Lithium ion battery

Abstract

To provide a lithium ion battery including a novel electrolyte layer.SOLUTION: A lithium ion battery includes an electrolyte layer between a negative electrode layer and a positive electrode layer. The electrolyte layer includes a gel and a solid material. The gel includes a polymer chain. As the solid material, a solid electrolyte is preferably used or an oxide material may be used. As a solvent of the gel, ion liquid is preferably used. In the gel, the polymer chain preferably has a three-dimensional mesh-shaped structure. Thus, liquid spill is suppressed.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to lithium-ion batteries.

[0002] Furthermore, the present invention is not limited to the above-mentioned fields, but relates to semiconductor devices, display devices, light-emitting devices, energy storage devices, lighting devices, electronic devices, vehicles, and methods for manufacturing the same. The above-mentioned semiconductor devices, display devices, light-emitting devices, energy storage devices, lighting devices, electronic devices, and vehicles can be supplied with the lithium-ion battery of the present invention as a necessary power source. For example, the above-mentioned electronic devices include information terminal devices equipped with lithium-ion batteries. Furthermore, the above-mentioned energy storage devices include stationary energy storage devices.

[0003] A lithium-ion battery (sometimes referred to as a lithium-ion secondary battery) refers to a battery that uses lithium ions as carrier ions, but the carrier ions in this invention are not limited to lithium ions. For example, alkali metal ions or alkaline earth metal ions can be used as carrier ions in this invention, and specifically, sodium ions or magnesium ions, etc., can be applied. In this case, lithium ions can be read as sodium ions or magnesium ions, etc. [Background technology]

[0004] Lithium-ion batteries use organic solvents with high lithium-ion conductivity as the electrolyte. However, these organic solvents can leak from the lithium-ion battery, potentially causing ignition or fire. Efforts are being made to resolve these issues related to electrolyte leakage.

[0005] For example, Patent Document 1 states that by using an electrolyte-containing gel layer, the electrolyte is retained in the gel matrix, and leakage of the electrolyte is suppressed.

[0006] Patent Document 2 discloses a semi-solid electrolyte layer, in which a low-viscosity organic solvent is added to reduce the viscosity of the semi-solid electrolyte. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 00 / 13252 Pamphlet [Patent Document 2] Japanese Patent Publication No. 2019-212576 [Overview of the project] [Problems that the invention aims to solve]

[0008] Patent Document 1 proposes a method of coating an electrolyte-containing gel layer in a sol state onto an active material layer because the electrolyte does not sufficiently permeate the active material layer. Furthermore, to achieve the sol state, a thermoreversible gel is used in the gel electrolyte composition, and the heating temperature for sol formation is described as 35 to 95°C. However, considering the possibility of lithium-ion batteries being exposed to high temperatures, thermoreversible gels were unsuitable.

[0009] In Patent Document 2, the viscosity of the semi-solid electrolyte is reduced by adding a low-viscosity organic solvent, but this does not solve the problem of leakage. Furthermore, in Patent Document 2, PDVF is mixed as a binder, and there are concerns that the capacity may decrease due to the binder, which can act as a resistive component.

[0010] In view of the above, one of the objectives of the present invention is to provide a new lithium-ion battery in which leakage is suppressed.

[0011] Furthermore, the problems described above do not preclude the existence of other problems. Moreover, the problems described above are considered independent of each other, and it is not necessary to solve all of them by one aspect of the present invention. In addition, it is possible to extract problems other than those described above from the description in the specification, drawings, and claims (collectively referred to as "this specification, etc."). [Means for solving the problem]

[0012] To solve the above problems, one aspect of the present invention is a lithium-ion battery having an electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the electrolyte layer comprises a gel and a solid material, and the gel has polymer chains.

[0013] Another aspect of the present invention is a lithium-ion battery having an electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the electrolyte layer comprises a gel and a solid electrolyte, the gel having polymer chains, and the solid electrolyte may be LLZAO.

[0014] Another aspect of the present invention is a lithium-ion battery having an electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the electrolyte layer comprises a gel and an oxide material, the gel having polymer chains, and the oxide material may be magnesium oxide.

[0015] In one embodiment of the present invention, the electrolyte layer is preferably in the form of a sheet.

[0016] A gel according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent is preferably an ionic liquid.

[0017] A gel according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent is preferably an ionic liquid in which a lithium salt is dissolved.

[0018] A gel according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent preferably contains EMI-FSI in which LiFSI is dissolved.

[0019] In a gel according to one aspect of the present invention, it is preferable that the polymer chains form a three-dimensional network structure.

[0020] Another aspect of the present invention is a lithium-ion battery having a semi-solid electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the semi-solid electrolyte layer has a solid material and the semi-solid electrolyte layer has polymer chains.

[0021] Another aspect of the present invention is a lithium-ion battery having a semi-solid electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the semi-solid electrolyte layer has a solid electrolyte and polymer chains, and the solid electrolyte preferably has LLZAO.

[0022] Another aspect of the present invention is a lithium-ion battery having a semi-solid electrolyte layer located between a negative electrode layer and a positive electrode layer, wherein the semi-solid electrolyte layer has an oxide material and polymer chains, and the oxide material preferably has magnesium oxide.

[0023] In one embodiment of the present invention, the semi-solid electrolyte layer is preferably in the form of a sheet.

[0024] A semi-solid electrolyte layer according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent is preferably an ionic liquid.

[0025] A semi-solid electrolyte layer according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent preferably has an ionic liquid in which a lithium salt is dissolved.

[0026] A semi-solid electrolyte layer according to one aspect of the present invention comprises a polymer chain and a solvent, wherein the solvent preferably contains EMI-FSI in which LiFSI is dissolved.

[0027] In a gel according to one aspect of the present invention, it is preferable that the polymer chains form a three-dimensional network structure.

[0028] In another embodiment of the present invention, a separator is preferably provided between the positive electrode layer and the negative electrode layer, and the semi-solid electrolyte layer is preferably located between the separator and the positive electrode layer, or between the separator and the negative electrode layer.

[0029] In another embodiment of the present invention, it is preferable that the lithium-ion battery has a separator between the positive and negative electrode layers and has a bent shape. [Effects of the Invention]

[0030] According to one aspect of the present invention, a lithium-ion battery in which leakage is suppressed can be provided.

[0031] Furthermore, the effects described above do not preclude the existence of other effects. Also, the effects described above are considered independent of each other, and one aspect of the present invention does not need to exhibit all of the effects described above. Moreover, it is possible to extract effects other than those described above from this specification and other documents. [Brief explanation of the drawing]

[0032] [Figure 1] Figures 1(A) to 1(C) illustrate a lithium-ion battery according to one embodiment of the present invention. [Figure 2] Figure 2 illustrates a lithium-ion battery according to one embodiment of the present invention. [Figure 3] Figure 3 illustrates a lithium-ion battery according to one embodiment of the present invention. [Figure 4] Figure 4 illustrates a manufacturing apparatus for a lithium-ion battery according to one embodiment of the present invention. [Figure 5] Figures 5(A) and 5(B) illustrate a laminate-type lithium-ion battery according to one embodiment of the present invention. [Figure 6] Figures 6(A) to 6(C) illustrate a coin-type lithium-ion battery according to one embodiment of the present invention. [Figure 7] Figures 7(A) to 7(D) illustrate a cylindrical lithium-ion battery and energy storage system according to one embodiment of the present invention. [Figure 8] Figures 8(A) to 8(C) illustrate a lithium-ion battery according to one embodiment of the present invention. [Figure 9] Figures 9(A) to 9(C) illustrate a lithium-ion battery according to one embodiment of the present invention. [Figure 10] Figures 10(A) to 10(C) illustrate an electric vehicle according to one embodiment of the present invention. [Figure 11] Figures 11(A) to 11(D) illustrate a transport vehicle according to one embodiment of the present invention. [Figure 12] Figures 12(A) to 12(C) illustrate a motorcycle and the like according to one embodiment of the present invention. [Figure 13] Figures 13(A) to 13(D) illustrate an electronic device, etc., according to one embodiment of the present invention. [Figure 14] Figures 14(A) to 14(D) show examples of space equipment. [Figure 15] Figures 15(A) to 15(D) illustrate a bent lithium-ion battery according to one embodiment of the present invention. [Figure 16] Figure 16 illustrates a lithium-ion battery according to one embodiment of the present invention. [Figure 17] Figures 17(A) and 17(B) are perspective views showing an example of an aircraft according to one aspect of the present invention. Figure 17(C) is a cross-sectional view showing an example of an aircraft according to one aspect of the present invention. [Figure 18] Figures 18(A) and 18(B) are perspective views showing an example of an aircraft according to one embodiment of the present invention. [Figure 19] Figure 19 is a chart of nuclear magnetic resonance (1H NMR). [Figure 20] Figures 20(A) to 20(C) are photographs showing the process of preparing the electrolyte layer. [Figure 21] Figure 21 is a graph showing the discharge capacity of Sample 1 to Sample 3. [Figure 22] Figure 22 is a graph showing the discharge capacities of Sample 3 and Sample 4. [Modes for carrying out the invention]

[0033] Embodiments will be described in detail with reference to the drawings. However, it will be readily apparent to those skilled in the art that the present invention is not limited to the following description, and that its form and details can be modified in various ways without departing from the spirit and scope of the present invention. Accordingly, the present invention is not to be interpreted as being limited to the contents of the embodiments shown below. In addition, in the configuration of the invention described below, the same reference numerals are used in common between different drawings for the same parts or parts having similar functions, and the repetition of their descriptions may be omitted.

[0034] In this specification, ordinal numbers such as "first," "second," etc., are used to avoid confusion of constituent elements and do not indicate order or rank, such as process order or layering order. Furthermore, even if an ordinal number is not used for a term in this specification, it may be used in the claims to avoid confusion of constituent elements. Also, even if an ordinal number is used for a term in this specification, a different ordinal number may be used in the claims. Furthermore, even if an ordinal number is used for a term in this specification, the ordinal number may be omitted in the claims, etc.

[0035] In this specification, the phrase "A and / or B" may be used, but this is just one example of how it can refer to A alone, B alone, or A and B together.

[0036] In this specification, "high temperature" refers to a temperature higher than 25°C, and "room temperature" refers to a temperature higher than 0°C and 25°C or lower.

[0037] In this specification, the term "electrolyte layer" refers to a layer that exhibits sufficient ionic conductivity to function as a battery, and is free of liquid. Ionic conductivity typically includes lithium ion conductivity. Furthermore, in the case of an electrolyte layer containing a lithium salt, the ionic conductivity of the lithium salt anion may also be included in the ionic conductivity.

[0038] In this specification, "semi-solid" refers to an intermediate state between liquid and solid at room temperature, for example, 25°C. In other words, a "semi-solid" is a state that possesses solid properties, such as small volume change at room temperature, for example, 25°C, while also having some liquid-like properties, such as flexibility. However, expansion and contraction may occur even in semi-solids with small volume changes due to the insertion and deinsertion of carrier ions. Furthermore, volume expansion may occur even in semi-solids with small volume changes at high temperatures. As long as these conditions are met, a semi-solid may be composed of one material or multiple materials. Semi-solids composed of multiple materials include those in which a liquid is impregnated into a porous solid.

[0039] Furthermore, in this specification, the term "semi-solid" includes "gels." In this specification, "gels" include "physical gels" and "chemical gels." A "physical gel" refers to a material crosslinked by weak bonds with a bond energy such as thermal energy. Due to the weak bonds, physical gels are capable of sol-gel transitions, and a three-dimensional network structure is often not observed. On the other hand, in "chemical gels," the polymer chains forming the three-dimensional network structure are linked by covalent bonds or coordination bonds, and sol-gel transitions are often not possible. A crosslinking agent may be present in part of the polymer chains forming the three-dimensional network structure. Of course, a polymer chain forming a three-dimensional network structure can be formed even without the presence of a crosslinking agent. In this specification, "crosslinking agent" refers to a material that has the function of linking polymers together.

[0040] Furthermore, in this specification, "gel" preferably refers to a polymer having a three-dimensional network structure insoluble in a solvent, and its swollen form. In one embodiment of the present invention, the electrolyte layer may use a polymer compound with a molecular weight of 5,000, preferably more than 10,000. The above polymer can be said to have polymer chains that form a three-dimensional network structure. The three-dimensional network structure is also sometimes called a crosslinked structure, and polymers having a three-dimensional network structure are sometimes called crosslinked polymers.

[0041] The swollen body mentioned above refers to a gel in which the solvent has been swollen, and may be referred to as a "swollen gel" in this specification. The swelling capacity of a swollen gel is finite and differs from the state in which polymers are dispersed in a solvent. Furthermore, a swollen gel can exhibit a firmness ranging from a viscous liquid to something close to a solid, making it suitable for an electrolyte layer in one embodiment of the present invention. Unless otherwise specified in this specification, the term "gel" includes swollen gels.

[0042] In this specification, the value representing the magnitude of viscosity is referred to as "viscosity." In one embodiment of the present invention, when a semi-solid electrolyte layer is used as the electrolyte layer, the viscosity of the semi-solid electrolyte layer should preferably be 1 mPaS or more and 80 mPaS or less at room temperature, for example at 25°C, preferably 5 mPaS or more and 70 mPaS or less, and more preferably 10 mPaS or more and 60 mPaS or less. However, these are just examples, and it is not necessary to satisfy the above viscosity as long as leakage from the lithium-ion battery is suppressed.

[0043] The electrolyte layer in one aspect of the present invention may contain one or more materials selected from ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes, which should exhibit sufficient ionic conductivity for use as a battery. Specifically, one or more materials selected from ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes should exhibit an ionic conductivity of 0.1 mS / cm to 20 mS / cm, preferably 1 mS / cm to 15 mS / cm, and more preferably 5 mS / cm to 10 mS / cm at room temperature, for example, 25°C. The ionic conductivity of ionic liquids and organic solvents can be measured using a conductivity meter. Conductivity meters can measure not only carrier ions but also lithium salt anions. The ionic conductivity of solid electrolytes and semi-solid electrolytes can be determined by the AC impedance method. The ionic conductivity of semi-solid electrolytes can also include the ionic conductivity of lithium salt anions. However, these are just examples, and it is not necessary to satisfy the above values ​​as long as the battery can be charged and discharged as a lithium-ion battery.

[0044] In this specification, the "positive electrode layer" includes a positive electrode current collector and a layer having positive electrode active material, and the "negative electrode layer" includes a negative electrode current collector and a layer having negative electrode active material. In this specification, the layer having positive electrode active material may be referred to as the "positive electrode active material layer," and the layer having negative electrode active material may be referred to as the "negative electrode active material layer," distinguishing them from the positive electrode layer and the negative electrode layer, respectively. Since an electrolyte layer, which is one aspect of the present invention, can suppress leakage from a lithium-ion battery, the components other than the electrolyte layer, such as the positive electrode layer and / or negative electrode layer, are not limited to the configurations disclosed in this specification.

[0045] The electrolyte layer according to one embodiment of the present invention may exhibit insulating properties. When it exhibits insulating properties, short circuits between the positive electrode layer and the negative electrode layer in a lithium-ion battery can be suppressed, thus eliminating the need for a separator. One or more selected from the ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes described above may exhibit insulating properties. Furthermore, an inorganic material may be used as the solid material to create an electrolyte layer that exhibits insulating properties.

[0046] (Embodiment 1) Based on the above, Embodiment 1 will describe a lithium-ion battery, which is one aspect of the present invention, with reference to the drawings. In the drawings of the lithium-ion battery shown in this embodiment, straight lines are used for the boundary between the electrolyte layer and the positive electrode layer, and the boundary between the electrolyte layer and the negative electrode layer, etc., but straight lines are not observed in actual lithium-ion batteries. Also, in the drawings above, straight lines are used for the boundary between the positive electrode current collector and the positive electrode active material layer, and the boundary between the negative electrode current collector and the negative electrode active material layer, etc., but straight lines are not observed in actual lithium-ion batteries.

[0047] Figure 1(A) shows a perspective view of a lithium-ion battery 100. The lithium-ion battery 100 has a negative electrode layer 106, a positive electrode layer 107, and an electrolyte layer 103 located between them. The negative electrode layer 106 has a negative electrode current collector 101 and a negative electrode active material layer 102, and the positive electrode layer 107 has a positive electrode current collector 105 and a positive electrode active material layer 104. The electrolyte layer 103 is preferably in the form of a sheet as shown in Figure 1(A). The negative electrode layer 106 and / or the positive electrode layer 107 are also preferably in the form of a similar sheet. In this specification, "sheet-like" does not limit the thickness, width, length, etc., but can have any shape with any thickness. That is, the thickness, width, length, etc. of the negative electrode layer 106, the positive electrode layer 107, and the electrolyte layer 103 do not need to match as shown in Figure 1(A). During the manufacturing process described later, the sheet-like electrolyte layer 103 is preferable because it is easy to handle, similar to the negative electrode layer 106 and the positive electrode layer 107. The electrolyte layer 103 only needs to be sheet-like at room temperature, for example, 25°C. Therefore, the electrolyte layer 103 does not need to maintain its sheet-like form at high temperatures, for example, 45°C. In order to be sheet-like, it is preferable for the electrolyte layer to have a "semi-solid" state. An electrolyte layer 103 having a semi-solid state is sometimes called a "semi-solid electrolyte layer".

[0048] The sheet-like electrolyte layer 103 comprises a gel 115 and a solid material 113. The gel 115 preferably uses polymer chains 114 forming a three-dimensional network structure, as shown in Figure 1(B), but it does not necessarily have to be a three-dimensional network structure. Furthermore, the gel 115 contains a solvent 111 in addition to the polymer chains 114. When forming a three-dimensional network structure, the solvent 111 can be said to be located between the polymer chains 114. Considering the swelling gel, the solvent 111 may be located not only between the polymer chains 114, but also around the polymer chains 114. Therefore, the state of the solvent 111 being located both between and around the polymer chains 114 is sometimes described as the solvent 111 being dispersed around the polymer chains 114.

[0049] The gel 115 may exhibit adhesive properties. Therefore, it is preferable that the gels adhere to each other and can be processed into a sheet without mixing a binder into the electrolyte layer 103.

[0050] Solvent 111 can be any liquid (sometimes referred to as a liquid material). Furthermore, if sufficient ionic conductivity is desired for a battery, an ionic liquid and / or organic solvent may be used as solvent 111. The ionic conductivity of ionic liquids and organic solvents can be determined by referring to values ​​measured at 25°C. Additionally, in the case of an ionic liquid requiring a lithium salt, solvent 111 should be an ionic liquid in which the lithium salt is dissolved; similarly, in the case of an organic solvent requiring a lithium salt, solvent 111 should be an organic solvent in which the lithium salt is dissolved. In this specification, "lithium salt" refers to a substance that dissociates into a carrier ion (a positive ion) and an anion in an ionic liquid or organic solvent. The carrier ion is typically a lithium ion.

[0051] Any solid material can be used for the solid material 113. Furthermore, if sufficient ionic conductivity is desired for the battery, a solid electrolyte may be used for the solid material 113. The ionic conductivity of the solid electrolyte can be determined by referring to the value measured at 25°C. Solid electrolytes that do not require lithium salts are suitable for the solid material 113. Additionally, if the ionic conductivity of the solid material 113 is high, it becomes easier to apply liquids other than ionic liquids and organic solvents to the solvent 111.

[0052] A semi-solid electrolyte may be used in the electrolyte layer 103 instead of the solid electrolyte, or in addition to the solid electrolyte. In the case of a semi-solid electrolyte requiring a lithium salt, a semi-solid electrolyte in which the lithium salt is dissolved may be used.

[0053] Furthermore, inorganic materials can also be used as the solid material 113. Examples of inorganic materials include oxide materials, such as magnesium oxide and titanium oxide. The inorganic material should be mixed into the gel in powder form, typically in particulate form.

[0054] The solid material 113 is preferably mixed into the electrolyte layer 103 in powder form, typically in particulate form. The solid material 113 described above is preferable because it can increase the viscosity of the electrolyte layer 103. In particular, since the solid material does not easily change state even at high temperatures, it is preferable because it can suppress the decrease in viscosity of the electrolyte layer even when the lithium-ion battery 100 is exposed to high temperatures.

[0055] Here, we consider the ionic conductivity of the solvent 111 and the ionic conductivity of the solid material 113. For example, in the electrolyte layer 103, it is preferable that the ionic conductivity of the solvent 111 is higher than the lithium ion conductivity of the solid material 113. The solvent 111 constitutes the gel 115. It is clear that the gel 115 has a larger contact area with the positive electrode layer and / or negative electrode layer compared to the solid material 113. Since the positive electrode layer and the negative electrode layer each contain a positive electrode active material and a negative electrode active material, the gel 115 has a large contact area with the positive electrode active material and the negative electrode active material at the boundary where the contact area should be considered. It is preferable to use a solvent 111 with high ionic conductivity in the gel 115, which has such a large contact area, as this can lower the resistance generated at the boundary. Furthermore, when the ionic conductivity of the solvent 111 is sufficiently high, it becomes easier to apply an inorganic material as the solid material 113.

[0056] Next, we consider the ratio of solvent 111 to solid material 113 in the electrolyte layer 103. For example, in the electrolyte layer 103, it is preferable that the ratio of solid material 113 is higher than the ratio of solvent 111, as this can lower the viscosity of the electrolyte layer 103. On the other hand, in the electrolyte layer 103, it is preferable that the ratio of solvent 111 is higher than the ratio of solid material 113, as this increases ionic conductivity. The ratio can be expressed as a weight ratio or a volume ratio.

[0057] The ionic liquids, organic solvents, solid electrolytes, semi-solid electrolytes, and inorganic materials described above all exhibit insulating properties. Therefore, an electrolyte layer 103 having one or more selected from the ionic liquids, organic solvents, solid electrolytes, semi-solid electrolytes, and inorganic materials can also exhibit insulating properties. A lithium-ion battery 100 equipped with an insulating, sheet-like electrolyte layer 103 is preferable because it eliminates the need for a separator, as shown in Figure 1(A). Eliminating the separator makes the lithium-ion battery 100 thinner and / or lighter, and is also expected to improve its capacity.

[0058] Of course, as shown in Figure 1(C), a separator 110 may be placed on the lithium-ion battery 100. The separator 110 can suppress short circuits between the negative electrode layer 106 and the positive electrode layer 107. For example, if the lithium-ion battery 100 is to be movable, specifically in a bent form, it is advisable to place the separator 110 to enhance the short-circuit suppression effect.

[0059] The configurations of the electrolyte layer 103, the negative electrode layer 106, and the positive electrode layer 107 in Figure 1(C) are the same as in Figure 1(A). However, in the lithium-ion battery 100 shown in Figure 1(C), a configuration example is shown in which two electrolyte layers are arranged with a separator 110 in between. Therefore, these are distinguished and the one located on the negative electrode layer 106 side is called the first electrolyte layer 103_1, and the one located on the positive electrode layer 107 side is called the second electrolyte layer 103_2.

[0060] The details of the first electrolyte layer 103_1 and the second electrolyte layer 103_2 can be the same as those of the electrolyte layer 103 in Figure 1(A). That is, the first electrolyte layer 103_1 and the second electrolyte layer 103_2 can each have the gel 115 shown in Figure 1(B) and the solid material 113 shown in Figure 1(A).

[0061] Furthermore, the first electrolyte layer 103_1 may have a different configuration from the second electrolyte layer 103_2. For example, if the first electrolyte layer 103_1 has the same configuration as the electrolyte layer 103 in Figure 1(A), the gel and / or solid material of the second electrolyte layer 103_2 may be different from that of the electrolyte layer 103 in Figure 1(A). Of course, the second electrolyte layer 103_2 may have the same configuration as the electrolyte layer 103 in Figure 1(A), while the gel and / or solid material of the first electrolyte layer 103_1 may be different from that of the electrolyte layer 103 in Figure 1(A).

[0062] The separator 110 shown in Figure 1(C) can be made of known materials, but may also have a gel, similar to the electrolyte layer 103 in Figure 1(A). Ionic liquids and / or organic solvents can be used as the solvent for the gel. Furthermore, the separator 110 may also have a solid material, similar to the electrolyte layer 103 in Figure 1(A). Solid electrolytes and / or inorganic materials can be used as the solid material. Since the separator 110 should exhibit high insulating properties, inorganic materials are preferable, and the inorganic material should be mixed in a higher proportion than the gel.

[0063] If the separator 110 and the first electrolyte layer 103_1 and / or the second electrolyte layer 103_2 use the same material, the common material may dissolve at their boundaries. Dissolution eliminates the boundary, suppressing interfacial resistance, which is preferable. In this case, the separator 110 shown in Figure 1(C), the first electrolyte layer 103_1, and the second electrolyte layer 103_2 become a single integrated unit, performing both the functions of a separator and an electrolyte layer. This enables miniaturization of the lithium-ion battery 100.

[0064] Next, we consider the thickness of the separator 110. For example, if the thickness of the separator 110 is smaller than the thickness of the first electrolyte layer 103_1 and / or the second electrolyte layer 103_2, it is preferable that the lithium-ion battery 100 is easier to bend. Also, if the thickness of the separator 110 is greater than the thickness of the first electrolyte layer 103_1 and / or the second electrolyte layer 103_2, it is preferable that a short circuit between the positive electrode layer 107 and the negative electrode layer 106 can be suppressed.

[0065] As an example of a new configuration, there is a lithium-ion battery 100 in which the first electrolyte layer 103_1 is omitted, as shown in Figure 1(C). There is also a lithium-ion battery 100 in which the second electrolyte layer 103_2 is omitted, as shown in Figure 1(C). In other words, one of the electrolyte layers in Figure 1(C) can be omitted, thereby achieving thinner and / or lighter lithium-ion battery 100.

[0066] Next, using Figure 2, the configuration of the positive electrode active material layer 104 of the lithium-ion battery 100 shown in Figure 1(A) or Figure 1(C) will be explained. A cross-sectional view will be used in Figure 2.

[0067] The positive electrode active material layer 104 shown in Figure 2 comprises a positive electrode active material 117, a binder (sometimes referred to as a "binding agent"), and / or a conductive material (sometimes referred to as a "conductivity imparting agent" or "conductivity aid"). While known materials can be used for these components, preferred materials will be discussed later.

[0068] Furthermore, in order to exhibit sufficient ionic conductivity as a battery, the positive electrode active material layer 104 may contain one or more selected from ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes. Ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes are sometimes collectively referred to as "electrolytes" in this specification. An electrolyte is a substance that exhibits sufficient ionic conductivity as a battery, and is not limited in any way to the state of the substance (liquid, solid, or semi-solid).

[0069] Even when an ionic liquid and / or organic solvent, which are liquid materials at 25°C, is used as the electrolyte for the positive electrode active material layer 104, leakage from the lithium-ion battery 100 can be sufficiently suppressed by the electrolyte layer 103 described using Figure 1(A) or Figure 1(C).

[0070] Furthermore, the positive electrode active material layer 104 may have a gel as the electrolyte, using an ionic liquid and / or an organic solvent as the solvent. In addition to the gel, the positive electrode active material layer 104 may also have a solid material. The ionic liquid and / or organic solvent can be the same material as the solvent 111 of the electrolyte layer 103. The solid material can be the same material as the solid material 113 of the electrolyte layer 103. When a common material is used, the common material may dissolve at the boundary between the positive electrode active material layer 104 and the electrolyte layer 103. Dissolution eliminates the boundary, which is preferable as it suppresses interfacial resistance.

[0071] Furthermore, since the gel exhibits adhesive properties, it can bind the positive electrode active material 117 and / or the conductive material. In other words, using the gel in the positive electrode active material layer 104 is preferable because it eliminates the need for a binder. This enables the lithium-ion battery 100 to be made thinner and / or lighter.

[0072] Next, using Figure 3, the configuration of the negative electrode active material layer 102 of the lithium-ion battery 100 shown in Figure 1(A) or Figure 1(C) will be explained. A cross-sectional view will be used in Figure 3.

[0073] The negative electrode active material layer 102 shown in Figure 3 comprises a negative electrode active material 119, a binder, and / or a conductive material. Known materials can be used for these components, but preferred materials will be discussed later.

[0074] Furthermore, in order to exhibit sufficient ionic conductivity as a battery, the negative electrode active material layer 102 may contain one or more selected from ionic liquids, organic solvents, solid electrolytes, and semi-solid electrolytes.

[0075] Even when an ionic liquid and / or organic solvent, which are liquid materials at 25°C, is used as the electrolyte for the negative electrode active material layer 102, leakage from the lithium-ion battery 100 can be sufficiently suppressed by the electrolyte layer 103 described using Figure 1(A) or Figure 1(C).

[0076] Furthermore, the negative electrode active material layer 102 may have a gel using an ionic liquid and / or organic solvent as the electrolyte. In addition to the gel, the negative electrode active material layer 102 may also have a solid material. The ionic liquid and / or organic solvent can be the same material as the solvent 111 of the electrolyte layer 103. The solid material can be the same material as the solid material 113 of the electrolyte layer 103. When a common material is used, the common material may dissolve at the boundary between the negative electrode active material layer 102 and the electrolyte layer 103. Dissolution eliminates the boundary, which is preferable as it suppresses interfacial resistance.

[0077] Furthermore, since the gel exhibits adhesive properties, it can bind the negative electrode active material 119 and / or conductive material. In other words, using the gel in the negative electrode active material layer 102 is preferable because it eliminates the need for a binder when applied to the negative electrode active material layer 102. This enables the lithium-ion battery 100 to be made thinner and / or lighter.

[0078] <Ionic Liquid> This section explains ionic liquids. Ionic liquids are sometimes referred to as room-temperature molten salts and contain both cations and anions.

[0079] <Anion> Let's explain anions. Anions include halide ions, tetrafluoroborates, hexafluorophosphates, bis(trifluoromethylsulfonyl)amides, or bis(fluorosulfonyl)imides.

[0080] In one embodiment of the present invention, one or more anions can be used in the ionic liquid, such as monovalent amide anions, monovalent methide anions, fluorosulfonic acid anions, perfluoroalkyl sulfonic acid anions, tetrafluoroborate anions, perfluoroalkyl borate anions, hexafluorophosphate anions, perfluoroalkyl phosphate anions, or tetrafluoroborate anions.

[0081] Monovalent amide anions have the general formula (C n F 2n+1 SO2)2N- (where n is between 0 and 3)

[0082] In the general formula above, when n is 0, it is a bis(fluorosulfonyl)imide anion, represented by the structural formula (H11). The abbreviation for bis(fluorosulfonyl)imide anion is FSI or FSA.

[0083] [ka]

[0084] In the general formula above, when n is 1, it is a bis(trifluoromethanesulfonyl)imide anion, represented by the structural formula (H12). The abbreviation for bis(trifluoromethanesulfonyl)imide anion is TFSI or TFSA.

[0085] [ka]

[0086] Another example of a monovalent cyclic amide anion is 4,4,5,5-tetrafluoro-1,3,2-dithiazolidinetetraoxide anion, which is represented by the structural formula (H13).

[0087] [ka]

[0088] Monovalent methide anions have the general formula (C n F 2n+1 SO2)3C - (where n is between 0 and 3)

[0089] One example of a monovalent cyclic methide anion is 4,4,5,5-tetrafluoro-2-[(trifluoromethyl)sulfonyl]-1,3-dithiolanetetraoxide anion, which is represented by the structural formula (H14).

[0090] [Chemical]

[0091] The fluoroalkyl sulfonate anion is represented by the general formula (C m F 2m+1 SO3) - (where m is 0 or more and 4 or less).

[0092] In the above general formula, when m is 0, it is a fluorosulfonate anion, and when m is 1, 2, 3, or 4, it is a perfluoroalkyl sulfonate anion.

[0093] The fluoroalkyl borate anion is represented by the general formula {BF n (C m H k F 2m+1-k ) 4-n} - (where n is 0 or more and 3 or less, m is 1 or more and 4 or less, and k is 0 or more and 2m or less).

[0094] The fluoroalkyl phosphate anion is represented by the general formula {PF n (C m H k F 2m+1-k ) 6-n} - (where n is 0 or more and 5 or less, m is 1 or more and 4 or less, and k is 0 or more and 2m or less).

[0095] One or more of these anions can be used.

[0096] <Cation> The cation will be described. The basic skeleton of the cation has an imidazolium-based, ammonium-based, pyrrolidinium-based, piperidinium-based, pyridinium-based, or phosphonium-based structure. The ionic liquid with an imidazolium-based basic skeleton of the cation shows a lower viscosity compared to the ammonium-based ionic liquid. When the viscosity is low, the ionic conductivity tends to increase. Furthermore, physical properties such as viscosity can be controlled by the alkyl group or the like in the side chain of the cation.

[0097] An ionic liquid according to one aspect of the present invention has an imidazolium-based cation represented by the general formula (G1). In the general formula (G1), A - This represents one of the anions mentioned above.

[0098] [ka]

[0099] In the above general formula (G1), R 1 R represents an alkyl group with 1 to 10 carbon atoms. 2 ~R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 A represents an alkyl group having 1 to 6 carbon atoms, or an ether group, thioether group, or siloxane having a main chain composed of two or more atoms selected from C, O, Si, N, S, and P. In the above general formula (G1), A - This should preferably be an FSI anion or a TFSI anion.

[0100] An ionic liquid according to one aspect of the present invention has a pyridinium-based cation represented by the general formula (G2). - This represents one of the anions mentioned above.

[0101] [ka]

[0102] In the above general formula (G2), R 6 It has a main chain composed of an alkyl group with 1 to 6 carbon atoms, or two or more atoms selected from C, O, Si, N, S, and P. 7 ~R 11 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 8 or R 9 A can represent a hydroxyl group. In the above general formula (G2), A -It is preferable that it be an FSI anion or a TFSI anion.

[0103] An ionic liquid according to one aspect of the present invention has a quaternary ammonium cation. For example, it has a quaternary ammonium cation represented by general formula (G3). In general formula (G3), A - This represents one of the anions mentioned above.

[0104] [ka]

[0105] In the above general formula (G3), R 28 ~R 31 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom. In the above general formula (G3), A - It is preferable that it be an FSI anion or a TFSI anion.

[0106] An ionic liquid according to one aspect of the present invention has a cation represented by the general formula (G4). In the general formula (G4), A - This represents one of the anions mentioned above.

[0107] [ka]

[0108] In the above general formula (G4), R 12 and R 17 Each of these independently represents an alkyl group with 1 to 3 carbon atoms. 13 ~R 16 Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the above general formula (G4), A - It is preferable that it be an FSI anion or a TFSI anion.

[0109] An ionic liquid according to one aspect of the present invention has a cation represented by the general formula (G5). In the general formula (G5), A - This represents one of the anions mentioned above.

[0110] [ka]

[0111] In the above general formula (G5), R 18 and R 24 Each of these independently represents an alkyl group with 1 to 3 carbon atoms. 19 ~R 23 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the above general formula (G5), A - It is preferable that it be an FSI anion or a TFSI anion.

[0112] An ionic liquid according to one aspect of the present invention has a cation represented by the general formula (G6). In the general formula (G6), A - This represents the anion mentioned above.

[0113] [ka]

[0114] In the above general formula (G6), n and m are 1 to 3, α is 0 to 6, β is 0 to 6, and X or Y represents a linear or side-chain alkyl group having 1 to 4 carbon atoms as a substituent, a linear or side-chain alkoxy group having 1 to 4 carbon atoms, or a linear or side-chain alkoxyalkyl group having 1 to 4 carbon atoms. In the above general formula (G6), A - It is preferable that it be an FSI anion or a TFSI anion.

[0115] An ionic liquid according to one aspect of the present invention has a tertiary sulfonium cation represented by the general formula (G7). In the general formula (G7), A - This represents the anion mentioned above.

[0116] [ka]

[0117] In the above general formula (G7), R 25 ~R 27 Each of these independently represents a hydrogen atom, or an alkyl group with 1 to 4 carbon atoms, or a phenyl group. 25 ~R 27 Each has a main chain composed of two or more atoms independently selected from C, O, Si, N, S, and P. In general formula (G7), A - It is preferable that it be an FSI anion or a TFSI anion.

[0118] An ionic liquid according to one aspect of the present invention has a quaternary phosphonium cation represented by the following general formula (G8). In general formula (G8), A - This represents the anion mentioned above.

[0119] [ka]

[0120] In the above general formula (G8), R 32 ~R 35 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group. 32 ~R 35 Each has a main chain composed of two or more atoms independently selected from C, O, Si, N, S, and P. In general formula (G8), A - It is preferable that it be an FSI anion or a TFSI anion.

[0121] Specific examples of the cation of the above general formula (G1) include structural formulas (111) to (174). Structural formula (111) is a 1-ethyl-3-methylimidazolium cation, abbreviated as EMI. Structural formula (113) is a 1-butyl-3-methylimidazolium cation, abbreviated as BMI.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] Specific examples of the cation of the above general formula (G2) include, for example, structural formulas (701) to (719).

[0129] [ka]

[0130] [ka]

[0131] Specific examples of the cation of the above general formula (G4) include, for example, structural formulas (501) to (520).

[0132] [ka]

[0133] Specific examples of the cation of the above general formula (G5) include, for example, structural formulas (601) to (630).

[0134] [ka]

[0135] [ka]

[0136] Specific examples of the cation of the above general formula (G6) include, for example, structural formulas (301) to (309) and structural formulas (401) to (419).

[0137] [ka]

[0138] [ka]

[0139] Furthermore, structural formulas (301) to (309) and structural formulas (401) to (419) show examples where m is 1 in general formula (G6), but in structural formulas (301) to (309) and structural formulas (401) to (419), m may be replaced with 2 or 3.

[0140] Furthermore, specific examples of the cation of the general formula (G7) mentioned above include structural formulas (201) to (215).

[0141] [ka]

[0142] Because such ionic liquids consist solely of ions, they exhibit strong electrostatic interactions, non-volatility, thermal stability, low gas generation, and high heat resistance. Lithium-ion batteries using these ionic liquids are highly safe as they will not ignite even when exposed to high temperatures.

[0143] <organic solvents> Organic solvents will be described below. Aprotic organic solvents can be used as organic solvents. For example, one or more selected from ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, sultone, etc. can be used.

[0144] In this specification, "carbonate" refers to a compound having at least one carbonate ester in its molecular structure, and unless otherwise specified, includes "cyclic carbonates" and "chain carbonates." Furthermore, "chain" includes both linear and branched chains.

[0145] Furthermore, organic solvents such as fluorinated carbonates or carbonates may be used. Examples of fluorinated carbonates include fluorinated cyclic carbonates (sometimes written as fluorinated cyclic carbonates) or fluorinated chain carbonates. Fluorinated cyclic carbonates or fluorinated chain carbonates (sometimes written as fluorinated chain carbonates) are considered preferable because they have lower viscosity when lithium-ion batteries are operated in low-temperature environments (specifically, below freezing point at 0°C or below).

[0146] It is believed that mixing cyclic fluoride carbonate or fluoride chain carbonate with the aforementioned ionic liquid can broaden the operating temperature range of lithium-ion batteries.

[0147] As the fluorocyclic carbonate, fluoroethylene carbonates such as monofluoroethylene carbonate (fluoroethylene carbonate, FEC, F1EC), difluoroethylene carbonate (DFEC, F2EC), trifluoroethylene carbonate (F3EC), or tetrafluoroethylene carbonate (F4EC) can be used. Note that DFEC has isomers such as cis-4,5 and trans-4,5.

[0148] As the cyclic fluoride carbonate, ethylene fluoride carbonates such as fluoroethylene carbonate (fluoroethylene carbonate, FEC, F1EC), difluoroethylene carbonate (DFEC, F2EC), trifluoroethylene carbonate (F3EC), or tetrafluoroethylene carbonate (F4EC) can be used. Note that DFEC has isomers such as cis-4,5 and trans-4,5. Since all of these cyclic fluoride carbonates have substituents that exhibit electron-withdrawing properties, the solvation energy of lithium ions is considered to be low.

[0149] The following structural formula (H10) is the structural formula for FEC.

[0150] [ka]

[0151] Methyl 3,3,3-trifluoropropionate is an example of a fluorinated chain carbonate. The structural formula (H22) below is that of methyl 3,3,3-trifluoropropionate. The abbreviation for methyl 3,3,3-trifluoropropionate is "MTFP". Since MTFP also has substituents that exhibit electron-withdrawing properties, it is thought to have a low solvation energy of lithium ions.

[0152] [ka]

[0153] Trifluoromethyl 3,3,3-trifluoropropionate is an example of a fluorinated chain carbonate. The structural formula (H23) below is that of trifluoromethyl 3,3,3-trifluoropropionate. Since trifluoromethyl 3,3,3-trifluoropropionate also has substituents that exhibit electron-withdrawing properties, it is thought to have a low solvation energy of lithium ions.

[0154] [ka]

[0155] Trifluoromethyl propionate is an example of a fluorinated chain carbonate. The structural formula (H24) below is that of trifluoromethyl propionate. Since trifluoromethyl propionate also has substituents that exhibit electron-withdrawing properties, it is thought to have a low solvation energy of lithium ions.

[0156] [ka]

[0157] Methyl 2,2-difluoropropionate is an example of a fluorinated chain carbonate. The structural formula (H25) below is that of methyl 2,2-difluoropropionate. Since methyl 2,2-difluoropropionate also has substituents that exhibit electron-withdrawing properties, it is thought to have a low solvation energy of lithium ions.

[0158] [ka]

[0159] In one aspect of the present invention, the electrolyte organic solvent may contain two or more selected from the above-mentioned cyclic fluoride carbonates and fluoride chain carbonates, for example, FEC and MTFP. Even when the lithium-ion battery is exposed to a freezing point below 0°C, the inclusion of FEC and MTFP results in a low solvation energy, preventing the interfacial resistance between the active material and the electrolyte from becoming excessively high. The above-mentioned active material may be either a positive electrode active material or a negative electrode active material.

[0160] <Solid electrolyte> Solid electrolytes will be explained. Solid electrolytes include oxide-based, sulfide-based, or halide-based materials, and mixed materials containing these can also be used.

[0161] Examples of oxide-based solid electrolytes include materials having a perovskite crystal structure, a NASICON crystal structure, a garnet crystal structure, a LISICON crystal structure, or oxide glass or oxide crystallized glass. Materials having a perovskite crystal structure include La 2 / 3-x Li 3x Examples include TiO3 (sometimes written as LLTO, for example, satisfying x=0.1). Furthermore, after micronization processing, the particle size of LLTO can be made between 150 nm and 500 nm, preferably between 200 nm and 300 nm or more. Smaller LLTO particle size is preferable because it makes it easier to thin the electrolyte layer 103. The lithium ion conductivity of LLTO is 10 -3is on the order of S / cm. Materials having a NASICON-type crystal structure include Li 1+X Al X Ti 2-X (PO4)3 (sometimes denoted as LATP, for example, satisfying x = 0.3), Li 1+X Al X Ge 2-X (PO4)3 (sometimes denoted as LAGP, for example, satisfying x = 0.5), etc. The lithium ion conductivity of LATP or LAGP is on the order of 10 -4 S / cm. Materials having a garnet-type crystal structure include Li7La3Zr2O 12 (sometimes denoted as LLZO), Li 6.25 La3Zr2Al 0.25 [[ID=|20]]O 12 (sometimes denoted as LLZAO), etc. The lithium ion conductivity of LLZO or LLZAO is on the order of 10 -4 S / cm. Materials having a LISICON-type crystal structure include Li 14 ZnGe4O 16 etc. Oxide glasses include Li3PO4-Li4SiO4, 50Li4SiO4·50Li3BO3, etc., and oxide crystallized glasses include Li 1.07 Al 0.69 Ti 1.46 (PO4)3, Li 1.5 Al 0.5 Ge 1.5 (PO4)3, etc. The above-mentioned oxide-based solid electrolytes have the advantage of being stable in air.

[0162] As sulfide-based solid electrolytes, there are thio-LISICON-based, sulfide glasses, or sulfide crystallized glasses, etc. Thio-LISICON-based materials include Li 10 GeP2S 12 , Li 3.25 Ge 0.25 P 0.75 S4, etc. Sulfide glasses include 70Li2S·30P2S5, 30Li2S·26B2S3·44LiI, 63Li2S·36SiS2·1Li3PO4, 57Li2S·38SiS2·5Li4SiO4, 50Li2S·50GeS2, etc. Sulfide crystallized glasses include Li7P3S 11 , Li3.25 P 0.95 Examples include S4. Sulfide-based solid electrolytes include materials that exhibit lithium-ion conductivity.

[0163] Examples of halide-based solid electrolytes include LiAlCl4, Li3InBr6, LiF, LiCl, LiBr, and LiI.

[0164] <Semi-solid electrolyte> This section describes semi-solid electrolytes. Examples of semi-solid electrolytes include lithium-ion conductive polymers. In this specification, "lithium-ion conductive polymer" refers to a polymer having conductivity for cations such as lithium. Specifically, a lithium-ion conductive polymer is a polymer compound having polar groups to which cations can coordinate. Preferably, the polar groups include ether groups, ester groups, nitrile groups, carbonyl groups, siloxanes, etc.

[0165] Examples of lithium-ion conductive polymers that can be used include polyethylene oxide (PEO), derivatives having polyethylene oxide as the main chain, polypropylene oxide, polyacrylic acid esters, polymethacrylate esters, polysiloxanes, and polyphosphazenes.

[0166] The lithium-ion conductive polymer may be branched, crosslinked, or copolymerized. The molecular weight of the lithium-ion conductive polymer is preferably, for example, 10,000 or more, and more preferably 100,000 or more.

[0167] In lithium-ion conductive polymers, lithium ions move while changing the polar groups they interact with through partial motion (also called segmental motion) of the polymer chains. For example, in PEO, lithium ions move while changing the oxygen groups they interact with through segmental motion of the ether chains. When the temperature is close to or higher than the melting or softening point of the lithium-ion conductive polymer, the crystalline region dissolves and the amorphous region increases, and the motion of the ether chains becomes more active, resulting in higher ionic conductivity. Therefore, when using PEO as a lithium-ion conductive polymer, it is preferable to perform charging and discharging at 60°C or higher.

[0168] <Inorganic materials> Inorganic materials will now be described. Oxide materials are often used as inorganic materials, and examples of oxide materials include aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, and silicon oxide. In addition, inorganic materials may be mixed with solid electrolytes and / or semi-solid electrolytes and used in the electrolyte layer. For example, a mixture in which the pores of porous aluminum oxide or porous silica are filled with the above-mentioned solid electrolyte may be applied to the electrolyte layer 103.

[0169] <Polymer> Polymers (also written as polymer materials) include poly(dimethylaminoethyl methacrylate) (written as PDMAEMA), poly(4-vinylpyridine), poly(pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene hexafluoride phosphate) (PICPM-PF6), poly(pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene chloride) (PICPM-Cl), poly(pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene iodide) (PICPM-I), and poly(pyridinium-1,4-thiocyanate). Poly(-diyliminocarbonyl-1,4-phenylenemethylene)(PICPM-SCN), poly(pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene)(PICPM-BF4), poly[pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylenebis(trifluoromethanesulfonyl)amide](PICPM-TFSA), and poly(trifluoromethylsulfonylpyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene)(PICPM-OTf) can be used.

[0170] <Crosslinking agent> When crosslinking a polymer using a crosslinking agent, N,N,N',N'-tetra(trifluoromethanesulfonyl)-dodecane-1,12-diamine (denoted as C12TFSA) and N,N,N',N'-tetra(trifluoromethanesulfonyl)-hexane-1,6-diamine can be used as crosslinking agents. A gel can be obtained by heating a mixture of the above crosslinking agent and the polymer at 75°C to 110°C, preferably 80°C to 100°C. The crosslinking agent can be used as desired to obtain the gel.

[0171] When performing the above heating in a vacuum atmosphere, a vacuum drying oven can be used. A vacuum drying oven has a vacuum pump connected to a drying oven. If a vacuum drying oven is adjacent to a glove box or the like, heat treatment can be carried out without exposing the mixture to the atmosphere after the synthesis of the mixture. As the vacuum pump of the vacuum drying oven, a dry pump, a turbo molecular pump, an oil rotary pump, a cryopump or a mechanical booster pump can be used. The vacuum atmosphere in the vacuum drying oven includes an atmosphere depressurized so that the differential pressure gauge of each device is -80 kPa or more and -120 kPa or less. Instead of the vacuum drying oven, a bell jar type vacuum device having a container (referred to as a bell jar) capable of evacuating the inside to a vacuum and a vacuum pump connected to the bell jar can also be used.

[0172] By this heating step, impurities can also be removed from the mixture. Examples of the impurities include organic solvents such as toluene. Although the boiling point of toluene is 110 °C, if toluene is heated in a vacuum atmosphere, it can be removed even by heating at 110 °C or lower. That is, even if the above-described temperature range is below the boiling point of the impurity, the impurity or the like can be removed.

[0173] In this way, a gelled liquid material, specifically, a gelled ionic liquid and / or a gelled organic solvent can be obtained. The heat treatment may be carried out before or after mixing the solid material with the liquid material.

[0174] <Lithium salt> The lithium salt will be described. The lithium salt is added to the electrolyte layer when using an ionic liquid, an organic solvent, and a semi-solid electrolyte. Examples of the lithium salt include LiPF6, LiClO4, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiBr, LiI, Li2SO4, Li2B 10 Cl 10 、Li2B 12 Cl 12One or more of the following can be used: LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiC(C2F5SO2)3, LiN(FSO2)2 (denoted as LiFSI), LiN(CF3SO2)2 (denoted as LiTFSI), LiN(C4F9SO2)(CF3SO2), LiN(C2F5SO2)2, and lithium bis(oxalate)borate (LiBOB). The lithium salt should be mixed with a solvent such as an ionic liquid, organic solvent, or semi-solid electrolyte to a concentration of 0.5 mol / L to 3 mol / L.

[0175] <Additives> The additives are described below. For the purpose of improving safety, etc., the electrolyte layer 103 may contain additives such as vinylene carbonate (VC), propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis(oxalate) borate (LiBOB), or a dinitrile compound such as succinonitrile or adiponitrile, in order to form a film (Solid Electrolyte Interphase: SEI film) at the interface between the electrode (positive electrode active material layer or negative electrode active material layer) and the electrolyte.

[0176] <Cathode active material> The positive electrode active material will now be described. In this specification, the positive electrode active material refers to a compound having a transition metal and oxygen that allows for the insertion and removal of carrier ions. The compound may be called an oxide or a complex oxide. Lithium ions are typically used as the carrier ions, but sodium ions or magnesium ions may also be used. Carbonic acid and hydroxyl groups adsorbed after the preparation of the positive electrode active material are not included in the positive electrode active material. Furthermore, electrolytes, organic solvents, binders, conductive materials, or compounds derived therefrom that adhere to the positive electrode active material are also not included in the positive electrode active material.

[0177] In this specification, the term "particle" as used for positive electrode active material particles, etc., is not limited to spherical (circular cross-section). For example, particles may include elliptical or asymmetrical cross-sections, and the individual particles do not need to be uniform in shape; they may be irregular in shape.

[0178] In this specification, space groups are expressed using international notation (or Hermann-Mauguin notation) in short notation. Crystal planes and crystal directions are expressed using Miller indices. Individual crystal planes are indicated using ( ). In crystallography, space groups, crystal planes, and crystal directions are indicated by a bar above the number, but in this specification, due to formatting constraints, a minus sign (-) may be placed before the number instead of a bar above it. Individual orientations within a crystal are indicated by [ ], aggregate orientations indicating all equivalent directions are indicated by < >, individual crystal planes are indicated by ( ), and aggregate planes with equivalent symmetry are indicated by {}. Furthermore, trigonal crystals represented by space group R-3m are sometimes expressed as a composite hexagonal lattice for ease of understanding the structure, and in this specification, trigonal crystals represented by space group R-3m may also be expressed as a composite hexagonal lattice.

[0179] Furthermore, the space group of a crystal structure is identified by X-ray diffraction (XRD), electron diffraction, neutron diffraction, etc. Therefore, in this specification, "belonging to a certain space group," "being part of a certain space group," or "being a certain space group" can be rephrased as "being identified to a certain space group."

[0180] In this specification, "rock salt type crystal structure" refers to a structure in which cations and anions are arranged alternately. Note that a "rock salt type crystal structure" may have vacancies in either cations or anions.

[0181] In this specification and the like, the "layered rock salt-type crystal structure" refers to a crystal structure having a layered rock salt-type ion arrangement in which cations and anions are alternately arranged, and transition metals and lithium are regularly arranged to form a two-dimensional plane, enabling two-dimensional diffusion of lithium. Note that in the "layered rock salt-type crystal structure", there may be defects such as cation or anion deficiencies. Also, strictly speaking, the above "layered rock salt-type crystal structure" may be a structure in which the lattice of the "rock salt-type crystal structure" is distorted.

[0182] <LiNi x Co y Mn z O2> The positive electrode active material can use a composite oxide obtained using three types of nickel, cobalt, and manganese, and this may be referred to as a nickel-cobalt-manganese composite oxide. The nickel-cobalt-manganese composite oxide can be said to be a precursor of the lithium nickel-cobalt-manganese composite oxide, referring to the state before lithium is mixed. Also, the lithium nickel-cobalt-manganese composite oxide is denoted as NCM, and this can be expressed by the chemical formula LiNi x Co y Mn z O2 (x > 0, y > 0, 0.8 < x + y + z < 1.2). In NCM, since lithium changes during charge and discharge, Li is not limited to 1 based on the above chemical formula. The above LiNi x Co y Mn zIn O2, the ranges within which x, y, and z can be taken may preferably satisfy, for example, 0.1x < y < 8x and 0.1x < z < 8x. As a specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 1:1:1. As another specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 5:2:3. As another specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 8:1:1. As another specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 9:0.5:0.5. As another specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 6:2:2. As another specific example, x, y, and z preferably satisfy values in the vicinity of x:y:z = 1:4:1. The above x, y, and z may be described as the mixing ratios of nickel, cobalt, and manganese, and when the mixing ratios described as x, y, and z are satisfied, a layered rock salt-type crystal structure can be adopted.

[0183] NCM may further contain elements other than the exemplified elements (referred to as additive elements). The additive elements can be one or more selected from nickel, cobalt, magnesium, calcium, chlorine, fluorine, aluminum, manganese, titanium, zirconium, yttrium, vanadium, iron, chromium, niobium, lanthanum, hafnium, zinc, silicon, sulfur, phosphorus, boron, and arsenic.

[0184] The additive elements are preferably located at the interface between primary particles. In this specification and the like, the "primary particle" refers to the smallest unit of particles (lumps) confirmed when observed, for example, at 20,000 times magnification by SEM (scanning electron microscope). That is, the primary particle is the smallest unit of particles. Also, in this specification and the like, the "secondary particle" refers to particles in which the above primary particles aggregate so as to share a part of the grain boundary (the outer periphery of the primary particle, etc.) and are not easily separated (particles independent of others).

[0185] A higher proportion of nickel among the transition metals is preferable because it allows for the provision of an inexpensive positive electrode active material, and furthermore, a positive electrode active material with a high potential or high capacity. For example, when the sum of the number of nickel, cobalt, and manganese atoms in the positive electrode active material is taken as 100, it is preferable that the number of nickel atoms be 33 or more, more preferably 50 or more, and even more preferably 80 or more. However, if the proportion of nickel is too high, the chemical stability and heat resistance may decrease. Therefore, when the sum of the number of nickel, cobalt, and manganese atoms in the positive electrode active material is taken as 100, it is preferable that the number of nickel atoms be 95 or less.

[0186] The presence of cobalt as a transition metal is preferable because it results in a higher average discharge voltage and improved cycle characteristics or a more reliable lithium-ion battery, as cobalt contributes to stabilizing the layered rock salt structure. However, cobalt is more expensive and less stable than nickel and manganese, so if the proportion of cobalt is too high, manufacturing costs may increase. Therefore, for example, when the sum of the number of atoms of nickel, cobalt, and manganese in the positive electrode active material is taken as 100, it is preferable that the number of cobalt atoms be between 2.5 and 34.

[0187] The presence of manganese as a transition metal is preferable because it improves heat resistance and chemical stability. However, if the proportion of manganese is too high, the discharge voltage and discharge capacity tend to decrease. Therefore, for example, when the sum of the number of atoms of nickel, cobalt, and manganese in the positive electrode active material is taken as 100, it is preferable that the number of manganese atoms be between 2.5 and 33.

[0188] <lixcoo2> The positive electrode active material can use lithium cobaltate. Lithium cobaltate is represented by LixCoO2. When x in LixCoO2 is 1, lithium cobaltate has a layered rock salt-type crystal structure belonging to the space group R-3m. When x in LixCoO2 is in the charged state of 0.1 < x ≤ 0.24, lithium cobaltate preferably has a crystal structure with the space group P2 / m, lattice constant a = 0.488 ± 0.001 (nm), lattice constant b = 0.282 ± 0.001 (nm), lattice constant c = 0.484 ± 0.001 (nm), α = 90°, β = 109.58 ± 0.01°, and γ = 90°. [[ID=​​​​​​​​​​​​​In lithium cobalt oxide, the surface layer portion is, for example, a region within 50 nm, more preferably within 35 nm, still more preferably within 20 nm, and most preferably within 10 nm from the surface toward the interior. Or the surface layer portion may be referred to as near the surface, the near-surface region, or the shell. The region within 50 nm, more preferably within 35 nm, still more preferably within 20 nm, and most preferably within 10 nm from the surface toward the interior refers to the depth direction distance along a direction perpendicular or substantially perpendicular to the surface. The perpendicular or substantially perpendicular on the surface refers to a direction in which the angle formed with the tangent line on the surface is 80° or more and 100° or less. The bulk portion refers to a region deeper than the surface layer portion. The bulk portion may be referred to as the interior, and may also be referred to as the core. The central portion of the positive electrode active material may be included in the bulk portion.

[0193] Lithium cobalt oxide may have elements other than the exemplified elements (referred to as additive elements). The additive elements can be one or more selected from nickel, cobalt, magnesium, calcium, chlorine, fluorine, aluminum, manganese, titanium, zirconium, yttrium, vanadium, iron, chromium, niobium, lanthanum, hafnium, zinc, silicon, sulfur, phosphorus, boron, and arsenic.

[0194] The additive element located in the surface layer portion is preferably magnesium and / or aluminum. The additive element located in the bulk portion is preferably nickel.

[0195] Lithium cobalt oxide having magnesium and / or aluminum enables charge and discharge at a high charging voltage (hereinafter, also referred to as "high charging voltage"). Unless otherwise specified in this specification or the like, the "charging voltage" is expressed based on the potential of lithium metal. Also, in this specification or the like, the "high charging voltage" when lithium cobalt oxide is used as the positive electrode is, for example, a charging voltage of 4.6 V or more, preferably 4.65 or more, and still more preferably 4.7 V or more.

[0196] <limpo4> Lithium composite oxides having an olivine-type crystal structure are represented as LiMPO4 (where M = one or more of Fe, Mn, Ni, or Co). Since Fe and Mn also exhibit excellent thermal stability, using Fe or Mn as M, or using Fe and Mn as M, makes them suitable as positive electrode active materials. When Fe is used as M, it is represented as LiFePO4, which is sometimes written as lithium iron phosphate or LFP. LFP is sometimes written as a composite oxide containing lithium, iron, and phosphorus.

[0197] Lithium iron phosphate may contain elements other than those exemplified (referred to as additive elements). The additive elements may be one or more selected from nickel, cobalt, magnesium, calcium, chlorine, fluorine, aluminum, manganese, titanium, zirconium, yttrium, vanadium, iron, chromium, niobium, lanthanum, hafnium, zinc, silicon, sulfur, phosphorus, boron, and arsenic.

[0198] <Negative electrode active material> The negative electrode active material will now be described. In this specification, the negative electrode active material can be an element capable of undergoing charge-discharge reactions through alloying and dealloying reactions with carrier ions. Lithium ions are typically used as carrier ions, but sodium ions or magnesium ions may also be used.

[0199] In this specification, the term "particle" as used for negative electrode active material particles, etc., is not limited to spherical (circular cross-section). For example, particles may include elliptical or asymmetrical cross-sections, and the individual particles do not need to be uniform in shape; they may be irregular in shape.

[0200] The negative electrode active material can be one or more materials selected from, for example, silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, indium, etc. Such elements have high capacities, and silicon is particularly preferred because it has a high theoretical capacity of 4200 mAh / g. Compounds containing these elements may also be used. Examples include SiO, Mg2Si, Mg2Ge, SnO, SnO2, Mg2Sn, SnS2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag3Sb, Ni2MnSb, CeSb3, LaSn3, La3Co2Sn7, CoSb3, InSb, SbSn, etc.

[0201] In this specification, "SiO" refers to silicon monoxide, for example. Alternatively, SiO refers to SiO x It can also be expressed as follows. Here, x is preferably 1 or a value in its immediate vicinity. For example, x is preferably between 0.2 and 1.5, and preferably between 0.3 and 1.2.

[0202] The above materials include elements capable of undergoing charge-discharge reactions through alloying and de-alloying reactions with lithium, and compounds containing such elements, and these may be referred to as "alloy materials" in this specification.

[0203] Furthermore, titanium dioxide (TiO2) and lithium titanium oxide (Li4Ti5O2) are used as negative electrode active materials. 12 ), lithium-graphite intercalation compound (Li x One or more oxides selected from C6, niobium pentoxide (Nb2O5), tungsten oxide (WO2), molybdenum oxide (MoO2), etc., can be used.

[0204] Furthermore, as the negative electrode active material, a Li3N type structure is used, which is a lithium and transition metal binitride. 3-x M x N (M = Co, Ni, Cu) can be used. For example, Li 2.6 Co 0.4 N3 has a large discharge capacity (900mAh / g, 1890mAh / cm²). 3 ) indicates a preference.

[0205] Using a lithium-transition metal complex nitride is preferable because it contains lithium ions in the negative electrode active material, allowing it to be combined with lithium-ion-free materials such as V2O5 and Cr3O8 as the positive electrode active material. Even when using a lithium-ion-containing material as the positive electrode active material, the lithium-transition metal complex nitride can be used as the negative electrode active material by pre-desorbing the lithium ions contained in the positive electrode active material.

[0206] Furthermore, materials that undergo a conversion reaction can also be used as the negative electrode active material. Examples of materials that undergo a conversion reaction include cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO). These are transition metal oxides that do not form alloys with lithium, but they may also be used as negative electrode active materials. Other materials that undergo a conversion reaction include oxides such as Fe2O3, CuO, Cu2O, RuO2, Cr2O3, and CoS 0.89 This can also occur with sulfides such as NiS and CuS, nitrides such as Zn3N2, Cu3N, and Ge3N4, phosphides such as NiP2, FeP2, and CoP3, and fluorides such as FeF3 and BiF3.

[0207] Furthermore, the negative electrode active material may be, for example, a carbon material. The carbon material may be one or more selected from graphite, easily graphitizable carbon (soft carbon), difficult-to-graphitize carbon (hard carbon), carbon fibers (carbon nanotubes), graphene, carbon black, etc.

[0208] Graphite can be artificial graphite or natural graphite. Examples of artificial graphite include mesocarbon microbeads (MCMB), coke-based artificial graphite, and pitch-based artificial graphite. Spheroidal graphite, which has a spherical shape, can be used as the artificial graphite. For example, MCMB may have a spherical shape and is therefore preferable. Furthermore, it is relatively easy to reduce the surface area of ​​MCMB, which may also be preferable. Examples of natural graphite include flake graphite and spheroidized natural graphite.

[0209] When lithium ions are inserted into graphite (during the formation of lithium-graphite intercalation compounds), graphite exhibits a potential as low as that of lithium metal (0.05V to 0.3V vs. Li / Li). + This allows lithium-ion batteries using graphite to exhibit a high operating voltage. Furthermore, graphite is preferable because it has advantages such as a relatively high capacity per unit volume, relatively small volume expansion, low cost, and higher safety compared to lithium metal.

[0210] <Current collector> The current collector will now be described. The positive electrode current collector and the negative electrode current collector can be made of highly conductive materials such as stainless steel, gold, platinum, aluminum, copper, titanium, and alloys thereof. Furthermore, it is preferable that the material used for the positive electrode current collector does not dissolve at the potential of the positive electrode. In addition, aluminum alloys to which elements that improve heat resistance, such as silicon, titanium, neodymium, scandium, and molybdenum, have been added can be used. Alternatively, they may be made of metallic elements that react with silicon to form silicides. Metallic elements that react with silicon to form silicides include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, and nickel. The current collector can be made in various shapes such as foil, plate, sheet, mesh, perforated metal, or expanded metal as appropriate. It may also have a layer of carbon black or graphene as an undercoat. The current collector should preferably have a thickness of 5 μm to 30 μm. The term "foil-like" refers to a material with a thickness of 1 μm to 100 μm, preferably 5 μm to 30 μm.

[0211] Furthermore, especially when using LiFSI as the lithium salt, it is preferable that the positive electrode current collector 105 and the negative electrode current collector 101 are made of materials that are resistant to corrosion by LiFSI. For example, titanium and titanium compounds are preferable because they are resistant to corrosion. Similarly, titanium, titanium compounds, or aluminum coated with carbon are also preferable.

[0212] <Separator> A separator may be disposed between the positive electrode layer and the negative electrode layer. The separator will be described. The separator may have a gel. The separator may also be made of fibers having cellulose such as paper, non-woven fabric, glass fiber, ceramics, or synthetic fibers using nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polypropylene (abbreviated as PP), polyimide (abbreviated as PI), polyester, acrylic, polyolefin, polyurethane, etc. The porosity of the separator in terms of film thickness can be 35% or more and 90% or less, preferably 60% or more and 85% or less. The porosity of the separator using polypropylene can be 35% or more and 45% or less. The porosity of the separator using polyimide can be 75% or more and 85% or less. The film thickness of the separator is preferably 10 μm or more and 80 μm or less, and more preferably 20 μm or more and 60 μm or less. The separator using polyimide can have a high porosity and can be thickened (typically, the film thickness is 50 μm or more and 60 μm or less), which is preferable.

[0213] The separator is preferably processed into a bag shape and arranged to wrap either the positive electrode or the negative electrode.

[0214] The separator may have a multilayer structure. For example, an organic material film such as polypropylene or polyethylene can be coated with a ceramic-based material, a fluorine-based material, a polyamide-based material, or a mixture thereof. As the ceramic-based material, for example, aluminum oxide particles, silicon oxide particles, etc. can be used. As the fluorine-based material, for example, PVDF, polytetrafluoroethylene, etc. can be used. As the polyamide-based material, for example, nylon, aramid (meta-aramid, para-aramid), etc. can be used.

[0215] When using a separator with a multilayer structure, even if the overall thickness of the separator is thin, the safety of the lithium-ion battery can be maintained, so the capacity per unit volume of the lithium-ion battery can be increased.

[0216] <Exterior> Let's describe the exterior. For the exterior, metal materials such as aluminum or resin materials can be used. Resin materials include rubber. There are natural rubber and synthetic rubber. Synthetic rubbers include rubber materials such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene-propylene-diene copolymer.

[0217] Furthermore, the outer casing of the lithium-ion battery is preferably in the form of a film. Materials that enable a film shape for the outer casing include, for example, polyethylene, polypropylene, polycarbonate, ionomer, and polyamide. Alternatively, a highly flexible metal thin film such as aluminum, stainless steel, copper, or nickel may be used for the outer casing.

[0218] Furthermore, the outer casing that enables the film shape may have a laminated structure. The first layer may have a material such as polyethylene, polypropylene, polycarbonate, ionomer, or polyamide, and the second layer may have a highly flexible metal thin film such as aluminum, stainless steel, copper, or nickel.

[0219] Furthermore, the outer surface of the exterior body may be provided with an insulating synthetic resin film such as a polyamide resin or polyester resin. By applying this outer surface configuration to the laminated structure of the first and second layers described above, a three-layer film can be used.

[0220] A lithium-ion battery having an electrolyte layer according to one aspect of the present invention is preferred because it is easily bendable. The outer casing using the insulating synthetic resin film described above is suitable for a bent lithium-ion battery, or a lithium-ion battery that changes between a bent and an extended state.

[0221] <Binder> The positive electrode layer and the negative electrode layer may have a binder. Furthermore, the electrolyte layer may also have a binder. The binder will now be described. The binder may be a gel. Preferably, the binder is made of rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, or ethylene-propylene-diene copolymer. Fluororubber can also be used as the binder.

[0222] Furthermore, it is preferable to use a water-soluble polymer as the binder. Examples of water-soluble polymers include polysaccharides. Examples of polysaccharides include cellulose derivatives such as carboxymethylcellulose (CMC), methylcellulose, ethylcellulose, hydroxypropylcellulose, diacetylcellulose, and regenerated cellulose, as well as starch. It is even preferable to use these water-soluble polymers in combination with the aforementioned rubber material.

[0223] Alternatively, it is preferable to use one or more materials selected from polystyrene, polyvinyl butyral (PVB), methyl polyacrylate, polymethyl methacrylate (polymethyl methacrylate, PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride, polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), ethylene propylene diene polymer, polyvinyl acetate, nitrocellulose, etc., as the binder.

[0224] You may use a combination of several of the binders mentioned above.

[0225] <Conductive material> The positive electrode layer and / or negative electrode layer may have a conductive material. The conductive material will be described below. A carbon material can be used as the conductive material. By attaching the conductive material between multiple active materials, the multiple active materials are electrically connected to each other, and the conductivity is increased. In this specification, "attachment" does not only refer to the physical close contact between the active material and the conductive material, but also includes cases where covalent bonding occurs, bonding occurs by van der Waals forces, the conductive material covers a part of the surface of the active material, the conductive material fits into surface irregularities of the active material, and cases where they are electrically connected even if they are not in contact with each other.

[0226] Specific examples of carbon materials that can be used as conductive materials include carbon black (furnace black, acetylene black, graphite, etc.), graphene, graphene compounds, or carbon fibers.

[0227] <Graphene and graphene compounds> In this specification, graphene is defined as a carbon-containing material having a plate-like or sheet-like shape and a two-dimensional structure formed of six-membered carbon rings. This includes not only graphene but also multilayer graphene, multigraphene, and the like. Graphene may also be rolled up to resemble carbon nanofibers. Furthermore, the two-dimensional structure formed of these six-membered carbon rings may be referred to as a carbon sheet.

[0228] In this specification, graphene compounds have shapes such as plates or sheets, and include graphene oxide, multilayer graphene oxide, multi-graphene oxide, reduced graphene oxide, reduced multilayer graphene oxide, reduced multi-graphene oxide, graphene quantum dots, etc. Graphene compounds may also be rolled up into nanofibers. Furthermore, graphene compounds may have functional groups, preferably epoxy groups, carboxyl groups, or hydroxyl groups.

[0229] In this specification, reduced graphene oxide, reduced multilayer graphene oxide, or reduced multi-graphene oxide preferably has a portion in which the carbon concentration is greater than 80 atomic% and the oxygen concentration is between 2 atomic% and 15 atomic%. Such carbon and oxygen concentrations allow it to function as a highly conductive material even in small quantities. Furthermore, reduced graphene oxide, reduced multilayer graphene oxide, and reduced multi-graphene oxide preferably have a G / D intensity ratio of 1 or more in the Raman spectrum. Such an intensity ratio allows it to function as a highly conductive material even in small quantities. Additionally, reducing graphene oxide, multilayer graphene oxide, or multi-graphene oxide may create pores in the graphene compound.

[0230] This embodiment can be used in combination with other embodiments.

[0231] (Embodiment 2) The manufacturing process described above is preferably carried out continuously using a roll-to-roll manufacturing apparatus or the like. In this embodiment, the manufacturing process using the manufacturing apparatus shown in Figure 4 will be explained.

[0232] Using the manufacturing apparatus shown in Figure 4, the following steps can be performed: a step 310 of applying slurry onto the positive electrode current collector 105; a step 320 of drying the slurry to form a positive electrode active material layer 104; a step 330 of superimposing an electrolyte layer 103 onto the positive electrode active material layer 104; and a step 340 of passing the positive electrode current collector 105 with the positive electrode active material layer 104 formed on it, together with the electrolyte layer 103, between a pair of pressure rolls (a first pressure roll 325 and a second pressure roll 326).

[0233] The above process 310 will now be explained. As shown in Figure 4, the manufacturing apparatus has a feeding mechanism 311 (also called an unwinder), and a first bobbin 312 on which the positive electrode current collector 105 is wound is placed in the feeding mechanism 311. The positive electrode current collector 105 is moved by using the rotation of the roller 313, and slurry is applied to one surface of the positive electrode current collector 105 by the first slurry application means 314a. The rollers 313 are paired, and it is also possible to press the applied slurry as it passes between them.

[0234] The slurry in step 310 contains the starting materials for the positive electrode active material layer, and includes the positive electrode active material, conductive material, binder, etc. Furthermore, it is preferable to appropriately disperse each material in the slurry, so it is preferable to include a dispersant in the slurry. If a liquid material is used as the electrolyte for the positive electrode active material layer, it is preferable to drop it onto the positive electrode active material layer before step 320 or before step 330, without including it in the slurry. Similarly, if a gel is used as the electrolyte, it is preferable to drop it onto the positive electrode active material layer before step 320 or before step 330, without including it in the slurry. If a gel requiring a crosslinking reaction is used, the drop onto the electrolyte layer may be completed before step 320, and the heat treatment required for the crosslinking reaction may be carried out using step 320. Furthermore, if a solid material is used as the electrolyte, it is preferable to include it in the slurry.

[0235] As the first slurry coating means 314a, for example, a slot die coater, lip coater, blade coater, reverse coater, gravure coater, etc. may be used. Depending on the type of coater used, the number of rollers for reversing the positive electrode current collector 105 may be increased. Furthermore, as the first slurry coating means 314a, methods such as the dip method or spray method may be used. In addition, depending on the material used, the slurry may be applied while heating the first slurry coating means 314a. That is, heated slurry may be applied.

[0236] In step 320, the slurry applied to the positive electrode current collector 105 is dried in a heating chamber 321a having an air intake port 322, an exhaust port 323, and a drying means 324. By drying the slurry, a positive electrode active material layer 104 can be formed on the positive electrode current collector 105. The air intake port 322 and exhaust port 323 are preferably installed on the ceiling (also referred to as the top surface) of the heating chamber 321a, but they may also be installed on the walls (also referred to as the sides) or floor (also referred to as the bottom surface) of the heating chamber 321a. As the drying means 324, one or more methods selected from hot air heating, lamp heating, induction heating, blowing air, etc., can be used.

[0237] Step 320 shows an example where the slurry is allowed to cool naturally after drying, and no cooling means are provided. However, a cooling means may be provided in or near the heating chamber 321a for forced cooling.

[0238] In step 330, the electrolyte layer 103 is provided on the positive electrode active material layer 104 by the adhesion means 314b. The electrolyte layer 103 is in sheet form, which is preferable as it is easy to handle in step 330. Furthermore, the electrolyte layer 103 may exhibit adhesiveness, making it easy to adhere to the positive electrode active material layer 104. In addition, if a common material is used for both the electrolyte layer 103 and the positive electrode active material layer 104, the common material may dissolve after adhesion or due to heating after charging and discharging the lithium-ion battery. When the common material dissolves, the boundary between the positive electrode active material layer 104 and the electrolyte layer 103 disappears, thus suppressing interfacial resistance.

[0239] In parallel with the processing of the positive electrode current collector 105, the negative electrode current collector 101 is also processed. The second bobbin 405 on which the negative electrode current collector 101 is wound is placed in the feeding mechanism 315, and the slurry is applied to one side of the negative electrode current collector 101 by the second slurry application means 314c using the rotation of the roller 316. The rollers 316 are paired, and it is also possible to press the applied slurry as it passes between them.

[0240] The slurry in the negative electrode layer contains the starting materials for the negative electrode active material layer, and includes the negative electrode active material, conductive material, binder, etc. Furthermore, it is preferable to appropriately disperse each material in the slurry, so it is preferable to include a dispersant in the slurry. When a liquid material is used as the electrolyte in the negative electrode active material layer, it is preferable to drop it onto the negative electrode active material layer before it is brought into the heating chamber 321b or before process 340, without including it in the slurry. When a gel is used as the electrolyte, it is preferable to drop it onto the negative electrode active material layer before it is brought into the heating chamber 321b or before process 340, without including it in the slurry. When a gel requiring a crosslinking reaction is used, it may be possible to drop it onto the electrolyte layer before it is brought into the heating chamber 321b, and then perform the heat treatment necessary for the crosslinking reaction in the heating chamber 321b. Furthermore, when a solid material is used as the electrolyte, it is preferable to include it in the slurry.

[0241] As the second slurry coating means 314c, for example, a slot die coater, lip coater, blade coater, reverse coater, or gravure coater can be used. Depending on the type of coater used, the number of rollers for reversing the negative electrode current collector 101 may be increased. Alternatively, a dip method or spray method can be used as the second slurry coating means 314c. Depending on the material used, the slurry may be applied while the second slurry coating means 314c is heated. It is preferable that the slurry be applied while heated.

[0242] Next, the slurry applied to the negative electrode current collector 101 is dried in the heating chamber 321b. The heating chamber 321b may have the same configuration as the heating chamber 321a. By drying the slurry, a negative electrode active material layer 102 can be formed on the negative electrode current collector 101. After drying the slurry, it may be allowed to cool naturally, or it may be forcibly cooled by installing a cooling means in or near the heating chamber 321b.

[0243] In step 340, the rotation of a pair of pressure rolls (first pressure roll 325, second pressure roll 326) is used to press the positive electrode current collector 105 against the negative electrode current collector 101. Heating may be performed during pressing. Since there is no step of injecting electrolyte, any gas generated can be released.

[0244] Finally, the laminate is wound onto a second bobbin 328 installed in the winding mechanism 327 (also called a winder). Then, it is cut into the desired shape by a cutting means such as a laser cutter or cutter (not shown). When wound, the electrolyte layer 103 is in a semi-solid state, which is preferable as it suppresses liquid leakage.

[0245] Furthermore, although Figure 4 shows an example of winding the laminate, it may also be cut into the desired shape using a cutting method such as laser cutting or a cutter, which are not shown in the figure, instead of winding.

[0246] By following the above steps, a lithium-ion battery can be manufactured.

[0247] This embodiment can be implemented in appropriate combination with other embodiments.

[0248] (Embodiment 3) This embodiment describes examples of lithium-ion battery configurations.

[0249] [Laminated lithium-ion battery] Examples of the configuration of a laminate-type lithium-ion battery 100 are shown in Figures 5(A) and 5(B). Figures 5(A) and 5(B) are external views, and the lithium-ion battery 100 has an electrolyte layer (not shown in Figure 5), a negative electrode layer 106, and a positive electrode layer 107, etc., as described in the above embodiment. In the lithium-ion battery 100, it is preferable that the negative electrode layer 106 has a larger area than the positive electrode layer 107.

[0250] The electrolyte layer, the negative electrode layer 106, and the positive electrode layer 107 are housed in an outer casing 509, with a portion of the negative electrode lead electrode 510 and a portion of the positive electrode lead electrode 511 protruding from the outer casing 509. The negative electrode lead electrode 510 is electrically connected to the negative electrode layer 106, and the positive electrode lead electrode 511 is electrically connected to the positive electrode layer 107. The outer casing 509 has an adhesive region 508 along its outer circumference. Figure 5(A) shows an example configuration in which the negative electrode lead electrode 510 and the positive electrode lead electrode 511 protrude from the same side of the outer casing 509, and the adhesive region 508 is located at least on the side from which each lead electrode protrudes and on two sides adjacent to that side. Figure 5(B) shows an example configuration in which the side of the negative lead electrode 510 protruding from the outer casing 509 faces the side of the positive lead electrode 511 protruding from the outer casing 509, and the adhesive region 508 is located at least on the two sides from which each lead electrode protrudes and on the side sandwiched between those two sides. In Figures 5(A) and 5(B), one side of the outer casing 509 corresponds to a bent side, and an adhesive region is not required on this bent side.

[0251] By applying an electrolyte layer according to one aspect of the present invention to a laminate-type lithium-ion battery 100, leakage can be suppressed. The manufacturing process of the laminate-type lithium-ion battery 100 does not include a step of injecting the electrolyte after bonding the outer casing. Since the outer casing can be bonded last, any gas generated during the manufacturing process can be released.

[0252] [Coin-type lithium-ion battery] An example of a coin-type (single-layer flat-type) lithium-ion battery is described below. Coin-type lithium-ion batteries are mainly used in small electronic devices, and in this specification, the term "coin-type battery" includes button-type batteries. Figure 6(A) is an external view of a coin-type lithium-ion battery, Figure 6(B) is a cross-sectional view of a coin-type lithium-ion battery, and Figure 6(C) is an exploded perspective view of a coin-type lithium-ion battery. Figures 6(B) and 6(C) are not perfectly identical corresponding figures, but Figure 6(C) is used to illustrate the overlapping of components (up-down relationship and positional relationship).

[0253] Figure 6(A) shows a coin-type lithium-ion battery 300 in which a positive electrode can 301 and a negative electrode can 302 are crimped together via a gasket 303. The gasket is sometimes called an insulating packing. The gasket 303 insulates the negative electrode can 302 from the positive electrode can 301. For this reason, it is preferable to use an insulating material such as polypropylene for the gasket 303. The positive electrode can 301 and the negative electrode can 302 are preferably made of metals such as nickel, aluminum, or titanium, or alloys thereof, or alloys of these with other metals (e.g., stainless steel), and the positive electrode can 301 and the negative electrode can 302 can each also function as current collectors. The positive electrode can 301 and the negative electrode can 302 can also serve as terminals.

[0254] Figure 6(B) shows a cross-sectional view of a coin-type lithium-ion battery 300, with the positive electrode layer 304 located on the positive electrode can 301 side and the negative electrode layer 307 located on the negative electrode can 302 side. An electrolyte layer 319 is located between the positive electrode layer 304 and the negative electrode layer. The positive electrode layer 304 has a positive electrode current collector 305 and a positive electrode active material layer 306. The negative electrode layer 307 has a negative electrode current collector 308 and a negative electrode active material layer 309. In both the positive electrode layer 304 and the negative electrode layer 307, the active material layer only needs to be formed on one side of the current collector. Furthermore, the negative electrode layer 307 is not limited to a laminated structure, and lithium metal foil or a lithium-aluminum alloy foil can also be used. The positive electrode active material layer 306 is arranged so that the negative electrode active material layer 309 faces it via the electrolyte layer 103. Furthermore, the gasket 303 is positioned along the outer circumference of the coin-type lithium-ion battery 300, insulating the negative electrode can 302 from the positive electrode can 301. A gap 333 may be placed in the coin-type lithium-ion battery 300. Solutes such as the electrolyte layer 319 may be released into the gap 333.

[0255] Although the gasket is not shown in Figure 6(C), it shows the positive electrode layer 304 housed in the positive electrode can 301, with the electrolyte layer 319 on top of the positive electrode layer 304, the negative electrode layer 307 on top of the electrolyte layer 319, and the negative electrode can 302 on top of the negative electrode layer 307. The electrolyte may be dripped onto the positive electrode layer 304 before the electrolyte layer 319 is placed on top. Alternatively, the electrolyte may be dripped onto the negative electrode can 302 with the negative electrode layer 307 housed in it, and then the positive electrode can 301 may be pressed against it.

[0256] Although not shown in the illustration, the coin-type lithium-ion battery may have washers and / or spacers.

[0257] By applying an electrolyte layer according to one aspect of the present invention to a coin-type lithium-ion battery 100, leakage can be suppressed.

[0258] [Cylindrical lithium-ion battery] An example of a cylindrical lithium-ion battery will be explained with reference to Figure 7(A). As shown in Figure 7(A), the cylindrical lithium-ion battery 616 has a positive electrode cap (battery cover) 601 on the top surface and a battery casing (outer casing) 602 on the sides and bottom. The positive electrode cap 601 and the battery casing (outer casing) 602 are insulated by a gasket 610.

[0259] Figure 7(B) is a schematic diagram showing a cross-section of a cylindrical lithium-ion battery. As described above, the cylindrical lithium-ion battery shown in Figure 7(B) has a positive electrode cap 601 on the top surface and battery casings 602 on the sides and bottom. The battery casing 602 has a hollow cylindrical shape, and inside it, a positive electrode layer 604 and a negative electrode layer 606 are provided wound with an electrolyte layer 605 in between. The wound state may also be called a battery element. The positive electrode layer 604, the negative electrode layer 606, and the electrolyte layer 605 are in the shape of a strip. A strip shape is included in a sheet shape, but refers to one in which the long side is three times or more the short side. The battery casing 602 has one side, which is the bottom surface, closed, and the top surface opposite the bottom surface is open. The battery casing 602 can be made of metals such as nickel, aluminum, titanium, or alloys thereof, or alloys of these with other metals (for example, stainless steel). In addition, nickel and aluminum may be used to coat the inside of the battery can 602. Inside the battery can 602, the battery elements are sandwiched between an insulating plate 608 located on the top side and an insulating plate 609 located on the bottom side.

[0260] The positive and negative electrode layers used in cylindrical lithium-ion batteries are wound as described above, and it is preferable to form the active material on both sides of the current collector. Figures 7(A) to 7(D) illustrate a lithium-ion battery 616 in which the height of the cylinder is greater than the diameter of the cylinder, but the battery is not limited to this. A lithium-ion battery in which the diameter of the cylinder is greater than the height of the cylinder is also possible. The size of the lithium-ion battery can be reduced by changing the shape of the cylinder.

[0261] A positive electrode terminal (also called a positive electrode current collector lead) 603 is connected to the positive electrode layer 604, and the positive electrode terminal 603 is located on the upper side. A negative electrode terminal (also called a negative electrode current collector lead) 607 is connected to the negative electrode layer 606, and the negative electrode terminal 607 is located on the bottom side. Both the positive electrode terminal 603 and the negative electrode terminal 607 can be made of metal materials such as aluminum.

[0262] The positive electrode terminal 603 is resistance-welded to the safety valve mechanism 613, and the negative electrode terminal 607 is resistance-welded to the bottom of the battery can 602. The safety valve mechanism 613 is electrically connected to the positive electrode cap 601 via a PTC element (Positive Temperature Coefficient) 611. The safety valve mechanism 613 has the function of disconnecting the electrical connection between the positive electrode cap 601 and the positive electrode layer 604 when the rise in the internal pressure of the lithium-ion battery exceeds a predetermined threshold. The PTC element 611 is a thermal resistance element whose resistance increases when the temperature of the lithium-ion battery rises, and it prevents abnormal heat generation by limiting the amount of current through the increase in resistance. Barium titanate (BaTiO3) based ceramic material can be used for the PTC element 611.

[0263] Figure 7(C) shows an example of an energy storage system 615. The energy storage system 615 has multiple lithium-ion batteries 616 and is sometimes called a battery pack. To prevent the positive terminals from being connected between the multiple lithium-ion batteries, an insulator 625 is placed, and the positive terminals of each battery are in contact with a conductor 624 separated by the insulator 625. The energy storage system in Figure 7(C) consists of multiple lithium-ion batteries connected in parallel, which allows for a large capacity to be secured.

[0264] Furthermore, the conductor 624 is electrically connected to the control circuit 620 via wiring 623. The negative terminals of multiple lithium-ion batteries are in contact with the conductor 614, and the conductor 614 is electrically connected to the control circuit 620 via wiring 626. The control circuit 620 can be a protective circuit to prevent overcharging or over-discharging, etc.

[0265] Multiple lithium-ion batteries 616 may be connected in parallel, in series, or connected in parallel and then in series. By configuring a power storage system 615 having multiple lithium-ion batteries 616, a large amount of power can be extracted. As an example of such a power storage system 615, Figure 7(D) shows multiple lithium-ion batteries 616 that satisfy the series connection relationship in addition to the parallel connection relationship shown in Figure 7(C).

[0266] Wiring 622 connected to the control circuit 620 is electrically connected to the conductor 614b, and multiple lithium-ion batteries 616a are arranged so that multiple negative terminals contact the conductor 614b. The positive terminals 627 of these multiple lithium-ion batteries 616a contact the conductor 628b. The conductor 628b also contacts the positive terminals of adjacent multiple lithium-ion batteries 616b. The negative terminals of the multiple lithium-ion batteries 616b contact the conductor 614a. The conductor 614a also contacts the negative terminals of further adjacent multiple lithium-ion batteries 616c. The positive terminals of the multiple lithium-ion batteries 616c contact the conductor 628a. The conductor 628a is electrically connected to the control circuit 620 via wiring 621.

[0267] This configuration allows for multiple lithium-ion batteries to be connected in series as well as in parallel, enabling the extraction of a large amount of power.

[0268] A temperature control device may be provided in the gap between the multiple lithium-ion batteries 616a to 616c. When the multiple lithium-ion batteries 616a to 616c become overheated, they can be cooled by the temperature control device, and when the multiple lithium-ion batteries 616a to 616c become too cold, they can be heated by the temperature control device. The presence of the temperature control device is preferable because it makes the performance of the energy storage system 615 less susceptible to the influence of ambient temperature.

[0269] Furthermore, the control circuit 620 can be modified to include a protection circuit to prevent overcharging or over-discharging.

[0270] By applying an electrolyte layer according to one aspect of the present invention to a cylindrical lithium-ion battery 616, leakage can be suppressed.

[0271] [Other structural examples of lithium-ion batteries] Examples of lithium-ion battery structures are explained using Figures 8 and 9.

[0272] The lithium-ion battery 913 shown in Figure 8(A) has a wound body 950 housed in a rectangular casing 930. The wound body 950 has a negative electrode terminal 951 and a positive electrode terminal 952, and since these extend to the outside of the casing 930, an opening is provided on the top surface of the casing 930. The opening is formed so that the positive electrode terminal 952 is in contact with the casing 930, and the negative electrode terminal 951 is not in contact with the casing 930 by using an insulating material or the like. In Figure 8(A), the casing 930 is shown separated, but in an actual lithium-ion battery 913, the wound body 950 is covered by the casing 930, and the negative electrode terminal 951 and positive electrode terminal 952 extend to the outside of the casing 930. The casing 930 can be made of a metal material (e.g., aluminum), but a resin material may be used instead of a metal material.

[0273] As shown in Figure 8(B), the housing 930 may be divided into multiple parts. For example, in the lithium-ion battery 913 shown in Figure 8(B), housing 930a and housing 930b are bonded together, and the winding body 950 is provided in the area enclosed by housing 930a and housing 930b.

[0274] For the housing 930a, an insulating material such as organic resin can be used. In particular, by using a material such as organic resin on the surface where the antenna is formed, shielding of the electric field by the lithium-ion battery 913 can be suppressed. If the shielding of the electric field by the housing 930a is small, the antenna may be placed inside the housing 930a. For the housing 930b, for example, a metal material can be used.

[0275] Furthermore, the structure of the wound body 950 is shown in Figure 8(C). The wound body 950 has a negative electrode layer 931, a positive electrode layer 932, and an electrolyte layer 933. The wound body 950 is a wound body in which the negative electrode layer 931 and the positive electrode layer 932 are stacked with the electrolyte layer 933 in between, and the stacked sheet is wound up. Note that multiple stacked structures of the negative electrode layer 931, positive electrode layer 932, and electrolyte layer 933 may be prepared and stacked.

[0276] Alternatively, the lithium-ion battery 913 may have a wound body 950a as shown in Figures 9(A) to 9(C). The wound body 950a shown in Figure 9(A) has a negative electrode layer 931, a positive electrode layer 932, and an electrolyte layer 933. The negative electrode layer 931 has a negative electrode active material layer 931a. The positive electrode layer 932 has a positive electrode active material layer 932a.

[0277] The electrolyte layer 933 is preferably wider than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound so as to overlap with the negative electrode active material layer 931a and the positive electrode active material layer 932a. Furthermore, a configuration in which the negative electrode active material layer 931a is wider than the positive electrode active material layer 932a is preferable from a safety standpoint. In addition, a wound body 950a of this shape is preferable because it is easy to produce.

[0278] As shown in Figure 9(B), the negative electrode layer 931 is electrically connected to the negative electrode terminal 951. The negative electrode terminal 951 is electrically connected to terminal 911a. The positive electrode layer 932 is electrically connected to the positive electrode terminal 952. The positive electrode terminal 952 is electrically connected to terminal 911b.

[0279] As shown in Figure 9(C), the coiled body 950a is covered by the housing 930, forming a lithium-ion battery 913. It is preferable to provide a safety valve, an overcurrent protection element, etc., in the housing 930. The safety valve is a valve that opens the inside of the housing 930 at a predetermined internal pressure to prevent the battery from rupturing. In one embodiment of the present invention, the lithium-ion battery having an electrolyte layer suppresses gas generation, so the safety valve can be omitted.

[0280] As shown in Figure 9(B), the lithium-ion battery 913 may have multiple windings 950a. By using multiple windings 950a, a lithium-ion battery 913 with a larger capacity can be made. Other elements of the lithium-ion battery 913 shown in Figures 9(A) and (B) can be considered in reference to the description of the lithium-ion battery 913 shown in Figures 8(A) to 8(C).

[0281] By applying an electrolyte layer according to one aspect of the present invention to a lithium-ion battery 913 having a wound body, leakage can be suppressed.

[0282] The contents of this embodiment can be appropriately combined with the contents of other embodiments.

[0283] (Embodiment 4) In this embodiment, an example of application to an electric vehicle (EV) is shown using Figure 10.

[0284] As shown in Figure 10(A), the electric vehicle is equipped with a first battery 1301a, 1301b as the main lithium-ion battery for propulsion, and a second battery 1311 that supplies power to the inverter 1312 for starting the motor 1304. By applying an electrolyte layer according to one aspect of the present invention to the first batteries 1301a, 1301b, leakage can be suppressed.

[0285] The second battery 1311 is also called the cranking battery (or starter battery). The second battery 1311 only needs to be able to output high power, and does not require a large capacity. Therefore, the capacity of the second battery 1311 is smaller than that of the first batteries 1301a and 1301b.

[0286] The internal structure of the first battery 1301a may be wound or stacked.

[0287] In this embodiment, an example is shown in which two first batteries 1301a and 1301b are connected in parallel, but three or more may be connected in parallel. Also, if the first battery 1301a can store sufficient power, the first battery 1301b may not be necessary. By configuring a battery pack with multiple lithium-ion batteries, a large amount of power can be extracted. Multiple lithium-ion batteries may be connected in parallel, in series, or connected in parallel and then in series. Multiple lithium-ion batteries are also called a battery pack.

[0288] Furthermore, the lithium-ion battery for use in vehicles has a service plug or circuit breaker that can cut off high voltage without using tools in order to cut off power from multiple lithium-ion batteries, and this is provided in the first battery 1301a.

[0289] Furthermore, the power from the first batteries 1301a and 1301b is mainly used to rotate the motor 1304, but also supplies power to 42V onboard components (electric power steering 1307, heater 1308, defogger 1309, etc.) via the DC-DC circuit 1306. If a rear motor 1317 is located on the rear wheels, the first battery 1301a is used to rotate the rear motor 1317.

[0290] Furthermore, the second battery 1311 supplies power to 14V automotive components (audio 1313, power windows 1314, lights 1315, etc.) via the DC-DC circuit 1310.

[0291] Furthermore, the first battery 1301a will be explained using Figure 10(B).

[0292] Figure 10(B) shows an example where nine rectangular lithium-ion batteries 1300 are arranged in a single battery pack 1415. In this example, nine rectangular lithium-ion batteries 1300 are connected in series, with one electrode fixed by an insulating fixing part 1413 and the other electrode fixed by an insulating fixing part 1414. While this embodiment shows an example of fixing with fixing parts 1413 and 1414, the batteries may also be housed in a battery housing box (also called a casing). Since vehicles are expected to be subjected to vibrations or shaking from external sources (such as the road surface), it is preferable to fix multiple lithium-ion batteries using fixing parts 1413, 1414 and a battery housing box. Furthermore, one electrode is electrically connected to the control circuit unit 1320 by wiring 1421, and the other electrode is electrically connected to the control circuit unit 1320 by wiring 1422.

[0293] Furthermore, the control circuit unit 1320 may also use a memory circuit that includes a transistor made of an oxide semiconductor. A charging control circuit or battery control system having a memory circuit that includes a transistor made of an oxide semiconductor may be referred to as a BTOS (Battery operating system or Battery oxide semiconductor).

[0294] It is preferable to use a metal oxide that functions as an oxide semiconductor. For example, as the oxide, a metal oxide such as In-M-Zn oxide (where element M is one or more selected from aluminum, gallium, yttrium, copper, vanadium, beryllium, boron, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, or magnesium) is preferable. In particular, the In-M-Zn oxide that can be applied as the oxide is preferably CAAC-OS (C-Axis Aligned Crystal Oxide Semiconductor) or CAC-OS (Cloud-Aligned Composite Oxide Semiconductor). Alternatively, In-Ga oxide or In-Zn oxide may be used as the oxide. CAAC-OS is an oxide semiconductor having multiple crystalline regions, the c-axis of which is oriented in a specific direction. The specific direction is the thickness direction of the CAAC-OS film, the normal direction to the surface on which the CAAC-OS film is formed, or the normal direction to the surface of the CAAC-OS film. Furthermore, a crystalline region is a region in which the atomic arrangement has periodicity. If the atomic arrangement is considered as a lattice arrangement, then a crystalline region is also a region in which the lattice arrangement is aligned. In addition, CAAC-OS has regions in which multiple crystalline regions are connected in the ab-plane direction, and these regions may have strain. Strain refers to a point in the region in which multiple crystalline regions are connected where the orientation of the lattice arrangement changes between a region with an aligned lattice arrangement and another region with an aligned lattice arrangement. In other words, CAAC-OS is an oxide semiconductor that is c-axis oriented and does not have a clear orientation in the ab-plane direction. Furthermore, CAC-OS is a material composition in which, for example, the elements constituting the metal oxide are unevenly distributed in sizes of 0.5 Nm to 10 nm, preferably 1 nm to 3 nm, or close to that size. In the following, in a metal oxide, a state in which one or more metal elements are unevenly distributed, and the regions containing the metal elements are mixed in a size of 0.5 Nm to 10 nm, preferably 1 nm to 3 nm, or close to that size, is also referred to as a mosaic or patchy state.

[0295] Furthermore, since it can be used in low-temperature environments, it is preferable that the control circuit section 1320 uses a transistor made of oxide semiconductor. To simplify the process, the control circuit section 1320 may be formed using a unipolar transistor. Transistors using oxide semiconductors in the semiconductor layer have an operating ambient temperature range of -40°C to 150°C, which is wider than that of single-crystal Si, and the change in characteristics is smaller than that of single crystals even when the lithium-ion battery is heated. The off-current of a transistor using an oxide semiconductor is below the lower limit of measurement regardless of temperature, even at 150°C, but the off-current characteristics of a single-crystal Si transistor are highly temperature-dependent. For example, at 150°C, the off-current of a single-crystal Si transistor increases, and the current on / off ratio does not become sufficiently large. The control circuit section 1320 can improve safety.

[0296] The control circuit unit 1320, which uses a memory circuit including an oxide semiconductor transistor, can also function as an automatic control device for lithium-ion batteries to address 10 causes of instability, such as micro-short circuits. Functions to eliminate the 10 causes of instability include overcharge prevention, overcurrent prevention, overheat control during charging, cell balancing in the battery pack, over-discharge prevention, remaining charge indicator, automatic control of charging voltage and current according to temperature, control of charging current according to the degree of degradation, detection of abnormal behavior related to micro-short circuits, and prediction of abnormalities related to micro-short circuits. The control circuit unit 1320 has at least one of these functions. Furthermore, it is possible to miniaturize the automatic control device for lithium-ion batteries.

[0297] Furthermore, a micro-short refers to a tiny short circuit inside a lithium-ion battery. It does not mean that the positive and negative electrodes of the lithium-ion battery are short-circuited, rendering charging and discharging impossible. Rather, it refers to a phenomenon where a small short-circuit current flows through a tiny short circuit. Because even a relatively short-term short circuit in a small area can cause a significant voltage change, this abnormal voltage value may affect subsequent estimations.

[0298] One of the causes of micro-short circuits is said to be that, due to the uneven distribution of the positive electrode active material after multiple charge-discharge cycles, localized current concentration occurs in parts of the positive electrode and parts of the negative electrode, or micro-short circuits occur due to the generation of by-reactants from side reactions.

[0299] Furthermore, in addition to detecting micro-shorts, the control circuit unit 1320 also detects the terminal voltage of the lithium-ion battery and manages the charging and discharging state of the lithium-ion battery. For example, to prevent overcharging, both the output transistor and the cutoff switch of the charging circuit can be turned off almost simultaneously.

[0300] Furthermore, an example of a block diagram of the battery pack 1415 shown in Figure 10(B) is shown in Figure 10(C).

[0301] The control circuit unit 1320 includes at least a switch to prevent overcharging, a switch unit 1324 including a switch to prevent over-discharging, a control circuit 1322 that controls the switch unit 1324, and a voltage measurement unit for the first battery 1301a. The control circuit unit 1320 has upper and lower voltage limits set for the lithium-ion battery used, and limits the upper limit of external current and the upper limit of output current to the outside. Within the range between the lower voltage limit and the upper voltage limit of the lithium-ion battery, it is within the voltage range for which use is recommended, and if it goes outside this range, the switch unit 1324 activates and functions as a protection circuit. The control circuit unit 1320 can also be called a protection circuit because it controls the switch unit 1324 to prevent over-discharge and overcharge. For example, if the control circuit 1322 detects a voltage that is likely to cause overcharging, it cuts off the current by turning off the switch of the switch unit 1324. Furthermore, a PTC element may be provided in the charge / discharge path to provide a function to cut off the current in response to the rise in temperature. Furthermore, the control circuit unit 1320 has an external terminal 1325 (+IN) and an external terminal 1326 (-IN).

[0302] The switch section 1324 can be constructed by combining an n-channel transistor and a p-channel transistor. The switch section 1324 is not limited to a switch having a Si transistor using single-crystal silicon, but can also be made of, for example, Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), InP (indium phosphide), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), GaO x The switch section 1324 may be formed using a power transistor having a gallium oxide (where x is a real number greater than 0) or the like. Furthermore, since memory elements using OS transistors can be freely arranged by stacking them on circuits using Si transistors, integration can be easily achieved. Also, since OS transistors can be manufactured using the same manufacturing equipment as Si transistors, they can be manufactured at low cost. That is, by stacking a control circuit section 1320 using OS transistors on the switch section 1324 and integrating them, it is possible to create a single chip. Since the volume occupied by the control circuit section 1320 can be reduced, miniaturization becomes possible.

[0303] The first batteries 1301a and 1301b primarily supply power to 42V (high-voltage) onboard equipment, while the second battery 1311 supplies power to 14V (low-voltage) onboard equipment. Lead-acid batteries are often used for the second battery 1311 due to their cost advantages. Lead-acid batteries have the disadvantage of higher self-discharge and are more susceptible to degradation due to a phenomenon called sulfation compared to lithium-ion batteries. Using a lithium-ion battery for the second battery 1311 offers the advantage of being maintenance-free, but after long-term use, for example more than three years, there is a risk of malfunctions occurring that could not be detected at the time of manufacture. In particular, if the second battery 1311, which starts the inverter, becomes inoperable, it will be impossible to start the motor even if the first batteries 1301a and 1301b have remaining capacity. To prevent this, if the second battery 1311 is a lead-acid battery, power is supplied from the first battery to the second battery to keep it constantly charged to a full state.

[0304] This embodiment shows an example in which lithium-ion batteries are used for both the first battery 1301a and the second battery 1311. The second battery 1311 may be a lead-acid battery, an all-solid-state battery, or an electric double-layer capacitor. For example, the all-solid-state battery of Embodiment 5 may be used. By using the all-solid-state battery of Embodiment 5 for the second battery 1311, high capacity can be achieved, and the device can be made smaller and lighter.

[0305] Furthermore, the regenerative energy generated by the rotation of the tire 1316 is sent to the motor 1304 via the gear 1305 and charged to the second battery 1311 via the control circuit unit 1321 from the motor controller 1303 and battery controller 1302. Alternatively, it is charged to the first battery 1301a via the control circuit unit 1320 from the battery controller 1302. Alternatively, it is charged to the first battery 1301b via the control circuit unit 1320 from the battery controller 1302. In order to efficiently charge the regenerative energy, it is desirable that the first batteries 1301a and 1301b are capable of rapid charging.

[0306] The battery controller 1302 can set the charging voltage and charging current of the first batteries 1301a and 1301b. The battery controller 1302 can set the charging conditions according to the charging characteristics of the lithium-ion battery being used and enable rapid charging.

[0307] Although not shown in the diagram, when connected to an external charger, the charger's outlet or connection cable is electrically connected to the battery controller 1302. Power supplied from the external charger charges the first batteries 1301a and 1301b via the battery controller 1302. In some cases, the charger may have a control circuit and may not use the functions of the battery controller 1302, but it is preferable to charge the first batteries 1301a and 1301b via the control circuit unit 1320 to prevent overcharging. In some cases, the connection cable or the charger's connection cable may also have a control circuit. The control circuit unit 1320 is sometimes called an ECU (Electronic Control Unit). The ECU is connected to a CAN (Controller Area Network) installed in the electric vehicle. CAN is one of the serial communication standards used as an in-vehicle LAN. The ECU also includes a microcomputer. The ECU also uses a CPU or GPU.

[0308] External chargers installed at charging stations and other locations include 100V outlets, 200V outlets, and 3-phase 200V with 50kW output. Additionally, it is possible to charge by receiving power from external charging equipment using contactless power supply methods.

[0309] For rapid charging, lithium-ion batteries that can withstand high-voltage charging are desirable in order to achieve short charging times.

[0310] Next, we will describe an example in which a lithium-ion battery, which is one aspect of the present invention, is implemented in a vehicle, typically a transport vehicle.

[0311] Furthermore, by installing lithium-ion batteries in vehicles, next-generation clean energy vehicles such as hybrid vehicles (HV), electric vehicles (EV), or plug-in hybrid vehicles (PHV) can be realized. Lithium-ion batteries can also be installed in agricultural machinery, motorized bicycles including electric-assist bicycles, motorcycles, electric wheelchairs, electric carts, small or large ships, submarines, aircraft such as fixed-wing and rotary-wing aircraft, rockets, artificial satellites, space probes, planetary probes, and spacecraft. A lithium-ion battery according to one aspect of the present invention can be a high-capacity lithium-ion battery. Therefore, a lithium-ion battery according to one aspect of the present invention is suitable for miniaturization and weight reduction and can be suitably used in transport vehicles.

[0312] Figures 11(A) to 11(D) illustrate a transport vehicle using one embodiment of the present invention. The automobile 2001 shown in Figure 11(A) is an electric vehicle that uses an electric motor as a power source for driving. Alternatively, it is a hybrid vehicle that can appropriately select and use an electric motor and an engine as power sources for driving. When a lithium-ion battery is installed in the vehicle, one or more examples of the lithium-ion battery shown in the above embodiment are installed in one location. By applying an electrolyte layer according to one embodiment of the present invention to the lithium-ion battery installed in the vehicle, leakage can be suppressed.

[0313] The automobile 2001 shown in Figure 11(A) has a battery pack 2200, which has a lithium-ion battery module in which multiple lithium-ion batteries are connected. Furthermore, it is preferable to have a charge control device that is electrically connected to the lithium-ion battery module.

[0314] Furthermore, the automobile 2001 can be charged by receiving power from an external charging facility via a plug-in method or a contactless power supply method to the lithium-ion battery it possesses. For charging, the charging method and connector specifications may be carried out appropriately using a prescribed method such as CHAdeMO® or Combo. The lithium-ion battery may be supplied by a charging station located in a commercial facility, or by a household power supply. For example, the energy storage device mounted on the automobile 2001 can be charged by an external power supply using plug-in technology. Charging can be performed by converting AC power to DC power via a conversion device such as an AC / DC converter.

[0315] Although not shown in the diagram, the vehicle can also be charged by mounting a power receiving device on the vehicle and receiving power wirelessly from a ground-based power transmission device. In this wireless power supply method, charging can be performed not only when the vehicle is stopped but also while it is in motion by incorporating the power transmission device into the road or exterior wall. Furthermore, this wireless power supply method can be used to transmit and receive power between two vehicles. In addition, solar panels can be installed on the exterior of the vehicle to charge the lithium-ion battery when the vehicle is stopped and when it is in motion. For such wireless power supply, an electromagnetic induction method or a magnetic resonance method can be used.

[0316] Figure 11(B) shows a large transport vehicle 2002 equipped with an electrically controlled motor as an example of a transport vehicle. The lithium-ion battery module of the transport vehicle 2002 has a maximum voltage of 170V, achieved by connecting 48 cells in series, each consisting of four lithium-ion batteries with a nominal voltage of 3.0V to 5.0V. Except for differences in the number of lithium-ion batteries constituting the lithium-ion battery module of the battery pack 2201, it has the same functions as Figure 10(B), so the explanation is omitted. By applying an electrolyte layer according to one aspect of the present invention to the lithium-ion batteries of the battery pack 2201, leakage can be suppressed.

[0317] Figure 11(C) shows, as an example, a large transport vehicle 2003 equipped with an electrically controlled motor. The lithium-ion battery module of the transport vehicle 2003 has the same functions as that of Figure 10(B), except that it has a maximum voltage of 600V, achieved by connecting more than 100 lithium-ion batteries in series, for example, with a nominal voltage of 3.0V to 5.0V, and the number of lithium-ion batteries constituting the lithium-ion battery module of the battery pack 2202 is different, so the explanation is omitted. By applying an electrolyte layer, which is one aspect of the present invention, to the lithium-ion batteries in the module, leakage can be suppressed.

[0318] Figure 11(D) shows an example of an aircraft 2004 having a fuel-burning engine. The aircraft 2004 shown in Figure 11(D) has wheels for takeoff and landing, and can therefore be considered part of a transport vehicle. It has a battery pack 2203 which includes a lithium-ion battery module formed by connecting multiple lithium-ion batteries and a charging control device.

[0319] The lithium-ion battery module for aircraft 2004 has a maximum voltage of 32V, for example, by connecting eight 4V lithium-ion batteries in series. The lithium-ion battery module of battery pack 2203 has the same functionality as Figure 10(B), except for differences in the number of lithium-ion batteries that make up the module, so a detailed explanation is omitted.

[0320] The contents of this embodiment can be appropriately combined with the contents of other embodiments.

[0321] (Embodiment 5) This embodiment shows an example in which a lithium-ion battery according to one aspect of the present invention is mounted on a vehicle such as a motorcycle or bicycle.

[0322] Figure 12(A) shows an example of an electric bicycle using a lithium-ion battery according to one embodiment of the present invention. The lithium-ion battery according to one embodiment of the present invention can be applied to the electric bicycle 8700 shown in Figure 12(A). The lithium-ion battery according to one embodiment of the present invention may have a protection circuit.

[0323] The electric bicycle 8700 is equipped with a power storage device 8702. The power storage device 8702 can supply electricity to a motor that assists the rider. The power storage device 8702 is also portable, and Figure 12(B) shows it detached from the bicycle. The power storage device 8702 also contains multiple lithium-ion batteries 8701 according to one embodiment of the present invention, and the remaining battery level and other information can be displayed on a display unit 8703. By applying an electrolyte layer according to one embodiment of the present invention to the lithium-ion batteries 8701, leakage can be suppressed.

[0324] Furthermore, the energy storage device 8702 has a control circuit 8704 capable of controlling the charging of the lithium-ion battery or detecting abnormalities, as exemplified in Embodiment 7. The control circuit 8704 is electrically connected to the positive and negative electrodes of the lithium-ion battery 8701. This can greatly contribute to eliminating accidents such as fires caused by lithium-ion batteries.

[0325] Figure 12(C) shows an example of a motorcycle using a lithium-ion battery according to one embodiment of the present invention. The scooter 8600 shown in Figure 12(C) is equipped with a power storage device 8602, side mirrors 8601, and turn signals 8603. The power storage device 8602 can supply electricity to the turn signals 8603. By applying an electrolyte layer according to one embodiment of the present invention to the lithium-ion battery, leakage can be suppressed.

[0326] The scooter 8600 shown in Figure 12(C) can accommodate the power storage device 8602 in the under-seat storage compartment 8604. The power storage device 8602 can be stored in the under-seat storage compartment 8604 even if the under-seat storage compartment 8604 is small.

[0327] The contents of this embodiment can be appropriately combined with the contents of other embodiments.

[0328] (Embodiment 6) This embodiment describes an example of mounting a lithium-ion battery, which is one aspect of the present invention, in an electronic device. Examples of electronic devices that mount lithium-ion batteries include television equipment (also called televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (also called mobile phones or mobile phone devices), portable game consoles, personal information terminals, sound playback devices, and large game machines such as pachinko machines. Personal information terminals include notebook personal computers, tablet terminals, e-book readers, and mobile phones.

[0329] Figure 13(A) shows an example of a mobile phone. The mobile phone 2100 includes a display unit 2102 built into the housing 2101, as well as operation buttons 2103, an external connection port 2104, a speaker 2105, a microphone 2106, and the like. The mobile phone 2100 also has a lithium-ion battery 2107. By applying an electrolyte layer according to one aspect of the present invention to the lithium-ion battery, leakage can be suppressed.

[0330] The mobile phone 2100 can run various applications such as making phone calls, sending emails, reading and creating documents, playing music, communicating on the internet, and playing computer games.

[0331] The operation button 2103 can be assigned various functions, including time setting, power on / off operation, wireless communication on / off operation, silent mode activation / deactivation, and power saving mode activation / deactivation. For example, the function of the operation button 2103 can be freely configured by the operating system built into the mobile phone 2100.

[0332] Furthermore, the 2100 mobile phone is capable of performing standardized short-range wireless communication. For example, it can communicate with a wireless headset to enable hands-free calling.

[0333] Furthermore, the mobile phone 2100 is equipped with an external connection port 2104, which allows for direct data exchange with other information terminals via a connector. It can also be charged via the external connection port 2104. Note that charging may also be performed wirelessly without using the external connection port 2104.

[0334] The mobile phone 2100 preferably has sensors. For example, it is preferable that the sensor includes a human body sensor such as a fingerprint sensor, pulse sensor, or body temperature sensor, as well as a touch sensor, pressure sensor, acceleration sensor, etc.

[0335] Figure 13(B) shows an unmanned aerial vehicle 2300 having multiple rotors 2302. The unmanned aerial vehicle 2300 is sometimes called a drone. The unmanned aerial vehicle 2300 has a lithium-ion battery 2301, a camera 2303, and an antenna (not shown), which are embodiments of the present invention. The unmanned aerial vehicle 2300 can be remotely controlled via the antenna. By applying an electrolyte layer, which are embodiments of the present invention, to the lithium-ion battery, leakage can be suppressed.

[0336] Figure 13(C) shows an example of a robot. The robot 6400 shown in Figure 13(C) is equipped with a lithium-ion battery 6409, an illuminance sensor 6401, a microphone 6402, an upper camera 6403, a speaker 6404, a display unit 6405, a lower camera 6406, an obstacle sensor 6407, a movement mechanism 6408, a computing device, and the like.

[0337] Microphone 6402 has the function of detecting the user's voice and ambient sounds. Speaker 6404 has the function of emitting sound. Robot 6400 can communicate with the user using microphone 6402 and speaker 6404.

[0338] The display unit 6405 has the function of displaying various types of information. The robot 6400 can display the user's desired information on the display unit 6405. The display unit 6405 may be equipped with a touch panel. The display unit 6405 may also be a detachable information terminal, and by installing it in a fixed position on the robot 6400, charging and data transfer can be enabled.

[0339] The upper camera 6403 and the lower camera 6406 have the function of imaging the area around the robot 6400. In addition, the obstacle sensor 6407 can detect the presence or absence of obstacles in the direction of travel when the robot 6400 moves forward using the movement mechanism 6408. The robot 6400 can recognize its surrounding environment and move safely using the upper camera 6403, the lower camera 6406 and the obstacle sensor 6407.

[0340] The robot 6400 is equipped with a lithium-ion battery 6409 according to one aspect of the present invention and a semiconductor device or electronic components in its internal region. By applying an electrolyte layer according to one aspect of the present invention to the lithium-ion battery, leakage can be suppressed.

[0341] Figure 13(D) shows an example of a cleaning robot. The cleaning robot 6300 has a display unit 6302 located on the top surface of the housing 6301, multiple cameras 6303 located on the sides, a brush 6304, operation buttons 6305, a lithium-ion battery 6306, and various sensors. Although not shown, the cleaning robot 6300 is equipped with wheels, a suction port, etc. The cleaning robot 6300 is self-propelled, can detect dirt 6310, and can suck up the dirt from a suction port located on the bottom surface.

[0342] For example, the cleaning robot 6300 can analyze images captured by the camera 6303 to determine the presence or absence of obstacles such as walls, furniture, or steps. Furthermore, if the image analysis detects an object that might become entangled in the brush 6304, such as wiring, the rotation of the brush 6304 can be stopped. The cleaning robot 6300 is equipped with a lithium-ion battery 6306 according to one aspect of the present invention and a semiconductor device or electronic component in its internal region. By applying an electrolyte layer according to one aspect of the present invention to the lithium-ion battery, leakage can be suppressed.

[0343] This embodiment can be implemented in appropriate combination with other embodiments.

[0344] (Embodiment 7) This embodiment describes an example of implementing a lithium-ion battery, which is one aspect of the present invention, in space equipment.

[0345] Figure 14(A) shows satellite 6800 as an example of space equipment. Satellite 6800 consists of the airframe 6801, solar panels 6802, an antenna 6803, and a lithium-ion battery 6805. The solar panels are sometimes called solar cell modules.

[0346] When sunlight shines on the solar panel 6802, the power necessary for the satellite 6800 to operate is generated. However, in situations where, for example, sunlight does not shine on the solar panel, or when the amount of sunlight shining on the solar panel is low, the amount of power generated will decrease. Therefore, there is a possibility that the power necessary for the satellite 6800 to operate will not be generated. To operate the satellite 6800 even under conditions where the amount of power generated is low, it is advisable to provide the satellite 6800 with a lithium-ion battery 6805. By applying an electrolyte layer, which is one aspect of the present invention, to the lithium-ion battery, leakage can be suppressed.

[0347] The satellite 6800 can generate a signal. This signal is transmitted via antenna 6803, and can be received by, for example, a receiver on the ground or another satellite. By receiving the signal transmitted by satellite 6800, the position of the receiver that received the signal can be measured, for example. Thus, satellite 6800 can constitute, for example, a satellite positioning system.

[0348] Alternatively, the satellite 6800 can be configured to include sensors. For example, by configuring it to include a visible light sensor, the satellite 6800 can have the function of detecting sunlight reflected off objects on the ground. Alternatively, by configuring it to include a thermal infrared sensor, the satellite 6800 can have the function of detecting thermal infrared radiation emitted from the Earth's surface. Thus, the satellite 6800 can function, for example, as an Earth observation satellite.

[0349] Figure 14(B) shows a spacecraft 6900 equipped with a solar sail as an example of space equipment. The spacecraft 6900 comprises a body 6901, a solar sail 6902, and a lithium-ion battery 6905. By applying an electrolyte layer, which is one aspect of the present invention, to the lithium-ion battery, leakage can be suppressed. When photons emitted from the sun strike the surface of the solar sail 6902, momentum is transferred to the solar sail 6902. Therefore, the surface of the solar sail 6902 preferably has a thin film with high reflectivity, and more preferably faces the direction of the sun.

[0350] Alternatively, the Solar Sail 6902 may be designed to remain compactly folded until it leaves the Earth's atmosphere (in outer space), where it unfolds into a large sheet-like structure as shown in Figure 14(B).

[0351] Figure 14(C) shows a spacecraft 6910 as an example of space equipment. The spacecraft 6910 comprises a body 6911, a solar panel 6912, and a lithium-ion battery 6913. By applying an electrolyte layer, which is one aspect of the present invention, to the lithium-ion battery, leakage can be suppressed. The body 6911 may have, for example, a pressurized chamber and an unpressurized chamber. The pressurized chamber may be designed to accommodate a crew. The electricity generated when sunlight is shone on the solar panel 6912 can be used to charge the lithium-ion battery 6913.

[0352] Figure 14(D) shows a rover 6920 as an example of space equipment. The rover 6920 comprises a body 6921 and a lithium-ion battery 6923. By applying an electrolyte layer according to one aspect of the present invention to the lithium-ion battery, leakage can be suppressed. The rover 6920 may also have a solar panel 6922.

[0353] The rover 6920 may be designed to accommodate a crew. The lithium-ion battery 6923 may be charged with electricity generated by sunlight irradiating the solar panel 6912, or it may be charged with electricity generated by other power sources, such as a fuel cell or a radioisotope thermoelectric converter.

[0354] The contents of this embodiment can be appropriately combined with the contents of other embodiments.

[0355] (Embodiment 8) This embodiment describes an example of the form of the lithium-ion battery described in the previous embodiment.

[0356] For example, the laminated lithium-ion battery 100 described above can be bent. In other words, the lithium-ion battery 100 is flexible.

[0357] Figure 15(A) shows a bent lithium-ion battery 100. Figure 15(A) shows a lithium-ion battery 100 having a positive electrode layer 107, an electrolyte layer 103, and a negative electrode layer 106, in a bent shape toward the positive electrode layer 107. Of course, the lithium-ion battery 100 can also have a shape bent toward the negative electrode layer 106. Applying the electrolyte layer 103, which is one aspect of the present invention, to the bent lithium-ion battery 100 is preferable because it suppresses leakage. Note that the bent shape includes a shape in which one cross-section of the lithium-ion battery 100 has an arc-shaped portion.

[0358] The smallest unit constituting a lithium-ion battery is referred to as a battery unit, and the battery unit is defined as having a positive electrode layer 107, an electrolyte layer 103, and a negative electrode layer 106. In one embodiment of the present invention, the lithium-ion battery 100 may have a plurality of such battery units. That is, the lithium-ion battery 100 may have a configuration in which a plurality of such battery units are stacked. Applying the electrolyte layer 103, which is one embodiment of the present invention, to a curved lithium-ion battery 100 suppresses leakage, making it suitable when stacking units.

[0359] Figure 15(A) shows a single battery unit, but a configuration with multiple battery units stacked on top of each other is also possible.

[0360] Although the lithium-ion battery 100 also has an outer casing, the outer casing described in the above embodiment can conform to a bent battery unit. Therefore, the outer casing is not shown in Figure 15(A).

[0361] Next, we will describe the bent state in detail. As shown in Figure 15(A), in the lithium-ion battery 100, the radius of curvature of the layer closer to the center of curvature 1800, for example, the positive electrode layer 107, is smaller than the radius of curvature of the layer further away from the center of curvature 1800, for example, the negative electrode layer 106, is smaller. To make it easier to bend, it is preferable to make the thickness of the layer with a smaller radius of curvature, for example, the positive electrode layer 107, smaller than that of the negative electrode layer 106.

[0362] As shown in Figure 15(B), when the lithium-ion battery 100 is bent as shown in Figure 15(A), compressive stress is applied to the surface of the positive electrode layer 107 and tensile stress is applied to the surface of the negative electrode layer 106, as indicated by the arrows. To alleviate the compressive stress, the layer with a smaller radius of curvature, such as the positive electrode layer 107, may be made thicker than the negative electrode layer 106.

[0363] As one way to alleviate the compressive and tensile stresses mentioned above, a configuration in which recesses and protrusions are provided on the exterior body will be explained using Figure 16.

[0364] The recesses and protrusions are formed on the surface of the exterior body 509, creating a pattern-like appearance. As can be seen in one cross-section of the exterior body 509, when protrusions are provided on the exterior body, recesses are also formed simultaneously, and when recesses are provided on the exterior body, protrusions are also formed simultaneously. In other words, it is not necessary to form both recesses and protrusions on the exterior body; providing one will simultaneously form the other.

[0365] The outer casing 509 can alleviate the compressive and tensile stresses mentioned above. In other words, the lithium-ion battery 100 can be deformed within a range where the radius of curvature of the outer casing on the side closer to the center of curvature is 30 mm or more, preferably 10 mm or more.

[0366] The end of the outer casing 509 shown in Figure 16 has an adhesive region 1807. The adhesive region 1807 is the area where the outer casing 509 is bonded by heat compression or the like. In the adhesive region 1807, an adhesive layer 1803 is preferably located between the outer casing 509.

[0367] In the bonding region 1807, it is preferable that the recesses or protrusions provided on the upper and lower parts of the outer casing 509 overlap. To ensure that the recesses or protrusions overlap, recesses or protrusions may be formed on the outer casing 509 again when bonding the outer casing. This configuration can increase the bonding strength.

[0368] Figure 16 shows a lithium-ion battery 100 in which the end portion of the outer casing 509, region 1808 which is not the adhesive region 1807, has a space 1810.

[0369] The shape of the curved lithium-ion battery 100 is not limited to a simple arc shape in cross-sectional view, but may also have a shape that is partly an arc. For example, it can be the shape shown in Figure 15(C), or the wavy or S-shaped shape shown in Figure 15(D). The lithium-ion battery 100 shown in Figures 15(C) and 15(D) can also be fitted with the casing having the aforementioned recesses or protrusions, and multiple stacked battery units can be fitted.

[0370] As shown in Figure 15(C) or Figure 15(D), if the curved surface of the lithium-ion battery 100 has a shape with multiple centers of curvature, the lithium-ion battery can be bent in a range where the radius of curvature of the outer casing closest to the center of curvature is 10 mm or more, preferably 30 mm or more.

[0371] This embodiment can be used in combination with other embodiments.

[0372] (Embodiment 9) This embodiment describes an example of an application of lithium-ion batteries.

[0373] Figure 17(A) is a perspective view showing an example of an aircraft. Figure 17(B) is a perspective view illustrating the interior of the main wing section shown in Figure 17(A).

[0374] The aircraft 8900 shown in Figure 17(A) has a main wing section 8901, a propeller 8902, a vertical stabilizer section 8903, a horizontal stabilizer section 8904, a control device 8905, and a solar panel 8906. The solar panel is sometimes called a solar cell module.

[0375] The aircraft 8900 may have skids. The skids may, for example, be mounted on the underside of the main wing section 8901. Wheels may also be mounted on the underside of the skids.

[0376] Furthermore, as shown in Figure 17(B), the aircraft 8900 has lithium-ion batteries 8907 inside the main wing section 8901. Figure 17(B) shows an example in which multiple lithium-ion batteries 8907, each having a roughly rectangular top surface shape, are arranged inside the main wing section 8901. In Figure 17(B), multiple lithium-ion batteries 8907 are shown arranged in a single row inside the main wing section 8901, but multiple lithium-ion batteries 8907 may be arranged in multiple rows. Also, the top surface shape of the lithium-ion battery 8907 is not limited to a rectangle, and can take various shapes such as polygons other than rectangles, polygons with rounded corners, circles, ellipses, L-shapes, etc.

[0377] Figure 17(C) is a cross-sectional view along the dashed line A1-A2 shown in Figures 17(A) and 17(B).

[0378] In Figure 17(C), the solar panel 8906 is provided so as to be embedded in the surface of the housing 8911 of the main wing portion 8901. The solar panel 8906 has, for example, a region that is in contact with the housing 8911. When the solar panel 8906 is provided so as to be embedded in the housing 8911, the light-receiving portion of the solar panel 8906 has a region that is exposed to the outside. Also, although Figure 17(C) shows an example in which the solar panel 8906 is provided so as to be embedded in the housing 8911, the solar panel 8906 may also be provided on the outer surface of the housing 8911.

[0379] Furthermore, in Figure 17(C), the lithium-ion battery 8907 is provided along the inner wall 8912 of the housing 8911 of the main wing portion 8901. The lithium-ion battery 8907 has, for example, a region that is in contact with the inner wall 8912.

[0380] By using an electrolyte layer according to one embodiment of the present invention as the lithium-ion battery 8907, leakage can be suppressed.

[0381] It is preferable to use a bendable (or flexible) lithium-ion battery as the lithium-ion battery 8907. The main wing section 8901 may deform in response to external forces during the flight of the aircraft 8900. Using a flexible lithium-ion battery as the lithium-ion battery 8907 is preferable because it allows the lithium-ion battery 8907 to deform in accordance with the deformation of the main wing section 8901. Furthermore, with a flexible lithium-ion battery, it is possible to increase the weight and miniaturize the lithium-ion battery by using a thin film for the outer casing of the lithium-ion battery. This makes it possible to lighten the aircraft 8900, thus reducing the power required for the flight of the aircraft 8900. In addition, because the lithium-ion battery can be miniaturized, the energy density per unit volume of the lithium-ion battery can be increased, and the flight distance of the aircraft 8900 per unit volume of lithium-ion battery can be increased.

[0382] Because the flexible lithium-ion battery can be bent, the upper and lower surfaces of the main wing section 8901 can be made into smooth curved surfaces, as shown in Figures 18(A) and 18(B). Figure 18(A) is a perspective view showing an example of an aircraft, and Figure 18(B) is a perspective view illustrating the interior of the main wing section in Figure 18(A).

[0383] In Figure 18(A), the solar panel 8906 is mounted along the smooth upper surface of the main wing section 8901. A solar cell module mounted on a flexible substrate may be used as the solar panel 8906.

[0384] In Figure 18(B), the lithium-ion battery 8907 is provided along the inner wall of the housing of the main wing section 8901. It is preferable to use a flexible lithium-ion battery as the lithium-ion battery 8907 shown in Figure 18(B).

[0385] By using a flexible lithium-ion battery as the lithium-ion battery 8907, the main wing section 8901 can be made into various shapes, which may improve the flight performance of the aircraft 8900.

[0386] It is preferable that the control device 8905 be positioned opposite the solar panel 8906, with the main wing section 8901 in between. For example, if the solar panel 8906 is positioned on the upper side of the main wing section 8901, the control device 8905 should be positioned on the lower side of the main wing section 8901. The temperature of the solar panel 8906 may rise during the period when it is generating electricity by receiving sunlight. By positioning the control device 8905 on the opposite side of the main wing section 8901, it may be possible to suppress the temperature rise of the control device 8905 and ensure stable operation of each component and circuit of the control device.

[0387] The main wing section 8901 of the aircraft 8900 may have thermal insulation. The thermal insulation may be provided, for example, along the inner wall 8912 of the housing 8911, or embedded in the housing 8911. By providing thermal insulation, the influence of temperature from the outside to the inside of the housing 8911 can be reduced.

[0388] By placing an insulating material between the solar panel 8906 and the lithium-ion battery 8907, it may be possible to reduce the thermal impact from the solar panel 8906 to the lithium-ion battery 8907.

[0389] When the lithium-ion battery 8907 is operated at high temperatures, degradation of the lithium-ion battery 8907, such as a decrease in discharge capacity, may occur. Furthermore, the output characteristics of the lithium-ion battery 8907 may deteriorate at low temperatures. By reducing temperature fluctuations inside the housing 8911, the lifespan of the lithium-ion battery can be extended. Additionally, the operation of the lithium-ion battery can be stabilized.

[0390] In the aircraft 8900, it is preferable that the power generated by the solar panel 8906 is stored in the lithium-ion battery 8907. The aircraft 8900 has a power control circuit. The power control circuit has the function of controlling the charging and discharging of the lithium-ion battery 8907. It is also preferable that the power control circuit has the function of measuring at least one of the amount of light received and the amount of power generated by the solar panel 8906. The power generated by the solar panel 8906 is charged into the lithium-ion battery 8907 via the power control circuit. It is also preferable that the power control circuit has the function of measuring the remaining charge of the lithium-ion battery 8907.

[0391] The control device 8905 has the function of controlling the flight of the aircraft 8900. The control device 8905 can control the flight of the aircraft 8900, for example, by controlling the rotation of the propeller 8902.

[0392] The power control circuit has the function of supplying power stored in the lithium-ion battery 8907 to the propeller 8902. Preferably, the power control circuit has the function of converting direct current to alternating current.

[0393] It is preferable that at least a portion of the power control circuit be located in the control device 8905. Alternatively, a portion of the power control circuit may be provided inside the housing 8911 of the main wing section 8901. For example, as part of the power control circuit, a protection circuit corresponding to each of the multiple lithium-ion batteries 8907 may be provided. The protection circuit has a function to suppress one or more of the lithium-ion batteries, such as overcharging, over-discharging, overcurrent during charging, overcurrent during discharging, and short circuits. Furthermore, if there are multiple lithium-ion batteries 8907 connected in series, it is preferable that the power control circuit has a cell balancing circuit that equalizes the charge levels of each of the multiple lithium-ion batteries 8907.

[0394] In addition, in the aircraft 8900, the charging of the lithium-ion battery 8907 with electricity generated by the solar panel 8906 and the supply of power from the lithium-ion battery 8907 to the propeller 8902 may occur simultaneously.

[0395] Furthermore, the aircraft 8900 has an antenna. The aircraft 8900 has the function of performing wireless communication using the antenna. Multiple antennas may be provided on the aircraft 8900. For example, a multi-beam antenna can be used as the antenna.

[0396] For example, the 8900 aircraft can function as a radio base station.

[0397] The aircraft 8900 can, for example, fly in the stratosphere and provide a stratospheric platform. The aircraft 8900 can also communicate with base stations installed on the ground. Furthermore, multiple aircraft 8900s may each form a base station. In such cases, communication between multiple aircraft is preferable. The aircraft 8900 may also have the function of sending and receiving signals with artificial satellites. The aircraft 8900 can provide wireless communication services from the stratospheric platform to user terminals on the ground. Here, a user terminal is, for example, a smartphone. The aircraft 8900 may orbit above the area where the wireless communication service is to be provided. Standardized communication protocols or technologies such as LTE (Long Term Evolution), GSM (Global System for Mobile Communication: registered trademark), EDGE (Enhanced Data Rates for GSM Evolution), CDMA2000 (Code Division Multiple Access 2000), and W-CDMA (registered trademark) can be used. Additionally, it is possible to use third-generation mobile communication systems (3G), fourth-generation mobile communication systems (4G), or fifth-generation mobile communication systems (5G) as defined by the International Telecommunication Union (ITU).

[0398] The control device 8905 may have an imaging device. The aircraft 8900 can use the imaging device to photograph the air, ground, or sky while flying.

[0399] The control device 8905 may have sensors (including those with functions to measure force, displacement, position, velocity, acceleration, angular velocity, rotational speed, distance, light, liquid, magnetism, temperature, chemical substances, sound, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor, or infrared radiation).

[0400] The contents of this embodiment can be freely combined with the contents of other embodiments. [Examples]

[0401] <Preparation of the electrolyte layer> In this embodiment, an electrolyte layer according to one aspect of the present invention was prepared.

[0402] First, the polymer material and solvent were mixed for 5 minutes to obtain mixture A. The polymer material used was PDMAEMA (manufactured by Kanto Chemical Co., Ltd.) dissolved in toluene (containing 30% toluene). The solvent used was an ionic liquid (hereinafter referred to as EMI-FSI) with EMI as the cation and FSI as the anion, and a liquid material was prepared by adding LiFSI, a lithium salt, to EMI-FSI at a concentration of 2.15 mol / L. 80 g of the polymer material was mixed with 1 L of this liquid material to obtain mixture A.

[0403] Subsequently, a crosslinking agent was added and the mixture was mixed for another 5 minutes to obtain a fluid mixture B. C12TFSA (manufactured by Kanto Chemical Co., Ltd.) was used as the crosslinking agent.

[0404] <Toluene Removal> To investigate the conditions for removing toluene, an impurity, from mixture B, the mixture B was placed in a vacuum drying oven and subjected to three treatments: treatment condition 1 at 100°C for 1 hour and 30 minutes, treatment condition 2 at 80°C for 1 hour and 30 minutes, and treatment condition 3 without heat treatment. Before starting the heat treatment, the differential pressure gauge in the vacuum drying oven was below -100 kPa.

[0405] Mixture B, which has undergone treatment conditions 1 to 3, is dissolved in a deuterium acetonitrile solution, and then subjected to nuclear magnetic resonance ( 1 The measurements were taken by 1H NMR. Figure 19(A) shows the chart corresponding to mixed solution B treated under treatment condition 1. Figure 19(B) shows the chart corresponding to mixed solution B treated under treatment condition 2. Figure 19(C) shows the chart corresponding to mixed solution B treated under treatment condition 3.

[0406] In Figure 19(C), an arrow is drawn to indicate the toluene peak. Since the toluene peak was not observed in Figures 19(A) and 19(B), it was determined that to remove toluene from mixture B, mixture B should be treated under treatment condition 2 or treatment condition 3. Furthermore, considering that the time for treatment condition 2 is equal to the time for treatment condition 3, it is considered preferable to perform heat treatment at 80°C or higher to remove toluene from mixture B.

[0407] <llzao> Next, using a Pasteur pipette, add 30 drops (equivalent to 0.68 g) of mixture A, and the solid electrolyte Li 6.25 La3Zr2Al 0.25 O 12 Mixture C was prepared by dropping it onto (manufactured by Toyoshima Seisakusho, hereinafter referred to as LLZAO in this embodiment) and kneading it with a spatula. Mixture C was semi-solid, i.e., a gel. Subsequently, mixture C was placed in a vacuum drying oven and heated at 80°C for 1 hour and 30 minutes, corresponding to the above processing conditions 2, to obtain mixture D shown in Figure 20(A). Through holes were visually observed in mixture D. These through holes were thought to have been caused by the volatilization of toluene.

[0408] Therefore, the inventors used a Pasteur pipette to add 10 drops (equivalent to 0.2 g) of mixture A, and kneaded the mixture A with 0.5 g of LLZAO using a spatula to prepare mixture E. Then, mixture E was placed in a vacuum drying oven and heated at 80°C for 1 hour and 30 minutes, corresponding to the above processing conditions 2, to obtain mixture F shown in Figure 20(B). No through-holes were observed in mixture F by visual inspection. Mixture F, which does not have through-holes, is suitable for the electrolyte layer.

[0409] Next, the mixture F was sandwiched between PFA sheets and processed into a sheet with a film thickness between 0.7 mm and 0.8 mm. After heating at 80°C for 1 hour and 30 minutes according to processing conditions 2, a mixture G without visible through-holes was created, as shown in Figure 20(C). Mixture G could be easily punched out in a circular shape. By using mixture G, which has no visible through-holes, as the electrolyte layer, a lithium-ion battery without a separator can be created. Furthermore, since mixture G has ionic conductivity and also acts as a binder to bind particles such as solid materials together, there is no need to add a binder that would create resistance, and an improvement in capacity can be expected.

[0410] <Coin cell fabrication> Next, coin cells were fabricated for charge-discharge testing. Mixture G was used for the electrolyte layer of the coin cells.

[0411] For the positive electrode active material of the coin cell, a lithium nickel-cobalt-manganese composite oxide (hereinafter referred to as NCM811) with a nickel, cobalt, and manganese ratio of Ni:Co:Mn=8:1:1 was used. Aluminum foil was used for the positive electrode current collector.

[0412] AB was used as the conductive material for the coin cell, and PVDF was used as the binder. The mixing ratio of these materials was NCM811:AB;PVDF = 95:3:2. No separator was placed in the coin cell.

[0413] Lithium metal was used as the negative electrode of the coin cell. Coin cells using lithium metal are sometimes called half cells, and the lithium metal is sometimes referred to as the counter electrode.

[0414] Mixture A was used as the electrolyte for the positive and negative electrodes of the coin cell. Specifically, mixture A was added dropwise to the positive or negative electrode active material layer using a Pasteur pipette. Sample 1 was prepared by adding 2 drops (equivalent to 0.04 g) to both the positive and negative electrode layers, Sample 2 was prepared by adding 2 drops (equivalent to 0.04 g) only to the positive electrode layer, and Sample 3 was prepared by not adding mixture A.

[0415] <Measurement of discharge capacity> Next, the discharge capacities of samples 1 through 3 were measured using a charge / discharge measurement system (TOSCAT-3100) manufactured by Toyo System Co., Ltd. as the charge / discharge measuring instrument.

[0416] When measuring the discharge capacity, the rate conditions were set to 0.05C, 0.1C, 0.2C, and 0.5C. The above rates are explained below. Rate is the relative ratio of the discharge current to the battery capacity, or the relative ratio of the charge current, and is expressed in units of C. For example, in a battery with a rated capacity of X (Ah), the current equivalent to 1C is X (A). When measuring the discharge capacity and cycle characteristics, if the battery is discharged with a current of 2X (A), it is said to have been discharged at a rate of 2C, and if it is discharged with a current of X / 2 (A), it is said to have been discharged at a rate of 0.5C. Note that this rate can be understood by substituting charge for discharge. In this embodiment, 1C = 200mA / g.

[0417] Other conditions included placing samples 1 to 3 in a 25°C environment and performing constant-current charging (referred to as CC charging) until the cutoff voltage reached 4.3V, at which point charging was terminated. Subsequently, constant-current discharge (referred to as CC discharge) was performed at the same rate until the cutoff voltage reached 2.5V. The amount of current flowing through the charge / discharge measurement system during CC discharge was measured, and the integrated amount of current flowing during discharge was calculated and converted into discharge capacity.

[0418] The discharge capacity (mAh / g) results for samples 1 to 3 are shown in Figure 21. The horizontal axis of Figure 21 shows the rate conditions.

[0419] Samples 1 through 3 were found to be able to be charged and discharged without the placement of a separator. The discharge capacity of samples 1 and 2 was higher than that of sample 3. In all samples 1 through 3, the discharge capacity increased as the rate decreased. [Examples]

[0420] In this example, instead of LLZAO used in Samples 1 to 3, magnesium oxide (MgO) powder, an inorganic material, was used, and the same experiment as in Sample 3 of Example 1 was conducted. In this case, 1.00 g of MgO and 0.85 g of mixed solution A were used. The sample using MgO was designated as Sample 4. Sample 4 exhibited high tackiness.

[0421] The discharge capacity (mAh / g) results for samples 3 and 4 are shown in Figure 22. The horizontal axis of Figure 22 shows the rate conditions.

[0422] Sample 4 was found to be able to be charged and discharged without the placement of a separator. Furthermore, it was found that Sample 4, which used MgO, had a higher discharge capacity than Sample 3, which used LLZAO. [Explanation of Symbols]

[0423] 100 Lithium-ion batteries 101 Negative electrode current collector 102 Negative electrode active material layer 103_1 First electrolyte layer 103_2 Second electrolyte layer 103 Electrolyte layer 104 Cathode active material layer 105 Positive electrode current collector 106 Negative electrode layer 107 Positive electrode layer 110 Separator 111 Solvent 113 Solid materials 114 Polymer chain 115 Gel 117 Cathode active material 119 Negative electrode active material< / llzao>

Claims

1. A sheet-shaped electrolyte layer is disposed between an anode layer and a cathode layer, the electrolyte layer does not contain polyvinylidene fluoride and contains a gel and a solid electrolyte; The gel has polymer chains. Lithium-ion battery.

2. A battery comprising a sheet-shaped electrolyte layer located between an anode layer and a cathode layer, the electrolyte layer does not include polyvinylidene fluoride and includes a mixture including a polymer material, an ionic liquid, and a solid electrolyte; The mixture forms a semi-solid. Lithium-ion battery.

3. In claim 1 or 2, The solid electrolyte comprises LLZAO. Lithium-ion battery.

4. A sheet-shaped electrolyte layer is disposed between an anode layer and a cathode layer, the electrolyte layer is free of polyvinylidene fluoride and includes a gel and an oxide material; The gel has polymer chains. Lithium-ion battery.

5. In claim 4, The oxide material comprises magnesium oxide. Lithium-ion battery.

6. In claim 1 or 4, The gel includes the polymer chains and a solvent, The solvent comprises an ionic liquid. Lithium-ion battery.

7. In claim 1 or 4, The gel includes the polymer chains and a solvent, The solvent comprises an ionic liquid having a lithium salt dissolved therein. Lithium-ion battery.

8. In claim 1 or 4, The gel includes the polymer chains and a solvent, The solvent comprises EMI-FSI having LiFSI dissolved therein; Lithium-ion battery.

9. a sheet-shaped semi-solid electrolyte layer located between an anode layer and a cathode layer; The semi-solid electrolyte layer does not contain polyvinylidene fluoride, and has a solid electrolyte and a polymer chain. Lithium-ion battery.

10. A battery comprising a sheet-like semi-solid electrolyte layer located between an anode layer and a cathode layer, The semi-solid electrolyte layer does not include polyvinylidene fluoride, and includes a mixture including a polymer material, an ionic liquid, and a solid electrolyte. Lithium-ion battery.

11. In claim 9 or 10, The solid electrolyte comprises LLZAO. Lithium-ion battery.

12. a sheet-shaped semi-solid electrolyte layer located between an anode layer and a cathode layer; The semi-solid electrolyte layer does not include polyvinylidene fluoride, and includes an oxide material and a polymer chain. Lithium-ion battery.

13. In claim 12, The oxide material comprises magnesium oxide. Lithium-ion battery.

14. In claim 9 or 12, the semi-solid electrolyte layer includes the polymer chain and a solvent, The solvent comprises an ionic liquid. Lithium-ion battery.

15. In claim 9 or 12, the semi-solid electrolyte layer includes the polymer chain and a solvent, The solvent comprises an ionic liquid having a lithium salt dissolved therein. Lithium-ion battery.

16. In claim 9 or 12, the semi-solid electrolyte layer includes the polymer chain and a solvent, The solvent comprises EMI-FSI having LiFSI dissolved therein; Lithium-ion battery.

17. In any one of claims 9, 10 and 12, A separator is provided between the positive electrode layer and the negative electrode layer, The semi-solid electrolyte layer is located between the separator and the positive electrode layer or between the separator and the negative electrode layer. Lithium-ion battery.

18. In any one of claims 1, 2, 4, 9, 10 and 12, A separator is provided between the positive electrode layer and the negative electrode layer, and the battery is bent. Lithium-ion battery.

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