’s modulus of 200 [MPa] or lower is not particularly limited, and a binder having a conventionally known chemical structure can be appropriately used. As an example, the binder having a Young’s modulus of 200 [MPa] or lower preferably contains one kind or two or more kinds selected from the group consisting of acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), polyvinylidene fluoride (PVdF) (including a compound in which a hydrogen atom is substituted with another halogen element), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyethylene carbonate (PEC), and polyethylene oxide (PEO), and more preferably contains sulfide solid electrolyte or styrene-butadiene rubber (SBR), from the viewpoint of easily achieving a low Young’s modulus. Even in the case of binders having an identical chemical structure, the value of Young’s modulus can be controlled by adjusting the composition, the degree of polymerization, the crosslinking density, and the like. In the secondary battery according to the present aspect, the solid electrolyte layer preferably contains a binder having a Young’s modulus of 200 [MPa] or lower. From the viewpoint of improving the ion conductivity of the solid electrolyte layer, the Young’s modulus of the binder is preferably as low as possible. For example, the Young’s modulus of the binder is preferably 100 [MPa] or lower, more preferably 50 [MPa] or lower, still more preferably 20 [MPa] or lower, yet still more preferably 7 [MPa] or lower, particularly preferably 3 [MPa] or lower, and most preferably 1 [MPa] or lower. The lower limit of the Young’s modulus of the binder is not particularly limited, but is, for example, 0.1 [MPa] or higher.
In the secondary battery according to the present aspect, the solid electrolyte layer may further contain another binder (i.e., a binder having a Young’s modulus of greater than 200 [MPa]) as long as the binder has a Young’s modulus of 200 [MPa] or lower. The chemical structure of such a binder is also not particularly limited, and it is possible to use conventionally known binders for all-solid batteries and non-aqueous electrolyte secondary batteries.
However, from the viewpoint of sufficiently exhibiting the action and effect of the present invention, among the binders contained in the solid electrolyte layer, a binder having a Young’s modulus of 200 [MPa] or lower is preferably a main component. Hence, a ratio of a content of the binder having a Young’s modulus of 200 [MPa] or lower to a total of 100 mass% of the binder contained in the solid electrolyte layer is preferably 50 mass% or more. Further, the ratio of the content is more preferably 70 mass% or more, still more preferably 80 mass% or more, still more preferably 90 mass% or more, particularly preferably 95 mass%, and most preferably 100 mass%.
The thickness of the solid electrolyte layer varies depending on the configuration of the intended lithium-ion secondary battery, but is preferably 600 µm or less, more preferably 500 µm or less, and still more preferably 400 µm or less from the viewpoint that the volume energy density of the battery can be improved. Meanwhile, the lower limit of the thickness of the solid electrolyte layer is not particularly limited, but is preferably 10 µm or more, more preferably 50 µm or more, and still more preferably 80 µm or more.
The content of the binder having a Young’s modulus of 200 [MPa] or lower in the solid electrolyte layer is not particularly limited, and is, for example, in a range of 1 to 12 mass%. From the viewpoint of enhancing the flexibility of the solid electrolyte layer to improve the flex resistance, the content is preferably 3 mass% or more with respect to 100 mass% of the solid electrolyte. Further, from the viewpoint of the effect of improving the ion conductivity of the solid electrolyte layer, the content is preferably 3 mass% or more and 5 mass% or less with respect to 100 mass% of the solid electrolyte.
In the secondary battery according to the present aspect, the negative electrode active material layer 13 contains a negative electrode active material. The type of the negative electrode active material is not particularly limited, and examples thereof include a carbon material, a metal oxide, and a metal active material. Examples of the carbon material include natural graphite, artificial graphite, mesocarbon microbead (MCMB), highly oriented graphite (HOPG), hard carbon, soft carbon, and the like. Examples of the metal oxide include Nb2O5, Li4TisO12, and the like. Further, a silicon-based negative electrode active material or a tin-based negative electrode active material may be used. Here, silicon and tin belong to a Group 14 element, and are known to be a negative electrode active material that can greatly improve the capacity of a non-aqueous electrolyte secondary battery. Since simple substances of silicon and tin can occlude and release a large number of charge carriers (lithium ions and the like) per unit volume (mass), they become a high-capacity negative electrode active material. Here, a Si simple substance is preferably used as the silicon-based negative electrode active material. Similarly, it is also preferable to use a silicon oxide such as SiOx(0.3 ≤ x ≤ 1.6) disproportionated into two phases: a Si phase and a silicon oxide phase. At this time, the range of x is more preferably 0.5 ≤ x ≤ 1.5, and still more preferably 0.7 ≤ x ≤ 1.2. Further, an alloy containing silicon (silicon-containing alloy-based negative electrode active material) may be used. Meanwhile, examples of the negative electrode active material containing a tin element (tin-based negative electrode active material) include a Sn simple substance, a tin alloy (a Cu-Sn alloy and a Co—Sn alloy), an amorphous tin oxide, a tin silicon oxide, and the like. Among them, SnB0.4P0.6O3.1 is exemplified as the amorphous tin oxide. In addition, SnSiO3 is exemplified as the tin silicon oxide. As the negative electrode active material, a metal containing lithium may be used. Such a negative electrode active material is not particularly limited as long as it is an active material containing lithium, and examples thereof include lithium-containing alloys in addition to metal lithium. Examples of the lithium-containing alloys include an alloy of Li and at least one of In, Al, Si, and Sn. In some cases, two or more kinds of negative electrode active materials may be used in combination. Needless to say, a negative electrode active material other than the above-described negative electrode active materials may be used. The negative electrode active material preferably contains metal lithium, a silicon-based negative electrode active material, or a tin-based negative electrode active material, and particularly preferably contains metal lithium.
Examples of a shape of the negative electrode active material include a particle shape (a spherical shape, a fibrous shape), a thin film shape, and the like. In a case where the negative electrode active material has a particle shape, for example, the average particle diameter (D50) of the particles is preferably within a range of 1 nm to 100 µm, more preferably within a range of 10 nm to 50 µm, still more preferably within a range of 100 nm to 20 µm, and particularly preferably within a range of 1 to 20 µm. In the meantime, the value of the average particle diameter (D50) of active materials can be measured by laser diffraction scattering method.
The content of the negative electrode active material in the negative electrode active material layer is not particularly limited, but for example, is preferably within a range of 40 to 99 mass%, and more preferably within a range of 50 to 90 mass%.
Preferably, the negative electrode active material layer further contains a solid electrolyte. When the negative electrode active material layer contains the solid electrolyte, the ion conductivity of the negative electrode active material layer can be improved. The specific form of the solid electrolyte contained in the negative electrode active material layer is not particularly limited, and the examples and preferred forms described in the section of the solid electrolyte layer are similarly adopted. The content of the solid electrolyte in the negative electrode active material layer is, for example, preferably within a range of 1 to 60 mass%, and more preferably within a range of 10 to 50 mass%.
The negative electrode active material layer may further contain at least one of a binder and a conductive aid in addition to the negative electrode active material and the solid electrolyte described above. Here, the specific form of the binder that can be contained in the negative electrode active material layer is not particularly limited, and the examples and preferred forms described in the section of the solid electrolyte layer are similarly adopted. Hence, it is preferable that the negative electrode active material layer also contains a binder having a Young’s modulus of 200 [MPa] or lower.
Examples of the conductive aid include, but are not limited to, metals such as aluminum, stainless steel (SUS), silver, gold, copper, and titanium, alloys or metal oxides containing these metals; carbon such as carbon fibers (specifically, vapor grown carbon fibers (VGCF), polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, rayon-based carbon fibers, and activated carbon fibers), carbon nanotubes (CNT), and carbon black (specifically, acetylene black, Ketjen black (registered trademark), furnace black, channel black, thermal lamp black, and the like). In addition, a particle-shaped ceramic material or resin material coated with the metal material by plating or the like can also be used as the conductive aid. Among these conductive aids, the conductive aid preferably contains at least one selected from the group consisting of aluminum, stainless steel, silver, gold, copper, titanium, and carbon, more preferably contains at least one selected from the group consisting of aluminum, stainless steel, silver, gold, and carbon, and still more preferably contains at least one kind of carbon from the viewpoint of electrical stability. These conductive aids may be used singly or in combination of two or more kinds thereof.
The shape of the conductive aid is preferably a particle shape or a fibrous shape. In a case where the conductive aid has a particle shape, the shape of the particles is not particularly limited, and may be any shape such as a powder shape, a spherical shape, a rod shape, a needle shape, a plate shape, a columnar shape, an irregular shape, a scaly shape, and a spindle shape.
The thickness of the negative electrode active material layer varies depending on the configuration of the intended all-solid battery, but is preferably, for example, within a range of 0.1 to 1000 µm.
In the secondary battery according to the present aspect, a positive electrode active material layer 15 contains a positive electrode active material. The specific form of the positive electrode active material is not particularly limited, and there is appropriately referred to the conventionally known knowledge. Particularly, it is preferable that the positive electrode active material layer contains a sulfur-containing positive electrode active material. The kind of the sulfur-containing positive electrode active material is not particularly limited, and examples thereof include particles or a thin film of an organic sulfur compound or an inorganic sulfur compound in addition to the sulfur simple substance (S). Any material may be used as long as the material can release lithium ions during charging and occlude lithium ions during discharging by utilizing the oxidation-reduction reaction of sulfur. Examples of the organic sulfur compound include a disulfide compound, sulfur-modified polyacrylonitrile represented by the compounds described in WO 2010/044437 A, sulfur-modified polyisoprene, rubeanic acid (dithiooxamide), carbon polysulfide, and the like. Among the compounds, disulfide compounds, sulfur-modified polyacrylonitrile, and rubeanic acid are preferred, and sulfur-modified polyacrylonitrile is particularly preferred. As the disulfide compound, a disulfide compound having a dithiobiurea derivative, a thiourea group, a thioisocyanate or a thioamide group is more preferred. Here, the sulfur-modified polyacrylonitrile is modified polyacrylonitrile containing a sulfur atom obtained by mixing sulfur powder and polyacrylonitrile and heating the mixture under an inert gas or under reduced pressure. The estimated structure is a structure in which ring closure causes polyacrylonitrile to be polycyclic, and at least a part of the S is bound to C, as shown in, for example, Chem. Mater. 2011, 23, 5024-5028. The compound described in this literature has strong peak signals around 1330 cm-1 and 1560 cm-1 in the Raman spectrum, and further has peaks around 307 cm-1, 379 cm-1, 472 cm-1, and 929 cm-1. Meanwhile, the inorganic sulfur compound is preferred because it is excellent in stability, and specific examples thereof include sulfur simple substance (S), S-carbon composite, TiS2, TiS3, TiS4, NiS, NiS2, CuS, FeS2, Li2S, MoS2, MoS3, and the like. Among the compounds, S, S-carbon composite, TiS2, TiS3, TiS4, FeS2, and MoS2 are preferred, sulfur simple substance (S), S-carbon composite, TiS2, and FeS2 are more preferred, and sulfur simple substance (S) is particularly preferred. Here, the S-carbon composite contains sulfur powder and a carbon material, and is in the form of a composite obtained by subjecting these materials to heating treatment or mechanical mixing. More specifically, the S-carbon composite is in the form where sulfur is distributed on the surface or in fine pores of the carbon material, in the form where sulfur and the carbon material are uniformly dispersed at the nano level and the sulfur and the carbon material are aggregated into particles, in the form where the carbon material is distributed on the surface or inside of fine sulfur powder, or in the form where a plurality of these forms is combined.
The positive electrode active material layer may contain a sulfur-free positive electrode active material in place of or in addition to the sulfur-containing positive electrode active material. Examples of the sulfur-free positive electrode active material include layered rock salt-type active materials such as LiCoO2, LiMnO2, LiNiO2, LiVO2, and Li(Ni—Mn—Co)O2, spinel-type active materials such as LiMn2O4 and LiNi0.5Mn1.5O4, olivine-type active materials such as LiFePO4 and LiMnPO4, and Si-containing active materials such as Li2FeSiO4 and Li2MnSiO4. Examples of the oxide active material other than those described above include Li4Ti5O12.
In some cases, two or more kinds of positive electrode active materials may be used in combination. Needless to say, a positive electrode active material other than the above-described positive electrode active materials may be used.
Examples of a shape of the positive electrode active material include particle shapes (a spherical shape and a fibrous shape), a thin film shape, and the like. In a case where the positive electrode active material has a particle shape, for example, the average particle diameter (D50) of the particles is preferably within a range of 1 nm to 100 µm, more preferably within a range of 10 nm to 50 µm, still more preferably within a range of 100 nm to 20 µm, and particularly preferably within a range of 1 to 20 µm. In the present specification, the value of the average particle diameter (D50) of the active material can be measured by a laser diffraction scattering method.
The content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but for example, is preferably within a range of 40 to 99 mass%, and more preferably within a range of 50 to 90 mass%. The positive electrode active material layer may further contain a conductive aid and/or a binder. As for specific and preferred forms of these materials, those described in the section of the negative electrode active material layer described above can be similarly adopted. Hence, it is preferable that the positive electrode active material layer also contains a binder having a Young’s modulus of 200 [MPa] or lower.
A material constituting the current collecting plates (25 and 27) is not particularly limited, and a known highly conductive material conventionally used as a current collecting plate for a secondary battery can be used. As the material constituting the current collecting plates, for example, a metal material such as aluminum, copper, titanium, nickel, stainless steel (SUS), or an alloy thereof is preferred. From the viewpoint of weight reduction, corrosion resistance, and high conductivity, aluminum and copper are more preferred, and aluminum is particularly preferred. An identical material or different materials may be used for the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25.
Although not illustrated, the current collector (11′ or 11″) and the current collecting plate (25 or 27) may be electrically connected with a positive electrode lead or a negative electrode lead interposed therebetween. As a material constituting the positive electrode lead and the negative electrode lead, a material used in a known lithium-ion secondary battery can be similarly adopted. The portion taken out from an outer casing is preferably covered with a heat resistant and insulating heat shrinkable tube or the like so as not to affect a product (e.g., an automotive component, particularly an electronic device, or the like) due to electric leakage caused by contact with peripheral devices, wiring lines, or the like.
As the battery outer casing material, a known metal can case can be used, and a bag-shaped case using the aluminum-containing laminate film 29, which can cover a power-generating element as illustrated in
The laminate type battery 10a according to the embodiment shown in
Although one embodiment of the lithium-ion secondary battery has been described above, the present invention is not limited to only the configurations described in the above-described embodiment, and can be appropriately changed based on the description of the claims.
The type of battery to which the lithium-ion secondary battery according to the present invention is applied, is for example, a bipolar type (bipolar type) battery including a bipolar electrode having a positive electrode active material layer electrically coupled to one surface of a current collector and a negative electrode active material layer electrically coupled to an opposite surface of the current collector.
As illustrated in
The positive electrode active material layer 15, the solid electrolyte layer 17, and the negative electrode active material layer 13 that are adjacent constitute one single battery layer 19. Therefore, it can also be said that the bipolar type secondary battery 10b has a configuration in which the single battery layers 19 are laminated. The positive electrode active material layer 15 is formed only on one surface of an outermost layer current collector 11a on the positive electrode side located in an outermost layer of the power-generating element 21. Further, the negative electrode active material layer 13 is formed only on one surface of an outermost layer current collector 11b on the negative electrode side located in an outermost layer of the power-generating element 21.
Further, in the bipolar type secondary battery 10b illustrated in
The number of times of lamination of the single battery layers 19 is adjusted according to a desired voltage. Further, in the bipolar type secondary battery 10b, the number of times of lamination of the single battery layers 19 may be reduced as long as sufficient output can be secured even when the thickness of the battery is reduced as much as possible. Also, the bipolar type secondary battery 10b preferably has a structure in which the power-generating element 21 is sealed in the laminate film 29 as the battery outer casing body under reduced pressure, and the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25 are extended to the outside of the laminate film 29 in order to prevent external impact and environmental deterioration during use.
Further, the secondary battery according to the present aspect need not be an all-solid type. Hence, the solid electrolyte layer may further contain a conventionally known liquid electrolyte (electrolyte solution). The amount of the liquid electrolyte (electrolyte solution) that can be contained in the solid electrolyte layer is not particularly limited, but is preferably such an amount that the shape of the solid electrolyte layer formed by the solid electrolyte is maintained and liquid leakage of the liquid electrolyte (electrolyte solution) does not occur.
The liquid electrolyte (electrolyte solution) that can be used has a form in which a lithium salt is dissolved in an organic solvent. Examples of the organic solvent to be used include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propionate (MP), methyl acetate (MA), methyl formate (MF), 4-methyl dioxolane (4MeDOL), dioxolane (DOL), 2-methyltetrahydrofuran (2MeTHF), tetrahydrofuran (THF), dimethoxyethane (DME), propylene carbonate (PC), butylene carbonate (BC), dimethylsulfoxide (DMSO), γ-butyrolactone (GBL), and the like. Among all, the organic solvent is preferably chain carbonate, is more preferably at least one selected from the group consisting of diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC), and is more preferably selected from ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC), from the viewpoint of further improving rapid charge characteristics and output characteristics.
Examples of the lithium salt include Li(FSO2)2N (lithium bis(fluorosulfonyl)imide); LiFSI), Li(C2F5SO2)2N, LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, and the like. Above all, the lithium salt is preferably Li(FSO2)2N(LiFSI) from the viewpoint of battery output and charge and discharge cycle characteristics.
The liquid electrolyte (electrolyte solution) may further contain an additive other than the components described above. Specific examples of such a compound include ethylene carbonate, vinylene carbonate, methylvinylene carbonate, dimethylvinylene carbonate, phenylvinylene carbonate, diphenylvinylene carbonate, ethylvinylene carbonate, diethylvinylene carbonate, vinylethylene carbonate, 1,2-divinylethylene carbonate, 1-methyl-1-vinylethylene carbonate, 1-methyl-2-vinylethylene carbonate, 1-ethyl-1-vinylethylene carbonate, 1-ethyl-2-vinylethylene carbonate, vinylvinylene carbonate, arylethylene carbonate, vinyloxymethylethylene carbonate, aryloxymethylethylene carbonate, acryloxymethylethylene carbonate, methacryloxymethylethylene carbonate, ethynylethylene carbonate, propargylethylene carbonate, ethynyloxymethylethylene carbonate, propargyloxyethylene carbonate, methylene ethylene carbonate, 1,1-dimethyl-2-methylene ethylene carbonate, and the like. These additives may be used singly or in combination of two or more kinds thereof. The amount of the additive used in the electrolyte solution can be appropriately adjusted.
The secondary battery according to one aspect of the present invention described above is preferably in a state of being pressurized in a direction of lamination of the power-generating element at the time of operating the battery. Thus, the secondary battery according to one aspect of the present invention is preferably used together with a pressurizing member that pressurizes the power-generating element of the secondary battery in the direction of lamination. Therefore, according to another aspect of the present invention, there is also provided a battery device including the secondary battery according to one aspect of the present invention described above and the pressurizing member that pressurizes the power-generating element of the secondary battery in the direction of lamination.
As illustrated in
According to the battery device of the present aspect, the laminate type battery 10 is in a state of being pressurized in a direction of lamination of the power-generating element 21 at the time of operating the battery. As a result, even at the time of operating the battery, it is possible to enjoy the advantages obtained by causing the solid electrolyte layer to contain the binder having a low Young’s modulus, as described with reference to
Hereinbelow, the present invention will be described in more detail with reference to Examples. However, the technical scope of the present invention is not limited to the following Examples. The following operation was performed inside an argon globe box (23° C., moisture: 0.1 ppm or less, oxygen concentration: 10 ppm or less) having a dew point of -70° C. or lower. The Young’s modulus of the binder used in each of the following experimental examples was measured in the following manner.
First, the Young’s modulus was measured by the nanoindentation method using a nanoindenter “TI 980” manufactured by Hysitron Inc. as a measuring device. As the measurement indenter, a spherical diamond indenter having an indenter tip radius of 100 µm was used. The measurement conditions were as follows:
In the measurement, a binder to be measured for its Young’s modulus was fixed to a glass substrate with an adhesive, and then the substrate was fixed to a sample stage with a vacuum chuck. Then, the relationship between the indentation depth and the indentation load was measured under the measurement conditions described above, and the relationship between the indentation strain and the average contact pressure was determined from the obtained measurement value (stress-strain curve). From the slope of the stress-strain curve thus determined, the composite elastic modulus Er at the time of pushing was determined based on Hertz contact equation, and a yield contact pressure Py was determined from the yield point. The Hertz contact equation is expressed by the following equation. Hertz contact equation
where P represents the indentation load [mN], Er represents the composite elastic modulus [GPa], R represents the indenter tip radius [µm], and h represents the indentation depth [nm].
Then, a Poisson’s ratio v of the sample was assumed based on the value of the composite elastic modulus Er obtained above, the Young’s modulus value was calculated using the following equation. The value of the Young’s modulus of the binder used in each of the experimental examples is shown in Table 1 below.
where E is a Young’s modulus [GPa] of a sample (binder), v is a Poisson’s ratio of the sample (binder) (ratio between longitudinal strain and transverse strain when a load is applied to the sample (binder)), and Er is the composite elastic modulus [GPa] of the sample (binder) calculated above. Further, vi is a Poisson’s ratio (0.06) of the diamond indenter, and Ei is a Young’s modulus (1141 [GPa]) of the diamond indenter.
An argyrodite type solid electrolyte (Li6PS5Cl) as a lithium ion conductive sulfide solid electrolyte was prepared. 100 mg of this solid electrolyte was weighed, put in a Macor tube with a size of 10 mm cp so as to be sandwiched between aluminum foils (thickness: 20 µm) functioning as electrodes, and uniaxially press-molded at 300 to 400 [MPa] at 25° C. to produce a blocking cell (deactivated cell) having a configuration of aluminum foil (20 µm)/solid electrolyte layer (600 µm)/aluminum foil (20 µm).
Styrene-butadiene rubber (SBR) having a Young’s modulus of 1229 [MPa] was prepared as a binder. Then, a dehydrated 1,3,5-trimethylbenzene solution in which 10.0 mass% of styrene-butadiene rubber produced in advance was dissolved was mixed with the binder so that the amount of the binder was 5 mass% with respect to 100 mass% of the same argyrodite type solid electrolyte (Li6PS5Cl) described above to prepare a primary mixed liquid. Further, a secondary mixed liquid was prepared by adding an appropriate amount of dehydrated 1,3,5-trimethylbenzene to the primary mixed liquid for viscosity adjustment. Furthermore, in order to improve the dispersibility of the mixed powder and the binder, the mixed powder was charged into a planetary centrifugal mixer and stirred at 2000 rpm for 4 minutes to prepare an electrolyte layer coating liquid.
An aluminum current collecting foil having a thickness of 20 µm was placed on an applicator on the table, and the electrolyte layer coating liquid prepared above was applied onto the aluminum current collecting foil using a bar coater so that the gap was 230 µm. Thereafter, the resultant was dried on a hot plate at 80° C. for 10 minutes, and then vacuum-dried at 80° C. for 12 hours to form a solid electrolyte layer. The total thickness of the solid electrolyte layer after drying was around 80 µm.
Two sheets of the solid electrolyte layer produced above were punched out together with the aluminum current collecting foil with a punching machine with a size of φ 10 mm, and these layers were bonded together such that the surfaces of the solid electrolyte layers faced each other. Uniaxial pressing was performed on the solid electrolyte layers at a pressure of 300 MPa using a flat plate pressing machine to produce a blocking cell (deactivated cell) having a configuration of aluminum foil (20 µm)/solid electrolyte layer (80 µm)/aluminum foil (20 µm).
A blocking cell (deactivated cell) of this Comparative Example was produced in the same manner as in Comparative Example 2 described above except that the addition amount of the binder was 10 mass% with respect to 100 mass% of the solid electrolyte.
Styrene-butadiene rubber (SBR) having a Young’s modulus of 600 [MPa] was prepared as a binder. A blocking cell (deactivated cell) of this Comparative Example was produced in the same manner as in Comparative Example 2 described above except that the addition amount of the binder was 2 mass% with respect to 100 mass% of the solid electrolyte.
Polyvinylidene fluoride (PVdF) having a Young’s modulus of 1229 [MPa] was prepared as a binder. Then, a blocking cell (deactivated cell) of this Example was produced in the same manner as in Comparative Example 2 described above except that dehydrated butyl butyrate was used as a solvent for dissolving the PVdF binder, and the binder was added and mixed in an amount of 2 mass% with respect to 100 mass% of the same argyrodite type solid electrolyte (Li6PS5Cl) described above.
Styrene-butadiene rubber (SBR) having a Young’s modulus of 0.864 [MPa] was prepared as a binder. Then, a blocking cell (deactivated cell) of this Example was produced in the same manner as in Comparative Example 2 described above except that the binder was added and mixed in an amount of 10 mass% with respect to 100 mass% of the same argyrodite type solid electrolyte (Li6PS5Cl) described above.
A blocking cell (deactivated cell) of this Comparative Example was produced in the same manner as in Example 1 described above except that the addition amount of the binder was 5 mass% with respect to 100 mass% of the solid electrolyte.
A blocking cell (deactivated cell) of this Comparative Example was produced in the same manner as in Example 1 described above except that the addition amount of the binder was 3 mass% with respect to 100 mass% of the solid electrolyte.
A blocking cell (deactivated cell) of this Comparative Example was produced in the same manner as in Example 1 described above except that the addition amount of the binder was 2 mass% with respect to 100 mass% of the solid electrolyte.
Polyvinylidene fluoride (PVdF) having a Young’s modulus of 6.98 [MPa] was prepared as a binder. Then, a blocking cell (deactivated cell) of this Example was produced in the same manner as in Example 1 described above except that dehydrated butyl butyrate was used as a solvent for dissolving the PVdF binder, and the binder was added and mixed in an amount of 10 mass% with respect to 100 mass% of the same argyrodite type solid electrolyte (Li6PS5Cl) described above.
A blocking cell (deactivated cell) of this Example was produced in the same manner as in Example 5 described above except that the addition amount of the binder was 3 mass% with respect to 100 mass% of the solid electrolyte.
A blocking cell (deactivated cell) of this Example was produced in the same manner as in Example 5 described above except that the addition amount of the binder was 2 mass% with respect to 100 mass% of the solid electrolyte.
A blocking cell (deactivated cell) of this example was produced in the same manner as in Example 7 described above except that polyvinylidene fluoride (PVdF) having a Young’s modulus of 42.4 [MPa] was used as a binder.
A blocking cell (deactivated cell) of this example was produced in the same manner as in Example 7 described above except that polyvinylidene fluoride (PVdF) having a Young’s modulus of 1.29 [MPa] was used as a binder.
A blocking cell (deactivated cell) of this example was produced in the same manner as in Example 7 described above except that polyvinylidene fluoride (PVdF) having a Young’s modulus of 200 [MPa] was used as a binder.
The effective ion conductivity of the blocking cell (deactivated cell) produced in each of the above-described experimental examples was measured by electrochemical impedance spectroscopy (EIS). Specifically, an impedance analyzer: model 1260A, manufactured by Solartron, was used as a measuring device, and as measurement conditions, the amplitude was set to 10 [mV], and the frequency was set to a range of 1 [MHz] to 0.1 [Hz]. Further, at the time of measurement, a pressing pressure of 100 [MPa] was applied in a direction of lamination of the sample. The resistance value was obtained from the intercept with the X-axis (real axis) of the Cole-Cole plot acquired by such EIS measurement, and normalized based on the cross-sectional area and the thickness of the sample to calculate the effective ion conductivity [S/cm]. The results are shown in Table 1 below. Table 1 also shows relative values in a case where the value of the effective ion conductivity of Comparative Example 1 is 100.
When the blocking cell (deactivated cell) produced in each of the above-described Examples was bent by 90 degrees, whether or not destruction occurred in the sample was visually examined. The results are shown in Table 1 below. In Table 1, “x” indicates that destruction occurred, and “o” indicates that destruction did not occur.
From the results shown in Table 1 and
In addition, comparing the respective Examples, it has been found that in a case where the addition amount of the binder was 3 mass% or more with respect to 100 mass% of the solid electrolyte, no destruction occurred in the sample, and this is preferred. It is presumed that this effect was obtained by a situation in which the flexibility of the solid electrolyte layer of the sample was also improved with an increase in the addition amount of the binder (having a small Young’s modulus and being flexible).
10, 10a
10
b
11
11′
11″
13
15
17
19
21
25
27
29
100
200
300
400
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2020/000526 | 6/12/2020 | WO |
