Patent Application
20210384558
The present invention relates to a sodium secondary battery and a method for manufacturing the same.
A sodium-ion secondary battery using intercalation and deintercalation reactions of sodium ions is less expensive than a lithium secondary battery because of abundant sodium resources. In addition, the sodium-ion secondary battery is less constrained in terms of resources and has thus gained great expectations for its future. Therefore, the research and development of the electrode material and electrolyte material of the sodium-ion secondary battery have been advanced.
Recently, with the development of information technology (IT) devices such as smartphones and internet-of-things (IoT) devices, secondary batteries for mobile power supply have attracted attention. With a view to differentiating the respective products, batteries for such devices may be required to have new characteristics. As the new characteristics, for example, flexibility and the like have emerged.
As a secondary battery having flexibility, an example of a lithium secondary battery has been reported in, for example, Non-Patent Literature 1. The battery has been reported to be thin and bendable and exhibit a discharge capacity of about 250 μAh/g at a discharge current with a current density of 0.1 mA/cm2.
Non-Patent Literature 1: Masahiko Hayashi, et al., “Preparation and electrochemical properties of purelithium cobalt oxide films by electron cyclotronresonance sputtering”, Journal of Power Sources 189 (2009) pp. 416-422
As described above, for the lithium secondary battery, studies on a battery having a new characteristic are underway. On the other hand, concerning the sodium secondary battery, there has been no report on such a battery having a new characteristic up to now. If a sodium secondary battery having both visible light transparency and flexibility or the like, for example, which is not available in the prior art, can be achieved, it is possible to greatly expand the ranges of design and applications of IoT devices. However, the problem is that such a battery does not yet exist.
An object of the present invention, which has been made in view of the problem, is to provide a sodium secondary battery having both visible light transparency and flexibility and to provide a method for manufacturing the sodium secondary battery.
A sodium secondary battery according to one aspect of the present invention includes: a positive electrode film that contains a material formed on a flexible transparent film substrate, the material being capable of intercalating and deintercalating sodium ions; a transparent electrolyte having sodium ion conductivity; and a negative electrode film that is formed of a material formed on a flexible transparent film substrate, the material being capable of dissolving and depositing sodium or intercalating and deintercalating sodium ions.
A method for manufacturing a sodium secondary battery according to one aspect of the present invention is a method for manufacturing a sodium secondary battery, the method including: a positive electrode film formation step of forming a positive electrode film that contains a material formed on a flexible transparent film substrate, the material being capable of intercalating and deintercalating sodium ions; an electrolyte formation step of forming a transparent electrolyte that has sodium ion conductivity; and a negative electrode film formation step of forming a negative electrode film that is formed of a material formed on a flexible transparent film substrate, the material being capable of dissolving and depositing sodium or intercalating and deintercalating sodium ions. In the positive electrode film formation step and the negative electrode film formation step, heat treatment is performed at 50° C. to 200° C. in an argon atmosphere after the formation of the electrode film.
According to the present invention, it is possible to provide a sodium secondary battery having both visible light transparency and flexibility and to provide a method for manufacturing the sodium secondary battery.
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
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In the same manner as the positive electrode film 1, the negative electrode film 3 is formed by forming a film of a material capable of intercalating and deintercalating sodium ions, with a predetermined thickness on a transparent electrode film 6 of ITO or the like formed all over one surface of the transparent film substrate 5. The transparent film substrates 4, 5 are identical and made of, for example, polyethylene terephthalate (PET) or the like.
The positive electrode film 1 and the negative electrode film 3 are disposed to face each other with the electrolyte 2 therebetween. As the electrolyte 2, an organic electrolyte or an aqueous electrolyte containing sodium ions can be used so long as being a conventional material having sodium ion conductivity as well as a material having no electron conductivity and having visible light transparency.
In addition, a conventional solid electrolyte containing sodium ions and a solid-state electrolyte such as a polymer electrolyte can also be used so long as transmitting visible light.
Note that a separator (not shown) may be included between the positive electrode film 1 and the negative electrode film 3. Examples of the separator having light transparency include polyethylene (PE), polypropylene (PP), and an ion-exchange membrane. In a case where the organic electrolyte or the aqueous electrolyte is used as the electrolyte, for example, the separator may be impregnated with the electrolyte.
The organic electrolyte or the aqueous electrolyte may be impregnated with a polymer electrolyte or the like. In a case where the solid electrolyte, the polymer electrolyte, and the like are used, both electrodes may be disposed to be in contact with these electrolytes.
As described above, the sodium secondary battery 100 according to the present embodiment includes the positive electrode film 1, the transparent electrolyte 2 having sodium ion conductivity, and the negative electrode film 3. Here, the positive electrode film 1 contains a material capable of intercalating and deintercalating sodium ions formed on the flexible transparent film substrate 4. The negative electrode film 3 is formed of a material capable of dissolving and depositing sodium or intercalating and deintercalating sodium ions formed on the flexible transparent film substrate 5.
Therefore, it is possible to provide a sodium secondary battery having both visible light transparency and flexibility.
First, each of transparent film substrates 4, 5 (hereinafter, reference numeral 5 is omitted) to be a substrate on which an electrode film is formed is cut into a predetermined size (step S1). The size of the transparent film substrate 4 is, for example, about 100 mm in length×50 mm in width. The thickness thereof is, for example, about 0.1 mm.
Next, a positive electrode film 1 is formed (step S2). In the formation of the positive electrode film 1, a transparent electrode film 6 is formed on the surface of the transparent film substrate 4.
The transparent electrode film 6 was coated with ITO to have a thickness of 150 nm by radio frequency (RF) sputtering method. Sputtering was performed using an ITO (5 wt % SnO2) target with an RF output of 100 W while argon (1.0 Pa) was allowed to flow.
Subsequently, for example, a film of sodium chromate (NaCrO2) was formed on the transparent electrode film 6 by RF sputtering method to have a thickness of 100 nm. The positive electrode film 1 was formed using a ceramic target of NaCrO2 with a flow partial pressure ratio of argon to oxygen of 3:1 and a total gas thickness of 3.7 Pa in a condition of an RF output of 600 W.
Next, a negative electrode film 3 is formed (step S3). The negative electrode film 3 is formed by the RF sputtering method in the same manner as the positive electrode film 1. The negative electrode film 3 is formed using a sodium titanate (Na2Ti3O7) target with a flow partial pressure ratio of argon to oxygen of 3:1 and a total gas pressure of 4.0 Pa at an RF output of 700 W.
The sizes of the positive electrode film 1 and the negative electrode film 3 are the same, for example, 90 mm in length×50 mm in width. The size of each electrode film is smaller than that of the transparent electrode film 6.
Subsequently, an electrode terminal is shaped (step S4). In each electrode film formed as described above, there is left a part where the electrode film (1, 3) is not formed in an area of a 10 mm in length×a 50 mm in width, and ITO is exposed. In the part, a portion of 10 mm in height×40 mm in width is cut out while a portion of 10 mm in height×10 mm in width is remained, to form a positive electrode terminal 8 and a negative electrode terminal 9.
Then, a film of an electrolyte is formed (step S4). An electrolyte 2 having a transparent film with a thickness of 1 μm was produced by a process as follows. The process as follows is a process in which a solution as follows is stirred at 60° C. for one hour in dry air having a dew point of −50° C. or less, 50 ml of the solution is poured into a 200-mmφ petri dish, which is then vacuum-dried at 50° C. for twelve hours. Here, the solution as follows is a solution obtained by mixing polyvinylidene fluoride (PVdF) powder as a binder, an organic electrolyte, and N-methyl-2 pyrrolidone (NMP) as a dispersion medium at a weight ratio of 1:9:10. Here, the organic electrolyte is an organic electrolyte obtained by dissolving 1 mol/L of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a sodium salt in propylene carbonate (PC).
Next, a battery is assembled (step S6). The transparent film substrate 4 formed with the positive electrode film 1, the transparent film substrate 5 formed with the negative electrode film 3, and the electrolyte 2 are laminated with the positive electrode film 1 and the negative electrode film 3 facing each other across the electrolyte 2. The positive electrode terminal 8 and the negative electrode terminal 9 are then put between the laminate films 7 of a 110 mm in length×a 70 mm in width×a 100 μm in thickness so as to be exposed to the outside, and hot-pressed at 130° C. The thickness of the hot-pressed battery is, for example, about 400 μm.
The sodium secondary battery 100 can be manufactured by the above process.
The charge/discharge characteristics of the sodium secondary battery 100 produced by the above manufacturing method were measured. A charge/discharge test was conducted using a general charge/discharge system. Charge conditions were that a current was applied at a current density of 1 μA/cm2 per effective area of the positive electrode film 1, and that a charge termination voltage was set to 2.0 V.
Discharge conditions were that discharge was performed at a current density of 1 μA/cm2, and that a discharge termination voltage was set to 0.7 V. The charge/discharge test was conducted in a thermostatic chamber at 25° C. (an atmosphere being left in a normal atmospheric environment).
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As thus described, the sodium secondary battery 100 according to the present embodiment has a stable charge cycle characteristic and light transmission characteristics.
For the purpose of examining the configuration of the present embodiment described above in detail, experiments were conducted under various conditions of the thickness of the negative electrode film 3, the thickness of the positive electrode film 1, heat treatment, and the like. The results of each experiment will be described.
The positive electrode film 1 was produced with the thickness varied to 30 nm, 50 nm, 200 nm, 300 nm, 400 nm, and 500 nm, and the charge/discharge characteristics were measured. As the active material of the positive electrode film 1, sodium chromate (NaCrO2), which is the same as in the above embodiment, was used. Table 1 shows the results of the experiment. A light transmissivity shown in Table 1 indicates the transmissivity of the entire battery.
Conditions except for the thickness of the positive electrode film 1 are the same as those in the above embodiment. The active material of the negative electrode film 3 is sodium titanate (Na2Ti3O7), and the thickness thereof is 100 nm.
As shown in Table 1, when the thickness of the positive electrode film 1 was 200 nm, the largest discharge capacity was shown. This is considered to be because the amount of sodium chromate (NaCrO2), which is the positive electrode active material, was equal to or more than the amount of negative electrode active material.
When the thickness of the positive electrode film 1 is 500 nm, the discharge capacity decreases. This is considered to be because the resistance in the thickness direction up to the transparent conductive film 6, which is a current collector, increased due to the low electronic conductivity of sodium chromate (NaCrO2) itself.
From the results in Table 1, it can be seen that when a capacity of, for example, 0.064 mAh or more is set as an allowable range, the thickness of the positive electrode film 1 is preferably from 50 nm to 400 nm. The capacity of 0.064 mAh or more is a capacity capable of utilizing a power of 1 mW for about five minutes.
A similar result can be obtained even when another positive electrode active material having an electronic conductivity equal to or higher than that of sodium chromate (NaCrO2) is used. The positive electrode active material is, for example, any of chromium oxide, manganese oxide, iron oxide, copper oxide, nickel oxide, molybdenum oxide, metal sulfide, metal nitride, metal fluoride, and metal titanium composite oxide.
When the negative electrode film 3 contains the sodium source as described above, the positive electrode film 1 is made to have a thickness of 50 nm to 400 nm by using any of chromium oxide, manganese oxide, iron oxide, copper oxide, nickel oxide, molybdenum oxide, metal sulfide, metal nitride, metal fluoride, and metal titanium complex oxide. In this way, the capacity of 0.064 mAh or more can be ensured.
However, as shown in Table 1, when the thickness of the positive electrode film 1 is set to 400 nm, the transmissivity decreases to 4.4%. Therefore, the thickness of the positive electrode film 1 is preferably from 50 nm to 200 nm in consideration of the light transmissivity. In this range, the capacity of 0.064 mAh or more and a light transmissivity of 10% or more can be ensured.
As other sodium sources to be contained in the negative electrode film 3, a sodium metal, a sodium alloy, a sodium nitride, a sodium phosphorylated portion, and the like can be considered.
The positive electrode film 1 was produced with the thickness set to 200 nm, which showed the best characteristics in Experimental Example 1, the negative electrode film 3 was produced with the thickness varied to 20 nm, 30 nm, 50 nm, 200 nm, and 300 nm, and the charge/discharge characteristics were measured. Table 1 shows the results of the experiment.
As shown in Table 2, the negative electrode film 3 having a thickness of 200 nm showed the largest discharge capacity. This is considered to be because the amount of sodium titanate (Na2Ti3O7), which is the negative electrode active material, was equal to or more than the amount of the positive electrode active material as in Experimental Example 1.
The thickness of the negative electrode film 3 is preferably from 30 nm to 200 nm. In this range, the capacity of 0.064 mAh or more can be ensured. The light transmissivity is 10% or more even when the thickness of the negative electrode film 3 is 300 nm. Hence the thickness of the negative electrode film 3 is preferably from 30 nm to 200 nm even in consideration of light transmissivity.
A similar result can be obtained even when another negative electrode active material having an electronic conductivity equal to or higher than that of sodium titanate (Na2Ti3O7) is used. The negative electrode active material is any of tin oxide, silicon oxide, titanium oxide, tungsten oxide, niobium oxide, molybdenum oxide, metal sulfide, metal nitride, metal fluoride, and metal titanium composite oxide.
When the positive electrode film 1 contains the sodium source as described above, the positive electrode film 1 is made to have a thickness of 30 nm to 200 nm by using any of tin oxide, silicon oxide, titanium oxide, tungsten oxide, niobium oxide, molybdenum oxide, metal sulfide, metal nitride, metal fluoride, and metal titanium complex oxide. In this way, the capacity of 0.064 mAh or more can be ensured.
As other sodium sources to be contained in the positive electrode film 1, any of the following can be considered: sodium complex oxide, sodium manganese complex oxide, sodium nickel complex oxide, sodium cobalt complex oxide, sodium chromium manganese complex oxide, sodium chromium nickel complex oxide, sodium chromium cobalt complex oxide, sodium nickel cobalt complex oxide, sodium manganese cobalt complex oxide, sodium manganese nickel complex oxide, sodium phosphate, sodium nickel cobalt manganese complex oxide, sodium nickel cobalt chromium complex oxide, sodium nickel manganese chromium complex oxide, sodium cobalt manganese chromium complex oxide, sodium silicon complex oxide, and sodium boron complex oxide.
It is known that by heat-treating the electrode film after formed, the surface of the electrode film is cleaned, and the crystallinity thereof is improved. Therefore, an experiment was conducted to compare charge cycle characteristics of sodium secondary batteries each produced by setting the thickness of the negative electrode film 3 to 200 nm and the thickness of the positive electrode film 1 to 200 nm, which showed good characteristics in Experimental Examples 1 and 2, and heat-treating the formed negative electrode film 3 in an argon atmosphere at any temperature of 50° C., 100° C., 200° C., and 300° C. for three hours. Table 3 shows the results of the experiment.
As shown in Table 3, the battery performance was improved by heat treatment. At 300° C., the transparent film substrate 5 was deformed, and the battery could not be produced.
Table 4 shows the results of performing a similar experiment on the positive electrode film 1.
As shown in Table 4, a similar heat treatment was applied to the negative electrode film 3 to obtain similar results to those of the positive electrode film 1.
From the results shown in Tables 3 and 4, it was found that the battery performance is improved when the electrode film is formed and then heat-treated for three hours at any temperature within the temperature range of 70° C. to 200° C. It is thus preferable to perform the heat treatment after the formation of the electrode film.
A method for manufacturing a sodium secondary battery according to the present embodiment includes a positive electrode film formation step, an electrolyte formation step, and a negative electrode film formation step. Here, in the positive electrode film formation step, a positive electrode film containing a material capable of intercalating and deintercalating sodium ions formed on a flexible transparent film substrate is formed. In the electrolyte formation step, a transparent electrolyte having sodium ion conductivity is formed. In the negative electrode film formation step, a negative electrode film formed of a material, formed on a flexible transparent film substrate, the material being capable of dissolving and depositing sodium or intercalating and deintercalating sodium ions, is formed. Then, in the positive electrode film formation step and the negative electrode film formation step, after the formation of the electrode film, heat treatment is performed for three hours in an argon atmosphere at any temperature within a temperature range of 70° C. to 200° C.
It is thereby possible to improve the performance of the sodium secondary battery.
In a case where a sodium secondary battery having visible light transparency is achieved, the surface roughness of the electrode film has a great influence on the light transmissivity. That is, while the transparent film substrate 4, the electrolyte 2, and the laminate film 7, which are other components, basically transmit light, the positive electrode film 1 and the negative electrode film 3 do not transmit light. Hence it is considered that when the surface roughness of each surface of the positive electrode film 1 and the negative electrode film 3 is large, light is irregularly reflected, and the transmissivity is lowered.
Therefore, an experiment was conducted on the relationship between the surface roughness of the negative electrode film 3 and the positive electrode film 1 and the light transmissivity.
The surface roughness is determined by measuring a surface of 500×500 nm with an atomic force microscope (AFM 5200S manufactured by Hitachi High-Tech Corporation). Table 4 shows the results of the experiment.
In Comparative Example 1 shown in Table 5, the surfaces of the positive electrode film 1 and the negative electrode film 3 produced in the above embodiment are scratched. The scratches were caused by rotating the substrate to which the electrode film was fixed at 10 rpm and bringing a brush, which has a Tylon resin tip with a diameter of about 0.2 mm, into contact with the surface of the electrode film.
As shown in Table 5, it can be seen that the surface of the electrode film is smoothed by performing heat treatment after the formation of the electrode film. The light transmissivity improves as the surface roughness decreases.
From the results shown in Table 5, it can be seen that a transmissivity of 20% or more can be obtained when the surface roughness of the negative electrode film 3 is 60 nm or less and the surface roughness of the positive electrode film is 90 nm or less, even without heat treatment.
The flexibility of the sodium secondary battery 100 according to the present embodiment was examined.
A load is vertically applied downward to the central portion of the battery with both ends of the battery as a fulcrum to evaluate the flexibility based on the relationship between the amount of bend of the sodium secondary battery 100 and the load.
Batteries in which the thicknesses of the laminate films 7 were 50 μm (battery thickness of 423 μm), 100 μm (battery thickness of 525 μm), and 150 μm (battery thickness of 628 μm) were produced, and the flexibility was evaluated. Table 6 shows the results of the evaluation. Of each load shown in Table 6, 200 g is the weight of the metal rod 30.
As shown in Table 6, the load for bending the battery by a certain amount increases with an increase in the thickness of the battery. As thus described, the flexibility is lost when the thickness of the battery increases.
Assuming that the sodium secondary battery 100 according to the present embodiment is mounted on a wearable device, its flexibility is considered sufficient when the battery is bent by the amount of bend described above with a load of 500 g. Hence the thickness of the sodium secondary battery 100 is preferably 500 μm or less.
When the thickness of the sodium secondary battery 100 is set to 500 μm or less, the sodium secondary battery 100 can be provided with practically sufficient flexibility in addition to light transparency.
For the purpose of making comparisons with the above embodiment and experimental examples, a sodium secondary battery of Comparative Example 2 was produced by mixing carbon, which is a conductive assistant, into an electrode film.
The sodium secondary battery of Comparative Example 2 was produced by forming a carbon thin film having a thickness of 20 nm on each of the positive electrode film 1 of sodium chromate (NaCrO2) and the negative electrode film 3 of sodium titanate (Na2Ti3O7) having a thickness of 80 nm. The configurations except for this were made the same as those in the above embodiment.
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By comparing Comparative Example 2 (
As described above, according to the present invention, it is possible to provide a sodium secondary battery having both visible light transparency and flexibility and to provide a method for manufacturing the sodium secondary battery. Note that the present invention is not limited to the above embodiment but can be modified within the scope of the gist thereof.
The present embodiment can produce a sodium secondary battery having both visible light transparency and flexibility and can be used as a power source for various electronic devices.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-217089 | Nov 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/043432 | 11/6/2019 | WO | 00 |
