Patent Application
20240047751
One embodiment of the present invention relates to an object, a method, or a manufacturing method. One embodiment of the present invention relates to a process, a machine, manufacture, or a composition of matter. One embodiment of the present invention relates to a semiconductor device, a display device, a light-emitting device, a power storage device, a lighting device, an electronic device, or a manufacturing method thereof. In particular, one embodiment of the present invention relates to a positive electrode active material that can be used for a secondary battery, a secondary battery, an electronic device including a secondary battery, and a vehicle including a secondary battery.
Another embodiment of the present invention relates to a power storage system including a secondary battery and a battery control circuit. Another embodiment of the present invention relates to an electronic device and a vehicle each including a power storage system.
Note that in this specification, a power storage device refers to every element and device having a function of storing power. Examples of the power storage device include a storage battery (also referred to as a secondary battery) such as a lithium-ion secondary battery, a lithium-ion capacitor, and an electric double layer capacitor.
In addition, electronic devices in this specification mean all devices including power storage devices, and electro-optical devices including power storage devices, information terminal devices including power storage devices, and the like are all electronic devices.
In recent years, a variety of power storage devices such as lithium-ion secondary batteries, lithium-ion capacitors, and air batteries have been actively developed. In particular, demand for lithium-ion secondary batteries with high output and high energy density has rapidly grown with the development of the semiconductor industry, for portable information terminals such as mobile phones, smartphones, tablets, and laptop computers, portable music players, digital cameras, medical equipment, and next-generation clean energy vehicles (e.g., hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs)), for example. The lithium-ion secondary batteries are essential as rechargeable energy supply sources for today's information society.
The performances required for lithium-ion secondary batteries are much higher energy density, improved cycle performance, safety under a variety of operation environments, and improved long-term reliability, for example.
In view of the above, improvement of positive electrode active materials has been studied to improve the cycle performance and increase the capacity of lithium-ion secondary batteries (Patent Document 1 and Patent Document 2). In addition, crystal structures of positive electrode active materials have been studied (Non-Patent Document 1 to Non-Patent Document 3).
Non-Patent Document 4 discloses the physical properties of metal fluorides.
X-ray diffraction (XRD) is one of methods used for analysis of a crystal structure of a positive electrode active material. With the use of the ICSD (Inorganic Crystal Structure Database) described in Non-Patent Document 5, XRD data can be analyzed.
An object of one embodiment of the present invention is to provide a lithium-ion secondary battery having high capacity and excellent charge and discharge cycle performance, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a secondary battery that can be rapidly charged, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a high-capacity secondary battery, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a secondary battery having excellent charge and discharge characteristics, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a secondary battery in which a reduction in capacity is suppressed even when a state being charged with a high voltage is held for a long time, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a highly safe or reliable secondary battery, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a secondary battery in which a reduction in capacity is suppressed even at high temperatures, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a long-life secondary battery, and a manufacturing method thereof.
An object of one embodiment of the present invention is to provide a safe, long-life, and extremely excellent secondary battery that can be rapidly charged, can be used at high temperatures, and can have a high energy density due to increased charge voltage.
An object of one embodiment of the present invention is to provide a positive electrode active material that has high capacity and excellent charge and discharge cycle performance for a lithium-ion secondary battery, and a manufacturing method thereof. Another object of one embodiment of the present invention is to provide a method for manufacturing a positive electrode active material with high productivity. Another object of one embodiment of the present invention is to provide a positive electrode active material that suppresses a reduction in capacity in charge and discharge cycles when used for a lithium-ion secondary battery. Another object of one embodiment of the present invention is to provide a positive electrode active material in which elution of a transition metal such as cobalt is suppressed even when a state being charged with a high voltage is held for a long time.
Another object of one embodiment of the present invention is to provide a novel material, novel active material particles, a novel power storage device, or a manufacturing method thereof.
Note that the description of these objects does not preclude the existence of other objects. One embodiment of the present invention does not have to achieve all these objects. Note that other objects can be taken from the description of the specification, the drawings, and the claims.
One embodiment of the present invention is a secondary battery including a positive electrode, a negative electrode, and an electrolyte. The amount of moisture in the electrolyte is less than 1000 ppm.
Another embodiment of the present invention is a secondary battery including a positive electrode, a negative electrode, and an electrolyte. The amount of moisture in the electrolyte is less than 1000 ppm. The amount of moisture in the electrolyte is measured with a Karl Fischer moisture titrator.
In the above structure, the electrolyte preferably contains a lithium salt and a cyclic carbonate.
In the above structure, the electrolyte preferably contains a lithium salt and an ionic liquid.
In the above structure, it is preferable to include one or more cations selected from an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a tertiary sulfonium cation, and a quaternary phosphonium cation, and one or more anions selected from a monovalent amide-based anion, a monovalent methide-based anion, a fluorosulfonate anion, a perfluoroalkylsulfonate anion, a tetrafluoroborate anion, a perfluoroalkylborate anion, a hexafluorophosphate anion, and a perfluoroalkylphosphate anion.
Another embodiment of the present invention is an electronic device including the secondary battery described in any of the above, a display portion, and a sensor.
Another embodiment of the present invention is a vehicle including the secondary battery described in any of the above, an electric motor, and a control device, and the control device has a function of supplying electric power from the secondary battery to the electric motor.
According to one embodiment of the present invention, a lithium-ion secondary battery having high capacity and excellent charge and discharge cycle performance, and a manufacturing method thereof can be provided. According to another embodiment of the present invention, a secondary battery that can be rapidly charged, and a manufacturing method thereof can be provided. According to another embodiment of the present invention, a secondary battery in which a reduction in capacity is suppressed even when a state being charged with a high voltage is held for a long time, and a manufacturing method thereof can be provided. According to another embodiment of the present invention, a highly safe or reliable secondary battery, and a manufacturing method thereof can be provided. According to another embodiment of the present invention, a secondary battery in which a reduction in capacity is suppressed even at high temperatures, and a manufacturing method thereof can be provided. According to another embodiment of the present invention, a long-life secondary battery, and a manufacturing method thereof can be provided.
According to one embodiment of the present invention, a safe, long-life, and extremely excellent secondary battery that can be rapidly charged, can be used at high temperatures, and can have a high energy density due to increased charge voltage can be provided.
According to one embodiment of the present invention, a positive electrode active material that has high capacity and excellent charge and discharge cycle performance for a lithium-ion secondary battery, and a manufacturing method thereof can be provided. A method for manufacturing a positive electrode active material with high productivity can be provided. According to one embodiment of the present invention, a positive electrode active material that suppresses a reduction in capacity in charge and discharge cycles when used for a lithium-ion secondary battery can be provided. According to one embodiment of the present invention, a positive electrode active material in which elution of a transition metal such as cobalt is suppressed even when a state being charged with a high voltage is held for a long time can be provided.
One embodiment of the present invention can provide a novel material, novel active material particles, a novel power storage device, or a manufacturing method thereof.
Note that the description of these effects does not preclude the existence of other effects. One embodiment of the present invention does not have to have all these effects. Note that effects other than these will be apparent from the description of the specification, the drawings, the claims, and the like and effects other than these can be taken from the description of the specification, the drawings, the claims, and the like.
Embodiments of the present invention will be described in detail below with reference to the drawings. Note that the present invention is not limited to the following description, and it is readily understood by those skilled in the art that modes and details of the present invention can be modified in various ways. In addition, the present invention should not be construed as being limited to the description of the embodiments below.
In this specification and the like, crystal planes and orientations are indicated by the Miller index. In the crystallography, a bar is placed over a number in the expression of crystal planes and orientations; however, in this specification and the like, because of application format limitations, crystal planes and orientations may be expressed by placing − (a minus sign) at the front of a number instead of placing a bar over the number. Furthermore, an individual direction that shows an orientation in a crystal is denoted by “[ ]”, a set direction that shows all of the equivalent orientations is denoted by “< >”, an individual plane that shows a crystal plane is denoted by “( )”, and a set plane having equivalent symmetry is denoted by “{ }”.
In this specification and the like, segregation refers to a phenomenon in which in a solid made of a plurality of elements (e.g., A, B, and C), a certain element (e.g., B) is spatially non-uniformly distributed.
In this specification and the like, a surface portion of a particle of an active material or the like refers to a region from a surface to a depth of approximately 10 nm. A plane generated by a split or a crack may also be referred to as a surface. In addition, a region whose position is deeper than that of the surface portion is referred to as an inner portion.
In this specification and the like, a layered rock-salt crystal structure, which belongs to the space group R-3m, of a composite oxide containing lithium and a transition metal such as cobalt refers to a crystal structure in which a rock-salt ion arrangement where cations and anions are alternately arranged is included and the transition metal and lithium are regularly arranged to form a two-dimensional plane, so that lithium can be two-dimensionally diffused. Note that a defect such as a cation or anion vacancy may exist. Moreover, in the layered rock-salt crystal structure, strictly, a lattice of a rock-salt crystal is distorted in some cases.
In this specification and the like, a rock-salt crystal structure refers to a structure in which a cubic crystal structure with the space group Fm-3m or the like is included and cations and anions are alternately arranged. Note that a cation or anion vacancy may exist.
In this specification and the like, an O3′ type crystal structure of a composite oxide including lithium and a transition metal belongs to a space group R-3m, and is a crystal structure in which an ion of cobalt, magnesium, or the like is coordinated to six oxygen atoms. Note that in the O3′ type crystal structure, a light element such as lithium is sometimes coordinated to four oxygen atoms.
A secondary battery includes a positive electrode and a negative electrode, for example. A positive electrode active material is a material included in the positive electrode. The positive electrode active material is a substance that performs a reaction contributing to the charge and discharge capacity, for example. Note that the positive electrode active material may partly contain a substance that does not contribute to the charge and discharge capacity.
In this specification and the like, the positive electrode active material of one embodiment of the present invention is expressed as a positive electrode material, a secondary battery positive electrode material, or the like in some cases. In this specification and the like, the positive electrode active material of one embodiment of the present invention preferably contains a compound. In this specification and the like, the positive electrode active material of one embodiment of the present invention preferably contains a composition. In this specification and the like, the positive electrode active material of one embodiment of the present invention preferably contains a composite.
In this embodiment, an example of a secondary battery of one embodiment of the present invention is described.
As described in Example below, it has been found that the secondary battery of one embodiment of the present invention has extremely stable characteristics even when charged with a high voltage. In addition, the secondary battery of one embodiment of the present invention can operate stably in a wide temperature range. The secondary battery of one embodiment of the present invention can have significantly excellent characteristics.
A positive electrode active material of one embodiment of the present invention is an oxide containing an element A and a metal M.
As the element A, one or more selected from alkali metals such as lithium, sodium, and potassium and Group 2 elements such as calcium, beryllium, and magnesium can be used, for example. The element A is preferably an element that functions as a carrier metal.
As the metal M, for example, a transition metal can be used. The positive electrode active material of one embodiment of the present invention contains one or more of cobalt, nickel, and manganese, particularly cobalt, as the metal M, for example. The positive electrode active material of one embodiment of the present invention may contain, as the metal M, an element that has no valence number change and can have the same valence number as the metal M, such as aluminum, specifically, a trivalent representative element, for example.
The positive electrode active material of one embodiment of the present invention may be represented by the chemical formula AMyOz (y>0 and z>0). Lithium cobalt oxide may be represented by LiCoO2. Lithium nickel oxide may be represented by LiNiO2.
The positive electrode active material of one embodiment of the present invention preferably contains an additive element X. An element such as magnesium, calcium, zirconium, lanthanum, barium, titanium, or yttrium can be used as the additive element X. An element such as nickel, aluminum, cobalt, manganese, vanadium, iron, chromium, or niobium can be used as the additive element X. An element such as copper, potassium, sodium, zinc, chlorine, fluorine, hafnium, silicon, sulfur, phosphorus, boron, or arsenic can be used as the additive element X. Two or more of the elements described above as the additive element X may be used in combination.
Part of the additive element X may substitute at the element A position, for example. Alternatively, part of the additive element X may substitute at the metal M position, for example.
The positive electrode active material of one embodiment of the present invention may be represented by the chemical formula A1−wXwMyOz (y>0, z>0, and 0<w<1). The positive electrode active material of one embodiment of the present invention may be represented by the chemical formula AMy−jXjOz (y>0, z>0, and 0<j<y). The positive electrode active material of one embodiment of the present invention may be represented by the chemical formula A1−wXwMy−jXjOz (y>0, z>0, 0<w<1, and 0<j<y).
Furthermore, the positive electrode active material of one embodiment of the present invention preferably contains halogen in addition to the additive element X. The positive electrode active material preferably contains halogen such as fluorine or chlorine. When the positive electrode active material of one embodiment of the present invention contains the halogen, substitution of the additive element X at the element A position is promoted in some cases.
As charge voltage of a secondary battery increases, the crystal structure of a positive electrode active material might become unstable and the characteristics of the secondary battery might be reduced. As an example, the case is described where a material having a layered crystal structure in which a metal A is extracted from a space between layers due to a charge reaction is used as a positive electrode active material. The increase in charge voltage of such a positive electrode active material can increase charge capacity and discharge capacity. Meanwhile, as charge voltage is increased, a larger amount of the metal A might be extracted from the positive electrode active material and a change in the crystal structure such as a change in the interlayer distance or generation of displacement of a layer might noticeably occur. In the case where a change in the crystal structure due to insertion and extraction of the metal A is irreversible, the crystal structure might be gradually broken along with repetitive charging and discharging and a noticeable reduction in capacity due to charge and discharge cycles might occur.
An increase in charge voltage may facilitate elution of the metal M contained in the positive electrode active material into an electrolyte. Elution of the metal M from the positive electrode active material into the electrolyte might decrease the amount of the metal M of the positive electrode active material and might decrease the capacity of a positive electrode.
In the positive electrode active material of one embodiment of the present invention, the metal M is mainly bonded to oxygen. Release of oxygen from the positive electrode active material might cause noticeable elution of the metal M.
When the oxidation number of the metal M contained in the positive electrode active material becomes large in charging, the positive electrode active material has high reactivity and is brought into a state where reactivity with an impurity or the like in an electrolyte is extremely high. For example, oxygen in the positive electrode active material is released and the electrolyte is oxidized. When oxygen is released, elution of the metal M easily occurs.
When charging and discharging are performed under high-voltage conditions at 4.5 V or higher or at a high temperature (45° C. or higher), a progressive defect (also referred to as a pit) might be generated in a positive electrode active material particle. In addition, a defect such as a crevice (also referred to as a crack) might be generated by expansion and contraction of a positive electrode active material particle due to charging and discharging.
A positive electrode active material particle has a defect and the defect might change before and after charging and discharging. When used in a secondary battery, a positive electrode active material particle might undergo a phenomenon such as chemical or electrochemical erosion or degradation due to environmental substances (e.g., an electrolyte) surrounding the positive electrode active material particle. This degradation does not occur uniformly in the surface of the positive electrode active material particle but occurs locally in a concentrated manner, and a defect is formed deeply from the surface toward the inner portion, for example, by repetitive charging and discharging of the secondary battery.
Progress of a defect in a positive electrode active material particle to form a hole can be referred to as pitting corrosion, and the hole generated by this phenomenon is also referred to as a pit in this specification.
In this specification, a crack and a pit are different from each other. Immediately after formation of a positive electrode active material particle, a crack can exist but a pit does not exist. In lithium cobalt oxide, for example, a pit can also be regarded as a hole formed by extraction of some layers of cobalt and oxygen due to charging and discharging under high-voltage conditions at 4.5 V or higher or at a high temperature (45° C. or higher), i.e., a portion from which cobalt has been eluted. A crack refers to a surface newly generated by application of physical pressure or a crevice generated owing to a grain boundary. A crack might be caused by expansion and contraction of a particle due to charging and discharging. A pit might be generated from a crack or a cavity in the particle.
Cobalt is eluted in lithium cobalt oxide due to charging and discharging with a high voltage or at a high temperature and discharging, whereby a crystal phase that is different from the lithium cobalt oxide may be formed in a surface portion. For example, one or more of Co3O4 having a spinel structure, LiCo2O4 having a spinel structure, and CoO having a rock-salt structure may be formed. These materials are materials having lower discharge capacity than lithium cobalt oxide or not contributing to charging and discharging, for example. Thus, formation of these materials in the surface portion might decrease the discharge capacity of the secondary battery. Furthermore, deterioration of output characteristics and deterioration of low-temperature characteristics might be caused in the secondary battery. These materials are formed in the vicinity of a pit in some cases.
The metal Mis eluted from the positive electrode active material, the electrolyte transfers an ion of the metal M, and the metal M may be precipitated at the surface of a negative electrode. In addition, at the surface of the negative electrode, a coating film may be formed from the metal M and a decomposition product of the electrolyte. The formation of the coating film makes insertion and extraction of carrier ions into/from a negative electrode active material difficult, which might lead to deterioration of the rate characteristics, low-temperature characteristics, or the like of the secondary battery.
Since the positive electrode active material of one embodiment of the present invention can have an O3′ structure described later in charging, charging can be performed to a large charge depth. The increase in charge depth can increase the capacity of the positive electrode, so that the energy density of the secondary battery can be increased. Even in the case of using an extremely high charge voltage, charging and discharging can be repeated.
The positive electrode active material of one embodiment of the present invention can have an extremely high purity by minimizing the amount of impurities mixed in a source material and in a manufacturing process. Increasing the purity of the positive electrode active material can further increase the structure stability of the positive electrode active material at a high charge voltage in some cases.
Note that in the case where charging is performed at a higher charge voltage, the metal M has a larger oxidation number. In such a state, elution of the metal M easily occurs as described above.
In the secondary battery of one embodiment of the present invention, elution of the metal M easily occurs due to an extremely high charge voltage, but a reduction of the amount of impurities in the electrolyte can suppress elution of the metal Min some cases. Thus, both a high charge voltage and suppression of elution of the metal M can be achieved.
Moisture can be given as an example of the impurities in the electrolyte.
Here, a surface portion is preferably a region that is less than or equal to 50 nm, preferably less than or equal to 35 nm, further preferably less than or equal to 20 nm from the surface, for example. In addition, a region in a deeper position than a surface portion is referred to as an inner portion.
The positive electrode active material of one embodiment of the present invention contains the additive element X. The additive element Xin the positive electrode active material of one embodiment of the present invention preferably has a concentration gradient. The concentration of the additive element X preferably has a gradient that increases from the inner portion toward the surface. The gradient of the concentration of the additive element X can be evaluated using energy dispersive X-ray spectroscopy (EDX).
For example, when the crystal structure of a material included in a positive electrode active material irreversibly changes due to charging at high temperatures, a secondary battery significantly deteriorates. For example, a significant reduction in capacity due to charge and discharge cycles might occur. The crystal structure of a positive electrode might become more unstable at higher temperatures and at a higher charge voltage.
When a positive electrode active material whose crystal structure is extremely stable at a high charge voltage and at high temperatures is used for the secondary battery of one embodiment of the present invention, excellent characteristics can be achieved even at high temperatures and at a high charge voltage, so that an electrolyte in which the amount of moisture is minimized can sufficiently exert its effect. In other words, a significant improvement in characteristics achieved by employing the structure of the secondary battery of one embodiment of the present invention is found when the structure is combined with the positive electrode active material of one embodiment of the present invention.
The positive electrode active material of one embodiment of the present invention preferably contains the additive element X as described later, and preferably contains halogen in addition to the additive element X. It is suggested that when the positive electrode active material of one embodiment of the present invention contains the additive element X or contains halogen in addition to the additive element X, a reaction with an electrolyte on the surface of the positive electrode active material is suppressed.
Furthermore, in the secondary battery of one embodiment of the present invention, the range of reaction potential is extremely wide. In such a wide reaction potential range, a reaction with an impurity in an electrolyte on the surface of an active material is concerned in some cases. When the electrolyte of one embodiment of the present invention is used, it is suggested that a reaction between the electrolyte and the surface of an active material is inhibited and a more stable secondary battery is provided.
The secondary battery of one embodiment of the present invention is preferably used in combination with a battery control circuit. The battery control circuit preferably has a function of controlling charging, for example. Controlling charging refers to, for example, monitoring a parameter of a secondary battery and changing charge conditions in accordance with a state. Examples of a parameter to be monitored of a secondary battery include the voltage, current, temperature, amount of electric charge, and impedance of the secondary battery.
The secondary battery of one embodiment of the present invention is preferably used in combination with a sensor. The sensor preferably has a function of measuring, for example, one or more of displacement, position, speed, acceleration, angular velocity, rotational frequency, distance, light, liquid, magnetism, temperature, chemical substance, sound, time, hardness, electric field, current, voltage, electric power, radiation, flow rate, humidity, gradient, oscillation, odor, and infrared rays.
Charging of the secondary battery of one embodiment of the present invention is preferably controlled in accordance with a value measured by the sensor. An example of control of the secondary battery using a temperature sensor will be described later.
A positive electrode active material that is preferably used for the secondary battery of one embodiment of the present invention will be described below.
The positive electrode active material preferably contains a metal serving as a carrier ion (hereinafter the element A). As the element A, an alkali metal such as lithium, sodium, or potassium or a Group 2 element such as calcium, beryllium, or magnesium can be used, for example.
In the positive electrode active material, carrier ions are extracted from the positive electrode active material due to charging. A larger amount of the extracted element A means a larger amount of ions contributing to the capacity of a secondary battery, increasing the capacity. Meanwhile, a large amount of the extracted element A easily causes the break of the crystal structure of a compound contained in the positive electrode active material. The broken crystal structure of the positive electrode active material might lead to a decrease in the discharge capacity due to charge and discharge cycles. The positive electrode active material of one embodiment of the present invention contains the additive element X, whereby the break of a crystal structure that would occur when carrier ions are extracted in charging of a secondary battery may be inhibited. Part of the additive element X substitutes at the element A position, for example. An element such as magnesium, calcium, zirconium, lanthanum, or barium can be used as the additive element X. As another example, an element such as copper, potassium, sodium, zinc, titanium, yttrium, nickel, aluminum, cobalt, manganese, vanadium, iron, chromium, niobium, or hafnium can be used as the additive element X. As another example, an element such as silicon, sulfur, phosphorus, boron, or arsenic can be used as the additive element X. Two or more of the elements described above as the additive element X may be used in combination.
Furthermore, the positive electrode active material of one embodiment of the present invention preferably contains halogen in addition to the additive element X. The positive electrode active material preferably contains halogen such as fluorine or chlorine. When the positive electrode active material of one embodiment of the present invention contains the halogen, substitution of the additive element X at the element A position is promoted in some cases.
In the case where the positive electrode active material of one embodiment of the present invention contains the additive element X or contains halogen in addition to the additive element X, electric conductivity on the surface of the positive electrode active material is sometimes suppressed.
The positive electrode active material of one embodiment of the present invention contains a metal whose valence number changes due to charging and discharging of a secondary battery (hereinafter the metal M). The metal Mis a transition metal, for example. The positive electrode active material of one embodiment of the present invention contains one or more of cobalt, nickel, and manganese, particularly cobalt, as the metal M, for example. The positive electrode active material may contain, at the metal M position, an element that has no valence number change and can have the same valence number as the metal M, such as aluminum, specifically, a trivalent representative element, for example. The above-described additive element X may substitute at the metal M position, for example. In the case where the positive electrode active material of one embodiment of the present invention is an oxide, the additive element X may substitute at the oxygen position.
As the positive electrode active material of one embodiment of the present invention, a lithium composite oxide having a layered rock-salt crystal structure is preferably used, for example. Specifically, as the lithium composite oxide having a layered rock-salt crystal structure, lithium cobalt oxide, lithium nickel oxide, a lithium composite oxide containing nickel, manganese, and cobalt, or a lithium composite oxide containing nickel, cobalt, and aluminum can be used, for example. Moreover, such a positive electrode active material is preferably represented by a space group R-3m.
In the positive electrode active material having a layered rock-salt crystal structure, increasing the charge depth may cause the break of a crystal structure. Here, the break of a crystal structure refers to displacement of a layer, for example. In the case where the break of a crystal structure is irreversible, the capacity of a secondary battery might be decreased by repetitive charging and discharging.
The positive electrode active material of one embodiment of the present invention contains the additive element X, whereby the displacement of a layer can be suppressed even when the charge depth is increased, for example. By suppressing the displacement, a change in volume due to charging and discharging can be small. Accordingly, the positive electrode active material of one embodiment of the present invention can achieve excellent cycle performance. In addition, the positive electrode active material of one embodiment of the present invention can have a stable crystal structure in a high-voltage charged state. Thus, the positive electrode active material of one embodiment of the present invention inhibits a short circuit in some cases while the high-voltage charged state is maintained. This is preferable because the safety is further improved.
The positive electrode active material of one embodiment of the present invention has a small crystal-structure change and a small volume difference per the same number of atoms of the transition metal between a sufficiently discharged state and a high-voltage charged state.
The positive electrode active material of one embodiment of the present invention may be represented by the chemical formula AMyOz (y>0 and z>0). For example, lithium cobalt oxide may be represented by LiCoO2. As another example, lithium nickel oxide may be represented by LiNiO2.
A material with the layered rock-salt crystal structure, such as lithium cobalt oxide (LiCoO2), is known to have a high discharge capacity and excel as a positive electrode active material of a secondary battery. As an example of the material with the layered rock-salt crystal structure, a composite oxide represented by LiMO2 is given. The metal M contains a first metal. The first metal is one or more kinds of metals including cobalt. The metal M can contain a second metal in addition to the first metal. An element selected from the elements described as the additive element X can be used as the second element. For example, the second metal is one or more metals selected from magnesium, calcium, zirconium, lanthanum, barium, copper, potassium, sodium, and zinc.
It is known that the Jahn-Teller effect in a transition metal compound varies in degree according to the number of electrons in the d orbital of the transition metal.
In a compound containing nickel, distortion is likely to be caused because of the Jahn-Teller effect in some cases. Accordingly, when high-voltage charging and discharging are performed on LiNiO2, the crystal structure might be lost because of the distortion. The influence of the Jahn-Teller effect is suggested to be small in LiCoO2; hence, LiCoO2 is preferable because the resistance to high-voltage charging and discharging is higher in some cases.
Here, the composition of the lithium composite oxide represented by LiMO2 is not limited to Li:M:O=1:1:2. As the lithium composite oxide represented by LiMO2, lithium cobalt oxide, lithium nickel-cobalt-manganese oxide, lithium nickel-cobalt-aluminum oxide, lithium nickel-cobalt-manganese-aluminum oxide, and the like can be given.
Using cobalt at greater than or equal to 75 atomic %, preferably greater than or equal to 90 atomic %, further preferably greater than or equal to 95 atomic % as the element M brings many advantages such as relatively easy synthesis, easy handling, and excellent cycle performance.
Using nickel at greater than or equal to 33 atomic %, preferably greater than or equal to 60 atomic %, further preferably greater than or equal to 80 atomic % as the element Mis preferable because in that case, the cost of the raw materials might be lower than that of the case of using a large amount of cobalt and charge and discharge capacity per weight might be increased.
When nickel at greater than or equal to 33 atomic %, preferably greater than or equal to 60 atomic %, further preferably greater than or equal to 80 atomic % is used as the element M, the particle diameter is reduced in some cases. Therefore, the above-described third particle preferably contains nickel as the element M at greater than or equal to 33 atomic %, preferably greater than or equal to 60 atomic %, further preferably greater than or equal to 80 atomic %, for example.
Moreover, when nickel is partly contained as the element M together with cobalt, a shift in a layered structure formed of octahedrons of cobalt and oxygen is sometimes inhibited. The inhibition of the shift enables higher stability of the crystal structure particularly in a high-temperature charged state in some cases, which is preferable. This is presumably because nickel is easily diffused into the inner portion of lithium cobalt oxide and exists in a cobalt site at the time of discharging but can be positioned in a lithium site owing to cation mixing at the time of charging. Nickel existing in the lithium site at the time of charging functions as a pillar supporting the layered structure formed of octahedrons of cobalt and oxygen and presumably contributes to stabilization of the crystal structure.
Note that manganese is not necessarily contained as the element M. In addition, nickel is not necessarily contained. Furthermore, cobalt is not necessarily contained.
At the time of charging, lithium is extracted from the particle surface; accordingly, the surface portion of the particle has a lower lithium concentration than the inner portion and tends to suffer loss of the crystal structure.
The particles of one embodiment of the present invention contain lithium, the element M, and oxygen. The particles of one embodiment of the present invention contain the lithium composite oxide represented by LiMO2 (Mis one or more metals including cobalt). The particles of one embodiment of the present invention contain one or more selected from magnesium, fluorine, aluminum, and nickel in their surface portions. When the particles of one embodiment of the present invention contain one or more of these elements in the surface portions, a structure change owing to charging and discharging is reduced and generation of a crack can be inhibited in the surface portions of the particles. Furthermore, an irreversible structure change in the surface portions of the particles can be inhibited, whereby capacity reduction due to the repetitive charging and discharging can be inhibited. The concentrations of these elements in the surface portion are preferably higher than the concentrations of these elements in the whole particle. In the surface portions of the particles of one embodiment of the present invention, the lithium composite oxide may have a structure in which one or more selected from magnesium, fluorine, aluminum, and nickel is substituted for some atoms, for example.
When the charge depth is greater than or equal to 0.8, the positive electrode active material of one embodiment of the present invention, which contains the additive element X, may have a structure that is represented by the space group R-3m and is not a spinel crystal structure but is a structure where oxygen is hexacoordinated to ions of the metal M (e.g., cobalt), the additive element X (e.g., magnesium), and the like in some cases. This structure is referred to as the O3′ type crystal structure in this specification and the like. Note that in the O3′ type crystal structure, oxygen is tetracoordinated to a light element such as lithium in some cases.
Extraction of carrier ions due to charging makes the structure of a positive electrode active material unstable. The O3′ type crystal structure is said to be a structure that can maintain high stability in spite of extraction of carrier ions.
The O3′ type crystal structure can also be regarded as a crystal structure that contains Li between layers at random but is similar to a CdCl2 crystal structure. The crystal structure similar to the CdCl2 type crystal structure is close to a crystal structure of lithium nickel oxide when charged up to a charge depth of 0.94 (Li0.06NiO2); however, pure lithium cobalt oxide or a layered rock-salt positive electrode active material containing a large amount of cobalt is known not to have this crystal structure in general.
Anions of a layered rock-salt crystal and anions of a rock-salt crystal have cubic closest packed structures (face-centered cubic lattice structures). Anions of an O3′ type crystal are also presumed to have cubic closest packed structures. Thus, when a layered rock-salt crystal and a rock-salt crystal are in contact with each other, there is a crystal plane at which orientations of cubic closest packed structures composed of anions are aligned with each other. Note that a space group of the layered rock-salt crystal and the O3′ type crystal is R-3m, which is different from the space group Fm-3m of a rock-salt crystal (a space group of a general rock-salt crystal); thus, the Miller index of the crystal plane satisfying the above conditions in the layered rock-salt crystal and the O3′ type crystal is different from that in the rock-salt crystal. In this specification, a state where the orientations of the cubic closest packed structures composed of anions in the layered rock-salt crystal, the O3′ type crystal, and the rock-salt crystal are aligned is sometimes referred to as a state where crystal orientations are substantially aligned.
The crystal structure with a charge depth of 0 (in the discharged state) in
Note that in the O3′ type crystal structure, a light element such as lithium is sometimes coordinated to four oxygen atoms.
In the positive electrode active material of one embodiment of the present invention, a change in the crystal structure when the positive electrode active material is charged with a high voltage and a large amount of lithium is extracted is inhibited as compared with a structure to be described later with reference to
More specifically, the structure of the positive electrode active material of one embodiment of the present invention is highly stable even when charge voltage is high. For example, an H1-3 type structure is formed at a voltage of approximately 4.6 V with the potential of a lithium metal as the reference in
Note that in the case where graphite is used as the negative electrode active material in the secondary battery, for example, the voltage of the secondary battery is lower than the above-mentioned voltage with reference to the potential of a lithium metal by the potential of graphite. The potential of graphite is approximately 0.05 V to 0.2 V with reference to the potential of a lithium metal. Thus, even in a secondary battery that contains graphite as a negative electrode active material and has a voltage higher than or equal to 4.3 V and lower than or equal to 4.5 V, for example, the positive electrode active material shown in
Thus, in the positive electrode active material shown in
A crystal structure shown in
Lithium cobalt oxide shown in
When x is 0, the positive electrode active material has a trigonal crystal structure of the space group P-3 ml, and one CoO2 layer exists in a unit cell. Thus, this crystal structure is referred to as an 01 type structure or a trigonal 01 type structure in some cases. Moreover, in some cases, this crystal structure is referred to as a hexagonal 01 type structure when a trigonal crystal is converted into a composite hexagonal lattice.
Lithium cobalt oxide shown in
For the H1-3 type crystal structure, as disclosed in Non-Patent Document 1, the coordinates of cobalt and oxygen in the unit cell can be expressed as follows, for example: Co (0, 0, 0.42150±0.00016), O1 (0, 0, 0.27671±0.00045), and O2 (0, 0, 0.11535±0.00045). O1 and O2 are each an oxygen atom. A unit cell that should be used for representing a crystal structure in a positive electrode active material can be judged by the Rietveld analysis of XRD patterns, for example. In this case, a unit cell is selected such that the value of GOF (goodness of fit) is small.
The change in the crystal structure between the discharged state when x in LixCoO2 is 1 and the state when x in LixCoO2 is 0.24 or less in the positive electrode active material in
In the positive electrode active material illustrated in
Note that in the unit cell of the O3′ type crystal structure, the coordinates of cobalt and oxygen can be represented by Co (0, 0, 0.5) and O (0, 0, x) within the range of 0.20≤x≤0.25. In the unit cell, the lattice constant of the a-axis is preferably 0.2797≤a≤0.2837 (nm), further preferably 0.2807≤a≤0.2827 (nm), typically a=0.2817 (nm). The lattice constant of the c-axis is preferably 1.3681≤c≤1.3881 (nm), further preferably 1.3751≤c≤1.3811 (nm), typically, c=1.3781 (nm).
A slight amount of magnesium existing between the CoO2 layers, i.e., in lithium sites at random, has an effect of inhibiting a shift in the CoO2 layers in high-voltage charging. Thus, the existence of magnesium between the CoO2 layers makes it easier to obtain the O3′ type crystal structure.
However, cation mixing occurs when the heat treatment temperature is excessively high; thus, magnesium is highly likely to enter cobalt sites. Magnesium in the cobalt sites is less effective in maintaining the R-3m structure in high-voltage charging in some cases. Furthermore, heat treatment at an excessively high temperature might cause an adverse effect; for example, cobalt might be reduced to have a valence of two or lithium might be evaporated.
In view of the above, a halogen compound such as a fluorine compound is preferably added to lithium cobalt oxide before the heat treatment for distributing magnesium throughout the particle. The addition of the halogen compound decreases the melting point of the lithium cobalt oxide. The decreased melting point makes it easier to distribute magnesium throughout the particle at a temperature at which the cation mixing is unlikely to occur. Furthermore, it is expected that the existence of the fluorine compound can improve corrosion resistance to hydrofluoric acid generated by decomposition of an electrolyte.
When the magnesium concentration is higher than or equal to a desired value, the effect of stabilizing a crystal structure becomes small in some cases. This is probably because magnesium enters the cobalt sites in addition to the lithium sites. The number of magnesium atoms in the positive electrode active material fabricated in accordance with one embodiment of the present invention is preferably more than or equal to 0.001 times and less than or equal to 0.1 times, further preferably more than 0.01 times and less than 0.04 times, still further preferably approximately 0.02 times the number of cobalt atoms. The magnesium concentration described here may be a value obtained by performing element analysis entirely on particles of the positive electrode active material using ICP-MS or the like, or may be a value based on the ratio of raw materials mixed in the process of fabricating the positive electrode active material, for example.
The number of nickel atoms in the positive electrode active material of one embodiment of the present invention is preferably 7.5% or lower, preferably 0.05% or higher and 4% or lower, further preferably 0.1% or higher and 2% or lower the number of cobalt atoms. The nickel concentration described here may be a value obtained by performing element analysis entirely on particles of the positive electrode active material using ICP-MS or the like, or may be a value based on the ratio of raw materials mixed in the process of fabricating the positive electrode active material, for example.
When the particle diameter of the positive electrode active material of one embodiment of the present invention is too large, there are problems such as difficulty in lithium diffusion and too much surface roughness of an active material layer at the time when the material is applied to a current collector. By contrast, when the particle diameter is too small, there are problems such as difficulty in loading of the active material layer at the time when the material is applied to the current collector and overreaction with the electrolyte. Therefore, an average particle diameter (D50, also referred to as median diameter) is preferably greater than or equal to 1 μm and less than or equal to 100 μm, further preferably greater than or equal to 2 μm and less than or equal to 40 μm, still further preferably greater than or equal to 5 μm and less than or equal to 30 μm.
Whether or not a positive electrode active material has the O3′ type crystal structure when charged with a high voltage can be determined by analyzing a high-voltage charged positive electrode using XRD, electron diffraction, neutron diffraction, electron spin resonance (ESR), nuclear magnetic resonance (NMR), or the like. XRD is particularly preferable because the symmetry of a transition metal such as cobalt contained in the positive electrode active material can be analyzed with high resolution, the degrees of crystallinity and the crystal orientations can be compared, the distortion of lattice periodicity and the crystallite size can be analyzed, and a positive electrode itself obtained by disassembling a secondary battery can be measured with sufficient accuracy, for example.
As described above, the positive electrode active material of one embodiment of the present invention features a small change in the crystal structure between a high-voltage charged state and a discharged state. A material 50 wt % or more of which has the crystal structure that largely changes between a high-voltage charged state and a discharged state is not preferable because the material cannot withstand high-voltage charging and discharging. In addition, it should be noted that an objective crystal structure is not obtained in some cases only by addition of impurity elements. For example, although the positive electrode active material that is lithium cobalt oxide containing magnesium and fluorine is a commonality, the positive electrode active material has the O3′ type crystal structure at 60 wt % or more in some cases, and has the H1-3 type crystal structure at 50 wt % or more in other cases, when charged with a high voltage. In some cases, lithium cobalt oxide containing magnesium and fluorine may have the O3′ type crystal structure at almost 100 wt % at a predetermined voltage, and increasing the voltage to be higher than the predetermined voltage may cause the H1-3 type crystal structure. Thus, the crystal structure of the positive electrode active material of one embodiment of the present invention is preferably analyzed by XRD or the like. The combination with XRD measurement or the like enables more detailed analysis.
However, the crystal structure of a positive electrode active material in a high-voltage charged state or a discharged state may be changed with exposure to the air. For example, the O3′ type crystal structure changes into the H1-3 type crystal structure in some cases. Thus, all samples are preferably handled in an inert atmosphere such as an atmosphere containing argon.
A positive electrode active material illustrated in
As illustrated in
Lithium cobalt oxide with a charge depth of 1 has the crystal structure belonging to the space group P-3 ml and includes one CoO2 layer in a unit cell. Hence, this crystal structure is referred to as an 01 type crystal structure in some cases.
Lithium cobalt oxide with a charge depth of approximately 0.8 has the crystal structure belonging to the space group R-3m. This structure can also be regarded as a structure in which CoO2 structures such as a structure belonging to P-3 ml (O1) and LiCoO2 structures such as a structure belonging to R-3m (O3) are alternately stacked. Thus, this crystal structure is referred to as an H1-3 type crystal structure in some cases. Note that the number of cobalt atoms per unit cell in the actual H1-3 type crystal structure is twice that in other structures. However, in this specification including
For the H1-3 type crystal structure, the coordinates of cobalt and oxygen in the unit cell can be expressed as follows, for example: Co (0, 0, 0.42150±0.00016), O1 (0, 0, 0.27671±0.00045), and O2 (0, 0, 0.11535±0.00045). O1 and O2 are each an oxygen atom. In this manner, the H1-3 type crystal structure is represented by a unit cell containing one cobalt and two oxygen. Meanwhile, the O3′ type crystal structure of one embodiment of the present invention is preferably represented by a unit cell containing one cobalt and one oxygen. This means that the symmetry of cobalt and oxygen differs between the O3′ type crystal structure and the H1-3 type structure, and the amount of change from the O3 structure is smaller in the O3′ type crystal structure than in the H1-3 type structure. A preferred unit cell for representing a crystal structure in a positive electrode active material can be selected such that the value of GOF (good of fitness) is smaller in Rietveld analysis of XRD patterns, for example.
When charging at a high voltage of 4.6 V or higher based on the redox potential of a lithium metal or charging at a large charge depth of 0.8 or more and discharging are repeated, a change in the crystal structure of lithium cobalt oxide between the R-3m (O3) structure in a discharged state and the H1-3 type crystal structure (i.e., an unbalanced phase change) occurs repeatedly.
However, there is a large shift in the CoO2 layers between these two crystal structures. As indicated by dotted lines and an arrow in
A difference in volume is also large. The O3 type crystal structure in a discharged state and the H1-3 type crystal structure that contain the same number of cobalt atoms have a difference in volume of 3.0% or more.
In addition, a structure in which CoO2 layers are arranged continuously, such as P-3 ml (O1), included in the H1-3 type crystal structure is highly likely to be unstable.
Thus, the repeated high-voltage charging and discharging breaks the crystal structure of lithium cobalt oxide. The broken crystal structure triggers deterioration of the cycle performance. This is because the broken crystal structure has a smaller number of sites where lithium can exist stably and makes it difficult to insert and extract lithium.
Examples of a method for forming the positive electrode active material of one embodiment of the present invention is described with reference to
In Step S11 in
As the lithium source, lithium carbonate or lithium fluoride can be used, for example.
For example, at least one of manganese, cobalt, and nickel can be used as the transition metal source. As the transition metal source, cobalt alone; nickel alone; two elements of cobalt and manganese; two elements of cobalt and nickel; or three elements of cobalt, manganese, and nickel may be used, for example.
As the transition metal source used in synthesis, a high-purity material is preferably used. Specifically, the purity of the material is higher than or equal to 3N (99.9%), preferably higher than or equal to 4N (99.99%), further preferably higher than or equal to 4N5 (99.995%), still further preferably higher than or equal to 5N (99.999%). The use of a high-purity material can increase the capacity of a secondary battery and/or increase the reliability of a secondary battery.
In addition, it is preferred that the transition metal source here have high crystallinity. For example, the transition metal source preferably includes single crystal particles. The crystallinity of the transition metal source can be evaluated using a TEM (transmission electron microscopy) image, a STEM (scanning transmission electron microscopy) image, a HAADF-STEM (high-angle annular dark-field scanning transmission electron microscopy) image, an ABF-STEM (annular bright-field scanning transmission electron microscopy) image, or the like. For evaluation of the crystallinity of the transition metal source, X-ray diffraction (XRD), electron diffraction, neutron diffraction, and the like can also be used. Note that the above evaluation of crystallinity can also be employed to evaluate the crystallinity of a primary particle or a secondary particle other than the transition metal source.
When metals that can form a layered rock-salt composite oxide are used, cobalt, manganese, and nickel are preferably mixed at the ratio at which the composite oxide can have a layered rock-salt crystal structure. In addition, the additive element X may be added to these transition metals as long as the composite oxide can have a layered rock-salt crystal structure.
As the additive element X, one or more selected from magnesium, calcium, zirconium, lanthanum, barium, titanium, yttrium, nickel, aluminum, cobalt, manganese, vanadium, iron, chromium, niobium, copper, potassium, sodium, zinc, chlorine, fluorine, hafnium, silicon, sulfur, phosphorus, boron, and arsenic can be used. In addition to the above elements, bromine and beryllium may be used as the additive element X. Note that the additive element X given earlier is more suitable because bromine and beryllium are elements having toxicity to living things.
As the transition metal source, an oxide or a hydroxide of the metal described as an example of the transition metal, or the like can be used. As a cobalt source, cobalt oxide, cobalt hydroxide, or the like can be used.
As a manganese source, manganese oxide, manganese hydroxide, or the like can be used. As a nickel source, nickel oxide, nickel hydroxide, or the like can be used. As an aluminum source, aluminum oxide, aluminum hydroxide, or the like can be used.
Next, in Step S12, the lithium source, the transition metal source, and the additive element X source are crushed and mixed. The crushing and mixing can be performed by a dry method or a wet method. Specifically, it is preferable to use dehydrated acetone whose moisture content is less than or equal to 10 ppm and whose purity is greater than or equal to 99.5% for crushing. Note that in this specification and the like, the term crushing can be rephrased as grinding. For the mixing, a ball mill, a bead mill, or the like can be used, for example. When a ball mill is used, zirconia balls are preferably used as media, for example. When a ball mill, a bead mill, or the like is used, the peripheral speed is preferably greater than or equal to 100 mm/s and less than or equal to 2000 mm/s in order to inhibit contamination from the media or the material. For example, mixing may be performed at a peripheral speed of 838 mm/s (the number of rotations: 400 rpm, the ball mill diameter: 40 mm). By using the above-described dehydrated acetone for the crushing and mixing, impurities that might enter the material can be reduced.
Next, in Step S13, the materials mixed in the above manner are heated. The heating in this step is preferably performed at higher than or equal to 800° C. and lower than 1100° C., further preferably at higher than or equal to 900° C. and lower than or equal to 1000° C., still further preferably at approximately 950° C. An excessively low temperature might lead to insufficient decomposition and melting of the lithium source and the transition metal source. An excessively high temperature might lead to a defect due to evaporation of lithium from the lithium source and/or excessive reduction of the metal used as the transition metal source, for example. The use of cobalt as the transition metal, for example, may lead to a defect in which cobalt has divalence.
For example, the heating time can be longer than or equal to 1 hour and shorter than or equal to 100 hours, and is preferably longer than or equal to 2 hours and shorter than or equal to 20 hours. The heating is preferably performed in an atmosphere with little water, such as dry air (e.g., the dew point is lower than or equal to −50° C., and the dew point is further preferably lower than or equal to −80° C.). For example, the heat treatment may be performed in an atmosphere with a dew point of −93° C. Furthermore, it is suitable to perform the heating in an atmosphere where the concentrations of impurities, CH4, CO, CO2, and H2, are each less than or equal to 5 ppb (parts per billion), in which case the impurities can be inhibited from entering the materials.
For example, in the case where the heating is performed at 1000° C. for 10 hours, it is preferable that the temperature rising rate be 200° C./h and the flow rate of dry air be 10 L/min. After that, the heated materials can be cooled to room temperature. The temperature decreasing time from the specified temperature to room temperature is preferably longer than or equal to 10 hours and shorter than or equal to 50 hours, for example. Note that the cooling to room temperature in Step S13 is not essential.
Note that a crucible used in the heating in Step S13 is suitably made of a material which is less likely to release impurities. For example, a crucible made of alumina with a purity of 99.9% may be used.
It is suitable to collect the materials subjected to the heating in Step S13 after the materials are transferred from the crucible to a mortar because impurities are prevented from entering the materials. The mortar is suitably made of a material which is less likely to release impurities. Specifically, it is suitable to use a mortar made of alumina with a purity of 90% or higher, preferably 99% or higher. Note that conditions equivalent to those in Step S13 can be employed in an after-mentioned heating step other than Step S13.
Through the above steps, the positive electrode active material 100 of one embodiment of the present invention can be formed (Step S14). The positive electrode active material 100 is sometimes referred to as a composite oxide containing lithium, the transition metal, and oxygen (LiMO2). Note that the positive electrode active material of one embodiment of the present invention only needs to have a crystal structure of a lithium composite oxide represented by LiMO2, and the composition is not strictly limited to Li:M:O=1:1:2.
A positive electrode active material is formed using a high-purity material for the transition metal source used in synthesis and using a process which hardly allows entry of impurities in the synthesis, whereby a material that has a low impurity concentration, in other words, is highly purified can be obtained. Moreover, the positive electrode active material obtained by such a method for forming a positive electrode active material is a material having high crystallinity. With the positive electrode active material obtained by the method for forming the positive electrode active material of one embodiment of the present invention, the capacity of a secondary battery can be increased and/or the reliability of a secondary battery can be increased.
Next, another example of a method for forming a positive electrode active material of one embodiment of the present invention will be described with reference to
In
Note that a pre-synthesized composite oxide may be used in Step S14. In that case, Step S11 to Step S13 can be omitted. In the case where a pre-synthesized composite oxide is prepared, a high-purity material is preferably used. The purity of the material is higher than or equal to 99.5%, preferably higher than or equal to 99.9%, further preferably higher than or equal to 99.99%.
Note that a step of performing heating may be provided between Step S14 and the following Step S20. The heating can make a surface of the composite oxide smooth, for example. For the heating, the conditions that are the same as the atmosphere and temperature for Step S33 described later are used and the treatment time is shorter than that for Step S33. Having a smooth surface refers to a state where the composite oxide has little unevenness and is rounded as a whole and its corner portion is rounded. A smooth surface also refers to a surface to which few foreign matters are attached. Foreign matters are deemed to cause unevenness and are preferably not attached to a surface.
In Step S20 in
In Step S21 in
As the magnesium source, for example, magnesium fluoride, magnesium oxide, magnesium hydroxide, or magnesium carbonate can be used.
As the fluorine source, for example, lithium fluoride (LiF), magnesium fluoride (MgF2), aluminum fluoride (AlF3), titanium fluoride (TiF4), cobalt fluoride (CoF2 and CoF3), nickel fluoride (NiF2), zirconium fluoride (ZrF4), vanadium fluoride (VF5), manganese fluoride, iron fluoride, chromium fluoride, niobium fluoride, zinc fluoride (ZnF2), calcium fluoride (CaF2), sodium fluoride (NaF), potassium fluoride (KF), barium fluoride (BaF2), cerium fluoride (CeF2), lanthanum fluoride (LaF3), or sodium aluminum hexafluoride (Na3AlF6) can be used. The fluorine source is not limited to a solid, and for example, fluorine (F2), carbon fluoride, sulfur fluoride, oxygen fluoride (OF2, O2F2, O3F2, O4F2, or O2F), or the like may be used and mixed in the atmosphere in a heating step described later. A plurality of fluorine sources may be mixed to be used. Among them, lithium fluoride, which has a relatively low melting point of 848° C., is preferable because it is easily melted in a heating step described later.
As the lithium source, for example, lithium fluoride or lithium carbonate can be used. That is, lithium fluoride can be used as both the lithium source and the fluorine source. In addition, magnesium fluoride can be used as both the fluorine source and the magnesium source.
In this embodiment, lithium fluoride (LiF) is prepared as the fluorine source, and magnesium fluoride (MgF2) is prepared as the fluorine source and the magnesium source. When lithium fluoride LiF and magnesium fluoride MgF2 are mixed at approximately LiF:MgF2=65:35 (molar ratio), the effect of reducing the melting point becomes the highest (Non-Patent Document 4). On the other hand, when the amount of lithium fluoride increases, cycle performance might deteriorate because of too large an amount of lithium. Therefore, the molar ratio of lithium fluoride LiF to magnesium fluoride MgF2 is preferably LiF:MgF2=x:1 (0≤x≤1.9), further preferably LiF:MgF2=x:1 (0.1≤x≤0.5), still further preferably LiF:MgF2=x:1 (x=0.33 and the neighborhood thereof). Note that in this specification and the like, the vicinity means a value greater than 0.9 times and less than 1.1 times a certain value.
In the case where the following mixing and crushing step is performed by a wet method, a solvent is prepared. As the solvent, it is preferable to use a protic solvent that hardly reacts with lithium, e.g., ketone such as acetone, alcohol such as ethanol or isopropanol, ether, dioxane, acetonitrile, or N-methyl-2-pyrrolidone (NMP).
Next, in Step S22 in
Next, in Step S23, the crushed and mixed materials are collected to obtain the additive element X source. Note that the additive element X source shown in Step S23 is formed using a plurality of materials and can be referred to as a mixture.
For example, D50 (median diameter) of the mixture is preferably greater than or equal to 600 nm and less than or equal to 20 μm, further preferably greater than or equal to 1 μm and less than or equal to 10 μm. When mixed with a composite oxide containing lithium, the transition metal, and oxygen in the later step, the mixture pulverized to such a small size is easily attached to surfaces of composite oxide particles uniformly. The mixture is preferably attached to the surfaces of the composite oxide particles uniformly because both halogen and magnesium are easily distributed to the vicinity of the surface of the composite oxide particle after heating. When there is a region containing neither halogen nor magnesium in the vicinity of the surface, the positive electrode active material might be less likely to have an O3′ type crystal structure, which is described later, in the charged state.
Note that a method in which two kinds of materials are mixed in Step S21 is shown in
Next, in Step S31 in
The conditions of the mixing in Step S31 are preferably milder than those of the mixing in Step S12 in order not to damage the particles of the composite oxide. For example, conditions with a lower rotation frequency or shorter time than the mixing in Step S12 are preferable. In addition, it can be said that the dry method has a milder condition than the wet method. For example, a ball mill, a bead mill, or the like can be used for the mixing. When a ball mill is used, zirconia balls are preferably used as media, for example.
In this embodiment, the mixing is performed with a ball mill using zirconia balls with a diameter of 1 mm by a dry method at 150 rpm for 1 hour. The mixing is performed in a dry room the dew point of which is higher than or equal to −100° C. and lower than or equal to −10° C.
Next, in Step S32 in
Note that this embodiment describes a method for adding the mixture of lithium fluoride and magnesium fluoride to lithium cobalt oxide with few impurities; however, one embodiment of the present invention is not limited thereto. A mixture obtained through heating after addition of a magnesium source, a fluorine source, and the like to the starting material of lithium cobalt oxide may be used instead of the mixture 903 in Step S32. In that case, there is no need to separate steps of Step S11 to Step S14 and steps of Step S21 to Step S23, which is simple and productive.
Alternatively, lithium cobalt oxide to which magnesium and fluorine are added in advance may be used. When lithium cobalt oxide to which magnesium and fluorine are added is used, the process can be simpler because the steps up to Step S32 can be omitted.
Alternatively, a magnesium source and a fluorine source may be further added to the lithium cobalt oxide to which magnesium and fluorine are added in advance.
Next, in Step S33, the mixture 903 is heated in an oxygen-containing atmosphere. The heating is preferably performed such that particles of the mixture 903 are not adhered to one another.
The additive is preferably added to the entire surface of the particle not unevenly but uniformly. However, when particles of the mixture 903 adhere to one another during the heating, the additive might be unevenly added to part of the surface. A surface of the particle, which is preferably smooth and even, might become uneven due to adhered particles and have more defects such as a split and/or a crack. This is probably because the adhesion of the particles of the mixture 903 reduces the contact area with oxygen in the atmosphere and blocks a path through which the additives diffuse.
As the heating in Step S33, heating by a rotary kiln may be performed. Heating by a rotary kiln can be performed while stirring is performed in either case of a sequential rotary kiln or a batch-type rotary kiln. As the heating in Step S33, heating by a roller hearth kiln may be performed.
The heating temperature in Step S33 needs to be higher than or equal to the temperature at which a reaction between LiMO2 and the additive element X source proceeds. Here, the temperature at which the reaction proceeds is a temperature at which interdiffusion between elements contained in LiMO2 and the additive element X source occurs. Thus, the heating temperature can be lower than the melting temperatures of these materials in some cases. For example, in an oxide, solid-phase diffusion occurs at a temperature that is 0.757 times (Tamman temperature Td) or more the melting temperature Tm. Accordingly, the heating temperature in Step S33 is higher than or equal to 500° C., for example.
Note that a temperature higher than or equal to the temperature at which at least part of the mixture 903 is melted is preferable because the reaction proceeds more easily. For example, in the case where LiF and MgF2 are included as the additive element X source, the eutectic point of LiF and MgF2 is around 742° C., and the heating temperature in Step S33 is preferably higher than or equal to 742° C.
The mixture 903 obtained by mixing such that LiCoO2:LiF:MgF2=100:0.33:1 (molar ratio) exhibits an endothermic peak at around 830° C. in differential scanning calorimetry measurement (DSC measurement). Thus, the heating temperature is further preferably higher than or equal to 830° C.
A higher heating temperature is preferable because it facilitates the reaction, shortens the heating time, and enables high productivity.
Note that the heating temperature needs to be lower than a decomposition temperature of LiMO2 (1130° C. in the case of LiCoO2). At around the decomposition temperature, a slight amount of LiMO2 might be decomposed. Thus, the heating temperature in Step S33 is preferably lower than 1130° C., further preferably lower than or equal to 1000° C., further preferably lower than or equal to 950° C., further preferably lower than or equal to 900° C.
Therefore, the temperature of the heating in Step S33 is preferably higher than or equal to 500° C. and lower than 1130° C., further preferably higher than or equal to 500° C. and lower than or equal to 1000° C., still further preferably higher than or equal to 500° C. and lower than or equal to 950° C., yet still further preferably higher than or equal to 500° C. and lower than or equal to 900° C. Furthermore, the temperature is preferably higher than or equal to 742° C. and lower than 1130° C., further preferably higher than or equal to 742° C. and lower than or equal to 1000° C., still further preferably higher than or equal to 742° C. and lower than or equal to 950° C., yet still further preferably higher than or equal to 742° C. and lower than or equal to 900° C. Furthermore, the temperature is preferably higher than or equal to 830° C. and lower than 1130° C., further preferably higher than or equal to 830° C. and lower than or equal to 1000° C., still further preferably higher than or equal to 830° C. and lower than or equal to 950° C., yet still further preferably higher than or equal to 830° C. and lower than or equal to 900° C.
In addition, at the time of heating the mixture 903, the partial pressure of fluorine or a fluoride in the atmosphere is preferably controlled to be within an appropriate range.
In the formation method described in this embodiment, some of the materials, e.g., LiF as the fluorine source, function as a flux in some cases. Owing to this function, the heating temperature can be lower than or equal to the decomposition temperature of LiMO2, e.g., a temperature higher than or equal to 742° C. and lower than or equal to 950° C., which allows distribution of the additive such as magnesium in the vicinity of the surface and formation of the positive electrode active material having favorable characteristics.
However, since LiF in a gas phase has a specific gravity less than that of oxygen, heating might volatilize LiF and in that case, LiF in the mixture 903 decreases. As a result, the function of a flux deteriorates. Thus, heating needs to be performed while volatilization of LiF is inhibited. Note that even when LiF is not used as the fluorine source or the like, there is a possibility in that Li and F at a surface of LiMO2 react with each other to generate LiF and volatilize. Therefore, the volatilization needs to be inhibited also when a fluoride having a higher melting point than LiF is used.
In view of this, the mixture 903 is preferably heated in an atmosphere containing LiF, i.e., the mixture 903 is preferably heated in a state where the partial pressure of LiF in a heating furnace is high. Such heating can inhibit volatilization of LiF in the mixture 903.
In the case of using a rotary kiln for the heating, the flow rate of an oxygen-containing atmosphere in the kiln is preferably controlled while the mixture 903 is heated. For example, the flow rate of an oxygen-containing atmosphere is preferably set low, or no flowing of an oxygen gas is preferably performed after an atmosphere is purged first and an oxygen gas is introduced into the kiln.
In the case of using a roller hearth kiln for the heating, the mixture 903 can be heated in an atmosphere containing LiF with the container containing the mixture 903 covered with a lid, for example.
The heating is preferably performed for an appropriate time. The appropriate heating time is changed depending on conditions, such as the heating temperature, and the particle size and composition of LiMO2 in Step S14. In the case where the particle size is small, the heating is preferably performed at a lower temperature or for a shorter time than heating in the case where the particle size is large, in some cases.
When the average particle diameter (D50) of the particles of the composite oxide in Step S14 in
On the other hand, when the average particle diameter (D50) of the particles of the composite oxide in Step S14 is approximately 5 μm, the heating temperature is preferably higher than or equal to 600° C. and lower than or equal to 950° C., for example. The heating time is preferably longer than or equal to 1 hour and shorter than or equal to 10 hours, further preferably approximately 2 hours, for example. The temperature decreasing time after the heating is, for example, preferably longer than or equal to 10 hours and shorter than or equal to 50 hours.
Then, the heated materials are collected, whereby the positive electrode active material 100 is formed. Here, the collected particles are preferably made to pass through a sieve. Through the above steps, the positive electrode active material 100 of one embodiment of the present invention can be formed (Step S34).
Next, another example of a method for forming a positive electrode active material of one embodiment of the present invention will be described with reference to
In
Note that a pre-synthesized composite oxide containing lithium, the transition metal, and oxygen may be used in Step S14. In that case, Step S11 to Step S13 can be omitted.
Note that a step of performing heating may be provided between Step S14 and Step S20 as described with reference to
In Step S20a in
Step S23 shown in
Steps S31 to S33 shown in
Next, the material heated in Step S33 is collected to form a composite oxide.
Then, in Step S40 in
Step S43 shown in
Step S40 shown in
In the case of employing a sol-gel method for addition of the additive element X2, a solvent used for the sol-gel method is prepared as well as the additive element X2 source. For the sol-gel method, a metal alkoxide can be used as the metal source, for example, and alcohol can be used as the solvent, for example. In the case of performing addition of aluminum, aluminum isopropoxide can be used as the metal source and isopropanol (2-propanol) can be used as the solvent, for example. In the case of performing addition of zirconium, zirconium(IV) tetrapropoxide can be used as the metal source and isopropanol can be used as the solvent, for example.
Next, Step S51 in
Then, the heated materials are collected, whereby the positive electrode active material 100 is formed. Here, the collected particles are preferably made to pass through a sieve. Through the above steps, the positive electrode active material 100 of one embodiment of the present invention can be formed (Step S54).
When the step of introducing the transition metal, the step of introducing the additive element X1, and the step of introducing the additive element X2 are separately performed as shown in
The formation method in which a high-purity material is used for the transition metal source used in synthesis; a process which hardly allows entry of impurities in the synthesis is employed; entry of impurities in the synthesis is thoroughly prevented; and desired additive elements (the additive element X, the additive element X1, or the additive element X2) are controlled to be introduced into the positive electrode active material can provide a positive electrode active material in which a region with a low impurity concentration and a region where the additive elements are introduced are controlled. In addition, the positive electrode active material having high crystallinity can be obtained. Furthermore, the positive electrode active material obtained by the method for forming a positive electrode active material, which is one embodiment of the present invention, can increase the capacity of a secondary battery and/or increase the reliability of the secondary battery.
The positive electrode active material of one embodiment of the present invention is not limited to the materials described above. A mixture of the above-described material and another material may be used as the positive electrode active material of one embodiment of the present invention.
As the positive electrode active material, a composite oxide with a spinel crystal structure can be used, for example. Alternatively, a polyanionic material can be used as the positive electrode active material, for example. Examples of the polyanionic material include a material with an olivine crystal structure and a material with a NASICON structure. Alternatively, a material containing sulfur can be used as the positive electrode active material, for example.
As the material with a spinel crystal structure, for example, a composite oxide represented by LiM2O4 can be used. It is preferable to contain Mn as the metal M. For example, LiMn2O4 can be used. It is preferable to contain Ni in addition to Mn as the metal M because the discharge voltage and the energy density of the secondary battery are increased in some cases. It is preferable to add a small amount of lithium nickel oxide (LiNiO2 or LiNi1−xMxO2 (M=Co, Al, or the like)) to a lithium-containing material with a spinel crystal structure which contains manganese, such as LiMn2O4, because the characteristics of the secondary battery can be improved.
As a polyanionic material, for example, a composite oxide containing oxygen, the metal A, the metal M, and an element X can be used. The metal A is one or more of Li, Na, and Mg; the metal Mis one or more of Fe, Mn, Co, Ni, Ti, V, and Nb; and the element X is one or more of S, P, Mo, W, As, and Si.
As the material with an olivine crystal structure, for example, a composite material (the general formula LiMPO4 (M is one or more of Fe(II), Mn(II), Co(II), and Ni(II)) can be used. Typical examples of the general formula LiMPO4 include lithium compounds such as LiFePO4, LiNiPO4, LiCoPO4, LiMnPO4, LiFeaNibPO4, LiFeaCobPO4, LiFeaMnbPO4, LiNiaCObPO4, LiNiaMnbPO4 (a+b≤1, 0<a<1, and 0<b<1), LiFecNidCoePO4, LiFecNidMnePO4, LiNicCOdMnePO4 (c+d+e≤1, 0<c<1, 0<d<1, and 0<e<1), and LiFefNigCOhMniPO4 (f+g+h+i≤1, 0<f<1, 0<g<1, 0<h<1, and 0<i<1).
Alternatively, a composite material such as a general formula Li(2−j)MSiO4 (M is one or more of Fe(II), Mn(II), Co(II), and Ni(II); 0≤j≤2) can be used. Typical examples of the general formula Li(2−j)MSiO4 include lithium compounds such as Li(2−j)FeSiO4, Li(2−j)NiSiO4, Li(2−j)CoSiO4, Li(2−j)MnSiO4, Li(2−j)FekNilSiO4, Li(2−j)FekColSiO4, Li(2−j)FekMnlSiO4, Li(2−j)NikColSiO4, Li(2−j)NikMnlSiO4 (k+l≤1, 0<k<1, and 0<l<1), Li(2−j)FemNinCoqSiO4, Li(2−j)FemNinMnqSiO4, Li(2−j)NimConMnqSiO4 (m+n+q≤1, 0<m<1, 0<n<1, and 0<q<1), and Li(2−j)FerNisCotMnuSiO4 (r+s+t+u<1, 0<r<1, 0<s<1, 0<t<1, and 0<u<1).
Still alternatively, a NASICON compound represented by a general formula AxM2(XO4)3 (A=Li, Na, or Mg, M=Fe, Mn, Ti, V, or Nb, X=S, P, Mo, W, As, or Si) can be used. Examples of the NASICON compound include Fe2(MnO4)3, Fe2(SO4)3, and Li3Fe2(PO4)3. Further alternatively, a compound represented by a general formula Li2MPO4F, Li2MP2O7, or Li5MO4 (M=Fe or Mn) can be used as the positive electrode active material.
Further alternatively, a perovskite fluoride such as NaFeF3 and FeF3, a metal chalcogenide (a sulfide, a selenide, or a telluride) such as TiS2 and MoS2, an oxide with an inverse spinel crystal structure such as LiMVO4, a vanadium oxide (V2O5, V6O13, LiV3O8, or the like), a manganese oxide, an organic sulfur compound, or the like may be used as the positive electrode active material.
Alternatively, a borate-based material represented by a general formula LiMBO3 (M is Fe(II), Mn(II), or Co(II)) may be used as the positive electrode active material.
As a material containing sodium, for example, an oxide containing sodium such as NaFeO2, Na2/3[Fe1/2Mn1/2]O2, Na2/3[Ni1/3Mn2/3]O2, Na2Fe2(SO4)3, Na3V2(PO4)3, Na2FePO4F, NaVPO4F, NaMPO4 (M is Fe(II), Mn(II), Co(II), or Ni(II)), Na2FePO4F, or Na4Co3(PO4)2P2O7 may be used as the positive electrode active material.
As the positive electrode active material, a lithium-containing metal sulfide may be used. Examples of the lithium-containing metal sulfide are Li2TiS3 and Li3NbS4.
As the positive electrode active material, a particle containing a plurality of the above-described positive electrode active materials may be used. For example, with the use of one of the above-described positive electrode active materials as a first material and another one of the above-described positive electrode active materials as a second material, a particle in which the second material covers at least part of the first material may be used. Such a particle in which the second material covers at least part of the first material is referred to as a positive electrode active material composite in some cases. As the composite-making process, any one or more of composite-making processes utilizing mechanical energy such as a mechanochemical method, a mechanofusion method, and a ball mill method; composite-making processes utilizing a liquid phase reaction such as a coprecipitation method, a hydrothermal method, and a sol-gel method; and composite-making processes utilizing a gas phase reaction such as a barrel sputtering method, an ALD (Atomic Layer Deposition) method, an evaporation method, and a CVD (Chemical Vapor Deposition) method can be performed, for example. Heat treatment is preferably performed after the composite-making process. Note that the composite-making process is also referred to as a surface coating process or a coating process in some cases.
Note that the positive electrode active material particles form a secondary particle in some cases.
The secondary battery of one embodiment of the present invention preferably includes an electrolyte. An organic electrolyte, an ionic liquid, a solid electrolyte, or the like can be used as the electrolyte. It is particularly preferable that an ionic liquid be included in the secondary battery of one embodiment of the present invention.
When moisture is contained in an electrolyte, the moisture reacts with the electrolyte and a compound is generated in some cases. The generated compound might react with a component of the battery, e.g., a current collector, an active material, or a conductive additive, to cause a decrease in charge and discharge efficiency.
The case where an electrolyte contains LiPF6 is considered as an example. In the case where the electrolyte contains LiPF6, the following reaction formulae (1) to (4) presumably sequentially occur due to a reaction with moisture.
H2O+LiPF6→LiF+POF3+2HF (1)
H2O+POF3→HPO2F2+HF (2)
H2O+HPO2F2→H2PO3F+HF (3)
H2O+HPO3F→H3PO4+HF (4)
The reactions of the above reaction formulae (1) to (4) can be collectively expressed as the following reaction formula (5).
H2O+LiPF6→LiF+H3PO4+HF (5)
Thus, in the case where the electrolyte contains LiPF6, hydrofluoric acid is presumably generated due to contained moisture. For example, hydrofluoric acid reacts with an aluminum current collector included in a positive electrode in some cases. Occurrence of such a reaction lowers charge and discharge efficiency and a discharge capacity.
A compound generated owing to a reaction between moisture and an electrolyte can be evaluated by nuclear magnetic resonance spectroscopy (NMR) in some cases. For example, a fluorine-containing compound is detected in a 19F-NMR spectrum in some cases. A phosphorus-containing compound is detected in a 31P-NMR spectrum in some cases.
The amount of moisture in the electrolyte included in the secondary battery of one embodiment of the present invention is less than 1000 ppm, preferably less than 100 ppm, further preferably less than 50 ppm, still further preferably less than 20 ppm, yet further preferably less than 10 ppm, yet further preferably less than 5 ppm, yet further preferably less than 1 ppm.
The content of a component such as an impurity in the electrolyte of the present invention can be measured by ICP atomic emission spectroscopy, by ion chromatography, with a Karl Fischer moisture titrator, or by gas chromatography, for example.
The amount of moisture in the electrolyte can be measured with a Karl Fischer moisture titrator, for example.
The amount of hydrogen fluoride in the electrolyte included in the secondary battery of one embodiment of the present invention is 100 ppm or less, preferably 50 ppm or less, further preferably 20 ppm or less, still further preferably less than 10 ppm, yet further preferably less than 5 ppm, yet further preferably less than 1 ppm.
The amount of moisture in the electrolyte can be reduced by performing processing under reduced pressure, heat treatment, or addition of a desiccant agent such as a molecular sieve, for example. A molecular sieve is preferably removed from the electrolyte after processing. An additive agent that absorbs moisture may be added to the electrolyte. Alternatively, such kinds of processing may be performed in combination.
The electrolyte included in the secondary battery of one embodiment of the present invention contains a salt containing a metal serving as a carrier ion.
The secondary battery of one embodiment of the present invention may contain as a carrier ion one or more selected from alkali metal ions such as a sodium ion and a potassium ion and alkaline earth metal ions such as a calcium ion, a strontium ion, a barium ion, a beryllium ion, and a magnesium ion.
In the case where a lithium ion is used as a carrier ion, for example, an electrolyte contains lithium salt. As the lithium salt, for example, LiPF6, LiClO4, LiAsF6, LiBF4, LiAlCl4, LiSCN, LiBr, LiI, Li2SO4, Li2B10Cl10, Li2B12Cl12, LiCF3SO3, LiC4F9SO3, LiC(CF3SO2)3, LiC(C2F5SO2)3, LiN(CF3SO2)2, LiN(C4F9SO2) (CF3SO2), or LiN(C2F5SO2)2 can be used.
In the electrolyte included in the secondary battery of one embodiment of the present invention, in addition to the above-mentioned salt, one selected from an ester, ether, nitrile, sulfoxide, a sulfone, a sulfonic ester, and the like, or a given combination of two or more selected from these in a given ratio can be used.
The electrolyte included in the secondary battery of one embodiment of the present invention preferably contains one or more of cyclic carbonates and linear carbonates. For example, a solution containing one or more of cyclic carbonates and linear carbonates and the above-mentioned salt can be used as the electrolyte. A fluorinated cyclic carbonate may be used as the cyclic carbonate. A fluorinated linear carbonate may be used as the linear carbonate. The electrolyte may contain a plurality of kinds of cyclic carbonate. The electrolyte may contain a plurality of kinds of linear carbonate.
Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, and γ-valerolactone.
Examples of the linear carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC).
Examples of the fluorinated cyclic carbonate include ethylene fluoride carbonate such as monofluoroethylene carbonate (fluoroethylene carbonate, FEC, or F1EC), difluoroethylene carbonate (DFEC or F2EC), trifluoroethylene carbonate (F3EC), and tetrafluoroethylene carbonate (F4EC). Note that DFEC includes an isomer such as cis-4,5 or trans-4,5.
Monofluoroethylene carbonate (FEC) is represented by Structural Formula (101) below. Tetrafluoroethylene carbonate (F4EC) is represented by Structural Formula (102) below. Difluoroethylene carbonate (DFEC) is represented by Structural Formula (103) below.
The fluorinated cyclic carbonate can improve nonflammability and increase the safety of the lithium-ion secondary battery. For operation at low temperatures, as the electrolyte, it is important to use one kind or two or more kinds of fluorinated cyclic carbonates to solvate a lithium ion and transport the lithium ion in the electrolyte included in the electrode in charging and discharging.
The use of the fluorinated cyclic carbonate for the electrolyte can reduce desolvation energy that is necessary for a solvated lithium ion to enter an active material particle in the electrolyte included in an electrode. The reduction in the desolvation energy can facilitate insertion or extraction of a lithium ion into or from the active material particle even in a low-temperature range. Although a lithium ion sometimes moves remaining in a solvated state, a hopping phenomenon in which coordinated solvent molecules are interchanged occurs in some cases. When desolvation of a lithium ion becomes easy, movement owing to the hopping phenomenon is facilitated and the lithium ion may easily move.
In the electrolyte included in the secondary battery of one embodiment of the present invention, in addition to the above-mentioned salt, one kind of methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), diethyl ether, methyl diglyme, tetrahydrofuran, acetonitrile, benzonitrile, dimethyl sulfoxide, sulfolane, and sultone can be used, or two or more of these can be used in a given combination in a given ratio. Furthermore, one or two or more kinds of these and one or more kinds of the above-mentioned cyclic carbonates and linear carbonates may be used in combination.
Furthermore, an additive such as vinylene carbonate (VC), propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis(oxalate)borate (LiBOB), succinonitrile, adiponitrile, fluorobenzene, cyclohexylbenzene, or biphenyl may be added to the electrolyte. The concentration of the material to be added in the whole solvent is, for example, higher than or equal to 0.1 wt % and lower than or equal to 5 wt %.
The electrolyte included in the secondary battery of one embodiment of the present invention preferably contains an ionic liquid and a salt containing a metal serving as a carrier ion.
In the case where the electrolyte contains an ionic liquid, as the salt containing a metal serving as a carrier ion, metal salts of a fluorosulfonate anion and a fluoroalkylsulfonate anion are preferable: among them, a metal salt of an amide-based anion represented by (CnF2n+1SO2)2N− (n is greater than or equal to 0 and less than or equal to 3) is preferable because of its high stability at high temperatures and high resistance to oxidation and reduction.
An ionic liquid contains a cation and an anion, specifically, an organic cation and an anion. Examples of the organic cation used for the electrolyte include aromatic cations such as an imidazolium cation and a pyridinium cation, and aliphatic onium cations such as a quaternary ammonium cation, a tertiary sulfonium cation, and a quaternary phosphonium cation. Examples of the anion used for the electrolyte include a monovalent amide-based anion, a monovalent methide-based anion, a fluorosulfonate anion, a perfluoroalkylsulfonate anion, a tetrafluoroborate anion, a perfluoroalkylborate anion, a hexafluorophosphate anion, and a perfluoroalkylphosphate anion.
The electrolyte may contain, in addition to an ionic liquid, an aprotic solvent. For example, one of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, chloroethylene carbonate, vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, 1,3-dioxane, 1,4-dioxane, dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyl diglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, and sultone may be contained, or two or more of these solvents may be contained in a given combination in a given ratio.
Furthermore, an additive such as vinylene carbonate (VC), propane sultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC), lithium bis(oxalate)borate (LiBOB), succinonitrile, adiponitrile, fluorobenzene, cyclohexylbenzene, or biphenyl may be added to the electrolyte containing an ionic liquid. The concentration of the material to be added in the whole solvent is, for example, higher than or equal to 0.1 wt % and lower than or equal to 5 wt %.
As an ionic liquid containing imidazolium cations, an ionic liquid represented by General Formula (G1) below can be used, for example. In General Formula (G1), R1 represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms and preferably represents an alkyl group having 1 to 4 carbon atoms, each of R2 to R4 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and preferably represents an alkyl group having 1 to 4 carbon atoms, and R5 represents an alkyl group or a main chain composed of two or more selected from C, O, Si, N, S, and P atoms. A substituent may be introduced into the main chain represented by R5. Examples of the substituent to be introduced include an alkyl group and an alkoxy group. The main chain represented by R5 may have a carboxy group. The main chain represented by R5 may have a carbonyl group.
As an ionic liquid containing pyridinium cations, an ionic liquid represented by General Formula (G2) below may be used, for example. In General Formula (G2), R6 represents an alkyl group or a main chain composed of two or more selected from C, O, Si, N, S, and P atoms, and each of R7 to R11 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A substituent may be introduced into the main chain represented by R6. Examples of the substituent to be introduced include an alkyl group and an alkoxy group.
As an ionic liquid containing quaternary ammonium cations, an ionic liquid represented by General Formula (G3), (G4), (G5), or (G6) below can be used, for example.
In General Formula (G3), each of R28 to R31 independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
In General Formula (G4), each of R12 to R17 independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
In General Formula (G5), each of R18 to R24 independently represents an alkyl group having 1 to 20 carbon atoms, a methoxy group, a methoxymethyl group, a methoxyethyl group, or a hydrogen atom.
In General Formula (G6), n and m are greater than or equal to 1 and less than or equal to 3. Assume that a is greater than or equal to 0 and less than or equal to 6. When n is 1, α is greater than or equal to 0 and less than or equal to 4. When n is 2, α is greater than or equal to 0 and less than or equal to 5. When n is 3, α is greater than or equal to 0 and less than or equal to 6. Assume that β is greater than or equal to 0 and less than or equal to 6. When m is 1, β is greater than or equal to 0 and less than or equal to 4. When m is 2, β is greater than or equal to 0 and less than or equal to 5. When m is 3, β is greater than or equal to 0 and less than or equal to 6. Note that “α or β is 0” means “unsubstituted”. The case where both α and β are 0 is excluded. X or Y represents a substituent such as a straight-chain or side-chain alkyl group having 1 to 4 carbon atoms, a straight-chain or side-chain alkoxy group having 1 to 4 carbon atoms, or a straight-chain or side-chain alkoxyalkyl group having 1 to 4 carbon atoms.
As an ionic liquid containing tertiary sulfonium cations, an ionic liquid represented by General Formula (G7) below can be used, for example. In General Formula (G7), each of R25 to R27 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Alternatively, as R25 to R27, a main chain composed of two or more selected from C, O, Si, N, S, and P atoms may be used.
As an ionic liquid containing quaternary phosphonium cations, an ionic liquid represented by General Formula (G8) below can be used, for example. In General Formula (G8), each of R32 to R35 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Alternatively, as R32 to R35, a main chain composed of two or more selected from C, O, Si, N, S, and P atoms may be used.
As A− shown in General Formulae (G1) to (G8), one or more of a monovalent amide-based anion, a monovalent methide-based anion, a fluorosulfonate anion, a perfluoroalkylsulfonate anion, a tetrafluoroborate anion, a perfluoroalkylborate anion, a hexafluorophosphate anion, and a perfluoroalkylphosphate anion can be used.
As a monovalent amide-based anion, (CnF2n+1SO2)2N− (n=0 to 3) can be used, and as a monovalent cyclic amide-based anion, (CF2SO2)2N− or the like can be used. As a monovalent methide-based anion, (CnF2n+1SO2)3C− (n=0 to 3) can be used, and as a monovalent cyclic methide-based anion, (CF2SO2)2C− (CF3SO2) or the like can be used. As a fluoroalkyl sulfonic acid anion, (CmF2m+1SO3)− (m=0 to 4) or the like is given. As a fluoroalkylborate anion, {BFn(CmHkF2m+1−k)4−n}− (n=0 to 3, m=1 to 4, and k=0 to 2m) or the like is given. As a fluoroalkylphosphate anion, {PFn(CmHkF2m+1−k)6−n}− (n=0 to 5, m=1 to 4, and k=0 to 2m) or the like is given.
As a monovalent amide-based anion, one or more of a bis(fluorosulfonyl)amide anion and a bis(trifluoromethanesulfonyl)amide anion can be used, for example.
An ionic liquid may contain one or more of a hexafluorophosphate anion and a tetrafluoroborate anion.
Hereinafter, an anion represented by (FSO2)2N− is sometimes represented by an FSA anion, and an anion represented by (CF3SO2)2N− is sometimes represented by a TFSA anion.
Specific examples of the cation represented by General Formula (G1) above include Structural Formula (111) to Structural Formula (174).
The ionic liquid shown in General Formula (G1) contains an imidazolium cation and an anion represented by A−. An ionic liquid containing an imidazolium cation has low viscosity and can be used in a wide temperature range. Moreover, an ionic liquid containing an imidazolium cation has high stability and a wide potential window and thus can be suitably used as an electrolyte of a secondary battery.
A mixture of the ionic liquid shown in General Formula (G1) and a salt such as a lithium salt can be used as an electrolyte of a secondary battery. The imidazolium cation shown in General Formula (G1) has high resistance to oxidation, high resistance to reduction, and a wide potential window and thus is suitable as a solvent used for an electrolyte. Here, the range of potentials in which the electrolysis of an electrolyte does not occur is referred to as a potential window. In a secondary battery, an increase in charge voltage can increase the energy density of the secondary battery. Thus, the use of an ionic liquid having a wide potential window and significantly high resistance to, in particular, oxidation can achieve an excellent secondary battery.
In particular, in General Formula (G1), when R1 represents a methyl group, an ethyl group, or a propyl group; one of R2, R3, and R4 represents a hydrogen atom or a methyl group and the other two represent hydrogen atoms; and either an anion represented by (FSO2)2N− (an FSA anion) or an anion represented by (CF3SO2)2N− (a TFSA anion) or a mixture thereof is used as the anion A−, it is possible to achieve an electrolyte that has a wide potential window, excellent resistance to oxidation, and can be used in a wide temperature range without being solidified even at low temperatures at which viscosity lowers.
In particular, metal salts of a fluorosulfonate anion and a fluoroalkylsulfonate anion are preferable as a salt used for an electrolyte in some cases: among them, a metal salt of an amide-based anion represented by (CnF2n+1SO2)2N− (n is greater than or equal to 0 and less than or equal to 3) is preferable because of its high stability at high temperatures and high resistance to oxidation reduction. In particular, by using either LiN(FSO2)2 or LiN(CF3SO2)2 or a mixture thereof, a secondary battery that is highly stable and can operate in a wide temperature range can be achieved.
Specific examples of the cation represented by General Formula (G2) above include Structural Formula (701) to Structural Formula (719).
Specific examples of the cation represented by General Formula (G4) above include Structural Formula (501) to Structural Formula (520).
Specific examples of the cation represented by General Formula (G5) above include Structural Formula (601) to Structural Formula (630).
Specific examples of the cation represented by General Formula (G6) above include Structural Formula (301) to Structural Formula (309) and Structural Formula (401) to Structural Formula (419).
Although Structural Formula (301) to Structural Formula (309) and Structural Formula (401) to Structural Formula (419) each show an example in which m is 1 in General Formula (G6), m may be changed into 2 or 3 in Structural Formula (301) to Structural Formula (309) and Structural Formula (401) to Structural Formula (419).
Specific examples of the cation represented by General Formula (G7) above include Structural Formula (201) to Structural Formula (215).
In the secondary battery of one embodiment of the present invention, a reduction in capacity can be inhibited and significantly excellent characteristics can be achieved even when the secondary battery is repeatedly used at a high charge voltage.
The negative electrode of one embodiment of the present invention includes a negative electrode active material. The negative electrode of one embodiment of the present invention preferably includes a conductive agent. The negative electrode of one embodiment of the present invention preferably includes a binder.
As the negative electrode active material, a material that can react with carrier ions of the secondary battery, a material into and from which carrier ions can be inserted and extracted, a material that enables an alloying reaction with a metal serving as a carrier ion, a material that enables melting and precipitation of a metal serving as a carrier ion, or the like is preferably used.
Carbon materials such as graphite, graphitizing carbon, non-graphitizing carbon, carbon nanotube, carbon black, and graphene can be used as the negative electrode active material, for example.
In addition, a material containing one or more elements selected from silicon, tin, gallium, aluminum, germanium, lead, antimony, bismuth, silver, zinc, cadmium, and indium can be used as the negative electrode active material, for example.
An impurity element such as phosphorus, arsenic, boron, aluminum, or gallium may be added to silicon so that silicon is lowered in resistance.
As a material containing silicon, a material represented by SiOx (x is preferably less than 2, further preferably greater than or equal to 0.5 and less than or equal to 1.6) can be used, for example.
A material containing silicon, which has a plurality of crystal grains in a single particle, for example, can be used. For example, a configuration where a single particle includes one or more silicon crystal grains can be used. The single particle may also include silicon oxide around the silicon crystal grain(s). The silicon oxide may be amorphous.
Silicon nanoparticles can be used as the negative electrode active material. The average diameter of silicon nanoparticles is preferably greater than or equal to 5 nm and less than 1 μm, further preferably greater than or equal to 10 nm and less than or equal to 300 nm, still further preferably greater than or equal to 10 nm and less than or equal to 100 nm.
The silicon nanoparticles may have crystallinity. The silicon nanoparticles may include a region with crystallinity and an amorphous region.
As the negative electrode active material, lithium silicate (Li2cSiO(2+c), 0<c<2) may be used. Furthermore, a zirconium compound, an yttrium compound, an iron compound, a nickel compound, or the like may be included in a lithium silicate phase, and these metal compounds are further preferably dispersed in the lithium silicate phase.
As a compound containing silicon, Li2SiO3 and Li4SiO4 can be used, for example. Each of Li2SiO3 and Li4SiO4 may have crystallinity, or may be amorphous.
As the negative electrode active material, a particle containing lithium silicate can be used. The particle containing lithium silicate may contain zirconium, yttrium, iron, or the like. One particle containing lithium silicate may include a plurality of silicon crystal grains.
The average diameter of the particles containing lithium silicate is preferably greater than or equal to 100 nm and less than or equal to 100 μm, further preferably greater than or equal to 500 nm and less than or equal to 50 μm.
The analysis of the compound containing silicon can be performed by NMR, XRD, a Raman spectroscopy method, or the like.
Furthermore, an oxide containing one or more elements selected from titanium, niobium, tungsten, and molybdenum can be used as a material that can be used for the negative electrode active material, for example.
As the negative electrode active material, it is possible to use a combination of two or more of the aforementioned metals, materials, compounds, and the like.
The negative electrode active material of one embodiment of the present invention may contain fluorine in a surface portion. When the negative electrode active material contains halogen in its surface portion, a decrease in charge and discharge efficiency can be suppressed. Moreover, it is considered that a reaction with an electrolyte at a surface of the active material is inhibited. In addition, at least part of the surface of the negative electrode active material of one embodiment of the present invention is covered with a region containing halogen in some cases. The region may have a film shape, for example. Fluorine is particularly preferable as halogen.
An example of a method for forming a negative electrode active material containing halogen in its surface portion is described.
The above-described material that can be used for the negative electrode active material and a compound containing halogen are mixed as a first material and a second material, respectively, and heat treatment is performed, whereby the negative electrode active material can be formed.
In addition to the first material and the second material, a material causing eutectic reaction with the second material may be mixed as a third material. The eutectic point caused by the eutectic reaction is preferably lower than at least one of the melting point of the second material and the melting point of the third material. A decrease in the melting point due to the eutectic reaction brings the feasibility of covering the surface of the first material with the second material and the third material during the heat treatment, which increases the coverage in some cases.
As the second material and the third material, a material containing a metal whose ion functions as a carrier ion in the reaction of the secondary battery is used, whereby such a metal can contribute to charging and discharging using its carrier ion, in some cases, when the metal is contained in a negative electrode active material.
As the third material, a material containing oxygen and carbon can be used, for example. As the material containing oxygen and carbon, carbonate can be used, for example. Alternatively, as the material containing oxygen and carbon, an organic compound can be used, for example.
Alternatively, as the third material, hydroxide may be used.
Materials such as carbonate and hydroxide are preferable because many of them are inexpensive and have a high level of safety. Furthermore, carbonate, hydroxide, and the like generate a eutectic point with a material containing halogen, which is preferable.
More specific examples of the second material and the third material are described. When lithium fluoride is used as the second material, the lithium fluoride does not cover the surface of the first material but is aggregated only with itself, in some cases, in heating after being mixed with the first material. In such a case, a material causing a eutectic reaction with lithium fluoride is used as the third material, whereby the coverage of the surface of the first material is improved in some cases.
When the first material is heated, reaction with oxygen in an atmosphere occurs in the heating, whereby an oxide film is formed on the surface in some cases. In the formation of the negative electrode active material of one embodiment of the present invention, eutectic reaction between a material containing halogen and a material containing oxygen and carbon is caused in an annealing process described later, whereby heating at low temperatures can be performed. As a result, oxidation reaction at the surface or the like can be inhibited.
When a carbon material is used as the first material, there is a concern that carbon dioxide is generated by reaction of the carbon material and oxygen in an atmosphere in the heating to cause a reduction in the weight of the first material, damage to the surface of the first material, and the like. In the formation of the negative electrode active material of one embodiment of the present invention, the heating can be performed at a low temperature; thus, a reduction in weight, the surface damage, and the like can be inhibited even when the carbon material is used as the first material.
Here, graphite is prepared as the first material. As the graphite, flake graphite, spherical natural graphite, MCMB, or the like can be used. The surface of graphite may be covered with a low-crystalline carbon material.
As the second material, a material containing halogen is prepared. As the material containing halogen, a halogen compound containing a metal A1 can be used. As the metal A1, one or more elements selected from lithium, magnesium, aluminum, sodium, potassium, calcium, barium, lanthanum, cerium, chromium, manganese, iron, cobalt, nickel, zinc, zirconium, titanium, vanadium, and niobium can be used, for example. As the halogen compound, for example, a fluoride or a chloride can be used. The halogen contained in the material containing halogen is represented by an element Z.
Here, lithium fluoride is prepared as an example.
A material containing oxygen and carbon is prepared as the third material. As the material containing oxygen and carbon, a carbonate containing a metal A2 can be used, for example. As the metal A2, one or more selected from lithium, magnesium, aluminum, sodium, potassium, calcium, barium, lanthanum, cerium, chromium, manganese, iron, cobalt, and nickel can be used, for example.
Here, lithium carbonate is prepared as an example.
The first material, the second material, and the third material are mixed to obtain a mixture.
The second material and the third material are preferably mixed to have a ratio such that (the second material):(the third material)=a1:(1−a1) [unit: mol.] where a1 is preferably greater than 0.2 and less than 0.9, further preferably greater than or equal to 0.3 and less than or equal to 0.8.
Furthermore, the first material and the second material are preferably mixed to have a ratio such that (the first material):(the second material)=1:b1 [unit: mol.] where b1 is preferably greater than or equal to 0.001 and less than or equal to 0.2.
Next, the annealing process is performed, whereby the negative electrode active material of one embodiment of the present invention is obtained.
It is preferable that the annealing process be performed in a reduction atmosphere because the oxidation of the surface of the first material and the reaction of the first material with oxygen can be inhibited. The reduction atmosphere may be a nitrogen atmosphere or a rare gas atmosphere, for example. Furthermore, two or more types of gases selected from nitrogen and a rare gas may be mixed and used. The heating may be performed under reduced pressure.
In the case where the melting point of the second material is represented by M2 [K], the heating temperature is preferably higher than (M2−550) [K] and lower than (M2+50) [K], further preferably higher than or equal to (M2−400) [K] and lower than or equal to (M2) [K].
Moreover, in a compound, solid-phase diffusion occurs easily at a temperature higher than or equal to the Tamman temperature. The Tamman temperature of an oxide, for example, is 0.757 times the melting point. Thus, the heating temperature is preferably higher than or equal to 0.757 times the melting point or higher than its vicinity, for example.
In the case of lithium fluoride that is a typical example of the material containing halogen, the amount of evaporation increases rapidly at a temperature higher than or equal to the melting point. Thus, the heating temperature is preferably lower than or equal to the melting point of the material containing halogen, for example.
In the case where the eutectic point of the second material and the third material is represented by M23 [K], the heating temperature is, for example, preferably higher than (M23×0.7) [K] and lower than (M2+50) [K], preferably higher than or equal to (M23×0.75) [K] and lower than or equal to (M2+20) [K], preferably higher than or equal to (M23×0.75) [K] and lower than or equal to (M2+20) [K], preferably higher than M23 [K] and lower than (M2+10) [K], further preferably higher than or equal to (M23×0.8) [K] and lower than or equal to M2 [K], further preferably higher than or equal to (M23) [K] and lower than or equal to M2 [K].
In the case where lithium fluoride is used as the second material and lithium carbonate is used as the third material, the heating temperature is, for example, preferably higher than 350° C. and lower than 900° C., further preferably higher than or equal to 390° C. and lower than or equal to 850° C., still further preferably higher than or equal to 520° C. and lower than or equal to 910° C., still further preferably higher than or equal to 570° C. and lower than or equal to 860° C., yet still further preferably higher than or equal to 610° C. and lower than or equal to 860° C.
The heating time is preferably longer than or equal to 1 hour and shorter than or equal to 60 hours, further preferably longer than or equal to 3 hours and shorter than or equal to 20 hours, for example.
The cross section of the negative electrode active material 400 is exposed by processing, whereby observation and analysis of the cross section can be performed.
The negative electrode active material 400 illustrated in
At least part of the region 402 preferably includes the surface of the negative electrode active material 400.
The region 401 is, for example, a region including an inner portion of the negative electrode active material 400.
The region 401 includes the first material described above. The region 402 includes the element Z, oxygen, carbon, the metal A1, and the metal A2, for example. The element Z is, for example, fluorine or chlorine. The region 402 does not include some of elements of the element Z, oxygen, carbon, the metal A1, and the metal A2, in some cases. Alternatively, in the region 402, some of the elements of the element Z, oxygen, carbon, the metal A1, and the metal A2 have low concentration and are not detected by analysis in some cases.
The region 402 is called a surface portion of the negative electrode active material 400 or the like, in some case.
The negative electrode active material 400 can have a variety of forms such as one particle, a group of a plurality of particles, and a thin film.
The region 401 may be a particle of the first material. Alternatively, the region 401 may be a group of a plurality of particles of the first material. Alternatively, the region 401 may be a thin film of the first material.
The region 402 may be part of a particle. For example, the region 402 may be a surface portion of the particle. Alternatively, the region 402 may be part of a thin film. For example, the region 402 may be an upper layer portion of a thin film.
The region 402 may be a coating layer formed on the surface of the particle.
The region 402 may be a region including a bond of a constituent element of the first material and the element Z. For example, in the region 402 or the interface between the region 401 and the region 402, the surface of the first material may be modified with the element Z or a functional group including the element Z. Thus, in the negative electrode active material of one embodiment of the present invention, the bond of a constituent element of the first material and the element Z is observed in some cases. As an example, in the case where the first material is graphite and the element Z is fluorine, a C—F bond is, for example, observed in some cases. As another example, in the case where the first material contains silicon and the element Z is fluorine, a Si—F bond is, for example, observed in some cases.
For example, in the case where graphite is used as the first material, the region 401 is a graphite particle, and the region 402 is a coating layer of the graphite particle. As another example, in the case where graphite is used as the first material, the region 401 is a region including an inner portion of a graphite particle, and the region 402 is a surface portion of the graphite particle.
The region 402 includes, for example, a bond of the element Z and carbon. The region 402 includes, for example, a bond of the element Z and the metal A1. The region 402 includes, for example, a carbonate group.
When the negative electrode active material 400 is analyzed by X-ray photoelectron spectroscopy (XPS), the element Z is preferably detected, in which case the concentration of the detected element Z is preferably higher than or equal to 1 atomic %. In this case, the concentration of the element Z can be calculated on the assumption that the total of concentrations of carbon, oxygen, the metal A1, the metal A2, and the element Z is 100%, for example. Alternatively, the calculation may be performed on the assumption that the value obtained by adding the nitrogen concentration to the concentrations of the above elements is set as 100%. The concentration of the element Z is, for example, lower than or equal to 60 atomic %, or lower than or equal to 30 atomic %.
When the negative electrode active material 400 is analyzed by XPS, a peak attributed to the bond of the element Z and carbon is preferably detected. A peak attributed to the bond of the element Z and the metal A1 may be detected.
In the case where the element Z is fluorine and the metal A1 is lithium, in the F1s spectrum by XPS, a peak indicating the carbon-fluorine bond (hereinafter, a peak F2) is observed in the vicinity of 688 eV (e.g., its peak position is observed in an energy range higher than 686.5 eV and lower than 689.5 eV), and a peak indicating the lithium-fluorine bond (hereinafter, a peak F1) is observed in the vicinity of 685 eV (e.g., its peak position is observed in an energy range higher than 683.5 eV and lower than 686.5 eV). The intensity of the peak F2 is preferably higher than 0.1 times the intensity of the peak F1 and lower than 10 times the intensity of the peak F1. For example, the intensity of the peak F2 is higher than or equal to 0.3 times the intensity of the peak F1 and lower than or equal to 3 times the intensity of the peak F1.
When the negative electrode active material 400 is analyzed by XPS, a peak corresponding to carbonate or a carbonate group is preferably observed. In the C1s spectrum by XPS, the peak corresponding to carbonate or a carbonate group is observed in the vicinity of 290 eV (e.g., its peak position is observed in an energy range higher than 288.5 eV and lower than 291.5 eV).
In XRD analysis of the negative electrode active material 400, a spectrum derived from Li2O represented by a space group Fm-3m is observed in some cases.
In the example shown in
In the negative electrode active material 400 illustrated in
The region 401b is a surface portion of the region 401.
The region 401b contains one or more elements of the element Z, oxygen, carbon, the metal A1, and the metal A2 contained in the region 402. In the region 401b, the elements contained in the region 402, such as the element Z, oxygen, carbon, the metal A1, and the metal A2, may have a concentration gradient such that the concentration decreases gradually from the surface or the vicinity of the surface to the inner portion.
The concentration of the element Z contained in the region 401b is higher than the concentration of the element Z contained in the region 401a. The concentration of the element Z contained in the region 401b is preferably lower than the concentration of the element Z contained in the region 402.
The concentration of oxygen contained in the region 401b is higher than the concentration of oxygen contained in the region 401a in some cases. The concentration of oxygen contained in the region 401b is lower than the concentration of oxygen contained in the region 402 in some cases.
When the negative electrode active material of one embodiment of the present invention is measured by energy dispersive X-ray spectroscopy using a scanning electron microscope, it is preferable that the element Z be detected. For example, the concentration of the element Z is preferably higher than or equal to 10 atomic % and lower than or equal to 70 atomic % on the assumption that the total of the concentrations of the element Z and oxygen is 100 atomic %.
The region 402 has a region whose thickness is smaller than or equal to 50 nm, preferably larger than or equal to 1 nm and smaller than or equal to 35 nm, further preferably larger than or equal to 5 nm and smaller than or equal to 20 nm, for example.
The region 401b has a region whose thickness is smaller than or equal to 50 nm, preferably larger than or equal to 1 nm and smaller than or equal to 35 nm, further preferably larger than or equal to 5 nm and smaller than or equal to 20 nm, for example.
In the case where fluorine is used as the element Z and lithium is used as the metal A1 and the metal A2, the region 402 may include a region covered with a region containing lithium fluoride and a region covered with a region containing lithium carbonate, with respect to the region 401. The region 402 does not obstruct the insertion and extraction of lithium and accordingly enables an excellent secondary battery to be achieved without a degradation of output characteristics or the like of the secondary battery.
This embodiment can be combined with the description of any of the other embodiments as appropriate.
In this embodiment, an example of a secondary battery of one embodiment of the present invention is described with reference to
The positive electrode of one embodiment of the present invention includes a positive electrode active material layer. The positive electrode active material layer contains a positive electrode active material. The positive electrode active material layer may include a conductive agent, a binder, and the like. The positive electrode of one embodiment of the present invention preferably includes a current collector, and the positive electrode active material layer is preferably provided over the current collector.
In
The negative electrode of one embodiment of the present invention includes a negative electrode active material layer. The negative electrode active material layer contains a negative electrode active material. The negative electrode active material layer may include a conductive agent, a binder, and the like. The negative electrode of one embodiment of the present invention preferably includes a current collector, and the negative electrode active material layer is preferably provided over the current collector.
The negative electrode 506 includes a negative electrode active material layer 505 and a negative electrode current collector 504. The negative electrode active material layer 505 includes a negative electrode active material 563, a conductive additive, and a binder. As an enlarged view of part of the negative electrode active material layer 505,
As the conductive agent, a carbon material, a metal material, a conductive ceramic material, or the like can be used. Alternatively, a fiber material may be used as the conductive agent. The content of the conductive agent to the total amount of the active material layer is preferably greater than or equal to 1 wt % and less than or equal to 10 wt %, further preferably greater than or equal to 1 wt % and less than or equal to 5 wt %.
A network for electric conduction can be formed in the active material layer by the conductive agent. The conductive agent also allows maintaining of a path for electric conduction between the active materials. The addition of the conductive agent to the active material layer increases the electric conductivity of the active material layer.
As the conductive agent, a graphene compound can be used. Moreover, natural graphite, artificial graphite such as mesocarbon microbeads, carbon fiber, or the like can be used as the conductive agent.
As carbon fiber, carbon fiber such as mesophase pitch-based carbon fiber or isotropic pitch-based carbon fiber can be used, for example. As the carbon fiber, carbon nanofiber, carbon nanotube, or the like can be used. Carbon nanotube can be formed by, for example, a vapor deposition method. Other examples of the conductive agent include carbon materials such as carbon black (e.g., acetylene black (AB)), graphite (black lead) particles, graphene, and fullerene. Alternatively, one or more selected from metal powder and metal fiber of copper, nickel, aluminum, silver, gold, or the like, a conductive ceramic material, and the like can be used.
A graphene compound in this specification and the like refers to graphene, multilayer graphene, multi graphene, graphene oxide, multilayer graphene oxide, multi graphene oxide, reduced graphene oxide, reduced multilayer graphene oxide, reduced multi graphene oxide, graphene quantum dots, and the like. A graphene compound contains carbon, has a plate-like shape, a sheet-like shape, or the like, and has a two-dimensional structure formed of a six-membered ring composed of carbon atoms. The two-dimensional structure formed of the six-membered ring composed of carbon atoms may be referred to as a carbon sheet. A graphene compound may include a functional group. A graphene compound is preferably bent. A graphene compound may be rounded like carbon nanofiber.
As the conductive agent, it is possible to use a combination of the above-described materials.
In this specification and the like, graphene oxide contains carbon and oxygen, has a sheet-like shape, and includes a functional group, in particular, an epoxy group, a carboxy group, or a hydroxy group.
In this specification and the like, reduced graphene oxide contains carbon and oxygen, has a sheet-like shape, and has a two-dimensional structure formed of a six-membered ring composed of carbon atoms. The reduced graphene oxide may also be referred to as a carbon sheet. The reduced graphene oxide functions by itself and may have a stacked-layer structure. The reduced graphene oxide preferably includes a portion where the carbon concentration is higher than 80 atomic % and the oxygen concentration is higher than or equal to 2 atomic % and lower than or equal to 15 atomic %. With such a carbon concentration and such an oxygen concentration, the reduced graphene oxide can function as a conductive agent with high conductivity even with a small amount. In addition, the intensity ratio G/D of a G band to a D band of the Raman spectrum of the reduced graphene oxide is preferably 1 or more. The reduced graphene oxide with such an intensity ratio can function as a conductive agent with high conductivity even with a small amount.
In the longitudinal cross section of the active material layer, the sheet-like graphene compounds are dispersed substantially uniformly in a region inside the active material layer. The plurality of graphene compounds are formed to partly coat a plurality of particles of the active material or adhere to the surfaces of the plurality of particles of the active material, so that the graphene compounds make surface contact with the particles of the active material.
Here, the plurality of graphene compounds can be bonded to each other to form a net-like graphene compound sheet (hereinafter, referred to as a graphene compound net or a graphene net). A graphene net that covers the active material can function as a binder for bonding the active materials. Accordingly, the amount of the binder can be reduced, or the binder does not have to be used. This can increase the proportion of the active material in the electrode volume and the electrode weight. That is, the charge and discharge capacity of the secondary battery can be increased.
Here, it is preferable to perform reduction after a layer to be the active material layer is formed in such a manner that graphene oxide is used as the graphene compound and mixed with an active material. That is, the formed active material layer preferably contains reduced graphene oxide. When graphene oxide with extremely high dispersibility in a polar solvent is used to form the graphene compounds, the graphene compounds can be substantially uniformly dispersed in a region inside the active material layer. The solvent is removed by volatilization from a dispersion medium containing the uniformly dispersed graphene oxide to reduce the graphene oxide; hence, the graphene compounds remaining in the active material layer partly overlap with each other and are dispersed such that surface contact is made, thereby forming a three-dimensional conductive path. Note that graphene oxide may be reduced by heat treatment or with the use of a reducing agent, for example. Unlike a particulate conductive agent such as acetylene black, which makes point contact with an active material, the graphene compound is capable of making low-resistance surface contact; accordingly, the electric conduction in the electrode can be improved with a smaller amount of the graphene compound than that of a normal conductive agent. This can increase the proportion of the active material in the active material layer. Thus, discharge capacity of the secondary battery can be increased.
As the binder, for example, a rubber material such as styrene-butadiene rubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, or an ethylene-propylene-diene copolymer is preferably used. Alternatively, fluororubber can be used as the binder.
As the binder, for example, water-soluble polymers are preferably used. As the water-soluble polymers, a polysaccharide can be used, for example. As the polysaccharide, one or more selected from starch, cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose, and the like can be used. It is further preferred that such water-soluble polymers be used in combination with any of the above-described rubber materials.
Alternatively, as the binder, a material such as polystyrene, poly(methyl acrylate), poly(methyl methacrylate) (PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO), polypropylene oxide, polyimide, polyvinyl chloride, polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene, polyethylene terephthalate, nylon, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), an ethylene-propylene-diene polymer, polyvinyl acetate, or nitrocellulose is preferably used.
Two or more of the above materials may be used in combination for the binder.
For example, a material having a significant viscosity modifying effect and another material may be used in combination. For example, a rubber material or the like has high adhesion and high elasticity but may have difficulty in viscosity modification when mixed in a solvent. In such a case, a rubber material or the like is preferably mixed with a material having a significant viscosity modifying effect, for example. As a material having a significant viscosity modifying effect, for instance, a water-soluble polymer is preferably used. As a water-soluble polymer having a significant viscosity modifying effect, one or more selected from the above-mentioned polysaccharides, for instance, starch and cellulose derivatives such as carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and regenerated cellulose can be used.
Note that a cellulose derivative such as carboxymethyl cellulose obtains a higher solubility when converted into a salt such as a sodium salt or an ammonium salt of carboxymethyl cellulose, and thus easily exerts an effect as a viscosity modifier. A high solubility can also increase the dispersibility of an active material and other components in the formation of slurry for an electrode. In this specification, cellulose and a cellulose derivative used as a binder of an electrode include salts thereof.
A water-soluble polymer stabilizes the viscosity by being dissolved in water and allows stable dispersion of the active material and another material combined as a binder, such as styrene-butadiene rubber, in an aqueous solution. Furthermore, a water-soluble polymer is expected to be easily and stably adsorbed onto an active material surface because it has a functional group. Many cellulose derivatives, such as carboxymethyl cellulose, have a functional group such as a hydroxyl group or a carboxyl group. Because of functional groups, polymers are expected to interact with each other and cover an active material surface in a large area.
In the case where the binder that covers or is in contact with the active material surface forms a film, the film is expected to serve also as a passivation film to suppress the decomposition of the electrolyte. Here, a passivation film refers to a film without electric conductivity or a film with extremely low electric conductivity, and can inhibit the decomposition of an electrolyte at a potential at which a battery reaction occurs when the passivation film is formed on the active material surface, for example. It is preferred that the passivation film can conduct lithium ions while suppressing electric conduction.
The active material layer can be formed in such a manner that an active material, a binder, a conductive additive, and a solvent are mixed to form slurry, the slurry is formed over a current collector, and the solvent is volatilized.
A solvent used for the slurry is preferably a polar solvent. For example, water, methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), or a mixed solution of two or more of the above can be used.
For each of a positive electrode current collector and a negative electrode current collector, it is possible to use a material which has high conductivity and is not alloyed with carrier ions such as lithium, e.g., a metal such as stainless steel, gold, platinum, zinc, iron, copper, aluminum, or titanium, an alloy thereof, or the like. It is also possible to use an aluminum alloy to which an element that improves heat resistance, such as silicon, titanium, neodymium, scandium, or molybdenum, is added. Alternatively, a metal element that forms silicide by reacting with silicon may be used. Examples of the metal element that forms silicide by reacting with silicon include zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, and nickel. The current collector can have a sheet-like shape, a net-like shape, a punching-metal shape, an expanded-metal shape, or the like as appropriate. The thickness of the current collector is preferably larger than or equal to 10 μm and smaller than or equal to 30 μm.
Note that a material that is not alloyed with carrier ions of lithium or the like is preferably used for the negative electrode current collector.
As each of the current collectors, a titanium compound may be stacked over the above-described metal element. As a titanium compound, for example, it is possible to use one selected from titanium nitride, titanium oxide, titanium nitride in which oxygen is substituted for part of nitrogen, titanium oxide in which nitrogen is substituted for part of oxygen, and titanium oxynitride (TiOxNy, where 0<x<2 and 0<y<1), or a mixture or a stack of two or more of them. Titanium nitride is particularly preferable because it has high conductivity and has a high capability of inhibiting oxidation. Provision of a titanium compound over the surface of the current collector inhibits a reaction between a material contained in the active material layer formed over the current collector and the metal, for example. In the case where the active material layer contains a compound containing oxygen, an oxidation reaction between the metal element and oxygen can be inhibited. In the case where aluminum is used for the current collector and the active material layer is formed using graphene oxide described later, for example, an oxidation reaction between oxygen contained in the graphene oxide and aluminum might occur. In such a case, provision of a titanium compound over aluminum can inhibit an oxidation reaction between the current collector and the graphene oxide.
As each of the graphene 554 and the graphene 557, graphene or a graphene compound can be used.
A graphene compound in this specification and the like refers to multilayer graphene, multi graphene, graphene oxide, multilayer graphene oxide, multi graphene oxide, reduced graphene oxide, reduced multilayer graphene oxide, reduced multi graphene oxide, graphene quantum dots, and the like. A graphene compound contains carbon, has a plate-like shape, a sheet-like shape, or the like, and has a two-dimensional structure formed of a six-membered ring composed of carbon atoms. The two-dimensional structure formed of the six-membered ring composed of carbon atoms may be referred to as a carbon sheet. A graphene compound may include a functional group. A graphene compound is preferably bent. A graphene compound may be rounded like carbon nanofiber.
In the positive electrode or the negative electrode of one embodiment of the present invention, graphene or a graphene compound can function as a conductive agent. A plurality of sheets of graphene or graphene compounds form a three-dimensional conductive path in the positive electrode or the negative electrode and can increase the conductivity of the positive electrode or the negative electrode. Because the graphene or graphene compounds can cling to the particles in the positive electrode or the negative electrode, the break of the particles in the positive electrode or the negative electrode can be suppressed and the strength of the positive electrode or the negative electrode can be increased. The graphene or graphene compound has a thin sheet-like shape and can form the excellent conductive path even though occupying a small volume in the positive electrode or the negative electrode, whereby the volume of the active material in the positive electrode or the negative electrode can be increased. Therefore, the capacity of the secondary battery can be increased.
The separator 507 can be formed using paper, nonwoven fabric, glass fiber, ceramics, or the like. Alternatively, the separator 507 can be formed using nylon (polyamide), vinylon (polyvinyl alcohol-based fiber), polyester, acrylic, polyolefin, polyurethane, polypropylene, polyethylene, or the like. The separator is preferably formed to have an envelope-like shape to wrap one of the positive electrode and the negative electrode.
For the separator 507, for example, a polymer film including polypropylene, polyethylene, polyimide, or the like can be used. Owing to its high wettability with respect to an ionic liquid, polyimide may be further preferable as a material of the separator 507.
A polymer film including polypropylene, polyethylene, or the like can be formed by a dry method or a wet method. The dry method is a method in which a polymer film including polypropylene, polyethylene, polyimide, or the like is stretched while being heated so that a space is formed between crystals, whereby a minute hole is formed. The wet method is a method in which a resin to which a solvent is mixed in advance is processed into a film and then the solvent is extracted, whereby a hole is formed.
On the left side of
After charging and discharging, the diameter of the hole in the separator may differ between a surface portion of a surface that faces the positive electrode and a surface portion of a surface that faces the negative electrode. In this specification and the like, a surface portion of the separator is preferably a region that is less than or equal to 5 μm, further preferably less than or equal to 3 μm from the surface, for example.
The separator may have a multilayer structure. For example, a structure in which two kinds of polymer materials are stacked may be employed.
For example, it is possible to employ a structure in which a polymer film including polypropylene, polyethylene, polyimide, or the like is coated with a ceramic-based material, a fluorine-based material, a polyamide-based material, a mixture thereof, or the like. Alternatively, for example, it is possible to employ a structure in which nonwoven fabric is coated with a ceramic-based material, a fluorine-based material, a polyamide-based material, a mixture thereof, or the like. Owing to its high wettability with respect to an ionic liquid, polyimide may be further preferable as a material used for coating.
Examples of the fluorine-based material include PVdF and polytetrafluoroethylene.
Examples of the polyamide-based material include nylon and aramid (meta-based aramid and para-based aramid).
For an exterior body included in the secondary battery, one or more selected from a metal material such as aluminum and a resin material can be used, for example. Alternatively, a film-like exterior body can also be used. As the film, for example, it is possible to use a film having a three-layer structure in which a highly flexible metal thin film of aluminum, stainless steel, copper, nickel, or the like is provided over a film formed of a material such as polyethylene, polypropylene, polycarbonate, ionomer, or polyamide, and an insulating synthetic resin film of a polyamide-based resin, a polyester-based resin, or the like is provided over the metal thin film as the outer surface of the exterior body.
This embodiment can be combined with any of the other embodiments as appropriate.
In this embodiment, a method for manufacturing a secondary battery will be described.
Here, an example of a method for manufacturing laminated secondary batteries whose external views are shown in
First, the positive electrode 503, the negative electrode 506, and the separator 507 are prepared.
Next, the negative electrode 506, the separator 507, and the positive electrode 503 are stacked.
Then, the tab regions of the positive electrodes 503 are bonded to each other, and the positive electrode lead electrode 510 is bonded to the tab region of the positive electrode on the outermost surface. The bonding is performed by ultrasonic welding, for example. In a similar manner, the tab regions of the negative electrodes 506 are bonded to each other, and the negative electrode lead electrode 511 is bonded to the tab region of the negative electrode on the outermost surface.
Next, the negative electrodes 506, the separators 507, and the positive electrodes 503 are placed over the exterior body 509.
Subsequently, the exterior body 509 is folded along a portion shown by a dashed line as illustrated in
Next, as illustrated in
In the above, the positive electrode lead electrode 510 and the negative electrode lead electrode 511 are drawn from the same side to the outside of the exterior body, so that the secondary battery 500 illustrated in
Next, an example of a method for manufacturing a laminated secondary battery 600 whose external view is shown in
The laminated secondary battery 600 can be manufactured using a manufacturing apparatus illustrated in
A procedure for manufacturing the laminated secondary battery 600 is as follows.
First, an exterior body 509b is placed over a stage 591 in the treatment chamber 573, and then the positive electrode 503 is placed over the exterior body 509b (
With movement of the nozzle 594, the electrolyte 515a can be dripped on the entire surface of the positive electrode 503. Alternatively, with movement of the stage 591, the electrolyte 515a may be dripped on the entire surface of the positive electrode 503.
It is preferable to drip the electrolyte from a position whose shortest distance from a surface where the electrolyte is dripped is greater than 0 mm and less than or equal to 1 mm.
The viscosity of the electrolyte dripped from the nozzle or the like is preferably adjusted as appropriate. When the viscosity of the whole electrolyte falls within the range of 0.3 mPa·s to 1000 mPa·s at room temperature (25° C.), the electrolyte can be dripped from the nozzle.
Since the viscosity of the electrolyte changes depending on the temperature of the electrolyte, the temperature of the electrolyte to be dripped is preferably adjusted as appropriate. The temperature of the electrolyte is preferably higher than or equal to the melting point and lower than or equal to the boiling point and flash point of the electrolyte.
Then, the separator 507 is placed over the positive electrode 503 to overlap with the entire surface of the positive electrode 503 (
In
Multiple formation can be performed by placing a plurality of stacks 512 on the exterior body 509b. The stacks 512 are each sealed with the exterior bodies 509a and 509b in the region 514 so that the active material layers are surrounded, and then the stacks 512 are divided outside the regions 514, whereby a plurality of secondary batteries can be individually separated.
In sealing, first, a frame-like resin layer 513 is formed over the exterior body 509b. Then, at least part of the resin layer 513 is irradiated with light under reduced pressure, so that at least part of the resin layer 513 is cured. Next, the sealing is performed in the region 514 by thermocompression bonding or welding under atmospheric pressure. Alternatively, it is possible that the sealing by light irradiation is not performed and only the sealing by thermocompression bonding or welding is performed.
Although
Through the above process, the laminated secondary battery 600 can be manufactured.
In the stack 550, one separator 507 is folded a plurality of times to be sandwiched between the positive electrode active material layer 502 and the negative electrode active material layer 505. Since six positive electrodes 503 and six negative electrodes 506 are stacked in
After the positive electrode 503 is placed, an electrolyte can be dripped on the positive electrode 503 in the method for manufacturing the secondary battery of one embodiment of the present invention. Similarly, after the negative electrode 506 is placed, an electrolyte can be dripped on the negative electrode 506. In the method for manufacturing the secondary battery of one embodiment of the present invention, an electrolyte can be dripped on the separator 507 before the separator is folded or after the folded separator 507 overlaps with the negative electrode 506 or the positive electrode 503. When an electrolyte is dripped on at least one of the negative electrode 506, the separator 507, and the positive electrode 503, the negative electrode 506, the separator 507, or the positive electrode 503 can be impregnated with the electrolyte.
A secondary battery 970 illustrated in
The stack 972 can have a stacked-layer structure of a positive electrode, a negative electrode, and a separator. Alternatively, the stack 972 can have a structure in which a positive electrode, a negative electrode, and a separator are wound, for example.
As the stack 972, the stack having the structure illustrated in
An example of a method for fabricating the stack 972 will be described with reference to
First, as illustrated in
Next, an example of a method for manufacturing the secondary battery 970 will be described with reference to
First, as illustrated in
One stack 972 may be placed inside the housing 971 or a plurality of stacks 972 may be placed inside the housing 971.
Next, as illustrated in
For the housing 971, a metal material (e.g., aluminum) can be used. In the case where a metal material is used for the housing 971, the surface is preferably coated with a resin or the like. Alternatively, a resin material can be used for the housing 971.
The housing 971 is preferably provided with a safety valve, an overcurrent protection element, or the like. A safety valve is a valve for releasing a gas, in order to prevent the battery from exploding, when the pressure inside the housing 971 reaches a predetermined pressure.
As illustrated in
As illustrated in
The method for manufacturing the secondary battery of one embodiment of the present invention can be utilized for fabricating the stacks. Specifically, in order to fabricate the stacks, an electrolyte is dripped on at least one of the negative electrode 506, the separator 507, and the positive electrode 503 at the time of stacking the negative electrode 506, the separator 507, and the positive electrode 503. Dripping a plurality of drops of the electrolyte enables the negative electrode 506, the separator 507, or the positive electrode 503 to be impregnated with the electrolyte.
As illustrated in
After the stacks 130 are placed, an electrolyte can be dripped on the stacks 130 in the method for manufacturing the secondary battery of one embodiment of the present invention. Similarly, after the stacks 131 are placed, an electrolyte can be dripped on the stacks 131. Moreover, an electrolyte can be dripped on the separator 507 before the separator 507 is folded or after the folded separator 507 overlaps with the stacks. Dripping a plurality of drops of the electrolyte enables the stacks 130, the stacks 131, or the separator 507 to be impregnated with the electrolyte.
A secondary battery of another embodiment of the present invention will be described with reference to
A secondary battery 913 illustrated in
Note that as illustrated in
For the housing 930a, an insulating material such as an organic resin can be used. In particular, when a material such as an organic resin is used for the side on which an antenna is formed, blocking of an electric field by the secondary battery 913 can be inhibited. When an electric field is not significantly blocked by the housing 930a, an antenna may be provided inside the housing 930a. For the housing 930b, a metal material can be used, for example.
Furthermore,
At the time of stacking the negative electrode 931, the separator 933, and the positive electrode 932 in the method for manufacturing the secondary battery of one embodiment of the present invention, an electrolyte is dripped on at least one of the negative electrode 931, the separator 933, and the positive electrode 932. That is, an electrolyte is preferably dripped before the sheet of the stack is wound. Dripping a plurality of drops of the electrolyte enables the negative electrode 931, the separator 933, or the positive electrode 932 to be impregnated with the electrolyte.
As illustrated in
The separator 933 has a larger width than the negative electrode active material layer 931a and the positive electrode active material layer 932a, and is wound to overlap with the negative electrode active material layer 931a and the positive electrode active material layer 932a. In terms of safety, the width of the negative electrode active material layer 931a is preferably larger than that of the positive electrode active material layer 932a. The wound body 950a having such a shape is preferable because of its high level of safety and high productivity.
As illustrated in
As illustrated in
As illustrated in
An example of a coin-type secondary battery is described.
For easy understanding,
In
The positive electrode 304 has a stack structure in which a positive electrode active material layer 306 is formed over a positive electrode current collector 305.
To prevent a short circuit between the positive electrode and the negative electrode, the separator 310 and a ring-shaped insulator 313 are placed to cover the side surface and top surface of the positive electrode 304. The separator 310 has a larger flat surface area than the positive electrode 304.
In a coin-type secondary battery 300, the positive electrode can 301 doubling as a positive electrode terminal and the negative electrode can 302 doubling as a negative electrode terminal are insulated from each other and sealed by a gasket 303 made of polypropylene or the like. The positive electrode 304 includes the positive electrode current collector 305 and the positive electrode active material layer 306 provided in contact with the positive electrode current collector 305. The negative electrode 307 includes a negative electrode current collector 308 and a negative electrode active material layer 309 provided in contact with the negative electrode current collector 308. The negative electrode 307 is not limited to having a stacked-layer structure, and lithium metal foil or lithium-aluminum alloy foil may be used.
Note that only one surface of each of the positive electrode 304 and the negative electrode 307 used for the coin-type secondary battery 300 may be provided with an active material layer.
For the positive electrode can 301 and the negative electrode can 302, a material having corrosion resistance to an electrolyte can be used. For example, a metal such as nickel, aluminum, or titanium, an alloy of such a metal, or an alloy of such a metal and another metal (e.g., stainless steel) can be used. The positive electrode can 301 and the negative electrode can 302 are preferably covered with nickel, aluminum, or the like in order to prevent corrosion due to the electrolyte. The positive electrode can 301 and the negative electrode can 302 are electrically connected to the positive electrode 304 and the negative electrode 307, respectively.
The coin-type secondary battery 300 is manufactured in the following manner: the negative electrode 307, the positive electrode 304, and the separator 310 are immersed in the electrolyte; as illustrated in
The secondary battery of one embodiment of the present invention can be the coin-type secondary battery 300 having high capacity, high charge and discharge capacity, and excellent cycle performance. Note that the separator 310 is unnecessary in the secondary battery in some cases.
An example of a cylindrical secondary battery is described with reference to
Inside the battery can 602 having a hollow cylindrical shape, a battery element in which a belt-like positive electrode 604 and a belt-like negative electrode 606 are wound with a separator 605 located therebetween is provided. Although not illustrated, the battery element is wound around a center pin. One end of the battery can 602 is close and the other end thereof is open. For the battery can 602, a material having corrosion resistance to an electrolyte can be used. For example, a metal such as nickel, aluminum, or titanium, an alloy thereof, or an alloy of such a metal and another metal (e.g., stainless steel) can be used. The battery can 602 is preferably covered with nickel, aluminum, or the like in order to prevent corrosion due to the electrolyte. Inside the battery can 602, the battery element in which the positive electrode, the negative electrode, and the separator are wound is provided between a pair of insulating plates 608 and 609 that face each other. The inside of the battery can 602 provided with the battery element is filled with an electrolyte (not illustrated). An electrolyte similar to that for the coin-type secondary battery can be used.
Since a positive electrode and a negative electrode that are used for a cylindrical storage battery are wound, active materials are preferably formed on both surfaces of a current collector.
A positive electrode terminal (positive electrode current collecting lead) 603 is connected to the positive electrode 604, and a negative electrode terminal (negative electrode current collecting lead) 607 is connected to the negative electrode 606. For both the positive electrode terminal 603 and the negative electrode terminal 607, a metal material such as aluminum can be used. The positive electrode terminal 603 and the negative electrode terminal 607 are resistance-welded to a safety valve mechanism 613 and the bottom of the battery can 602, respectively. The safety valve mechanism 613 is electrically connected to the positive electrode cap 601 through a PTC element (Positive Temperature Coefficient) 611. The safety valve mechanism 613 cuts off electrical connection between the positive electrode cap 601 and the positive electrode 604 when the internal pressure of the battery exceeds a predetermined threshold. The PTC element 611, which is a thermally sensitive resistor whose resistance increases as temperature rises, limits the amount of current by increasing the resistance, in order to prevent abnormal heat generation. Barium titanate (BaTiO3)-based semiconductor ceramic or the like can be used for the PTC element.
A temperature control device may be provided between the plurality of secondary batteries 616. The secondary batteries 616 can be cooled with the temperature control device when overheated, whereas the secondary batteries 616 can be heated with the temperature control device when cooled too much. Thus, the performance of the power storage system 615 is less likely to be influenced by the outside temperature.
In
This embodiment can be combined with any of the other embodiments as appropriate.
In this embodiment, application examples of the secondary battery of one embodiment of the present invention will be described with reference to
First, an example in which the secondary battery of one embodiment of the present invention is used in an electric vehicle (EV) will be described.
For example, as one or both of the first batteries 1301a and 1301b, the secondary battery manufactured by the method for manufacturing the secondary battery of one embodiment of the present invention can be used.
Although this embodiment shows an example in which the two first batteries 1301a and 1301b are connected in parallel, three or more batteries may be connected in parallel. In the case where the first battery 1301a can store sufficient electric power, the first battery 1301b may be omitted. With a battery pack including a plurality of secondary batteries, large electric power can be extracted. The plurality of secondary batteries may be connected in parallel, connected in series, or connected in series after being connected in parallel. The plurality of secondary batteries are also referred to as an assembled battery.
An in-vehicle secondary battery includes a service plug or a circuit breaker that can cut off high voltage without the use of equipment in order to cut off electric power from a plurality of secondary batteries. The first battery 1301a is provided with such a service plug or a circuit breaker.
Electric power from the first batteries 1301a and 1301b is mainly used to rotate the motor 1304 and is also supplied to in-vehicle parts for 42 V (for a high-voltage system) (such as an electric power steering 1307, a heater 1308, and a defogger 1309) through a DCDC circuit 1306. In the case where there is a rear motor 1317 for the rear wheels, the first battery 1301a is used to rotate the rear motor 1317.
The second battery 1311 supplies electric power to in-vehicle parts for 14 V (for a low-voltage system) (such as an audio 1313, power windows 1314, and lamps 1315) through a DCDC circuit 1310.
The first battery 1301a will be described with reference to
The control circuit portion 1320 may include a memory circuit including a transistor using an oxide semiconductor. A charging control circuit or a battery control system that includes a memory circuit including a transistor using an oxide semiconductor may be referred to as a BTOS (Battery operating system or Battery oxide semiconductor).
The control circuit portion 1320 senses a terminal voltage of the secondary battery and controls the charging and discharging state of the secondary battery. For example, to prevent overcharging, an output transistor of a charging circuit and an interruption switch can be turned off substantially at the same time.
The control circuit portion 1320 includes a switch portion 1324 that includes at least a switch for preventing overcharging and a switch for preventing overdischarging, a control circuit 1322 for controlling the switch portion 1324, and a portion for measuring the voltage of the first battery 1301a. The control circuit portion 1320 is set to have the upper limit voltage and the lower limit voltage of the secondary battery to be used, and imposes the upper limit of current from the outside, the upper limit of output current to the outside, or the like. The range from the lower limit voltage to the upper limit voltage of the secondary battery is a recommended voltage range, and when a voltage falls outside the range, the switch portion 1324 operates and functions as a protection circuit. The control circuit portion 1320 can also be referred to as a protection circuit because it controls the switch portion 1324 to prevent overdischarging or overcharging. For example, when the control circuit 1322 detects a voltage that is likely to cause overcharging, current is interrupted by turning off the switch in the switch portion 1324. Furthermore, a function of interrupting current in accordance with a temperature rise may be set by providing a PTC element in the charging and discharging path. The control circuit portion 1320 includes an external terminal 1325 (+IN) and an external terminal 1326 (−IN).
The switch portion 1324 can be formed by a combination of n-channel transistors and/or p-channel transistors. The switch portion 1324 is not limited to a switch including a Si transistor using single crystal silicon; the switch portion 1324 may be formed using a power transistor containing Ge (germanium), SiGe (silicon germanium), GaAs (gallium arsenide), GaAlAs (gallium aluminum arsenide), InP (indium phosphide), SiC (silicon carbide), ZnSe (zinc selenide), GaN (gallium nitride), GaOx (gallium oxide, where x is a real number greater than 0), or the like. A memory element using an OS transistor can be freely placed by being stacked over a circuit using a Si transistor, for example; hence, integration can be easy. Furthermore, an OS transistor can be fabricated with a manufacturing apparatus similar to that for a Si transistor and thus can be fabricated at low cost. That is, the control circuit portion 1320 using OS transistors can be stacked over the switch portion 1324 so that they can be integrated into one chip. Since the volume occupied by the control circuit portion 1320 can be reduced, a reduction in size is possible.
The first batteries 1301a and 1301b mainly supply electric power to in-vehicle parts for 42 V (for a high-voltage system), and the second battery 1311 supplies electric power to in-vehicle parts for 14 V (for a low-voltage system). A lead storage battery is usually used for the second battery 1311 due to cost advantage.
In this embodiment, an example in which a lithium-ion secondary battery is used as both the first battery 1301a and the second battery 1311 is described. As the second battery 1311, a lead storage battery, an all-solid-state battery, or an electric double layer capacitor may be used.
Regenerative energy generated by rolling of tires 1316 is transmitted to the motor 1304 through a gear 1305, and is stored in the second battery 1311 from a motor controller 1303 or a battery controller 1302 through a control circuit portion 1321. Alternatively, the regenerative energy is stored in the first battery 1301a from the battery controller 1302 through the control circuit portion 1320. Alternatively, the regenerative energy is stored in the first battery 1301b from the battery controller 1302 through the control circuit portion 1320. For efficient charging with regenerative energy, the first batteries 1301a and 1301b are desirably capable of fast charging.
The battery controller 1302 can set the charge voltage, charge current, and the like of the first batteries 1301a and 1301b. The battery controller 1302 can set charging conditions in accordance with charge characteristics of a secondary battery to be used, so that fast charging can be performed.
Although not illustrated, in the case of connection to an external charger, a plug of the charger or a connection cable of the charger is electrically connected to the battery controller 1302. Electric power supplied from the external charger is stored in the first batteries 1301a and 1301b through the battery controller 1302. Some chargers are provided with a control circuit, in which case the function of the battery controller 1302 is not used; to prevent overcharging, the first batteries 1301a and 1301b are preferably charged through the control circuit portion 1320. In addition, a connection cable or a connection cable of the charger is sometimes provided with a control circuit. The control circuit portion 1320 is also referred to as an ECU (Electronic Control Unit). The ECU is connected to a CAN (Controller Area Network) provided in the electric vehicle. The CAN is a type of a serial communication standard used as an in-vehicle LAN. The ECU includes a microcomputer. Moreover, the ECU uses a CPU or a GPU.
Next, examples in which the secondary battery of one embodiment of the present invention is mounted on a vehicle, typically a transport vehicle, will be described.
By mounting the secondary battery of one embodiment of the present invention on vehicles, next-generation clean energy vehicles such as hybrid vehicles (HVs), electric vehicles (EVs), and plug-in hybrid vehicles (PHVs) can be achieved. The secondary battery can also be mounted on transport vehicles such as agricultural machines such as electric tractors, motorized bicycles including motor-assisted bicycles, motorcycles, electric wheelchairs, electric carts, boats, ships, submarines, aircraft such as fixed-wing aircraft and rotary-wing aircraft, rockets, artificial satellites, space probes, planetary probes, and spacecraft. With the use of the method for manufacturing the secondary battery of one embodiment of the present invention, a large secondary battery can be provided. Thus, the secondary battery of one embodiment of the present invention can be suitably used in transport vehicles.
The automobile 2001 can be charged when the secondary battery included in the automobile 2001 is supplied with electric power from external charging equipment by a plug-in system, a contactless power feeding system, or the like. In charging, a given method such as CHAdeMO (registered trademark) or Combined Charging System can be employed as a charging method, the standard of a connector, or the like as appropriate. A charging device may be a charging station provided in a commerce facility or a power source in a house. For example, with the use of the plug-in technique, a secondary battery mounted on the automobile 2001 can be charged by being supplied with electric power from the outside. The charging can be performed by converting AC electric power into DC electric power through a converter such as an ACDC converter.
Although not illustrated, the vehicle may include a power receiving device so that it can be charged by being supplied with electric power from an above-ground power transmitting device in a contactless manner. In the case of the contactless power feeding system, by fitting a power transmitting device in a road or an exterior wall, charging can be performed not only when the vehicle is stopped but also when driven. In addition, the contactless power feeding system may be utilized to perform transmission and reception of electric power between two vehicles. Furthermore, a solar cell may be provided in the exterior of the vehicle to charge the secondary battery when the vehicle stops or moves. To supply electric power in such a contactless manner, an electromagnetic induction method or a magnetic resonance method can be used.
The secondary battery module of the aircraft 2004 has eight 4 V secondary batteries connected in series and has a maximum voltage of 32 V, for example. The battery pack 2203 has the same function as the battery pack in
The electric bicycle 2100 includes the power storage device 2102. The power storage device 2102 can supply electricity to a motor that assists a rider. The power storage device 2102 is portable, and
In the motor scooter 2300 illustrated in
Next, examples in which the secondary battery of one embodiment of the present invention is mounted on a building will be described with reference to
A house illustrated in
The electric power stored in the power storage device 2612 can also be supplied to other electronic devices in the house. Thus, with the use of the power storage device 2612 as an uninterruptible power source, electronic devices can be used even when electric power cannot be supplied from a commercial power source due to power failure or the like.
The power storage device 791 is provided with a control device 790, and the control device 790 is electrically connected to a distribution board 703, a power storage controller 705 (also referred to as a control device), an indicator 706, and a router 709 through wirings.
Electric power is transmitted from a commercial power source 701 to the distribution board 703 through a service wire mounting portion 710. Moreover, electric power is transmitted to the distribution board 703 from the power storage device 791 and the commercial power source 701, and the distribution board 703 supplies the transmitted electric power to a general load 707 and a power storage load 708 through outlets (not illustrated).
The general load 707 is, for example, an electric device such as a TV or a personal computer. The power storage load 708 is, for example, an electric device such as a microwave oven, a refrigerator, or an air conditioner.
The power storage controller 705 includes a measuring portion 711, a predicting portion 712, and a planning portion 713. The measuring portion 711 has a function of measuring the amount of electric power consumed by the general load 707 and the power storage load 708 during a day (e.g., from midnight to midnight). The measuring portion 711 may have a function of measuring the amount of electric power of the power storage device 791 and the amount of electric power supplied from the commercial power source 701. The predicting portion 712 has a function of predicting, on the basis of the amount of electric power consumed by the general load 707 and the power storage load 708 during a given day, the demand for electric power consumed by the general load 707 and the power storage load 708 during the next day. The planning portion 713 has a function of making a charging and discharging plan of the power storage device 791 on the basis of the demand for electric power predicted by the predicting portion 712.
The amount of electric power consumed by the general load 707 and the power storage load 708 and measured by the measuring portion 711 can be checked with the indicator 706. It can be checked with an electric device such as a TV or a personal computer through the router 709. Furthermore, it can be checked with a portable electronic terminal such as a smartphone or a tablet through the router 709. With the indicator 706, the electric device, or the portable electronic terminal, for example, the demand for electric power depending on a time period (or per hour) that is predicted by the predicting portion 712 can be checked.
The secondary battery of one embodiment of the present invention can be used for one or both of an electronic device and a lighting device, for example. Examples of the electronic device include portable information terminals such as mobile phones, smartphones, and laptop computers; portable game machines; portable music players; digital cameras; and digital video cameras.
A personal computer 2800 illustrated in
The large secondary battery obtained by the method for manufacturing the secondary battery of one embodiment of the present invention can be used as one or both of the secondary battery 2806 and the secondary battery 2807. The shape of the secondary battery obtained by the method for manufacturing the secondary battery of one embodiment of the present invention can be changed freely by changing the shape of the exterior body. When the shapes of the secondary batteries 2806 and 2807 fit with the shapes of the housings 2801 and 2802, for example, the secondary batteries can have high capacity and thus the operating time of the personal computer 2800 can be lengthened. Moreover, the weight of the personal computer 2800 can be reduced.
A flexible display is used for the display portion 2803 of the housing 2802. As the secondary battery 2806, the large secondary battery obtained by the method for manufacturing the secondary battery of one embodiment of the present invention is used. With the use of a flexible film as the exterior body in the large secondary battery obtained by the method for manufacturing the secondary battery of one embodiment of the present invention, a bendable secondary battery can be obtained. Thus, as illustrated in
Furthermore, the housing 2802 can be folded such that the display portion 2803 is placed inward as illustrated in
A bendable secondary battery to which the secondary battery of one embodiment of the present invention is applied can be mounted on an electronic device and incorporated along a curved inside/outside wall surface of a house or a building or a curved interior/exterior surface of an automobile.
The portable information terminal 7200 is capable of executing a variety of applications such as mobile phone calls, e-mailing, viewing and editing texts, music reproduction, Internet communication, and a computer game.
The display surface of the display portion 7202 is curved, and images can be displayed on the curved display surface. In addition, the display portion 7202 includes a touch sensor, and operation can be performed by touching the screen with a finger, a stylus, or the like. For example, by touching an icon 7207 displayed on the display portion 7202, application can be started.
With the operation button 7205, a variety of functions such as time setting, power on/off, on/off of wireless communication, setting and cancellation of a silent mode, and setting and cancellation of a power saving mode can be performed. For example, the functions of the operation button 7205 can be set freely by setting the operating system incorporated in the portable information terminal 7200.
The portable information terminal 7200 can perform near field communication that is standardized communication. For example, mutual communication between the portable information terminal 7200 and a headset capable of wireless communication enables hands-free calling.
The portable information terminal 7200 includes the input/output terminal 7206, and data can be directly transmitted to and received from another information terminal via a connector. In addition, charging via the input/output terminal 7206 is possible. Note that the charge operation may be performed by wireless power feeding without using the input/output terminal 7206.
The display portion 7202 of the portable information terminal 7200 includes the secondary battery of one embodiment of the present invention. When the secondary battery of one embodiment of the present invention is used, a lightweight portable information terminal with a long lifetime can be provided. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery may be electrically connected to the secondary battery. For example, the secondary battery 7104 illustrated in
The portable information terminal 7200 preferably includes a sensor. As the sensor, for example, a human body sensor such as a fingerprint sensor, a pulse sensor, or a temperature sensor, a touch sensor, a pressure sensitive sensor, or an acceleration sensor is preferably mounted.
The display surface of the display portion 7304 is curved, and images can be displayed on the curved display surface. A display state of the display device 7300 can be changed by, for example, near field communication that is standardized communication.
The display device 7300 includes an input/output terminal, and data can be directly transmitted to and received from another information terminal via a connector. In addition, charging via the input/output terminal is possible. Note that the charge operation may be performed by wireless power feeding without using the input/output terminal.
When the secondary battery of one embodiment of the present invention is used as the secondary battery included in the display device 7300, a lightweight display device with a long lifetime can be provided.
Examples of electronic devices each including the secondary battery of one embodiment of the present invention with excellent cycle performance are described with reference to
When the secondary battery of one embodiment of the present invention is used as a secondary battery of an electronic device, a lightweight product with a long lifetime can be provided. Examples of the daily electronic device include an electric toothbrush, an electric shaver, and electric beauty equipment. As secondary batteries of these products, small and lightweight stick type secondary batteries with high capacity are desired in consideration of handling ease for users.
Next,
The tablet terminal 7600 includes a power storage unit 7635 inside the housing 7630a and the housing 7630b. The power storage unit 7635 is provided across the housing 7630a and the housing 7630b, passing through the movable portion 7640.
The entire region or part of the region of the display portion 7631 can be a touch panel region, and data can be input by touching text, an input form, an image including an icon, and the like displayed on the region. For example, it is possible that keyboard buttons are displayed on the entire display portion 7631a on the housing 7630a side, and data such as text or an image is displayed on the display portion 7631b on the housing 7630b side.
It is possible that a keyboard is displayed on the display portion 7631b on the housing 7630b side, and data such as text or an image is displayed on the display portion 7631a on the housing 7630a side. Furthermore, it is possible that a switching button for showing/hiding a keyboard on a touch panel is displayed on the display portion 7631 and the button is touched with a finger, a stylus, or the like to display a keyboard on the display portion 7631.
Touch input can be performed concurrently in a touch panel region in the display portion 7631a on the housing 7630a side and a touch panel region in the display portion 7631b on the housing 7630b side.
The switch 7625 to the switch 7627 may function not only as an interface for operating the tablet terminal 7600 but also as an interface that can switch various functions. For example, at least one of the switch 7625 to the switch 7627 may function as a switch for switching power on/off of the tablet terminal 7600. For another example, at least one of the switch 7625 to the switch 7627 may have a function of switching the display orientation between a portrait mode and a landscape mode or a function of switching display between monochrome display and color display. For another example, at least one of the switch 7625 to the switch 7627 may have a function of adjusting the luminance of the display portion 7631. The luminance of the display portion 7631 can be optimized in accordance with the amount of external light in use of the tablet terminal 7600 detected by an optical sensor incorporated in the tablet terminal 7600. Note that another sensing device including a sensor for sensing inclination, such as a gyroscope sensor or an acceleration sensor, may be incorporated in the tablet terminal 7600, in addition to the optical sensor.
The tablet terminal 7600 is folded in half in
Note that as described above, the tablet terminal 7600 can be folded in half, and thus can be folded when not in use such that the housing 7630a and the housing 7630b overlap with each other. By the folding, the display portion 7631 can be protected, which increases the durability of the tablet terminal 7600. With the power storage unit 7635 including the secondary battery of one embodiment of the present invention, which has high capacity and excellent cycle performance, the tablet terminal 7600 that can be used for a long time over a long period can be provided. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery included in the power storage unit 7635 may be electrically connected to the secondary battery.
In addition, the tablet terminal 7600 illustrated in
The solar cell 7633, which is attached on the surface of the tablet terminal 7600, can supply electric power to a touch panel, a display portion, a video signal processing portion, and the like. Note that the solar cell 7633 can be provided on one surface or both surfaces of the housing 7630 and the power storage unit 7635 can be charged efficiently. The use of a lithium-ion battery as the power storage unit 7635 brings an advantage such as a reduction in size.
The structure and operation of the charging and discharging control circuit 7634 illustrated in
First, an operation example in which electric power is generated by the solar cell 7633 using external light is described. The voltage of electric power generated by the solar cell is raised or lowered by the DCDC converter 7636 to a voltage for charging the power storage unit 7635. When the display portion 7631 is operated with the electric power from the solar cell 7633, the switch SW1 is turned on and the voltage is raised or lowered by the converter 7637 to a voltage needed for the display portion 7631. When display on the display portion 7631 is not performed, the switch SW1 is turned off and the switch SW2 is turned on, so that the power storage unit 7635 is charged.
Note that the solar cell 7633 is described as an example of a power generation unit; however, one embodiment of the present invention is not limited to this example. The power storage unit 7635 may be charged using another power generation unit such as a piezoelectric element or a thermoelectric conversion element (Peltier element). For example, charging may be performed with a non-contact electric power transmission module that performs charging by transmitting and receiving electric power wirelessly (without contact), or with a combination of other charge units.
A semiconductor display device such as a liquid crystal display device, a light-emitting device in which a light-emitting element such as an organic EL element is provided in each pixel, an electrophoresis display device, a DMD (Digital Micromirror Device), a PDP (Plasma Display Panel), or an FED (Field Emission Display) can be used for the display portion 8002.
Note that the display device includes, in its category, all of information display devices for personal computers, advertisement displays, and the like besides information display devices for TV broadcast reception.
In
Note that although the installation lighting device 8100 provided in the ceiling 8104 is illustrated in
As the light source 8102, an artificial light source that emits light artificially by using electric power can be used. Specifically, an incandescent lamp, a discharge lamp such as a fluorescent lamp, and light-emitting elements such as an LED and/or an organic EL element are given as examples of the artificial light source.
In
Note that although the split-type air conditioner including the indoor unit and the outdoor unit is illustrated in
In
Note that among the electronic devices described above, a high-frequency heating apparatus such as a microwave oven and an electronic device such as an electric rice cooker require high electric power in a short time. Therefore, the tripping of a breaker of a commercial power source in use of the electronic device can be prevented by using the secondary battery of one embodiment of the present invention as an auxiliary power source for supplying electric power which cannot be supplied enough by a commercial power source.
In a time period when electronic devices are not used, particularly when the proportion of the amount of electric power which is actually used to the total amount of electric power which can be supplied from a commercial power supply source (such a proportion is referred to as a usage rate of electric power) is low, electric power is stored in the secondary battery, whereby an increase in the usage rate of electric power can be inhibited in a time period other than the above time period. For example, in the case of the electric refrigerator-freezer 8300, electric power is stored in the secondary battery 8304 in night time when the temperature is low and the refrigerator door 8302 and the freezer door 8303 are not opened or closed. Moreover, in daytime when the temperature is high and the refrigerator door 8302 and the freezer door 8303 are opened and closed, the usage rate of electric power in daytime can be kept low by using the secondary battery 8304 as an auxiliary power source.
According to one embodiment of the present invention, the secondary battery can have excellent cycle performance and improved reliability. Furthermore, according to one embodiment of the present invention, a secondary battery with high capacity can be obtained; thus, the secondary battery itself can be made more compact and lightweight as a result of improved characteristics of the secondary battery. Thus, the secondary battery of one embodiment of the present invention is used in the electronic device described in this embodiment, whereby a more lightweight electronic device with a longer lifetime can be obtained.
For example, the secondary battery of one embodiment of the present invention can be provided in a glasses-type device 9000 illustrated in
The secondary battery of one embodiment of the present invention can be provided in a headset-type device 9001. The headset-type device 9001 includes at least a microphone part 9001a, a flexible pipe 9001b, and an earphone portion 9001c. The secondary battery can be provided in the flexible pipe 9001b or the earphone portion 9001c. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery may be electrically connected to the secondary battery. With the use of the secondary battery of one embodiment of the present invention, space saving required with downsizing of a housing can be achieved.
The secondary battery of one embodiment of the present invention can be provided in a device 9002 that can be attached directly to a body. A secondary battery 9002b can be provided in a thin housing 9002a of the device 9002. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery 9002b may be electrically connected to the secondary battery 9002b. With the use of the secondary battery of one embodiment of the present invention, space saving required with downsizing of a housing can be achieved.
The secondary battery of one embodiment of the present invention can be provided in a device 9003 that can be attached to clothes. A secondary battery 9003b can be provided in a thin housing 9003a of the device 9003. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery 9003b may be electrically connected to the secondary battery 9003b. With the use of the secondary battery of one embodiment of the present invention, space saving required with downsizing of a housing can be achieved.
The secondary battery of one embodiment of the present invention can be provided in a belt-type device 9006. The belt-type device 9006 includes a belt portion 9006a and a wireless power feeding and receiving portion 9006b, and the secondary battery can be provided inside the belt portion 9006a. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery may be electrically connected to the secondary battery. With the use of the secondary battery of one embodiment of the present invention, space saving required with downsizing of a housing can be achieved.
The secondary battery of one embodiment of the present invention can be provided in a watch-type device 9005. The watch-type device 9005 includes a display portion 9005a and a belt portion 9005b, and the secondary battery can be provided in the display portion 9005a or the belt portion 9005b. To improve safety, a protection circuit that prevents overcharging and/or overdischarging of the secondary battery may be electrically connected to the secondary battery. With the use of the secondary battery of one embodiment of the present invention, space saving required with downsizing of a housing can be achieved.
The display portion 9005a can display various kinds of information such as time and reception information of an e-mail and/or an incoming call.
In addition, the watch-type device 9005 is a wearable device that is wound around an arm directly; thus, a sensor that measures the pulse, the blood pressure, or the like of the user may be incorporated therein. Data on the exercise quantity and health of the user can be stored to be used for health maintenance.
For example, the cleaning robot 9300 can determine whether there is an obstacle such as a wall, furniture, or a step by analyzing images taken by the cameras 9303. In the case where the cleaning robot 9300 detects an object, such as a wire, that is likely to be caught in the brush 9304 by image analysis, the rotation of the brush 9304 can be stopped. The cleaning robot 9300 includes the secondary battery 9306 of one embodiment of the present invention and a semiconductor device or an electronic component. The cleaning robot 9300 including the secondary battery 9306 of one embodiment of the present invention can be a highly reliable electronic device that can operate for a long time.
The microphone 9402 has a function of detecting a speaking voice of a user, an environmental sound, and the like. The speaker 9404 has a function of outputting sound. The robot 9400 can communicate with a user using the microphone 9402 and the speaker 9404.
The display portion 9405 has a function of displaying various kinds of information. The robot 9400 can display information desired by a user on the display portion 9405. The display portion 9405 may be provided with a touch panel. Moreover, the display portion 9405 may be a detachable information terminal, in which case charging and data communication can be performed when the display portion 9405 is set at the home position of the robot 9400.
The upper camera 9403 and the lower camera 9406 each have a function of taking an image of the surroundings of the robot 9400. The obstacle sensor 9407 can detect the presence of an obstacle in the direction where the robot 9400 advances with the moving mechanism 9408. The robot 9400 can move safely by recognizing the surroundings with the upper camera 9403, the lower camera 9406, and the obstacle sensor 9407.
The robot 9400 includes the secondary battery 9409 of one embodiment of the present invention and a semiconductor device or an electronic component. The robot 9400 including the secondary battery of one embodiment of the present invention can be a highly reliable electronic device that can operate for a long time.
For example, image data taken by the camera 9502 is stored in an electronic component 9504. The electronic component 9504 can analyze the image data to detect whether there is an obstacle in the way of the movement. Moreover, the electronic component 9504 can estimate the remaining battery level from a change in the power storage capacity of the secondary battery 9503. The flying object 9500 includes the secondary battery 9503 of one embodiment of the present invention. The flying object 9500 including the secondary battery of one embodiment of the present invention can be a highly reliable electronic device that can operate for a long time.
This embodiment can be implemented in appropriate combination with any of the other embodiments.
(Notes on Description of this Specification and the Like)
The description of the above embodiments and each structure in the embodiments are noted below.
One embodiment of the present invention can be constituted by combining, as appropriate, the structure described in each embodiment with the structures described in the other embodiments. In addition, in the case where a plurality of structure examples are described in one embodiment, the structure examples can be combined as appropriate.
Note that a content (or part thereof) described in one embodiment can be applied to, combined with, or replaced with another content (or part thereof) described in the embodiment and/or a content (or part thereof) described in another embodiment or other embodiments, for example.
Note that in each embodiment, a content described in the embodiment is a content described with reference to a variety of drawings or a content described with text disclosed in the specification.
Note that by combining a diagram (or part thereof) described in one embodiment with another part of the diagram, a different diagram (or part thereof) described in the embodiment, and/or a diagram (or part thereof) described in another embodiment or other embodiments, much more diagrams can be formed.
In addition, in this specification and the like, components are classified on the basis of the functions, and shown as blocks independent of one another in block diagrams. However, in an actual circuit or the like, it is difficult to separate components on the basis of the functions, and there is such a case where one circuit is associated with a plurality of functions or a case where a plurality of circuits are associated with one function. Therefore, blocks in the block diagrams are not limited by the components described in this specification, and the description can be changed appropriately depending on the situation.
In drawings, the size, the layer thickness, or the region is shown arbitrarily for description convenience. Therefore, they are not limited to the illustrated scale. Note that the drawings are schematically shown for clarity, and embodiments of the present invention are not limited to shapes, values, or the like shown in the drawings. For example, variation in signal, voltage, or current due to noise or variation in signal, voltage, or current due to difference in timing can be included.
In this specification and the like, expressions “one of a source and a drain” (or a first electrode or a first terminal) and “the other of the source and the drain” (or a second electrode or a second terminal) are used in the description of the connection relationship of a transistor. This is because a source and a drain of a transistor are interchangeable depending on the structure, operation conditions, or the like of the transistor. Note that the source or the drain of the transistor can also be referred to as a source (or drain) terminal, a source (or drain) electrode, or the like as appropriate depending on the situation.
In addition, in this specification and the like, the terms “electrode” and “wiring” do not functionally limit these components. For example, an “electrode” is used as part of a wiring in some cases, and vice versa. Furthermore, the term “electrode” or “wiring” also includes the case where a plurality of “electrodes”, a plurality of “wirings”, or a plurality of “electrodes” and a plurality of “wirings” are formed in an integrated manner, for example.
In this specification and the like, voltage and potential can be replaced with each other as appropriate. The voltage refers to a potential difference from a reference potential, and when the reference potential is a ground voltage, for example, the voltage can be rephrased into the potential. The ground potential does not necessarily mean 0 V. Note that potentials are relative, and the potential supplied to a wiring or the like is changed depending on the reference potential, in some cases.
Note that in this specification and the like, the terms “film”, “layer”, and the like can be interchanged with each other depending on the case or according to circumstances. For example, the term “conductive layer” can be changed into the term “conductive film” in some cases. As another example, the term “insulating film” can be changed into the term “insulating layer” in some cases.
In this specification and the like, a switch has a function of controlling whether current flows or not by being in a conduction state (an on state) or a non-conduction state (an off state). Alternatively, a switch has a function of selecting and changing a current path.
In this specification and the like, channel length refers to, for example, the distance between a source and a drain in a region where a semiconductor (or a portion where current flows in a semiconductor when a transistor is in an on state) and a gate overlap with each other or a region where a channel is formed in a top view of the transistor.
In this specification and the like, channel width refers to, for example, the length of a portion where a source and a drain face each other in a region where a semiconductor (or a portion where current flows in a semiconductor when a transistor is in an on state) and a gate electrode overlap with each other or a region where a channel is formed.
In this specification and the like, the expression “A and B are connected” includes the case where A and B are electrically connected as well as the case where A and B are directly connected. Here, the expression “A and B are electrically connected” means the case where electric signals can be transmitted and received between A and B when an object having any electric action exists between A and B.
In this example, secondary batteries of embodiments of the present invention were fabricated and evaluated.
A positive electrode active material was formed with reference to the formation method shown in
As LiMO2 in Step S14, with the use of cobalt as the transition metal M, commercially available lithium cobalt oxide (Cellseed C-10N manufactured by NIPPON CHEMICAL INDUSTRIAL CO., LTD.) not containing any additive was prepared. Lithium fluoride and magnesium fluoride were prepared as the X1 source as in Step S20a and the lithium fluoride and the magnesium fluoride were mixed by a solid phase method as in Step S31 and Step S32. Lithium fluoride and magnesium fluoride were added such that the number of molecules of lithium fluoride was 0.33 and the number of molecules of magnesium fluoride was 1 with the number of cobalt atoms assumed as 100. The mixture here is the mixture 903.
Next, annealing was performed in a manner similar to that of Step S33. In a square-shaped alumina container, 30 g of the mixture 903 was placed, a lid was put on the container, and heating was performed in a muffle furnace. The atmosphere in the furnace was purged and an oxygen gas was introduced; the oxygen flow was stopped during the heating. The annealing temperature was 900° C., and the annealing time was 20 hours.
To the composite oxide that had been heated, nickel hydroxide and aluminum hydroxide were added and mixed by a dry method in Step S101. The addition was performed such that the number of nickel atoms was 0.5 and the number of aluminum atoms was 0.5 with the number of cobalt atoms assumed as 100. The mixture here is the mixture 904.
Next, annealing was performed in a manner similar to that of Step S33. In a square-shaped alumina container, 30 g of the mixture 903 was placed, a lid was put on the container, and heating was performed in a muffle furnace. The atmosphere in the furnace was purged and an oxygen gas was introduced; the flow was performed during the heating. The annealing temperature was 850° C., and the annealing time was 10 hours.
After that, the mixture was made to pass through a sieve with 53 μmφ and powder was collected, so that a positive electrode active material was obtained.
Next, positive electrodes were formed using the positive electrode active material formed in the above manner. The positive electrode active material formed in the above manner, acetylene black (AB), and polyvinylidene fluoride (PVDF) were mixed at the positive electrode active material: AB:PVDF=95:3:2 (weight ratio) using NMP as a solvent, whereby slurry was formed. After a current collector was coated with the formed slurry, the solvent was volatilized. After that, at 120° C., a pressure of 120 kN/m was applied and a positive electrode active material layer was formed on the current collector; thus, each positive electrode was formed. Aluminum foil having a thickness of 20 μm was used as the current collector. The positive electrode active material layer was provided on one surface of the current collector. The carried amount was approximately 10 mg/cm2.
Next, CR2032 type coin-type secondary batteries (a diameter of 20 mm, a height of 3.2 mm) were fabricated for evaluation.
The positive electrode formed above, and lithium metal for a counter electrode were used. As a separator, either 23-μm-thick polyimide or 25-μm-thick polypropylene was used. Four kinds of electrolyte (hereinafter, an electrolyte A, an electrolyte B, an electrolyte C, and an electrolyte D) were prepared. For each of a secondary battery using the electrolyte A and a secondary battery using the electrolyte B, 25-μm-thick polypropylene was used as a separator. For each of a secondary battery using the electrolyte C and a secondary battery using the electrolyte D, 23-μm-thick polyimide was used as a separator.
A positive electrode can of the coin-type secondary battery formed of stainless steel was used for each of the secondary battery using the electrolyte A and the secondary battery using the electrolyte B. A positive electrode can of the coin-type secondary battery formed of stainless steel coated with aluminum was used for each of the secondary battery using the electrolyte C and the secondary battery using the electrolyte D. A negative electrode can was formed of stainless steel.
The electrolyte A was prepared. As a solvent of the electrolyte A, a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) at EC:DEC=3:7 (volume ratio) was used. As a lithium salt, lithium hexafluorophosphate (LiPF6) was used. The concentration of the lithium salt in the electrolyte was 1.00 mol/L. The moisture concentration in the electrolyte A was 4.4 ppm.
The electrolyte B, which was a comparative example of the electrolyte A, was adjusted so that the moisture concentration was approximately 1000 ppm. As a solvent of the electrolyte B, a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) at EC:DEC=3:7 (volume ratio) was used. As a lithium salt, lithium hexafluorophosphate (LiPF6) was used. The concentration of the lithium salt in the electrolyte solution was 1.00 mol/L. Then, moisture was added. Moisture was added in the amount corresponding to 1000 ppm with respect to the sum of the total amount of the electrolyte before moisture had been added and the amount of added moisture.
The electrolyte C was prepared. As a solvent of the electrolyte C, EMI-FSA represented by Structural Formula (G11) was used. As a lithium salt, LiFSA (lithium bis(fluorosulfonyl)amide) was used, and the concentration of the lithium salt in the electrolyte was 2.15 mol/L. The moisture concentration in the electrolyte C was 25.6 ppm.
The electrolyte D, which was a comparative example of the electrolyte C, was adjusted so that the moisture concentration was approximately 1000 ppm. As a solvent of the electrolyte D, EMI-FSA represented by Structural Formula (G11) was used. As a lithium salt, LiFSA (lithium bis(fluorosulfonyl)amide) was used, and the concentration of the lithium salt in the electrolyte was 2.15 mol/L. Moisture was added. Moisture was added in the amount corresponding to 1000 ppm with respect to the sum of the total amount of the electrolyte before moisture had been added and the amount of added moisture.
A Karl Fischer moisture titrator MKC-610 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) was used in measurement of the amounts of moisture in the electrolytes.
Through the above steps, the coin-type secondary batteries were fabricated.
The charge and discharge characteristics of the fabricated coin-type secondary batteries were evaluated. In an environment at 45° C., CCCV charging (0.5 C, a termination current of 0.05 C, a termination voltage of 4.6 V) was performed and CC discharging (0.5 C, a cut-off voltage of 2.5 V) was performed.
As shown in
In the case of a large amount of moisture, a reaction hindering charging and discharging is probably caused due to a reaction between the electrolyte and moisture.
Next, the cycle performances of the fabricated coin-type secondary batteries were evaluated.
Cycle tests were performed in an environment at 45° C. CCCV charging (0.5 C, a termination current of 0.05 C, 4.6 V) was performed, and CC discharging (0.5 C, 2.5 V) was performed. The capacity of the secondary battery was calculated using the weight of the positive electrode active material as a reference. The C rate was calculated on the assumption that 1 C was 200 mA/g (per weight of the positive electrode active material).
In the case of a large amount of moisture, it is assumed that a reaction hindering charging and discharging is caused to worsen characteristics. In addition, the result of the ionic liquid even in the case of a large amount of moisture was better than the result of the electrolyte A.
In this example, evaluation using NMR was performed. A nuclear magnetic resonance apparatus (AVANCEIII400 manufactured by Bruker Japan K.K., 400 MHz), and acetonitrile-d3 (CD3CN) as a solvent were used in measurement.
The electrolyte A and the electrolyte B described in Example 1 were subjected to NMR analysis.
A peak was observed at around −20 ppm in the case of a large amount of moisture. This peak probably corresponds to PO2F2−, and indicates a product due to a reaction between H2O and LiPF6. It is considered that the reaction between H2O and LiPF6 was inhibited by a reduction in the amount of moisture.
51: positive electrode active material particle, 52: depression, 53: barrier film, 54: hole, 55: crystal plane, 56: barrier film, 57: crack, 58: hole, 100: positive electrode active material, 130: stack, 131: stack, 300: secondary battery, 301: positive electrode can, 302: negative electrode can, 303: gasket, 304: positive electrode, 305: positive electrode current collector, 306: positive electrode active material layer, 307: negative electrode, 308: negative electrode current collector, 309: negative electrode active material layer, 310: separator, 312: washer, 313: ring-shaped insulator, 322: spacer, 400: negative electrode active material, 401: region, 401a: region, 401b: region, 402: region, 500: secondary battery, 501: positive electrode current collector, 502: positive electrode active material layer, 502a: region, 503: positive electrode, 504: negative electrode current collector, 505: negative electrode active material layer, 505a: region, 506: negative electrode, 507: separator, 507a: region, 507b: region, 508: electrolyte, 509: exterior body, 509a: exterior body, 509b: exterior body, 510: positive electrode lead electrode, 511: negative electrode lead electrode, 512: stack, 513: resin layer, 514: region, 515a: electrolyte, 515b: electrolyte, 515c: electrolyte, 516: inlet, 550: stack, 553: acetylene black, 554: graphene, 556: acetylene black, 557: graphene, 560: secondary battery, 561: positive electrode active material, 563: negative electrode active material, 570: manufacturing apparatus, 571: component introduction chamber, 572: transfer chamber, 573: treatment chamber, 580: transfer mechanism, 581: polymer film, 582: hole, 584: polymer film, 585: hole, 591: stage, 594: nozzle, 600: secondary battery, 601: positive electrode cap, 602: electrode can, 603: positive electrode terminal, 604: positive electrode, 605: separator, 606: negative electrode, 607: negative electrode terminal, 608: insulating plate, 609: insulating plate, 610: gasket (insulating gasket), 611: PTC element, 613: safety valve mechanism, 614: conductive plate, 615: power storage system, 616: secondary battery, 620: control circuit, 621: wiring, 622: wiring, 623: wiring, 624: conductor, 625: insulator, 626: wiring, 627: wiring, 628: conductive plate, 701: commercial power source, 703: distribution board, 705: power storage controller, 706: indicator, 707: general load, 708: power storage load, 709: router, 710: service wire mounting portion, 711: measuring portion, 712: predicting portion, 713: planning portion, 790: control device, 791: power storage device, 796: underfloor space, 799: building, 903: mixture, 904: mixture, 911a: terminal, 911b: terminal, 913: secondary battery, 930: housing, 930a: housing, 930b: housing, 931: negative electrode, 931a: negative electrode active material layer, 932: positive electrode, 932a: positive electrode active material layer, 933: separator, 950: wound body, 950a: wound body, 951: terminal, 952: terminal, 970: secondary battery, 971: housing, 972: stack, 973a: positive electrode lead electrode, 973b: terminal, 973c: conductor, 974a: negative electrode lead electrode, 974b: terminal, 974c: conductor, 975a: positive electrode, 975b: positive electrode, 976: separator, 977a: negative electrode, 1301a: battery, 1301b: battery, 1302: battery controller, 1303: motor controller, 1304: motor, 1305: gear, 1306: DCDC circuit, 1307: electric power steering, 1308: heater, 1309: defogger, 1310: DCDC circuit, 1311: battery, 1312: inverter, 1313: audio, 1314: power window, 1315: lamps, 1316: tire, 1317: rear motor, 1320: control circuit portion, 1321: control circuit portion, 1322: control circuit, 1324: switch portion, 1325: external terminal, 1326: external terminal, 1415: battery pack, 1421: wiring, 1422: wiring, 2001: automobile, 2002: transporter, 2003: transport vehicle, 2004: aircraft, 2005: transport vehicle, 2100: electric bicycle, 2101: secondary battery, 2102: power storage device, 2103: display portion, 2104: control circuit, 2201: battery pack, 2202: battery pack, 2203: battery pack, 2204: battery pack, 2300: motor scooter, 2301: side mirror, 2302: power storage device, 2303: indicator light, 2304: under-seat storage unit, 2603: vehicle, 2604: charging device, 2610: solar panel, 2611: wiring, 2612: power storage device, 2800: personal computer, 2801: housing, 2802: housing, 2803: display portion, 2804: keyboard, 2805: pointing device, 2806: secondary battery, 2807: secondary battery, 7100: portable display device, 7101: housing, 7102: display portion, 7103: operation button, 7104: secondary battery, 7200: portable information terminal, 7201: housing, 7202: display portion, 7203: band, 7204: buckle, 7205: operation button, 7206: input/output terminal, 7207: icon, 7300: display device, 7304: display portion, 7400: mobile phone, 7401: housing, 7402: display portion, 7403: operation button, 7404: external connection port, 7405: speaker, 7406: microphone, 7407: secondary battery, 7500: electronic cigarette, 7501: atomizer, 7502: cartridge, 7504: secondary battery, 7600: tablet terminal, 7625: switch, 7627: switch, 7628: operation switch, 7629: fastener, 7630: housing, 7630a: housing, 7630b: housing, 7631: display portion, 7631a: display portion, 7631b: display portion, 7633: solar cell, 7634: charging and discharging control circuit, 7635: power storage unit, 7636: DCDC converter, 7637: converter, 7640: movable portion, 8000: display device, 8001: housing, 8002: display portion, 8003: speaker portion, 8004: secondary battery, 8100: lighting device, 8101: housing, 8102: light source, 8103: secondary battery, 8104: ceiling, 8105: side wall, 8106: floor, 8107: window, 8200: indoor unit, 8201: housing, 8202: air outlet, 8203: secondary battery, 8204: outdoor unit, 8300: electric refrigerator-freezer, 8301: housing, 8302: refrigerator door, 8303: freezer door, 8304: secondary battery, 9000: glasses-type device, 9000a: frame, 9000b: display part, 9001: headset-type device, 9001a: microphone part, 9001b: flexible pipe, 9001c: earphone portion, 9002: device, 9002a: housing, 9002b: secondary battery, 9003: device, 9003a: housing, 9003b: secondary battery, 9005: watch-type device, 9005a: display portion, 9005b: belt portion, 9006: belt-type device, 9006a: belt portion, 9006b: wireless power feeding and receiving portion, 9300: cleaning robot, 9301: housing, 9302: display portion, 9303: camera, 9304: brush, 9305: operation button, 9306: secondary battery, 9310: dust, 9400: robot, 9401: illuminance sensor, 9402: microphone, 9403: upper camera, 9404: speaker, 9405: display portion, 9406: lower camera, 9407: obstacle sensor, 9408: moving mechanism, 9409: secondary battery, 9500: flying object, 9501: propeller, 9502: camera, 9503: secondary battery, 9504: electronic component.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-208516 | Dec 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2021/061207 | 12/2/2021 | WO |
