CN110832685A - Dual-ion battery - Google Patents
Dual-ion battery Download PDFInfo
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- CN110832685A CN110832685A CN201880034328.1A CN201880034328A CN110832685A CN 110832685 A CN110832685 A CN 110832685A CN 201880034328 A CN201880034328 A CN 201880034328A CN 110832685 A CN110832685 A CN 110832685A
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- negative electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The purpose of the present invention is to provide a bi-ion battery having excellent high-temperature durability. The double-ion battery provided by the invention is provided with a positive electrode and a negative electrode, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active substance arranged on the positive electrode current collector; the negative electrode includes a negative electrode current collector and a negative electrode active material disposed thereon. The positive electrode active material contains graphite. The negative electrode active material contains a metal oxide capable of occluding and releasing cations. The positive electrode collector and the negative electrode collector are made of an aluminum material covered with an amorphous carbon coating.
Description
Technical Field
The invention relates to a dual-ion battery.
Background
Currently, Electric double-layer capacitors (EDLCs) and secondary batteries are known as technologies for storing Electric energy. Examples of the secondary battery include a lithium-ion battery (LIB). The life, safety, and output density of the electric double layer capacitor are far superior to those of the secondary battery. However, the electric double layer capacitor has a technical problem that the energy density (volumetric energy density) is low as compared with the secondary battery.
On the other hand, lithium ion batteries have technical problems such as charging speed, output density, and life, although they have excellent energy density. For example, a lithium ion battery used in an automobile has high energy density, but has high resistance and short life, and is difficult to charge and discharge at a large current. Therefore, for example, the LIB for a hybrid vehicle has a prolonged service life by providing a restriction on the state of charge (SOC). When SOC 50% is reached, half of the battery performance is no longer used and the space and weight of the unused portion of the battery is wasted.
Heretofore, in conventional electric double layer capacitors, activated carbon has been mainly used as active materials for a positive electrode and a negative electrode. In order to improve the energy density of an electric double layer capacitor, as a capacitor of a new concept, a capacitor utilizing the following reaction has been developed (for example, see patent document 1): graphite is used as a positive electrode active material instead of activated carbon, and intercalation-deintercalation (intercalation-deintercalation) of electrolyte ions are carried out between the graphite layers. After the technology is used, the energy density can be improved by about 2 to 3 times compared with the conventional double-electric-layer capacitor. The cycle characteristics, low temperature characteristics, and output characteristics are also the same as or better than those of conventional electric double layer capacitors.
Further, an electric storage device has been proposed (for example, see patent documents 1 and 2), which utilizes the following reaction also in the negative electrode: a metal oxide is used as a negative electrode active material instead of activated carbon, and lithium ions are inserted and extracted between layers of lithium titanate. During charging, anions and cations (lithium ions) of an electrolyte contained in the electrolytic solution move to the positive electrode or the negative electrode, respectively, and therefore, this electric storage device is referred to as a "Dual Ion Battery". In other words, the electric storage device refers to a battery that utilizes the following reaction: the anions and the cations move in opposite directions, and the anions are inserted into and extracted from the layers of the positive electrode active material, and the cations are simultaneously inserted into and extracted from the layers of the negative electrode active material.
In the lithium ion battery, lithium ions in the positive electrode are deintercalated and intercalated between graphite layers as the negative electrode during charging. At this time, a coating film such as SEI (solid electrolyte interface) is formed at the entrance between graphite layers, and lithium ions are intercalated into the SEI coating film. Since lithium ions move through a solid such as SEI, the moving resistance at this time becomes the electrode resistance. In addition, the electrolyte ions undergo solvation with the solvent, and the solvation is released and moves to the graphite interlayer through the SEI film. Therefore, the resistance at the time of solvent desorption also increases the electrode resistance. Therefore, comparing the lithium ion battery with the bi-ion battery, the output characteristics of the bi-ion battery are higher than those of the lithium ion battery in which only lithium ions move. In addition, in the lithium ion battery, solvent desorption occurs via an SEI film. However, in the bi-ion battery, anions or cations of the electrolyte are directly inserted and released between layers of the positive electrode or negative electrode material, and therefore do not undergo a reaction as in the lithium ion battery. As a result, the service life of the bi-ion battery is superior to that of the lithium ion battery, and there is no need to place restrictions on the SOC. Therefore, the bi-ion battery is expected as a battery that does not generate an unused portion like LIB.
In addition, as a lithium ion battery, a lithium-containing oxide is used as a positive electrode active material, and lithium ions deintercalated from the positive electrode active material during charging are intercalated between graphite layers as a negative electrode active material. The bi-ion battery uses graphite as a negative electrode active material of a lithium ion battery as a positive electrode active material. In a lithium ion battery, since a lithium-containing oxide is used as a positive electrode active material, oxygen is easily released from the lithium-containing oxide to cause thermal runaway when a short circuit occurs in the battery. However, the bi-ion battery uses a graphite positive electrode, and the graphite does not contain oxygen, and therefore thermal runaway does not occur in principle, which is an advantage of the bi-ion battery.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-040180
Patent document 2: japanese patent No. 4465492
Patent document 3: japanese patent laid-open publication No. 2017-50131
Disclosure of Invention
Problems to be solved by the invention
However, the present inventors have found that when graphite having a high charge/discharge capacity is used as a positive electrode active material and a metal oxide capable of storing and releasing cations is used as a negative electrode active material in a bipolar battery, a current collector, particularly a negative electrode current collector, is corroded during charging at high temperatures, and thus the durability at high temperatures is insufficient. Further, the present inventors have found that when graphite having a high charge/discharge capacity is used as a positive electrode active material in a bipolar battery and a material having a higher charge/discharge capacity per unit weight of a negative electrode active material than that of the positive electrode active material is used, a current collector, particularly a negative electrode current collector, is corroded during charging at high temperature, and thus the durability at high temperature is insufficient.
Here, the durability test is generally performed by an accelerated test (high temperature durability test, cycle life test) while raising the temperature. This test can be performed by a method in accordance with "durability (continuous application of high-temperature rated voltage) test" described in JIS D1401: 2009. It is generally considered that if the temperature is increased by 10 ℃ from room temperature, the deterioration rate becomes about 2 times. As the high temperature durability test, for example, the following test is available: after the cells were kept (continuously charged) at a predetermined voltage (3V or more in the present invention) for 2000 hours in a thermostatic bath at 60 ℃, the cells were returned to room temperature to perform charge and discharge, and the discharge capacity at that time was measured. It is generally preferable that the discharge capacity retention rate after the high-temperature durability test satisfies 80% or more of the initial discharge capacity.
On the other hand, patent document 3 discloses a bi-ion battery including Graphite (Graphite) as a positive electrode active material, lithium titanate as a negative electrode active material, and aluminum materials as a positive electrode current collector and a negative electrode current collector. However, patent document 3 does not describe or suggest any technique for suppressing corrosion of the negative electrode current collector and improving the high-temperature durability.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a bi-ion battery having excellent high-temperature durability.
Means for solving the problems
In order to solve the above problems, the following means are provided.
[1] A bi-ion battery having a positive electrode and a negative electrode,
the positive electrode comprises a positive electrode current collector and a positive electrode active material arranged on the positive electrode current collector;
the negative electrode includes a negative electrode current collector and a negative electrode active material disposed thereon,
the positive electrode active material contains graphite,
the negative electrode active material contains a metal oxide capable of occluding and releasing cations,
the positive electrode current collector and the negative electrode current collector are formed of an aluminum material covered with an amorphous carbon coating.
[2] The bipolar battery according to [1], wherein the positive electrode current collector or/and the negative electrode current collector has a conductive carbon layer formed on an amorphous carbon coating.
[3] The diionic battery as recited in any one of [1] or [2], wherein said cation is an alkaline earth metal.
[4] The diionic battery according to any one of [1] to [3], wherein said cation is lithium.
[5] The bipolar battery according to any one of [1] to [4], wherein the metal in the metal oxide is at least one selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), and molybdenum (Mo).
[6] The diionic battery according to any one of [1] to [5], wherein the capacity per unit weight of said negative electrode active material is higher than the capacity per unit weight of said positive electrode active material.
Effects of the invention
According to the present invention, a bi-ion battery having excellent high-temperature durability can be provided.
Detailed Description
The materials, dimensions, and the like described in the following description are merely examples, and the present invention is not limited thereto, and can be implemented by appropriately changing the materials, dimensions, and the like within a range not changing the gist thereof.
[ Dual ion Battery ]
A bi-ion battery (DIB) in one embodiment of the invention has a positive electrode and a negative electrode, the positive electrode including a positive electrode current collector and a positive electrode active material disposed thereon; the negative electrode includes a negative electrode current collector and a negative electrode active material disposed thereon. The positive electrode active material contains graphite, and the negative electrode active material contains a metal oxide capable of occluding and releasing cations. The positive electrode collector and the negative electrode collector are made of an aluminum material covered with an amorphous carbon coating.
In a bi-ion battery, anions of an electrolyte contained in an electrolyte solution are intercalated between layers of a positive electrode active material and cations are intercalated between layers of a negative electrode active material during charging. At this time, anions and cations of the electrolyte are directly inserted into and extracted from the interlayer of the positive electrode active material or the negative electrode active material without going through the SEI film or the like, and thus resistance to insertion and extraction of ions is reduced. Therefore, the higher input-output characteristics are characteristic of the bi-ion battery as compared with the lithium ion battery. In addition, various kinds of anions and cations of the electrolyte that are intercalated and deintercalated into and from the positive electrode active material or the negative electrode active material used in the bipolar battery can be used, which is also a characteristic feature of the bipolar battery. For example, in positive electrode active materials of BF4Ions and PF6The ions and the like are typical substances, and alkali metal ions such as Li, Na, and K, and alkaline earth metal ions such as Mg and Ca can be used as the negative electrode active material. In the case of using Li, many materials capable of reversibly intercalating and deintercalating lithium ions into and from a positive electrode active material are available, and many materials have already been put into practical use, and therefore, a lithium ion battery is completed by moving only lithium ions on a positive electrode and a negative electrode in a so-called shuttlecock reaction type. However, many positive electrode materials that can reversibly intercalate and deintercalate other than Li are limited or have low reversibility. Therefore, it is difficult to complete an ion battery using these metal ions by a shuttlecock reaction type such as a lithium ion battery. Further, there are materials capable of being intercalated into and deintercalated from carbon materials such as graphite as cations such as Na, K, Mg, Ca, and the like. Therefore, as the bi-ion battery according to the present invention, it is possible to use an electrolyte capable of inserting and extracting anions into and from the positive electrode, and selectActive materials capable of inserting and extracting cations such as Na, K, Mg, and Ca into and from the negative electrode are completed as an electricity storage device.
In the present invention, a carbon material such as graphite is used as the positive electrode active material, and a metal oxide capable of occluding and releasing cations is used as the negative electrode active material. For example, the use of graphite as the positive electrode active material and lithium titanate as the negative electrode active material increases the charge/discharge capacity. In other words, the lithium titanate has a practical capacity of 160-170 mAh/g. Since the actual capacity of the activated carbon negative electrode is 30 to 50mAh/g, the capacity of the graphite provided to the negative electrode can be only about the same, but the capacity can be increased by using lithium titanate. By further utilizing the capacity of graphite as the positive electrode active material, the energy density of the battery can be improved. In addition, in the reaction of inserting and extracting the negative electrode active material or the negative electrode active material with the negative electrode and the positive electrode, the SEI film and the solvent-separated isoresistance component of the graphite negative electrode of the lithium ion battery are not present, the moving resistance of the negative electrode and the positive electrode is reduced, and the charge/discharge performance (high input/output performance) at a large current is higher than that of the lithium ion battery.
However, a problem of deterioration of cycle life characteristics has now arisen. The reason for this problem is that, when a metal oxide such as lithium titanate is used for the negative electrode, the potential curve of the metal oxide such as lithium titanate becomes flat as compared with the case where the electrode potential decreases and changes linearly in an oblique direction when activated carbon is used for the negative electrode. Therefore, the potential curve of the metal oxide such as lithium titanate in the negative electrode is exposed to a low potential for a longer time than that of the active carbon. Thereby, the negative electrode current collector of the bi-ion battery becomes more easily dissolved than the negative electrode current collector of the conventional capacitor. As a result, the high-temperature durability and the charge/discharge cycle life characteristics are reduced. In view of the above problem, we have found that the dissolution of the current collector can be suppressed by using the current collector having improved corrosion resistance of the present invention as a negative electrode current collector. That is, the energy density of the battery can be improved by using a negative electrode active material having a higher charge/discharge capacity than the active carbon, but the effect of dissolution of the negative electrode current collector is more significant. The problem can be solved by applying the current collector having improved corrosion resistance of the present invention.
< negative electrode >
The negative electrode used in the bipolar battery of one embodiment of the present invention includes a current collector (negative electrode current collector) and a negative electrode active material layer formed thereon. The negative electrode active material layer contains a negative electrode active material, a binder, and a conductive material.
Negative electrode active material layer "
The negative electrode active material layer contains a negative electrode active material, a binder, and a conductive material.
A slurry-like negative electrode material mainly containing a negative electrode active material, a binder, and a required amount of a conductive material is applied onto a negative electrode current collector and dried, whereby a negative electrode active material layer can be formed.
[ Binders ]
The negative electrode used in the bipolar battery of the present embodiment preferably further contains a binder.
As the binder, for example, it is possible to use: one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), fluororubber, ethylene propylene diene rubber, styrene butadiene, acrylic, olefin, carboxymethyl cellulose (CMC), gelatin, chitosan, and alginic acid.
[ conductive Material ]
The conductive material is not particularly limited as long as it can improve the conductivity of the negative electrode active material layer, and a known conductive material can be used. For example, carbon black, carbon fiber (including Carbon Nanotube (CNT), VGCF (registered trademark), and the like, but not limited to carbon nanotube), and the like can be used.
[ negative electrode active Material ]
The negative electrode active material is a material containing a metal oxide capable of occluding cations, which are electrolyte ions contained in an electrolyte solution described later. That is, any material can be used as long as it can reversibly intercalate and deintercalate cations. As the cation, for example, it is possible to use: alkali metal ions such as Li, Na and K, and alkaline earth metal ions such as Mg and Ca.
Here, an example using lithium will be illustrated. For example, a metal oxide which can intercalate and deintercalate lithium can be used. More specifically, a metal oxide containing lithium or a metal oxide containing no lithium can be used. As the metal of the metal oxide capable of inserting and extracting lithium, groups IVB, VB, VIB of periods 4, 5, 6 of the periodic table can be used. Specifically, transition metals such as titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), and molybdenum (Mo) are preferably used. As the metal oxide containing lithium, for example, Li as lithium-containing titanium oxide can be used4Ti5O12And LiNbO as lithium-containing niobium oxide2Li as lithium-vanadium-containing oxide1.1V0.9O2And the like. In addition, as the metal oxide containing no lithium, for example, TiO can be used2、NbO2、V2O5And the like.
From the viewpoint of further improving the effect of the present invention, it is preferable that the capacity per unit weight of the negative electrode active material is higher than the capacity per unit weight of the positive electrode active material (graphite). The theoretical capacity of graphite for the positive electrode was 372 mAh/g. However, the graphite positive electrode of the present invention is preferably such that anions larger than lithium ions are intercalated and deintercalated, and the capacity of the graphite positive electrode of the present invention is 50mAh/g to 100mAh/g from the viewpoint of cycle life and the degree of swelling of the graphite positive electrode. On the other hand, as the theoretical capacity of the active material for the negative electrode, Li4Ti5O12175mAh/g, LiNbO2203mAh/g, Li1.1V0.9O2313mAh/g, TiO2Is 335mAh/g, NbO2Is 214mAh/g, V2O5Is 147 mAh/g. Unlike the graphite positive electrode, the negative electrode using these negative electrode active materials can be charged and discharged to about the theoretical capacity. Therefore, the actual capacity of the negative electrode active material is larger than the actual capacity (50mAh/g to 100mAh/g) of the graphite positive electrode. That is, the positive electrode active material of the present invention is graphite having a capacity of 50mAh/g to 100mAh/g, and the negative electrode active material of the present invention is preferably higher than the capacity of the graphite positive electrode. The positive electrode active material of the present invention is graphite having a capacity of 50mAh/g to 100mAh/g, and the negative electrode active material of the present invention is more preferably graphiteIs selected from the group consisting of Li4Ti5O12、LiNbO2、Li1.1V0.9O2、TiO2、NbO2And V2O5At least one of the group consisting of. The positive electrode active material of the present invention is graphite having a capacity of 50mAh/g to 100mAh/g, and the negative electrode active material of the present invention is more preferably Li4Ti5O12。
The capacity of the negative electrode active material is larger than the actual capacity (30mAh/g to 50mAh/g) of the activated carbon negative electrode. In a conventional hybrid capacitor using an activated carbon negative electrode, the capacity of the negative electrode is limited, and therefore, it is difficult to increase the energy density. However, since the capacity of the negative electrode active material of the present invention is larger than that of activated carbon, the capacity of the graphite positive electrode can be increased by using the negative electrode active material of the present invention. As a result, the present invention provides a bi-ion battery with high energy density.
Negative current collector "
The negative electrode current collector is an aluminum material covered with an amorphous carbon coating film.
As the aluminum material used as the base material, an aluminum material generally used as a current collector can be used.
The shape of the aluminum material can be in the form of foil, sheet, film, mesh, or the like. As the current collector, an aluminum foil can be preferably used.
As the aluminum material, etched aluminum described later may be used in addition to the flat material.
The thickness of the aluminum material is not particularly limited when it is a foil, sheet or film, but when the size of the battery itself is the same, the strength is reduced, although there is an advantage that the thinner the aluminum material is, the more the active material to be incorporated into the battery case can be enclosed; therefore, an appropriate thickness is selected. The actual thickness is preferably 10 to 40 μm, more preferably 15 to 30 μm. When the thickness is less than 10 μm, fracture or crack of the aluminum material may occur in a surface roughening process or other manufacturing processes of the aluminum material.
As the aluminum material covered with the amorphous carbon film, etched aluminum may be used.
The etching aluminum is aluminum subjected to roughening treatment by etching. For the etching, a method of immersing in an acid solution such as hydrochloric acid (chemical etching) or electrolyzing aluminum as an anode in an acid solution such as hydrochloric acid (electrochemical etching) is generally used. In the electrochemical etching, the etching shape differs depending on the current waveform at the time of electrolysis, the composition of the solution, the temperature, and the like, and therefore, can be selected from the viewpoint of the performance of the bipolar battery.
As the aluminum material, a material having a passivation layer on the surface may be used, or a material not having a passivation layer may be used. When a passivation film as a natural oxide film is formed on the surface of the aluminum material, an amorphous carbon coating layer may be provided on the natural oxide film, or an amorphous carbon coating layer may be provided after the natural oxide film is removed by, for example, argon sputtering.
The natural oxide film on the aluminum material is a passive film which has an advantage of being not easily corroded by the electrolyte by itself, and on the other hand, it causes an increase in the resistance of the current collector, and therefore it is more preferable not to have a natural oxide film from the viewpoint of reducing the resistance of the current collector.
In the present specification, the amorphous carbon coating film is an amorphous carbon film or a hydrogenated carbon film, and includes a diamond-like carbon (DLC) film, a carbon hard film, an amorphous carbon (a-C) film, a hydrogenated amorphous carbon (a-C: H) film, and the like. As a method for forming the amorphous carbon film, a known method such as a plasma CVD method, a sputtering deposition method, an ion plating method, or a vacuum arc deposition method using a hydrocarbon gas can be used. Note that the amorphous carbon coating film preferably has conductivity capable of ensuring its function as a current collector.
Among the materials of the amorphous carbon coating film shown in the examples, diamond-like carbon has an amorphous structure in which both diamond bonds (sp3) and graphite bonds (sp2) are present in a mixed state, and has high chemical resistance. Among them, boron or nitrogen is preferably doped for improving the conductivity because the conductivity is low when used for a coating film of a current collector.
The thickness of the amorphous carbon coating is preferably 60nm or more and 300nm or less. If the film thickness of the amorphous carbon film is too thin, that is, less than 60nm, the effect of covering the amorphous carbon film is low, and corrosion of the current collector in the constant-current constant-voltage continuous charge test cannot be sufficiently suppressed, and if it is too thick, that is, more than 300nm, the amorphous carbon film becomes a resistor and resistance between the resistor and the active material layer becomes large, and therefore, an appropriate thickness is appropriately selected. The thickness of the amorphous carbon coating is more preferably 80nm to 300nm, and still more preferably 120nm to 300 nm. When the amorphous carbon coating is formed by a plasma CVD method using a hydrocarbon gas, the thickness of the amorphous carbon coating can be controlled by the energy injected into the aluminum material, specifically, the applied voltage, the applied time, and the applied temperature.
Since the negative electrode current collector of the bipolar battery according to the present embodiment has the amorphous carbon coating on the surface of the aluminum material, the aluminum material can be prevented from contacting the electrolyte, and the electrolyte can be prevented from corroding the current collector.
More preferably, the conductive carbon layer is formed on the amorphous carbon coating of the negative electrode current collector.
By providing the conductive carbon layer, even when the amorphous carbon coating film has pinholes, the pinholes can be closed, and the aluminum material is prevented from contacting the electrolyte, thereby preventing the electrolyte from corroding the current collector.
Further, by providing the conductive carbon layer, the contact resistance between the amorphous carbon coating covering the current collector and the negative electrode active material can be reduced, the discharge rate can be improved, the output characteristics can be improved, and the high-temperature durability can be improved.
In the current collector having the conductive carbon layer formed between the amorphous carbon coating and the negative electrode active material, the conductive carbon layer is further formed on the amorphous carbon coating layer. The thickness of the conductive carbon layer is preferably 5 μm or less, and more preferably 3 μm or less. This is because if the thickness exceeds 5 μm, the energy density becomes small after the battery or electrode is produced. The conductive carbon layer may be made of any carbon having high conductivity, but the carbon having high conductivity preferably contains graphite, and more preferably is only graphite.
The particle size of the material of the conductive carbon layer is preferably 1/10 or less, which is the size of graphite as the active material and the porous carbon material in the present invention. This is because if the particle diameter is within this range, the contact property at the interface where the conductive carbon layer and the active material layer are in contact with each other is improved, and the interface (contact) resistance can be reduced. Specifically, the particle diameter of the carbon material of the conductive carbon layer is preferably 1 μm or less, and more preferably 0.5 μm or less.
In addition, in forming the conductive carbon layer, a binder is added together with a solvent to make a coating material, and it is coated on the DLC-coated aluminum foil. As a coating method, screen printing, gravure printing, comma knife coater (registered trademark), spin coater, or the like can be used. As the binder, cellulose, acrylic, polyvinyl alcohol, thermoplastic resin, rubber, organic resin can be used. As the thermoplastic resin, polyethylene or polypropylene can be used, as the rubber, SBR (styrene butadiene rubber) or EPDM (ethylene propylene diene rubber) can be used, and as the organic resin, phenol resin, polyimide resin, or the like can be used.
The conductive carbon layer preferably has a small interparticle gap and a low contact resistance. In addition, as a solvent for dissolving the binder for forming the conductive carbon layer, there are two kinds of solvents, an aqueous solution and an organic solvent. If the binder used to form the electrode active material layer is a substance dissolved in an organic solvent, it is preferable to use a binder dissolved in an aqueous solution in the conductive carbon layer, and conversely, when the binder used to form the electrode active material layer is an aqueous solution, it is preferable to use a binder dissolved in an organic solvent in the conductive carbon layer. This is because, when the same kind of solvent is used for the electrode active material layer and the conductive carbon layer, the binder of the conductive carbon layer is easily dissolved and easily becomes uneven when the electrode active material layer is applied.
< Positive electrode >
The positive electrode used in the bipolar battery of one embodiment of the present invention includes a current collector (positive electrode current collector) and a positive electrode active material layer formed thereon. The positive electrode active material layer contains a positive electrode active material, a binder, and a conductive material.
Positive electrode active material layer "
The positive electrode active material layer contains a positive electrode active material, a binder, and a conductive material.
A positive electrode active material layer can be formed by applying a slurry-like positive electrode material mainly containing a positive electrode active material, a binder, and a required amount of a conductive material onto a positive electrode current collector and drying the material.
[ Binder ] and [ conductive Material ]
As the binder and the conductive material of the positive electrode, the same types as those of the binder and the conductive material of the negative electrode can be used.
[ Positive electrode active Material ]
The positive electrode active material contains graphite. As the graphite, any of artificial graphite and natural graphite can be used. As natural graphite, flake graphite and earth graphite are known. Natural graphite is obtained by crushing mined raw ore and repeating a beneficiation process called ore flotation. The artificial graphite is produced, for example, through a graphitization step of firing a carbon material at a high temperature. More specifically, for example, a binder such as pitch is added to coke as a raw material, the mixture is molded and heated to about 1300 ℃ to perform primary firing, and then the primary fired product is impregnated with a pitch resin and subjected to secondary firing at a high temperature of approximately 3000 ℃ to obtain artificial graphite. In addition, a graphite particle coated with carbon on the surface thereof may be used
The crystal structure of graphite is roughly classified into: hexagonal crystals of the layer structure consisting of ABAB, and rhombohedral crystals of the layer structure consisting of abcabcabc. These materials may be used alone or in a mixed state depending on the conditions, but graphite having any crystal structure may be used, or graphite in a mixed state may be used. For example, the proportion of rhombohedral crystals of Graphite of KS-6 (trade name) manufactured by Imerys Graphite & Carbon Japan (イメリス, ジーシー, ジャパン) and the proportion of rhombohedral crystals of artificial Graphite mesocarbon microbeads (MCMB) manufactured by Osakas Chemicals, Inc. used in examples described later were 26% and 0%.
"Positive current collector"
The positive electrode current collector is also an aluminum material covered with an amorphous carbon film, as in the negative electrode current collector described above.
In addition, as in the negative electrode current collector, it is also more preferable that a conductive carbon layer is formed on the amorphous carbon film of the positive electrode current collector.
In the case of providing the conductive carbon layer, even when the amorphous carbon coating film has pinholes, the pinholes can be closed, preventing the aluminum material from contacting the electrolyte, and thus preventing the electrolyte from corroding the current collector.
In addition, when the conductive carbon layer is provided, the contact resistance between the amorphous carbon coating covering the current collector and the positive electrode active material can be reduced, the discharge rate can be improved, the output characteristics can be improved, and the high-temperature durability can be improved.
< electrolyte solution >
As the electrolytic solution used in the bipolar battery of the present embodiment, for example, an organic electrolytic solution obtained by dissolving an electrolyte in an organic solvent can be used. The electrolyte solution contains electrolyte ions capable of inserting and extracting the electrode. Specifically, a lithium salt or the like can be used.
Examples of the organic solvent include: cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate, and chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate. These organic solvents may be used alone or in combination of two or more.
Examples of the lithium salt include: LiPF6、LiBF4、LiClO4、LiAsF6、LiN(CF3SO2)2And the like.
In addition, additives may be used in the electrolyte solution in order to improve high-temperature durability, charge-discharge cycle characteristics, input-output characteristics, and the like.
< separator >
The separator used in the bipolar battery of the present embodiment is preferably a cellulose-based paper-like separator, a glass fiber separator, a polyethylene or polypropylene microporous membrane, or the like, for the reasons of preventing short-circuiting between the positive electrode and the negative electrode and ensuring the liquid retention of the electrolyte solution.
Examples
(Synthesis example 1)
"lithium titanate (Li)4Ti5O12) Synthesis of "
Weighing anatase titanium oxide and lithium hydroxide with average particle diameter of 3 μm in a manner that the stoichiometric ratio of titanium to lithium is 5:4 mol, placing the anatase titanium oxide and lithium hydroxide into a crucible, placing the crucible into an electric atmosphere furnace, and firing the crucible at 700 ℃ for 10 hours in the atmosphere to obtain lithium titanate (Li)4Ti5O12)。
(Synthesis example 2)
"lithium vanadate (Li)1.1V0.9O2) Synthesis of "
And the stoichiometric ratio of vanadium to lithium is 0.9: 1.1 molar, weighing V2O5And Li2CO3Placing into a crucible, placing into an electric atmosphere furnace, and firing at 1100 deg.C for 5 hr under argon flow (500 mL/min) to obtain lithium vanadate (Li)1.1V0.9O2)。
(example 1)
< preparation of Current collector >
Production of DLC-coated aluminum foil "
A DLC-coated aluminum foil (hereinafter also referred to as "DLC-coated aluminum foil") corresponds to an aluminum material covered with an amorphous carbon coating film. As a method for producing a DLC-coated aluminum foil, an aluminum foil having a purity of 99.99% (a foil manufactured by UACJ (UACJ foil corporation) and having a thickness of 20 μm) was subjected to argon sputtering to remove a natural oxide film on the surface of the aluminum foil, and then discharge plasma was generated in the vicinity of the aluminum surface in a mixed gas of methane, acetylene, and nitrogen, and a negative bias voltage was applied to the aluminum material, thereby producing a DLC film. Here, the DLC film on the DLC-coated (covered) aluminum foil was measured to have a thickness of 160nm using a stylus type surface shape meter DektakXT manufactured by BRUKER (BRUKER).
Production of Current collectors consisting of DLC-coated aluminum foils coated with a conductive carbon layer "
The resultant DLC-coated aluminum foil (thickness 20 μm, DLC film thickness 160nm) was coated with graphite electroconductive slurry (trade name Banihaito (バニーハイト) T-602U, a cellulose-based resin binder, an aqueous solution) manufactured by japan graphite industries co, using a screen printer, to form an electroconductive carbon layer, and then dried in a hot air dryer at 100 ℃ for 20 minutes, to obtain a positive electrode collector and a negative electrode collector, i.e., a DLC-coated aluminum foil coated with an electroconductive carbon layer. The thickness of the conductive carbon layer was measured to be 3 μm using a micrometer.
< preparation of negative electrode >
As a negative electrode active material, lithium titanate (Li) obtained in Synthesis 1 was weighed so that the ratio of weight percent concentration (wt%) was 80:10:104Ti5O12) The negative electrode of this example was obtained by dissolving and mixing acetylene black (conductive material) and polyvinylidene fluoride (organic solvent binder) in N-methylpyrrolidone (organic solvent) to obtain a slurry, and coating the slurry on the obtained negative electrode current collector with a doctor blade. The thickness of the negative electrode was measured to be 60 μm using a micrometer.
< preparation of Positive electrode >
As the positive electrode active material, Graphite (trade name KS-6, average particle size 6 μm), acetylene black (conductive material), and polyvinylidene fluoride (organic solvent-based binder) manufactured by Imerys Graphite & Carbon Japan were weighed so that the ratio of the weight percentage concentration (wt%) was 80:10:10, and dissolved and mixed with N-methylpyrrolidone (organic solvent) to obtain a slurry, and the slurry was applied onto the obtained positive electrode current collector using a doctor blade to obtain the positive electrode of the present example. The thickness of the positive electrode was measured to be 80 μm using a micrometer.
< preparation of button cell >
The obtained positive electrode was punched into a disk shape having a diameter of 16mm, the obtained negative electrode was punched into a disk shape having a diameter of 14mm, and after vacuum-drying at 150 ℃ for 24 hours, it was transferred to an argon glove box. The dried positive and negative electrodes were stacked with a paper separator (trade name: TF40-30) made by Nipponkodoshi industries, Ltd., interposed therebetween, and 1M LiBF was added to the electrolyte4(lithium tetrafluoroborate), 0.1mL of an electrolyte solution using propylene carbonate was added to the solvent, and a 2032 type coin cell was produced in an argon glove box.
(example 2)
A coin cell was produced in the same manner as in example 1, except that DLC-coated aluminum foil (thickness 20 μm, DLC film thickness 160nm) was used as the negative electrode current collector.
(example 3)
A coin cell was produced in the same manner as in example 1, except that DLC-coated aluminum foil (thickness 20 μm, DLC film thickness 160nm) was used as the positive electrode current collector.
(example 4)
Button cells were produced in the same manner as in example 1, except that DLC-coated aluminum foil (thickness 20 μm, DLC film thickness 160nm) was used as the positive and negative electrode current collectors.
(example 5)
Button cells were produced in the same manner as in example 1, except that DLC-coated aluminum foils having a DLC film thickness of 100nm were used in the production of DLC-coated aluminum foils coated with conductive carbon layers as positive and negative current collectors.
Comparative example 1
A coin cell was produced in the same manner as in example 1, except that a flat aluminum foil (20 μm thick, manufactured by UACJ) was used as the negative electrode current collector.
Comparative example 2
A coin cell was produced in the same manner as in example 1, except that activated carbon YP-50F manufactured by KURARAAY K.K. was used as the negative electrode active material.
(test 1) evaluation of energy amount
The obtained batteries of example 1 and comparative example 2 were subjected to a charge and discharge test using a charge and discharge test apparatus BTS2004 manufactured by nagano, Inc., namely, in a thermostatic bath at 25 ℃ at 0.4mA/cm2Constant-current constant-voltage charging was performed at a voltage of 3.5V and then, a constant current (current density of 0.4 mA/cm)2) The discharge current value of (2) was discharged to 2.0V. The discharge capacity was calculated from the product of the time after discharging to 2.0V and the discharge current. The energy amount (Wh) is calculated from the product of the average voltage at the time of discharge and the discharge capacity. Will give a resultShown in table 1. Table 1 shows the energy amount of example 1 normalized by comparative example 2. At this time, the results of comparative example 2 were normalized as 100.
(test 2) evaluation of discharge Capacity conservation Rate
The obtained batteries of examples 1 to 5 and comparative example 1 were subjected to a charge and discharge test using a charge and discharge test apparatus BTS2004 manufactured by NAGANO (ナガノ), namely, a constant temperature bath at 25 ℃ and 0.4mA/cm2Constant-current constant-voltage charging at a voltage of 3.5V, and then, at a current density of 0.4mA/cm2The discharge current value was discharged to 2.0V, and the discharge capacity before the constant-current constant-voltage continuous charge test was measured.
Next, the charge/discharge test apparatus BTS2004 was used in a 60 ℃ incubator at 0.4mA/cm2The continuous charging test (constant current constant voltage continuous charging test) was carried out at a voltage of 3.5V. Specifically, during the charging, the charging was stopped for a predetermined time, the temperature of the thermostatic bath was changed to 25 ℃ and, after 5 hours had elapsed, the temperature was controlled to 0.4mA/cm in the same manner as described above2Constant-current constant-voltage charging at a voltage of 3.5V, and then, at a current density of 0.4mA/cm2The discharge current value (2) was discharged to 2.0V, and such a charge-discharge test was performed 5 times, thereby obtaining a discharge capacity. Then, the temperature of the thermostatic bath was returned to 60 ℃, and after 5 hours, the continuous charging test was restarted and the test was carried out until the total of the continuous charging test time reached 2000 hours.
The discharge capacity retention (%) at 2000 hours is shown as a discharge capacity ratio of the discharge capacity at 2000 hours after the start of the test to the discharge capacity before the start of the test (set to 100). The 60 ℃ durability was evaluated using the discharge capacity retention after 2000 hours at 60 ℃. The results are shown in table 1. In Table 1, values of the discharge capacity retention (%) of examples 1 to 5 normalized by comparative example 1 are shown. At this time, the results of comparative example 1 were normalized as 100.
TABLE 1
| Example/comparative example as a Standard | Retention rate of discharge capacity | Energy source |
| Example 1/comparative example 1 | 2500 | - |
| Example 2/comparative example 1 | 2200 | - |
| Example 3/comparative example 1 | 2300 | - |
| Example 4/comparative example 1 | 1750 | - |
| Example 5/comparative example 1 | 1850 | - |
| Example 1/comparative example 2 | - | 380 |
Example 2 differs from comparative example 1 only in the negative electrode current collector. The negative electrode current collector of example 2 was a DLC-coated aluminum foil, and the negative electrode current collector of comparative example 1 was a planar aluminum foil.
The discharge capacity retention rate of example 2 was 22 times that of comparative example 1, and showed greater durability at 60 ℃. This higher effect is due to the fact that the aluminum foil of the negative current collector has a DLC coating.
The DLC coating aluminum foil is used as the negative current collector, so that the discharge capacity retention rate is improved by more than 20 times, and the discharge capacity retention rate is greatly improved. It is considered that there is a cause other than the corrosion resistance effect of the DLC film. For example, it is considered that some interaction of the negative electrode active material and the DLC film of the negative electrode current collector contributes to such a high effect. That is, when a conventional planar aluminum foil is used, the metal oxide as the negative electrode active material of the present invention is in direct contact with the aluminum foil or an oxide thereof. However, when the DLC-coated aluminum foil of the present invention is used, the metal oxide as the negative electrode active material of the present invention is not in direct contact with the aluminum foil or its oxide, but is in contact with the DLC film. It is considered that the discharge capacity retention rate is greatly improved.
In example 1 described later, a conductive carbon layer is further formed on the DLC coating (coating film) of the DLC-coated aluminum foil. Higher effects than in example 2 were observed. It is known that a higher effect is also observed when it is formed on an aluminum foil through a carbonaceous film or layer without being in direct contact with the aluminum foil or its oxide. That is, it is considered that this is an effect produced in the following case: since lithium titanate as a negative electrode active material has low conductivity, the interface resistance is reduced by forming a conductive carbon layer at the interface with the current collector. This shows that the effect of the DLC-coated aluminum foil with a conductive carbon layer formed according to the present invention is more effective for the negative electrode.
Further, since a several-fold improvement effect is also observed in example 6 and the like described later, the magnitude of the interaction may depend on the kind of the metal oxide as the negative electrode active material.
In example 1, only the negative electrode current collector was different from example 2. The negative electrode collector of example 1 was formed with a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil, whereas the negative electrode collector of example 2 was not formed with a conductive carbon layer.
The discharge capacity retention rate of example 1 was 1.14 times that of example 2, and the durability at 60 ℃ could be further improved. This effect is attributed to the formation of a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil of the negative electrode current collector.
In example 2, only the positive electrode current collector was different from example 4. The positive electrode collector of example 2 was formed with a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil, whereas the positive electrode collector of example 4 was not formed with a conductive carbon layer.
The discharge capacity retention rate of example 2 was 1.26 times that of example 4, and the durability at 60 ℃ could be improved. This effect is attributed to the formation of a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil of the positive electrode current collector.
In example 3, only the negative electrode current collector was different from example 4. The negative electrode collector of example 3 had a conductive carbon layer formed on the DLC coating (coating film) of the DLC-coated aluminum foil, whereas the negative electrode collector of example 4 had no conductive carbon layer formed thereon.
The discharge capacity retention rate of example 3 was 1.31 times that of example 4, and the durability at 60 ℃ could be improved. This effect is attributed to the formation of a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil of the negative electrode current collector. That is, it is considered that this is an effect produced in the following case: since lithium titanate as a negative electrode active material has low conductivity, the interface resistance is reduced by forming a conductive carbon layer at the interface with the current collector. This shows that the effect of the DLC-coated aluminum foil with a conductive carbon layer formed according to the present invention is more effective for the negative electrode.
In example 1, only the negative electrode current collector and the positive electrode current collector were different from those in example 5. The DLC coatings (films) of the negative and positive electrode current collectors of example 1 were 160nm thick, while those of the negative and positive electrode current collectors of example 5 were 100nm thick.
The discharge capacity retention rate of example 1 was 1.35 times that of example 5, and the durability at 60 ℃ could be improved. This effect is attributed to the difference in the thickness of the DLC coating (coating film).
(example 6)
Using LiNbO2A coin cell was produced in the same manner as in example 1 except for using a negative electrode active material, and evaluated in the same manner as in example 1.
(example 7)
Using Li obtained in Synthesis 21.1V0.9O2A coin cell was produced in the same manner as in example 1 except for using a negative electrode active material, and evaluated in the same manner as in example 1.
(example 8)
Using anatase type TiO2A coin cell was produced in the same manner as in example 1 except for using a negative electrode active material, and evaluated in the same manner as in example 1.
(example 9)
Using V2O5A coin cell was produced in the same manner as in example 1 except for using a negative electrode active material, and evaluated in the same manner as in example 1.
Comparative example 3
A coin cell was produced in the same manner as in example 6 except that a planar aluminum foil (20 μm thick, manufactured by UACJ) was used as a negative electrode current collector, and evaluated in the same manner as in example 1.
Comparative example 4
A coin cell was produced in the same manner as in example 7 except that a planar aluminum foil (20 μm thick, manufactured by UACJ) was used as a negative electrode current collector, and evaluated in the same manner as in example 1.
Comparative example 5
A coin cell was produced in the same manner as in example 8 except that a planar aluminum foil (20 μm thick, manufactured by UACJ) was used as a negative electrode current collector, and evaluated in the same manner as in example 1.
Comparative example 6
A coin cell was produced in the same manner as in example 9 except that a planar aluminum foil (20 μm thick, manufactured by UACJ) was used as a negative electrode current collector, and evaluated in the same manner as in example 1.
The obtained discharge capacity retention rates as the results of the evaluations of examples 6 to 9 and comparative examples 3 to 6 are shown in table 2. Table 2 shows the discharge capacity retention rates of examples 6 to 9 normalized by comparative examples 3 to 6. At this time, the results of comparative examples 3 to 6 were normalized as 100.
TABLE 2
| Example/comparative example as a Standard | Retention rate of discharge capacity |
| Example 6/comparative example 3 | 250 |
| Example 7/comparative example 4 | 330 |
| Example 8/comparative example 5 | 285 |
| Example 9/comparative example 6 | 175 |
Examples 6 to 9 differ from comparative examples 3 to 6 only in the negative electrode current collector. The negative electrode current collectors of examples 6 to 9 were each formed with a conductive carbon layer on the DLC coating (coating film) of the DLC-coated aluminum foil, and the negative electrode current collectors of comparative examples 3 to 6 were each a planar aluminum foil.
The discharge capacity retention rates of examples 6 to 9 were 2.5 times, 3.3 times, 2.85 times, and 1.75 times, respectively, of the discharge capacity retention rates of comparative examples 3 to 6. This high effect is attributed to the aluminum foil of the negative electrode current collector having a DLC coating (film) and a conductive carbon layer. It is also shown that the effects of the present invention can be obtained by using any of the negative electrode active materials of the present invention.
Claims (6)
1. A bi-ion battery having a positive electrode and a negative electrode,
the positive electrode comprises a positive electrode current collector and a positive electrode active material arranged on the positive electrode current collector,
the negative electrode comprises a negative electrode current collector and a negative electrode active material arranged on the negative electrode current collector;
and the positive electrode active material contains graphite,
the negative electrode active material contains a metal oxide capable of occluding and releasing cations,
the positive electrode current collector and the negative electrode current collector are formed of an aluminum material covered with an amorphous carbon coating.
2. The bi-ion battery of claim 1,
and a conductive carbon layer is formed on the amorphous carbon film of the positive current collector or/and the negative current collector.
3. The bi-ion battery of any of claims 1 or 2,
the cation is an alkaline earth metal.
4. The bi-ion battery of any of claims 1-3,
the cation is lithium.
5. The bi-ion battery of any of claims 1-4,
the metal in the metal oxide is at least one selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), and molybdenum (Mo).
6. The bi-ion battery of any of claims 1-5,
the capacity per unit weight of the negative electrode active material is higher than the capacity per unit weight of the positive electrode active material.
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| CN104488118A (en) * | 2012-09-27 | 2015-04-01 | 东洋铝株式会社 | Conductive member, electrode, secondary battery, capacitor, method for producing conductive member, and method for producing electrode |
| JP2017050131A (en) * | 2015-09-01 | 2017-03-09 | 株式会社リコー | Nonaqueous electrolyte power storage device and charging/discharging method thereof |
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| JP2017050131A (en) * | 2015-09-01 | 2017-03-09 | 株式会社リコー | Nonaqueous electrolyte power storage device and charging/discharging method thereof |
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