Lithium ion storage battery

Abstract

To provide a material capable of being used in a wide temperature range.SOLUTION: A graphene compound has graphene or graphene oxide and a substituted or unsubstituted chain group, where the chain group has two or more ether linkages and the graphene or graphene oxide and the chain group are linked via a Si atom. A graphene compound manufacturing method includes: a first step of stirring graphene oxide and a base under a nitrogen air flow; and a second step of reducing a temperature to a room temperature after the first step, introducing a sililation reagent containing a group having two or more ether linkages, and performing stirring, the base being butylamine, pentylamine, hexylamine, diethylamine, dipropylamine, dibutyl amine, triethylamine, tripropylamine, or pyridine.SELECTED DRAWING: Figure 4

Description

Technical Field

[0001] One aspect of the present invention relates to graphene compounds.

[0002] Note that one aspect of the present invention is not limited to the above technical field. The technical field of one aspect of the invention disclosed in this specification etc. relates to an object, a method, or a manufacturing method. Or, one aspect of the present invention relates to a process, a machine, a manufacture, or a composition (composition of matter). Therefore, more specifically, the technical field of one aspect of the present invention disclosed in this specification can include semiconductor devices, display devices, light-emitting devices, power storage devices, storage devices, their driving methods, or their manufacturing methods, as an example.

Background Art

[0003] In recent years, various power storage devices such as rechargeable batteries such as lithium ion batteries, lithium ion capacitors, and air batteries have been actively developed. In particular, lithium ion batteries with high output and high energy density are used in portable information terminals such as mobile phones, smartphones, and notebook personal computers, electronic devices such as portable music players and digital cameras, or medical devices, hybrid electric vehicles (HEVs), electric vehicles (EVs), or plug-in hybrid vehicles (PHEVs). As the semiconductor industry develops, the demand for them has rapidly expanded, and they have become indispensable in modern information society as a rechargeable energy supply source. However, generally, lithium ion batteries use an organic solvent with a high energy density and a risk of ignition at high temperatures in the electrolyte. Therefore, if the protection circuit for controlling charge and discharge fails or the like, the demand for them has rapidly expanded, and they have become indispensable in modern information society as a rechargeable energy supply source.

[0004] However, generally, lithium ion batteries have a high energy density and use an organic solvent that may catch fire at high temperatures in the electrolyte. Therefore, if the protection circuit for controlling charge and discharge fails or not, there is a risk of ignition in the electrolyte at high temperatures, so a protection circuit for controlling charge and discharge is used.​​​​​ Due to damage to the cell or the like, there is a risk of heat generation, ignition, or explosion. Also, such accidents are often reported.

[0005] As one method of reducing such risks, all-solid-state batteries in which the electrolyte is replaced with a solid electrolyte are being studied. For example, as the solid electrolyte, a lithium-ion conductive polymer electrolyte is used in a rechargeable battery being studied.

[0006] However, even in a lithium-ion rechargeable battery using a polymer electrolyte, when the battery is at a low temperature, the ion conductivity greatly decreases, and the characteristics of the battery may be greatly impaired. For example, polyethylene oxide (PEO) is known as a polymer that can be used in a lithium-ion rechargeable battery (Patent Documents 1 to 3), but when used at low temperatures, the ion conductivity decreases, which may be a problem. Originally, the melting point of PEO is around 60°C, and when melted, there may be a short circuit between the electrodes, which is dangerous, so the usable temperature range is narrow.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] The basic performance required for the solid electrolyte in an all-solid-state battery is the movement of charge-carrying ions It has high on-conductivity, while on the other hand, it has low electron conductivity to prevent a short circuit between the positive electrode and the negative electrode. That is.

[0009] Since rechargeable batteries are widely used in various environments, in order to realize a practical all-solid-state lithium-ion rechargeable battery, a solid electrolyte that can exhibit the above-described basic performance even at high temperatures is required. That is, a solid electrolyte that can withstand a high-temperature environment is required. For example, a material having excellent heat resistance is required while having a structure that exhibits the performance as a solid electrolyte such as polyethylene oxide (PEO). That is, a solid electrolyte that can withstand a high-temperature environment is required. For example, a material having excellent heat resistance is required while having a structure that exhibits the performance as a solid electrolyte such as polyethylene oxide (PEO). That is, a solid electrolyte that can withstand a high-temperature environment is required.

[0010] In recent years, with the active development of electronic devices that can be deformed, in order to realize such a flexible electronic device, the members used in the electronic device also need to be deformable. It is required that the housing and display unit of the electronic device have flexibility, but it is also required that the rechargeable battery mounted on the electric device has flexibility. In order to realize a flexible solid rechargeable battery, each member used in the solid rechargeable battery needs to have flexibility. Therefore, the solid electrolyte is also required to have flexibility. In addition to polymer-based solid electrolytes such as PEO, solid electrolytes of ceramics are also widely studied. Solid electrolytes of ceramics tend to exhibit higher ionic conductivity than polymer-based solid electrolytes, but solid electrolytes of ceramics are prone to cracking and it is difficult to make contact between the active material and the solid electrolyte, so flexibility cannot be expected very much. Therefore, in view of the above, one aspect of the present invention provides a material used for the solid electrolyte of a solid rechargeable battery.

[0011] In order to realize a flexible solid rechargeable battery, each member used in the solid rechargeable battery needs to have flexibility. Therefore, the solid electrolyte is also required to have flexibility. In addition to polymer-based solid electrolytes such as PEO, solid electrolytes of ceramics are also widely studied. Solid electrolytes of ceramics tend to exhibit higher ionic conductivity than polymer-based solid electrolytes, but solid electrolytes of ceramics are prone to cracking and it is difficult to make contact between the active material and the solid electrolyte, so flexibility cannot be expected very much. In addition to polymer-based solid electrolytes such as PEO, solid electrolytes of ceramics are also widely studied. Solid electrolytes of ceramics tend to exhibit higher ionic conductivity than polymer-based solid electrolytes, but solid electrolytes of ceramics are prone to cracking and it is difficult to make contact between the active material and the solid electrolyte, so flexibility cannot be expected very much. Solid electrolytes of ceramics tend to exhibit higher ionic conductivity than polymer-based solid electrolytes, but solid electrolytes of ceramics are prone to cracking and it is difficult to make contact between the active material and the solid electrolyte, so flexibility cannot be expected very much. In addition to polymer-based solid electrolytes such as PEO, solid electrolytes of ceramics are also widely studied. Solid electrolytes of ceramics tend to exhibit higher ionic conductivity than polymer-based solid electrolytes, but solid electrolytes of ceramics are prone to cracking and it is difficult to make contact between the active material and the solid electrolyte, so flexibility cannot be expected very much. Therefore, in view of the above, one aspect of the present invention provides a material used for the solid electrolyte of a solid rechargeable battery.

[0012] In view of the above, one aspect of the present invention provides a material used for the solid electrolyte of a solid rechargeable battery. One of the problems is to do the following. Another problem is to provide a material that can be used in a wide temperature range. Another problem is to provide a material that can withstand shape changes. Another problem is to provide a chemically modified graphene compound. Another problem is to provide a novel graphene compound. One of the problems is to do the following. Another problem is to provide a material that can be used in a wide temperature range. Another problem is to provide a material that can withstand shape changes. Another problem is to provide a chemically modified graphene compound. Another problem is to provide a novel graphene compound. One of the problems is to do the following. Another problem is to provide a material that can be used in a wide temperature range. Another problem is to provide a material that can withstand shape changes. Another problem is to provide a chemically modified graphene compound. Another problem is to provide a novel graphene compound. One of the problems is to do the following. Another problem is to provide a material that can be used in a wide temperature range. Another problem is to provide a material that can withstand shape changes. Another problem is to provide a chemically modified graphene compound. Another problem is to provide a novel graphene compound.

[0013] One aspect of the present invention is to provide a storage battery having a function of being able to change its shape, that is, a flexible storage battery. Another problem is to provide a novel flexible storage battery using a novel graphene compound. One aspect of the present invention is to provide a storage battery having a function of being able to change its shape, that is, a flexible storage battery. Another problem is to provide a novel flexible storage battery using a novel graphene compound. One aspect of the present invention is to provide a storage battery having a function of being able to change its shape, that is, a flexible storage battery. Another problem is to provide a novel flexible storage battery using a novel graphene compound.

[0014] Note that the description of these problems does not prevent the existence of other problems. One aspect of the present invention is not required to solve all of these problems. Other problems will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other problems from the description in the specification, drawings, claims, etc. Note that the description of these problems does not prevent the existence of other problems. One aspect of the present invention is not required to solve all of these problems. Other problems will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other problems from the description in the specification, drawings, claims, etc. Note that the description of these problems does not prevent the existence of other problems. One aspect of the present invention is not required to solve all of these problems. Other problems will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other problems from the description in the specification, drawings, claims, etc. Note that the description of these problems does not prevent the existence of other problems. One aspect of the present invention is not required to solve all of these problems. Other problems will become apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other problems from the description in the specification, drawings, claims, etc.

Means for Solving the Problems

[0015] In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. In view of the above, one aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having two or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Another aspect of the present invention is a graphene compound having graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having four or more ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom. Yes. Another aspect of the present invention is graphene or graphene oxide and a substituted or unsubstituted chain group, the chain group having 2 to 20 ether bonds, and the graphene or graphene oxide and the chain group being bonded via an Si atom, which is a graphene compound. Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (200). Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (200). In the formula (200), GO represents graphene or graphene oxide, and R represents a substituted or unsubstituted chain group having at least 2 ether bonds.

[0016] Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (200). In the formula (200), GO represents graphene or graphene oxide, and R represents a substituted or unsubstituted chain group having at least 2 ether bonds.

[0017]

Chemical formula

[0018] In the formula (200), GO represents graphene or graphene oxide, and R represents a substituted or unsubstituted chain group having at least 2 ether bonds. In the formula (200), GO represents graphene or graphene oxide, and R represents a substituted or unsubstituted chain group having at least 2 ether bonds.

[0019] Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (201). Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (201).

[0020]

Chemical formula

[0021] In the formula (201), GO represents graphene or graphene oxide.

[0022] Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (202). Yes. Another aspect of the present invention is a graphene compound having a structure represented by the following formula (202).

[0023]

Chemical formula

[0024] In Formula (202), GO represents graphene or graphene oxide.

[0025] Moreover, a lithium-ion battery having the above-described graphene compound, an exterior body, a positive electrode current collector, and a negative electrode current collector is also one aspect of the present invention. It is also one aspect of the present invention.

[0026] Another aspect of the present invention is a method for producing a graphene compound, which includes a first step of stirring graphene oxide and a base under a nitrogen stream, and a second step of cooling to room temperature after the first step and introducing and stirring a silylating agent containing a group having two or more ether bonds. The base is butylamine, pentylamine, hexylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, or pyridine. After the first step, the temperature is lowered to room temperature, and a silylating agent containing a group having two or more ether bonds is introduced and stirred. The base is butylamine, pentylamine, hexylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, or pyridine. Hexylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, or pyridine. Or pyridine, and is a method for producing a graphene compound. It is.

[0027] Another aspect of the present invention is a method for producing a graphene compound, which includes a first step of stirring graphene oxide and butylamine under a nitrogen stream, and a second step of cooling to room temperature after the first step and dropping and stirring methoxy triethyleneoxypropyl trichlorosilane. After the first step, the temperature is lowered to room temperature, and methoxy triethyleneoxypropyl trichlorosilane is dropped and stirred. And is a method for producing a graphene compound. It is a method.

[0028] Another aspect of the present invention is a method for producing a graphene compound, which includes a first step of stirring graphene oxide and butylamine under a nitrogen stream, and a second step of cooling to room temperature after the first step and dropping and stirring 2-[methoxy(polyethyleneoxy)6-9 propyl]trichlorosilane. After the first step, the temperature is lowered to room temperature, and 2-[methoxy(polyethyleneoxy)6-9 propyl]trichlorosilane is dropped and stirred. Propyl]trichlorosilane is dropped and stirred. And is a method for producing a graphene compound.

Advantages of the Invention

[0029] According to one aspect of the present invention, a material used for a solid electrolyte of a solid-state battery can be provided. Moreover, materials that can be used in a wide temperature range can be provided. In addition, materials that can withstand shape changes can be provided. In addition, chemically modified graphene compounds can be provided. In addition, novel graphene compounds can be provided. Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided. It should be noted that the description of these effects does not prevent the existence of other effects. It should be noted that one aspect of the present invention does not necessarily have to have all of these effects. In addition, other effects will be apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other effects from the description in the specification, drawings, claims, etc.

[0030] Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided. Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided. Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided.

[0031] It should be noted that the description of these effects does not prevent the existence of other effects. It should be noted that one aspect of the present invention does not necessarily have to have all of these effects. In addition, other effects will be apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other effects from the description in the specification, drawings, claims, etc. It should be noted that the description of these effects does not prevent the existence of other effects. It should be noted that one aspect of the present invention does not necessarily have to have all of these effects. In addition, other effects will be apparent from the description in the specification, drawings, claims, etc., and it is possible to extract these other effects from the description in the specification, drawings, claims, etc. Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided. Moreover, according to one aspect of the present invention, a storage battery having a function capable of changing its shape, that is, a flexible storage battery can be provided. In addition, a novel flexible storage battery using a novel graphene compound can also be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0032]

Figure 1

Figure 2

Figure 3

Figure 4

[0033] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and those skilled in the art can make various changes to its form and details. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and those skilled in the art can make various changes to its form and details. This will be easily understood. Also, the present invention is not construed as being limited to the description of the embodiments shown below. It is not limited thereto.

[0034] In each of the figures described in this specification, the size, thickness, etc. of each component such as the positive electrode, negative electrode, active material layer, separator, and exterior body may be exaggerated for the sake of clarity of individual explanations. Therefore, each component is not necessarily limited to its size, nor is it limited to the relative size between each component. That is, each component is not necessarily limited to its size, nor is it limited to the relative size between each component. It is not limited to the relative size between each component.

[0035] Also, in this specification and the like, ordinal numbers such as first, second, and third are used for convenience and do not indicate the order of steps or the vertical positional relationship. Therefore, for example, "first" can be appropriately replaced with "second" or "third" and so on for explanation. That is, "first" can be appropriately replaced with "second", "third", etc. for explanation. Also, the ordinal numbers described in this specification and the like may not match the ordinal numbers used to specify an aspect of the present invention. They may not match.

[0036] Also, in the configuration of the present invention described in this specification and the like, the same reference numerals are commonly used between different drawings for the same part or parts having the same function, and the repeated explanation thereof is omitted. Also, when referring to parts having the same function, the hatching pattern may be the same, and there may be cases where no reference numerals are particularly assigned. When referring to parts having the same function, the hatching pattern may be the same, and there may be cases where no reference numerals are particularly assigned. There may be cases where no reference numerals are particularly assigned.

[0037] Also, in this specification, flexibility refers to the property that an object is flexible and can be bent. It is a property that an object can be deformed in response to an external force applied to the object, and the presence or absence of elasticity or the ability to restore to the shape before deformation is not a concern. An object having flexibility can be deformed in response to an external force. An object having flexibility can be deformed in response to an external force. An object having flexibility can also be used while being fixed in a deformed state. It may be used after being repeatedly deformed, or it may be used in a non-deformed state.

[0038] In addition, in this specification, modification may refer to chemically changing a graphene compound to change the function or property of the graphene compound. Further, it may also refer to adding a functional group having a specific function or property. Furthermore, the content described in the embodiments for carrying out the present invention can be used in appropriate combinations.

[0039]

[0040] (Embodiment 1) In this embodiment, a graphene compound produced according to one aspect of the present invention will be described. Also, a method for producing a graphene compound by chemical modification will be described together. A graphene compound produced according to one aspect of the present invention has a function of conducting metal ions such as lithium, sodium, magnesium, and calcium, and can be used, for example, as a solid electrolyte of a lithium-ion battery. However, one aspect of the present invention is not limited to this.

[0041] <Graphene compound> First, graphene and graphene compounds will be described.

[0042] Graphene is a sheet of carbon atoms with a thickness of one atom, and the carbon atoms are arranged in a hexagonal lattice structure on a plane. It is a material with a stronger bond between carbon atoms than diamond and has extremely high resistance to deformation and tension. On the other hand, its conductivity is extremely high, and since lithium ions do not penetrate sufficiently, it is not suitable for use as a solid electrolyte of a lithium-ion battery as it is.

[0043] However, generally, graphene may have various types of defects. For example, carbon atoms forming the lattice may be missing, and there may be five-membered or seven-membered rings in addition to six-membered rings in the lattice , and carbon may be bonded to atoms other than carbon. Such defect sites can be used to bond atoms or atomic groups to graphene to exhibit desired properties. Here, a graphene compound according to one aspect of the present invention will be described.

[0044] Graphene is a material in which carbon atoms are arranged in a single atomic layer and have π bonds between carbon atoms. The material in which two or more and 100 or less layers of graphene are stacked may be called multi-graphene . Graphene and multi-graphene have, for example, a length in the longitudinal direction or the major axis in the plane of 50 nm or more and 100 μm or less, or 800 nm or more and 50 μm or less.

[0045] In this specification and the like, a compound having graphene or multi-graphene as a basic skeleton is called a "graphene compound (also referred to as "graphene compound: Graphene Compound" ). Graphene compounds include graphene and multi-graphene .

[0046] Details of the graphene compound will be described below.

[0047] A graphene compound is, for example, a compound in which graphene or multi-graphene is modified with an atom other than carbon, or an atomic group having an atom other than carbon. Note that an atomic group that modifies graphene or multi-graphene may be referred to as a substituent, a functional group, or a characteristic group, etc. Here, in this specification and the like, modification means a substitution reaction, an addition reaction, or other reactions ​or graphene, multi-layer graphene, graphene compounds, or graphene oxide (described later) refers to introducing an atomic group having atoms other than carbon or an atomic group mainly composed of carbon .

[0048] Note that even if the front and back surfaces of graphene are modified with different atoms or atomic groups it is acceptable. Also, in the case of multi-layer graphene, each layer may be modified with different atoms or atomic groups .

[0049] As an example of graphene modified with the above-mentioned atoms or atomic groups, graphene or multi-layer graphene modified with oxygen or a functional group containing oxygen can be mentioned. A graphene compound modified with a functional group having oxygen may sometimes be referred to as graphene oxide . Also, in this specification, graphene oxide includes multi-layer graphene oxide . . .

[0050] The modification not only refers to introducing one type of atom or atomic group, but also refers to introducing a plurality of types of atoms or atomic groups through a plurality of types of chemical reactions. Also, the modification includes reactions of adding hydrogen, halogen atoms, hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic compound groups. Also , as reactions for introducing atomic groups into graphene, addition reactions, substitution reactions, etc. can be mentioned. Also , Friedel-Crafts reactions, Binge l reactions, etc. may be carried out. A radical addition reaction may be carried out on graphene, or a ring may be formed between graphene and an atomic group by a cycloaddition reaction . . .

[0051] Next, an example of a method for producing graphene oxide will be described. Graphene oxide is the above-mentioned graphene Or it can be obtained by oxidizing multi-graphene. Alternatively, graphene oxide can be obtained by separating oxidized graphite. Oxidized graphite can be obtained by oxidizing graphite Here, the above-mentioned atoms or atomic groups may be further used to modify graphene oxide .

[0052] A compound obtained by reducing graphene oxide may be referred to as "RGO (Reduced Graphene Oxide)". Note that in RGO, not all of the oxygen contained in graphene oxide is desorbed, and some oxygen or an atomic group containing oxygen may remain bonded to carbon .

[0053] The graphene compound may be in the form of a single sheet with a plurality of graphene compounds partially overlapping . Such a graphene compound may be referred to as a graphene compound sheet . The graphene compound sheet has, for example, a region with a thickness of 0.33 nm or more and 10 mm or less, more preferably more than 0.34 nm and 10 μm or less. The graphene compound sheet may be modified by an atom other than carbon, an atomic group having an atom other than carbon, or an atomic group mainly composed of carbon such as an alkyl group . Also, in each of the plurality of layers of the graphene compound sheet, different atoms or atomic groups may be used for modification .

[0054] In addition to the six-membered ring composed of carbon, the graphene compound may have a five-membered ring composed of carbon or a polycyclic ring of seven or more members composed of carbon . Here, in the vicinity of the polycyclic ring of seven or more members, a region through which lithium ions can pass may occur.

[0055] For example, a plurality of graphene compounds may aggregate to form a sheet-like shape.

[0056] Since the graphene compound has a planar shape, it enables surface contact.

[0057] <Chemically modified graphene compound> Next, the chemically modified graphene compound will be described. The graphene compound produced by the manufacturing method according to one aspect of the present invention can be used, for example, as a solid electrolyte of a lithium-ion battery. In that case, it must have insulation to prevent short-circuiting between the positive electrode and the negative electrode. Note that the graphene compound according to one aspect of the present invention has conductivity not only for lithium but also for metal ions such as sodium, magnesium, and calcium. Therefore, it can also be used for applications other than lithium-ion batteries. In the present embodiment, a battery using lithium ions as carriers will be described, representing such metal ions. However, the description can also be applied to batteries using other metal ions as carriers. Pure graphene is known to have high conductivity and cannot be used as it is as a solid electrolyte of a lithium-ion battery. Also, graphene oxide has relatively low conductivity but is poor in reduction resistance and is easily reduced to RGO with high conductivity. In order to stably make these insulating, it is preferable to insulate graphene oxide or graphene by chemical modification. For example, it is conceivable to chemically modify graphene oxide or graphene with a molecule having an alkyl chain with a relatively large number of carbon atoms. Both sides of sheet-like graphene oxide can be chemically modified.

[0058] Pure graphene is known to have high conductivity and cannot be used as it is as a solid electrolyte of a lithium-ion battery. Also, graphene oxide has relatively low conductivity but is poor in reduction resistance and is easily reduced to RGO with high conductivity. In order to stably make these insulating, it is preferable to insulate graphene oxide or graphene by chemical modification. For example, it is conceivable to chemically modify graphene oxide or graphene with a molecule having an alkyl chain with a relatively large number of carbon atoms. Both sides of sheet-like graphene oxide can be chemically modified. For example, it is conceivable to chemically modify graphene oxide or graphene with a molecule having an alkyl chain with a relatively large number of carbon atoms. Both sides of sheet-like graphene oxide When modified with a compound having a long-chain alkyl group, the alkyl chain becomes a functional group with poor electrical conductivity. Therefore, the distance between multiple graphene oxide sheets is increased, inhibiting electronic conduction. Therefore, insulation can be achieved.

[0059] However, alkyl groups are non-polar functional groups and are responsible for the battery reaction in lithium-ion batteries. It has low affinity with lithium ions. Therefore, it is difficult to use compounds with long-chain alkyl groups. When phene is chemically modified, the movement of lithium ions is inhibited, inhibiting the battery reaction. In addition, the lithium salt is difficult to dissociate. Therefore, compounds having long-chain alkyl groups are Lithium-ion batteries using graphene compounds modified with fluorine as solid electrolytes have the following characteristics: becomes lower.

[0060] In view of this, the graphene compound according to one embodiment of the present invention has insulating properties and at the same time has lithium ionization properties. For example, a graphene compound that has an affinity for cations can be chemically modified to form an ether bond. It is preferable that the graphene compound has a chain-like functional group having an ether bond. It is polar and classified as a hydrophilic group, and its polarity gives it affinity with lithium ions. The graphene compound can contribute to the movement of lithium ions. When used as a solid electrolyte for ion storage batteries, the ether functional group of the graphene compound is A larger number of alkene bonds is preferable because it improves the mobility of lithium ions.

[0061] In addition, the graphene compound according to one embodiment of the present invention has a property as a solid electrolyte that is similar to that of a polymer. Compared to electrolytes, one of their features is their high heat resistance. If an unexpected reaction occurs due to damage to internal structures, it may lead to major accidents such as ignition or explosion. Therefore, it is important to have high heat resistance. When lithium-ion batteries are used in harsh environments such as inside automobiles, low heat resistance of the components becomes a major problem. Since the graphene compound according to one aspect of the present invention has high heat resistance, it can withstand such environments and is thus suitable for use as a solid electrolyte of a lithium-ion battery. Here, a general example of the chemically modified graphene compound according to one aspect of the present invention is shown by the following formula. In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way. Here, a general example of the chemically modified graphene compound according to one aspect of the present invention is shown by the following formula. In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way.

[0062] Here, a general example of the chemically modified graphene compound according to one aspect of the present invention is shown by the following formula.

[0063]

Chemical formula

[0064] In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way. In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way. In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way. In the formula (200), R represents a substituted or unsubstituted chain-like group having at least two or more ether bonds, and R may be branched. Also, GO represents graphene or oxidized graphene. The graphene of the graphene compound according to one aspect of the present invention is not limited to just one molecular weight or structure, and graphene of any size is applicable. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds, and it may be impossible or impractical not to represent it in such a way. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it is impossible to specifically identify and fully represent the molecular structure of the graphene compound according to one aspect of the present invention. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds. Therefore, it may be practical to specify the chemically modified graphene compound according to one aspect of the present invention by an expression such as a manufacturing method as a graphene compound chemically modified with a silylating agent having a substituted or unsubstituted group having at least two or more ether bonds. ​​It may be practical. Also, GO and Si may be immobilized in a layer-like manner by two Si-O bonds as shown in the above formula, but may also be immobilized by one or three Si-O bonds. In some cases, the Si-O layer is fixed, but in other cases, it may be fixed by one or three Si-O bonds. Moreover, the bond is not limited to the Si-O bond and may be fixed by other bonds.

[0065] <Chemical modification> Next, a method for chemically modifying a graphene compound to produce a chemically modified graphene compound will be described using the following synthesis scheme (A-1).

[0066]

Chemical formula

[0067] As shown in the synthesis scheme (A-1), the target compound can be obtained by chemically modifying graphene oxide (GO) with a silylating agent containing a chain-like group having two or more ether bonds. In the synthesis scheme (A-1), R represents a chain-like group having at least two ether bonds, which may be substituted or unsubstituted, and R may be branched. In the synthesis scheme (A-1), examples of the base that can be used include organic bases such as butylamine, pentylamine, hexylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, and pyridine. However, the bases that can be used are not limited to these.

[0068] In the synthesis scheme (A-1), examples of the solvent that can be used include aromatic hydrocarbons such as toluene, xylene, and mesitylene, hydrocarbons such as hexane and heptane, and ethylene glycol

[0069] ​ Examples include ethers such as dimethyl ether for recall. However, the solvents that can be used are not limited to these. In particular, a combination of using a primary amine as the base and an aromatic hydrocarbon as the solvent is more preferred.

[0070] In addition to the silylating agent shown in the synthesis scheme (A-1), those having a trialkoxysilyl group may also be used. However, they are not limited to these.

[0071] <Specific examples> Here, examples of the silylating agent containing a chain-like group having two or more ether bonds are shown below. By using these silylating agents, a graphene compound chemically modified with a chain-like group having an ether bond can be prepared.

[0072]

Chemical formula

[0073]

Chemical formula

[0074]

Chemical formula

[0075]

Chemical formula

[0076]

Chemical formula

[0077]

Chemical formula

[0078] In formulas (137) to (148), OMe represents a methoxy group and OEt represents an ethoxy group. By using a silylating agent as described above, a graphene compound having a chain-like group with at least two or more ether bonds can be produced. The graphene compound chemically modified with these silylating agents has low electron conductivity while having high lithium ion conductivity, and thus is optimal as a material for use in a solid electrolyte or a separator of a lithium ion battery. However, the graphene compound according to one embodiment of the present invention is not limited to being produced using a silylating agent as described above. In the present embodiment, one embodiment of the present invention has been described. Or, in other embodiments, one embodiment of the present invention is described. However, one embodiment of the present invention is not limited thereto. For example, as one embodiment of the present invention, an example of a graphene compound having a chain-like group with at least two or more ether bonds has been shown, but one embodiment of the present invention is not limited thereto. Depending on the case or the situation, one embodiment of the present invention may not be a graphene compound having a chain-like group with at least two or more ether bonds. For example, depending on the case or the situation, one embodiment of the present invention may not have a chain-like structure having at least two or more ether bonds.

[0079]

[0080] Note that the present embodiment can be appropriately combined with other embodiments.

[0081] (Embodiment 2) In this embodiment, the configuration of a lithium-ion battery using a graphene compound according to one aspect of the present invention will be described. The configuration of the battery will be described.

[0082] A method for manufacturing a lithium-ion battery 110 according to one aspect of the present invention will be described below with reference to FIGS. 1(A) and (B). FIG. 1(B) is a cross-sectional view of the lithium-ion battery 110. It is a cross-sectional schematic view in a state where a positive electrode current collector 100, a positive electrode active material layer 101, a solid electrolyte layer 104, a negative electrode active material layer 103, and a negative electrode current collector 102 are stacked and sealed by an exterior body 207. Note that the active material layer can also be formed on both sides of the current collector, and the battery can be in a stacked structure. It is also possible.

[0083] ≪Configuration of positive electrode≫ The positive electrode will be described. The positive electrode includes a positive electrode active material layer 101 and a positive electrode current collector 100.

[0084] As the positive electrode active material used in the positive electrode active material layer 101, a material capable of inserting and extracting carriers such as lithium ions can be used. For example, a lithium-containing material having an olivine-type crystal structure, a layered rock salt-type crystal structure, or a spinel-type crystal structure can be mentioned. Further, for example, a polyanion-based positive electrode material can be used as the positive electrode active material. Examples of the polyanion-based positive electrode material include materials having an olivine-type crystal structure, NASICON-type materials, and the like. As the positive electrode active material, various complex oxides can be used. For example, compounds such as LiFeO2, L iCoO2, LiNiO2, LiMn2O4, V2O5, Cr2O5, and MnO2 can be used. compounds can be used.

[0085]

[0086]

[0086] As a material having a layered rock salt crystal structure, for example, a composite oxide represented by LiMO2 can be used. The element M is preferably one or more selected from Co or Ni. LiCoO2 is preferable because it has advantages such as a large capacity, stability in the air, and thermal stability. In addition, as the element M, it may have one or more selected from Al and Mn in addition to one or more selected from Co and Ni. For example, LiCo Mn x Mn y Ni z O w (x, y, z, and w are, for example, x = y = z = 1 / 3 or in the vicinity thereof , w = 2 or in the vicinity thereof) can be used.

[0087] The vicinity means, for example, a value greater than 0.9 times and less than 1.1 times that value.

[0088] In addition, as the positive electrode active material, for example, a solid solution obtained by combining a plurality of composite oxides can be used as the positive electrode active material. For example, a solid solution of LiCo 1 / 3 Mn 1 / 3 Ni 1 / 3 O2 and Li2Mn O3 can be used as the positive electrode active material.

[0089] As a material having a spinel crystal structure, for example, a composite oxide represented by LiM2O4 can be used. It is preferable that the element M has Mn. For example, LiMn2O 4 can be used. In addition, by having Ni in addition to Mn as the element M, the discharge voltage of the storage battery may be improved and the energy density may be improved, which is preferable. Also, a small amount of lithium nickelate (LiNiO2 or LiNi in a lithium-containing material having a spinel crystal structure containing manganese such as Li Mn2O4, etc. of lithium nickelate (LiNiO2 or LiNi (1-x)M x O2 (where M = Co, Al, etc.) By mixing them, the characteristics of the storage battery can be improved, which is preferable.

[0090] The positive electrode active material preferably has an average particle diameter of primary particles of 5 nm or more and 100 μm or less, more preferably 50 nm or more and 50 μm or less, and even more preferably 100 nm or more and 500 nm or less. Also, the specific surface area is preferably 5 m 2 / g or more and 15 m 2 / g or less. In addition, the average particle diameter of the secondary particles is preferably 5 μm or more and 50 μm or less. The average particle diameter can be measured by observation with an SEM (scanning electron microscope) or TEM, or by a particle size distribution meter using the laser diffraction / scattering method or the like. Also, the specific surface area can be measured by the gas adsorption method.

[0091] A conductive material such as a carbon layer may be provided on the surface of the positive electrode active material. By providing a conductive material such as a carbon layer, the conductivity of the electrode can be improved. For example, the coating of the carbon layer on the positive electrode active material can be formed by mixing a carbohydrate such as glucose during the firing of the positive electrode active material.

[0092] As a polyanion-based positive electrode material, for example, a polyanion-based positive electrode material having oxygen, element X, metal A, and metal M can be used. Metal M is one or more of Fe, Mn, Co, Ni, Ti, V, Nb, metal A is one or more of Li, Na, Mg, and element X is one or more of S, P, Mo, W, As, Si.

[0093] Also, a composite material (general formula LiMPO4, where M is Fe(II), Mn(II), Co(II ) One or more of Ni(II) can be used. Representative examples of the general formula LiMPO4 include LiFePO4, LiNiPO4, LiCoPO4, LiMnPO4, LiFe a Ni b PO4, LiFe a Co b PO4, LiFe a Mn b PO4, LiNi a Co b P O4, LiNi a Mn b PO4 (a + b is 1 or less, 0 < a < 1, 0 < b < 1), LiFe c Ni d Co e PO4, LiFe c Ni d Mn e PO4, LiNi c Co d Mn e PO4 (c + d + e is 1 or less, 0 < c < 1, 0 < d < 1, 0 < e < 1), LiFe f Ni g Co h Mn i PO4 (f + g + h + i is 1 or less, 0 < f < 1, 0 < g < 1, 0 < h < 1, 0 < i < 1), etc. Lithium compounds can be used.

[0094] In particular, LiFePO4 preferably satisfies the requirements for a cathode active material, such as safety, stability, high capacity density, and the presence of lithium ions that can be extracted during initial oxidation (charging), in a well-balanced manner. Therefore, it is preferable.

[0095] In addition, composite materials such as the general formula Li (2-j) MSiO4 (M is one or more of Fe(II), Mn(II), Co(I I), Ni(II), 0 ≤ j ≤ 2) can be used. General formula Li (2-j)Typical examples of MSiO4 include Li (2-j) FeSiO4, Li (2- j) NiSiO4, Li (2-j) CoSiO4, Li (2-j) MnSiO4, Li ( 2-j) Fe k Ni l SiO4, Li (2-j) Fe k Co l SiO4, Li (2-j) Fe k Mn l SiO4, Li (2-j) Ni k Co l SiO4, Li (2-j) Ni k M n l SiO4 (k + l is 1 or less, 0 < k < 1, 0 < l < 1), Li (2-j) Fe m Ni n Co q SiO4, Li (2-j) Fe m Ni n Mn q SiO4, Li (2-j) Ni m Co n Mn q SiO4 (m + n + q is 1 or less, 0 < m < 1, 0 < n < 1, 0 < q < 1), Li (2-j) Fe r Ni s Co t Mn u SiO4 (r + s + t + u is 1 or less, 0 < r < 1, 0 < s < 1, 0 < t < 1, 0 < u < 1), etc., can be used as materials of lithium compounds.

[0096] Also, A x M2(XO4)3 (A = Li, Na, Mg, M = Fe, Mn, Ti, V, Nb 、X = S, P, Mo, W, As, Si), can use a NASICON-type compound represented by the general formula is possible. As the NASICON-type compound, there are Fe2(MnO4)3, Fe2(SO4)3, Li3Fe2(PO4)3 and the like. Also, as the positive electrode active material, compounds represented by the general formula Li2MPO4F, Li 2MP2O7, Li5MO4 (M = Fe, Mn) can be used. is possible.

[0097] In addition, a polyanion-based positive electrode material containing V can be used. Representative examples include α-L iVOPO4, β-LiVOPO4, α1-LiVOPO4, LiVPO4F, LiVP O4O, LiVP2O7, LiVOSO4, Li2VOSiO4, LiVMoO6, etc. can be mentioned.

[0098] Also, as the positive electrode active material, perovskite-type fluorides such as NaFeF3, FeF3, Ti S2, metal chalcogenides (sulfides, selenides, tellurides) such as MoS2, oxides having an inverse spinel-type crystal structure such as LiMV O4, vanadium oxide-based (V2O5, V6 O 13 , LiV3O8, etc.), manganese oxides, organic sulfur compounds, and other materials can be used. is possible.

[0099] Also, as the positive electrode active material, borate-based positive electrode materials represented by the general formula LiMBO3 (M is Fe(II), Mn(II), C o(II)) can be used.

[0100] Also, as the positive electrode active material, lithium manganese a Mn b M c O d complex oxides that can be represented by can be used. Here, the element M is selected from elements other than lithium and manganese. from It is preferable to use a selected metal element, silicon, or phosphorus, and nickel is more preferable. Also, when measuring the entire particles of the lithium manganese composite oxide, during discharge, it is preferable to satisfy 0 < a / (b + c) < 2, c > 0, and 0.26 ≤ (b + c) / d < 0.5. In addition, in order to exhibit high capacity, it is preferable to use a lithium manganese composite oxide having regions with different crystal structures, crystal orientations, or oxygen contents in the surface layer portion and the central portion. To obtain such a lithium manganese composite oxide, for example, it is preferable to set 1.6 ≤ a ≤ 1.848, 0.19 ≤ c / b ≤ 0.935, and 2.5 ≤ d ≤ 3. Furthermore, it is particularly preferable to use a lithium manganese composite oxide represented by the composition formula LiMnNiO3. In this specification and the like, the lithium manganese composite oxide represented by the composition formula Li8MnNiO3 refers to a lithium manganese composite oxide formed by setting the ratio (molar ratio) of the raw material amounts to Li2CO3:MnCO3:NiO = 0.84:0.8062:0.318. Therefore, the lithium manganese composite oxide is represented by the composition formula Li2Mn2NiO3, but may deviate from this composition. In addition, the composition of metals, silicon, phosphorus, etc. in the entire particles of the lithium manganese composite oxide can be measured, for example, using ICP-MS (inductively coupled plasma mass spectrometer). Also, the oxygen composition of the entire particles of the lithium manganese composite oxide can be measured, for example, using EDX (energy dispersive type). Moreover, when measuring the entire particles of the lithium manganese composite oxide, during discharge it is preferable to satisfy 0 < a / (b + c) < 2, c > 0, and 0.26 ≤ (b + c) / d < 0.5 In addition, in order to exhibit high capacity, in the surface layer portion and the central portion, a lithium manganese composite oxide having regions with different crystal structures, crystal orientations, or oxygen contents is preferred To obtain such a lithium manganese composite oxide, for example, 1.6 ≤ a ≤ 1.848, 0.19 ≤ c / b ≤ 0.935, and 2.5 ≤ d ≤ 3 are preferred Furthermore, Li 1.68 Mn 0.8062 Ni 0.318 It is particularly preferred to use a lithium manganese composite oxide represented by the composition formula Li In this specification and the like, Li 1.6 8Mn 0.8062 Ni 0.318 The lithium manganese composite oxide represented by the composition formula Li refers to a lithium manganese composite oxide formed by setting the ratio (molar ratio) of the raw material amounts to Li2CO3:MnCO3:NiO = 0. 84:0.8062:0.318 Therefore, the lithium manganese composite oxide has the composition formula Li 1.68 Mn 0.806 2Ni 0.318 O3, but may deviate from this composition

[0101] In addition, the composition of metals, silicon, phosphorus, etc. in the entire particles of the lithium manganese composite oxide can be measured, for example using ICP-MS (inductively coupled plasma mass spectrometer). Also, the oxygen composition of the entire particles of the lithium manganese composite oxide can be measured, for example, using EDX (energy dispersive type X-ray spectroscopy). It can be measured using X-ray analysis. Also, by using melting gas analysis and valence evaluation of XAFS (X-ray absorption fine structure) analysis in combination with ICP-MS analysis, it can be determined. Note that the lithium manganese composite oxide refers to an oxide containing at least lithium and manganese, and may contain at least one element selected from the group consisting of chromium, cobalt, aluminum, nickel, iron, magnesium, molybdenum, niobium, zinc, indium, gallium, copper, titanium, niobium, silicon, and phosphorus.

[0102] Note that when the carrier ion is an alkali metal ion other than lithium ion or an alkaline earth metal ion, as the positive electrode active material, instead of lithium, an alkali metal (for example, sodium, potassium, etc.), an alkaline earth metal (for example, calcium, strontium, barium, beryllium, magnesium, etc.) may be used. For example, a sodium-containing layered oxide can be used.

[0103] Examples of materials having sodium include NaFeO2 and Na 2 / 3 [Fe 1 / 2 Mn1 / 2 O2, Na 2 / 3 [Ni 1 / 3 Mn 2 / 3 O2, Na2Fe2(SO4)3, N a3V2(PO4)3, Na2FePO4F, NaVPO4F, NaMPO4 (M is Fe(II), Mn(II), Co(II), Ni(II)), Na2FePO4F, Na 4Co3(PO4)2P2O7, etc. can be used as the positive electrode active material.

[0104] In addition, a lithium-containing metal sulfide can be used as the positive electrode active material. For example, Li 2TiS3, Li3NbS4, etc. can be mentioned.

[0105] As the positive electrode active material, it is preferable to use one having an average particle diameter of the primary particles of 50 nm or more and 100 μm or less .

[0106] The positive electrode active material, together with the negative electrode active material, plays a central role in the battery reaction of the storage battery and is a material that releases and absorbs carrier ions. In order to increase the life of the storage battery, it is preferably a material with a small capacity related to the irreversible reaction of the battery reaction, and it is preferably a material with high charge and discharge efficiency . . .

[0107] Since the active material is in contact with the electrolytic solution, if the active material and the electrolytic solution react and the active material is lost and deteriorated due to the reaction, the capacity of the storage battery decreases. Therefore, in order to realize a storage battery with less deterioration, it is desirable that such a reaction does not occur in the storage battery . .

[0108] As the conductive assistant of the electrode, acetylene black (AB), graphite (graphite) particles, carbon nanotubes, graphene, fullerenes, etc. can be used.

[0109] The conductive assistant can form an electric conduction network in the electrode. The conductive assistant can maintain the electric conduction path between the positive electrode active materials. By adding the conductive assistant to the positive electrode active material layer, a positive electrode active material layer 101 having high electric conductivity can be realized . . .

[0110] In addition, as the binder, in addition to typical polyvinylidene fluoride (PVDF), polyimide , polytetrafluoroethylene, polyvinyl chloride, ethylene propylene diene polymer Mores, fluororubber, polymethyl methacrylate, polyethylene, nitrocellulose, etc. can be used. It can be used.

[0111] The content of the binder with respect to the total amount of the positive electrode active material layer 101 is preferably 0.5 wt% or more and 10 wt% or less, more preferably 2 wt% or more and 8 wt% or less, and even more preferably 3 wt% or more and 5 wt% or less. Further, the content of the conductive assistant with respect to the total amount of the positive electrode active material layer 101 is preferably 1 wt% or more and 10 wt% or less, and more preferably 1 wt% or more and 5 wt% or less. It is more preferably 2 wt% or more and 8 wt% or less, and even more preferably 3 wt% or more and 5 wt% or less. When forming the positive electrode active material layer 101 using a coating method, the positive electrode active material, binder, conductive assistant, and dispersion medium are mixed to prepare an electrode slurry, which is then applied onto the positive electrode current collector 100 and dried. That's fine.

[0112] For the positive electrode current collector 100, metals such as stainless steel, gold, platinum, aluminum, titanium, etc., and alloys thereof, which have high conductivity and do not alloy with carrier ions such as lithium, can be used. Also, an aluminum alloy added with an element that improves heat resistance such as silicon, titanium, neodymium, scandium, molybdenum, etc. can be used. Further, it may be formed of a metal element that reacts with silicon to form a silicide. Examples of the metal element that reacts with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, etc. The positive electrode current collector can appropriately use shapes such as foil, plate (sheet), net, punching metal, expanded metal, etc. It can be applied and dried on the positive electrode current collector 100. That's okay.

[0113] For the positive electrode current collector 100, metals such as stainless steel, gold, platinum, aluminum, titanium, etc., and alloys thereof, which have high conductivity and do not alloy with carrier ions such as lithium, can be used. In addition, materials with high conductivity that do not alloy with carrier ions such as lithium, such as these alloys, can be used. Also, an aluminum alloy added with an element that improves heat resistance, such as silicon, titanium, neodymium, scandium, molybdenum, etc., can be used. In addition, an aluminum alloy added with an element that improves heat resistance, such as silicon, titanium, neodymium, scandium, molybdenum, etc., can be used. Also, it may be formed of a metal element that reacts with silicon to form a silicide. The metal elements that react with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, etc. Examples of the metal elements that react with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, etc. There are vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, etc. The positive electrode current collector can appropriately use shapes such as foil, plate (sheet), net, punching metal, expanded metal, etc. That's okay.

[0114] The positive electrode of the lithium-ion battery can be manufactured through the above steps.

[0115] ≪Configuration of Negative Electrode≫ Next, the negative electrode will be described. The negative electrode includes a negative electrode active material layer 103 and a negative electrode current collector 102. The steps for forming the negative electrode will be described below.

[0116] As the negative electrode active material used in the negative electrode active material layer 103, among carbon-based materials, there are graphite, graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon nanotubes, graphene, carbon black, etc. As graphite, there are artificial graphite such as mesocarbon microbeads (MCMB), coke-based artificial graphite, pitch-based artificial graphite, etc., and natural graphite such as spheroidized natural graphite. Also, the shape of graphite includes flaky and spherical ones, etc. In addition to carbon-based materials, materials capable of performing charge and discharge reactions through alloying and dealloying reactions with lithium can also be used as the negative electrode active material. For example, materials containing at least one of Ga, Si, Al, Ge, Sn, Pb, Sb, Bi, Ag, Zn, Cd, In, etc. can be used. Such elements have a larger capacity compared to carbon. In particular, silicon has a high theoretical capacity of 4200 mAh / g and is preferable. Examples of alloy-based materials using such elements include Mg2Si, Mg2Ge, Mg2Sn, SnS2, V2Sn3, FeSn2, CoSn2, Ni3Sn2, Cu6Sn5, Ag3Sn, Ag3Sb, Ni2MnSb, .

[0117]

[0118] ​​​​​​​​​In addition, as the negative electrode active material, SiO, SnO, SnO2, titanium dioxide (TiO2), lith ium titanate (Li4Ti5O 12 ), lithium-graphite intercalation compound (Li x C6), niobium pentoxide (Nb2O5), tungsten oxide (WO2), molybdenum oxide (MoO2 ) and other oxides can be used.

[0119] In addition, as the negative electrode active material, Li3N-type structured Li (3-x) M x N (M is Co, Ni or Cu), which is a complex nitride of lithium and a transition metal, can be used. For example, L i 2.6 Co 0.4 N3 exhibits a large charge-discharge capacity (900 mAh / g, 1890 mAh / cm 3 ) and is preferable.

[0120] When using a complex nitride of lithium and a transition metal, since lithium is contained in the negative electrode active material, it can be combined with materials such as V2O5 and Cr3O8 that do not contain lithium as the positive electrode active material . Even when using a material containing lithium as the positive electrode active material, by previously desorbing the lithium contained in the positive electrode active material, a complex nitride of lithium and a transition metal can be used as the negative electrode active material . .

[0121] In addition, a material that causes a conversion reaction can also be used as the negative electrode active material. For example , transition metal oxides such as cobalt oxide (CoO), nickel oxide (NiO), and iron oxide (FeO) that do not undergo an alloying reaction with lithium can be used as the negative electrode active material. As materials that cause a conversion reaction, furthermore, oxides such as Fe2O3, CuO, Cu2O, RuO2, and Cr2O 3, CoS 3, etc., 3, etc., 0.89, sulfides such as NiS and CuS, nitrides such as Zn3N2, Cu3N, G e3N4, phosphides such as NiP2, FeP2, and CoP3, fluorides such as FeF3 and BiF3 also occur.

[0122] As an example, the negative electrode active material may be one with a particle size of 50 nm or more and 100 μm or less. .

[0123] Note that in both the positive electrode active material layer 101 and the negative electrode active material layer 103, a plurality of active material materials may be used in combination at a specific ratio. By using a plurality of materials in the active material layer , the performance of the active material layer can be selected in more detail.

[0124] As the conductive assistant of the electrode, acetylene black (AB), graphite (carbon) particles, car bon nanotubes, graphene, fullerenes, etc. can be used.

[0125] The conductive assistant can form an electrical conduction network in the electrode. With the conductive assistant , the electrical conduction path between the negative electrode active materials can be maintained. By adding a conductive assistant to the negative electrode active material layer, a negative electrode active material layer 103 with high electrical conductivity can be realized. .

[0126] In addition, as the binder, in addition to typical polyvinylidene fluoride (PVDF), polyimide , polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene go m, acrylonitrile-butadiene rubber, fluorine rubber, polyvinyl acetate, polymethyl meth acrylate, polyethylene, nitrocellulose, etc. can be used.

[0127] The content of the binder with respect to the total amount of the negative electrode active material layer 103 is 1 wt% or more and 10 wt% or less. Preferably, it is 2 wt% or more and 8 wt% or less, more preferably 3 wt% or more and 5 wt% or less. Further, the content of the conductive assistant with respect to the total amount of the negative electrode active material layer 103 is preferably 1 wt% or more and 10 wt% or less, and more preferably 1 wt% or more and 5 wt% or less.

[0128] Next, the negative electrode active material layer 103 is formed on the negative electrode current collector 102. When forming the negative electrode active material layer 103 using the coating method, the negative electrode active material, binder, conductive assistant, and dispersion medium are mixed to prepare a slurry, which is then applied to the negative electrode current collector 102 and dried. Further, if necessary after drying, pressing treatment may be performed.

[0129] Note that for the negative electrode current collector 102, metals such as stainless steel, gold, platinum, iron, copper, titanium, tantalum, etc., and alloys thereof, which have high conductivity and do not alloy with carrier ions such as lithium, can be used. Also, it may be formed of a metal element that reacts with silicon to form a silicide. Examples of the metal element that reacts with silicon to form a silicide include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, etc. The negative electrode current collector 102 can be appropriately used in shapes such as foil, plate (sheet), net, columnar, coil, punched metal, expanded metal, etc. The negative electrode current collector 102 is preferably one with a thickness of 5 μm or more and 30 μm or less. Also, an undercoat layer may be provided on a part of the surface of the electrode current collector using graphite or the like.

[0130] The negative electrode of the lithium-ion battery can be manufactured through the above steps.​​​​​​

[0131] ≪Solid electrolyte layer≫ <Mixing of Li salt> When a graphene compound according to one embodiment of the present invention is used in a solid electrolyte, the graphene compound is mixed with a Li salt.

[0132] For example, a solution in which a graphene compound according to one embodiment of the present invention is dispersed in tetrahydrofuran (THF) and a solution in which LiTFSA (lithium bis(trifluoromethanesulfonyl)amide) is dispersed in THF are mixed. Next, one or more drops of this are dropped onto a material for forming a solid electrolyte layer, simply dried on a hot plate, and then dried under reduced pressure at a temperature of 90 °C to form a solid electrolyte layer. The solid electrolyte layer may be in the form of a film . The solid electrolyte layer 104 is sandwiched between a positive electrode and a negative electrode and housed in an exterior body.

[0133] Note that the method of mixing a Li salt for using a graphene compound according to one embodiment of the present invention in a solid electrolyte is not limited to this.

[0134] Also, together with the solid electrolyte layer 104, a separator may be sandwiched between the positive electrode and the negative electrode. The separator must have insulating performance to prevent contact between the two electrodes, performance to hold an electrolyte solution, and ion conductivity.

[0135] Also, when the separator is formed in a sheet shape or an envelope shape of a size that can cover both sides of one of the positive electrode or the negative electrode, and the electrode is formed by the separator, in the manufacture of a storage battery, the electrode can be protected from mechanical damage, and the handling of the electrode becomes easy. By housing the electrode wrapped by the separator and the other electrode together in an exterior body, a storage battery can be formed. ​

[0136] Furthermore, the separator can be used alone or in combination of two or more selected from fluorine-based polymers, polyethylene oxide, polyethers such as polypropylene oxide, polyolefins such as polyethylene and polypropylene, polyacrylonitrile, polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, polyvinyl pyrrolidone, polyethyleneimine, polybutadiene, polystyrene, polyisoprene, polyurethane-based polymers and their derivatives, cellulose, paper, non-woven fabric, and glass fiber. By using the solid electrolyte layer 10 4 and the separator together, the performance of the separator of the storage battery can be diversely selected as compared with the case of using one film alone. Furthermore, the storage battery may have flexibility, and even when a deformation stress is applied to the flexible storage battery, at the interface between the solid electrolyte layer 104 and the separator, the stress can be relaxed by the sliding of both, so the structure having the solid electrolyte layer 104 and the separator together is also suitable as the structure of the separator of the flexible storage battery. The solid electrolyte layer 104 can be incorporated into the lithium ion storage battery in the above steps.

[0137] ≪Configuration of the exterior body≫ Next, the exterior body 207 will be described. The exterior body 207 is, for example, on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, polyamide, etc., aluminum

[0138]

[0139] ≪Configuration of the exterior body≫ Next, the exterior body 207 will be described. The exterior body 207 is, for example, on a film made of a material such as polyethylene, polypropylene, polycarbonate, ionomer, polyamide, etc., aluminum ​​A metal thin film with excellent flexibility such as minium, stainless steel, copper, nickel, etc. is provided, and further, the metal On the thin film, an insulating synthetic resin such as a polyamide-based resin or a polyester-based resin is used as the outer surface of the exterior body. A film having a three-layer structure provided with a film can be used. By adopting such a three-layer structure, The permeation of electrolytic solution and gas is blocked, insulation is ensured, and at the same time, it has electrolyte resistance. When the exterior body is bent inward and overlapped, or the inner surfaces of two exterior bodies are faced to each other By applying heat while overlapping, the material on the inner surface melts and the two exterior bodies can be fused to create a Sealing structure.

[0140] If the location where the exterior body is fused or the like to form a sealing structure is defined as the sealing portion, when the exterior body is bent inward and overlapped, the sealing portion is formed at a location other than the fold, and the first region of the exterior body and The second region overlapping the first region are fused or the like. Also, when two exterior bodies are overlapped, the sealing portion is formed on the entire outer periphery by a method such as heat fusion. The second region overlapping the first region are fused or the like. Also, when two exterior bodies are overlapped, the sealing portion is formed on the entire outer periphery by a method such as heat fusion. When two exterior bodies are overlapped, the sealing portion is formed on the entire outer periphery by a method such as heat fusion.

[0141] ≪Flexible rechargeable battery≫ When a material having flexibility is selected and used from the materials of each member shown in the present embodiment, A flexible lithium-ion rechargeable battery can be manufactured. In recent years, research and development of deformable devices Have been actively carried out. As a rechargeable battery used for such devices, there is a demand for a rechargeable battery having flexibility.

[0142] When a rechargeable battery in which two films are used as exterior bodies and battery materials 1805 such as electrodes and solid electrolytes are sandwiched is bent, the radius of curvature 1 802 of the film 1801 on the side closer to the center of curvature 1800 of the rechargeable battery is smaller than the radius of curvature 1804 of the film 1803 on the side farther from the center of curvature 1800. 802 of the film 1801 on the side closer to the center of curvature 1800 of the rechargeable battery is smaller than the radius of curvature 1804 of the film 1803 on the side farther from the center of curvature 1800. ​Side (Fig. 2(A)). When the storage battery is curved to have an arc-shaped cross section, it is close to the center of curvature 1800 Compressive stress is applied to the surface of the film, and tensile stress is applied to the surface of the film far from the center of curvature 1800 (Fig. 2(B)).

[0143] When a flexible lithium-ion storage battery is deformed, a large stress is applied to the exterior body. However , if a pattern formed by concave or convex portions is formed on the surface of the exterior body, even if compressive stress or tensile stress is applied due to the deformation of the storage battery, the influence of strain can be suppressed. Therefore , the storage battery can be deformed within a range where the radius of curvature of the exterior body on the side close to the center of curvature is 50 mm, preferably 30 mm .

[0144] The radius of curvature of the surface will be described with reference to Fig. 3. In Fig. 3(A), in the plane 1701 obtained by cutting the curved surface 1700, a part of the curve 1702 included in the curved surface 1700 is approximated to an arc of a circle, the radius of the circle is defined as the radius of curvature 1703, and the center of the circle is defined as the center of curvature 1704. Fig. 3(B) shows a top view of the curved surface 1700. Fig. 3(C) shows a cross-sectional view obtained by cutting the curved surface 1700 with the plane 1701. When the curved surface is cut with a plane, the radius of curvature of the curve appearing in the cross section will vary depending on the angle of the plane with respect to the curved surface and the cutting position. However, in this specification etc., the smallest radius of curvature is defined as the radius of curvature of the surface. Note that the cross-sectional shape of the storage battery is not limited to a simple arc shape, and it can have a shape with a part having an arc, for example, the shape shown in Fig. 2(C), a wave shape (Fig. 2(D)), an S shape, etc.

[0145] Among the radii of curvature of each of the cores, in the surface with the smallest radius of curvature, the two exterior bodies The radius of curvature of the exterior body closer to the center of curvature is preferably in the range of 50 mm, more preferably 30 mm, so that the storage battery can be deformed.

[0146] ≪Assembly and Aging of Storage Battery≫ Next, by combining the above-described constituent members and sealing the exterior body 207, as shown in FIGS. 1(A) and (B), the positive electrode current collector 100, the positive electrode active material layer 101, the solid electrolyte layer 104 , the negative electrode active material layer 103, and the negative electrode current collector 102 are stacked and sealed by the exterior body 207 to be in a sealed state.

[0147] Next, an aging process may be performed. First, the ambient temperature is maintained at about room temperature, and constant current charging is performed at a low rate until the equalizing voltage. Next, the gas generated in the region inside the exterior body due to charging is released to the outside of the exterior body. Next, charging is performed at a rate higher than the first charging rate.

[0148] Thereafter, it is stored for a long time in a slightly higher temperature environment. For example, it is stored for 24 hours or more in an environment of 40 °C or higher .

[0149] After being stored for a long time in a slightly higher temperature environment, the gas generated in the region inside the exterior body is released again . Further, it is discharged at a rate of 0.2C in a room temperature environment, charged at the same rate, discharged again at the same rate , and then charged again at the same rate. Then, by discharging at the same rate, the aging process is completed.

[0150] As described above, the storage battery according to the present invention can be manufactured.

[0151] This embodiment can be implemented in appropriate combination with other embodiments.

[0152] In this specification, etc., in a drawing or text described in a certain embodiment, When at least one specific example is described, it is not possible to derive a generic concept of that specific example. It will be easily understood by those skilled in the art. When at least one specific example is described in a figure or text, the general outline of that specific example is The invention is also disclosed as an embodiment of the invention and may constitute an embodiment of the invention. And one aspect of the invention can be said to be clear.

[0153] In this specification, at least the contents shown in the drawings (or even a part of the drawings) This is disclosed as one aspect of the invention and can constitute one aspect of the invention. Therefore, if something is shown in a diagram, it does not need to be explained in words. However, the contents are disclosed as one aspect of the invention and constitute one aspect of the invention. Similarly, a part of the drawings may be regarded as an embodiment of the invention. This is disclosed as one embodiment of the present invention. It can be said that one aspect of the invention is clear. EXAMPLES

[0154] Example 1 This example is a synthesis example of a graphene compound according to one embodiment of the present invention described in Embodiment 1. This article explains:

[0155] <Synthesis Example 1> First, a synthesis example of graphene oxide having a structure represented by the following formula (201) explain.

[0156] [Chemical formula]

[0157] First, 0.31 g of graphene oxide (manufactured by Nippon Material Co., Ltd., product name: R ap dGO(TQ-11)-1) and 4.2 g (58 mmol l) of n-butylamine were added to a 50 mL two-necked flask. This mixture was irradiated with ultrasonic waves for 5 minutes under a nitrogen stream, and then stirred at 60 °C for 1 hour . After stirring, the mixture was cooled to room temperature, 15 mL of toluene was added, and ultrasonic waves were irradiated for 5 minutes. After cooling this mixture to 0 °C, 8.0 g (24 mmol) of methoxytriethyleneoxypropyltrichloro silane (CAS number: 228700-87-6) was added dropwise . This mixture was stirred at 60 °C for 5 hours. After stirring, toluene was added to this mixture for washing , and the solid was recovered by suction filtration. The obtained solid was further washed with ethanol and acetone . When the obtained solid was dried, 0.39 g of the target black powder was obtained. The following synthetic scheme (A) is shown below .

[0158] [Chemical formula]

[0159] [Synthesis Example 2] Next, another synthesis example of the graphene compound according to one aspect of the present invention described in Embodiment 1 will be shown . That is, a synthesis example of graphene oxide having a structure represented by the following formula (202) will be described .

[0160] [Chemical formula]

[0161] In a 50 mL two-necked flask, 0.30 g of graphene oxide (manufactured by Nippon Material Co., Ltd., trade name: Rap dGO(TQ-11)-1) and 4.3 g (59 mmol) of n-butylamine were added. This mixture was irradiated with ultrasonic waves for 5 minutes under a nitrogen stream, and further stirred at 60 °C for 1 hour After stirring, the mixture was cooled to room temperature, 15 mL of toluene was added, and ultrasonic waves were irradiated for 5 minutes After cooling this mixture to 0 °C, 14 g of 2-[methoxy(polyethyleneoxy)6-9 propyl yl]trichlorosilane (CAS No.: 36493-41-1) was added dropwise. This mix The mixture was stirred at 60 °C for 5 hours. After stirring, toluene was added to this mixture for washing, and the solid was recovered by suction filtration. The obtained solid was further washed with ethanol and acetone. When the obtained solid was dried, 0.37 g of the target black powder was obtained. The following synthetic scheme (B) is shown.

[0162] [Chemical formula]

[0163] [FT-IR analysis] In the above Synthesis Example 1, in order to confirm that the graphene compound was chemically modified, FT -IR analysis (Fourier transform infrared spectroscopy) was performed.

[0164] FT-IR analysis was performed on three samples: the chemically modified graphene compound (Sample 1) prepared in Synthesis Example 1 above, the chemically modified graphene compound (Sample 2) prepared in Synthesis Example 2 above, and unmodified graphene oxide (Comparative Sample 1).

[0165] The measurement was carried out using "Nicolet NEXUS 67 manufactured by Thermo SCIENTIFIC FT-IR analysis by the ATR method (total reflection measurement method) was performed using "0". Sample 1 and Sample 2 Since they became film-like when the above synthesis was completed, the ATR prism was pressed against the samples and installed in the analyzer. Comparative Sample 1 is powdery, but similarly, the ATR prism was pressed against the sample and installed in the analyzer.

[0166] The measurement range was from 700 cm -1 to 4000 cm -1 The resolution was 4.0 cm -1 and the scan was performed 256 times (background scan 256 times) at a mirror speed of 0.6329 was performed.

[0167] The measurement results are shown in Fig. 4. Fig. 4(A) is for Sample 1, Fig. 4(B) is for Sample 2, and Fig. 4(C) is the FT-IR spectrum of Comparative Sample 1.

[0168] In unmodified graphene oxide (Comparative Sample 1), peaks (around 1720 cm that seem to be attributed to C=O stretching vibration) and peaks (around 1620 cm -1 that may be attributed to C=C stretching vibration) are observed in the spectrum of Fig. 4(C). That is the FT-IR spectrum of unmodified graphene oxide was confirmed. -1

[0169] On the other hand, in the chemically modified graphene compounds (Sample 1 and Sample 2), as shown in Fig. 4(A) and Fig. 4(B), peaks (around 290 0 cm -1 that seem to be attributed to C-H stretching vibration) are observed, and peaks (around 1100 cm that may be attributed to C-O stretching vibration and C-O-C antisymmetric stretching vibration) are also observed. In Fig. 4(C) -1 ​​​Unlike the spectrum, peaks that are thought to be derived from groups having an ether bond were observed It was

[0170] Therefore, it was confirmed that Sample 1 and Sample 2 were chemically modified by groups having an ether bond. As described above, the generation of the chemically modified graphene compound according to one aspect of the present invention was confirmed

Explanation of Signs

[0171] 100 Positive electrode current collector 101 Positive electrode active material layer 102 Negative electrode current collector 103 Negative electrode active material layer 104 Solid electrolyte layer 110 Lithium ion battery 207 Outer package 1700 Curved surface 1701 Plane 1702 Curve 1703 Radius of curvature 1704 Center of curvature 1800 Center of curvature 1801 Film 1802 Radius of curvature 1803 Film 1804 Radius of curvature 1805 Battery material​

Claims

1. A lithium ion battery having a positive electrode active material layer, a solid electrolyte, and a negative electrode active material, wherein the solid electrolyte contains a graphene compound, the graphene compound has graphene oxide and a chain-like group having a plurality of ether bonds, the graphene oxide and the chain-like group are bonded via an Si atom, the graphene oxide and the Si atom are bonded by one or more Si—O bonds, and the number of oxygen atoms in the chain-like group is 2 or more and 10 or less.

2. The lithium ion battery according to claim 1, wherein an —OH group is further bonded to the Si atom.

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