WO2013077239A1 - Negative electrode collector for sodium batteries and production method therefor, negative electrode for sodium batteries, and sodium battery - Google Patents
Negative electrode collector for sodium batteries and production method therefor, negative electrode for sodium batteries, and sodium battery Download PDFInfo
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- WO2013077239A1 WO2013077239A1 PCT/JP2012/079599 JP2012079599W WO2013077239A1 WO 2013077239 A1 WO2013077239 A1 WO 2013077239A1 JP 2012079599 W JP2012079599 W JP 2012079599W WO 2013077239 A1 WO2013077239 A1 WO 2013077239A1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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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
Definitions
- the present invention relates to a negative electrode current collector for sodium batteries that conducts sodium ions (Na + ), a method for producing the same, a negative electrode for sodium batteries, and a sodium battery.
- Non-Patent Document 1 Various technical developments related to molten salt electrolyte batteries have been made (for example, Patent Document 1 and Non-Patent Document 1).
- Na has an overwhelmingly large Clark number of 2.64 and 0.006 of Li, and materials can be procured stably and easily.
- an alloy-based negative electrode made of an alloy of metal Na and tin (Sn) or the like has been used as the negative electrode of such a sodium battery.
- an alloy-based negative electrode repeatedly causes large volume changes (expansion and shrinkage) when the active material Na is occluded and desorbed, which may cause deterioration of capacity and cycle characteristics. .
- Cu copper
- Ni copper
- Al copper
- Al aluminum
- the present inventor has found that in the case of a conventional Al negative electrode current collector, an Al oxide film having a large electric resistance is easily formed on the surface, and when the Al oxide film is formed, overvoltage is generated. It became large and it was found that a sufficiently high voltage efficiency could not be obtained and the wettability with Na deteriorated.
- the Zn film can reduce the electric resistance as compared with the Al oxide film, and obtain a small overvoltage and high voltage efficiency as expected. be able to.
- this zincate treatment is performed by precipitating Zn on the exposed Al surface by dissolving an Al oxide film to form Al 3+ (Zn displacement plating). This is a technique for obtaining plating adhesion to a material.
- reaction will complete
- a Zn thin film is formed on the surface of Al, the subsequent formation of Al oxide is suppressed and wettability with Na is maintained.
- FIG. 2A and FIG. 2B show the movement of Na + and electrons (e ⁇ ) when an Al foil is used as a negative electrode current collector and Na as a negative electrode active material is deposited thereon (during charging).
- the figure to explain is shown and it explains per overvoltage.
- FIG. 2A shows a case where an Al foil not subjected to zincate treatment is used as a negative electrode current collector
- FIG. 2B shows a case where an Al foil subjected to zincate treatment is used as a negative electrode current collector.
- 1 is an Al foil
- 2 is a Zn film formed by zincate treatment
- 3 is an Al oxide film formed on the surface of the Al foil 1
- 4 is formed on the surface of the Zn film 2.
- Zn oxide film, 5 is deposited Na
- 6 is an electrolytic solution.
- Na + is supplied from the electrolytic solution 6 and e ⁇ is supplied from the Al foil 1 side, and Na 5 is deposited.
- Al An Al oxide film 3 is formed on the surface of the foil 1, and even if the Al oxide film 3 has a thickness of several nanometers, the electric resistance is large, so that the overvoltage increases. As a result, a sufficiently high voltage efficiency cannot be obtained.
- the Al oxide film 3 has poor wettability, Na cannot be deposited uniformly.
- the Zn coating 2 formed on the surface has much lower electrical resistance than the Al oxide coating.
- the oxidation of the Zn film 2 (formation of the Zn oxide film 4) is slower than the oxidation of Al, and the density of ZnO generated even once oxidized is small and the volume is large. The effect of suppressing the progress of the growth is great, and the amount of surface oxygen can be reduced.
- the electrical resistance of the Zn oxide film 4 is smaller than that of the Al oxide film, and the wettability with Na is good. For this reason, when Na is deposited on the surface of the zincate-treated Al foil, the overvoltage is reduced and sufficiently high voltage efficiency can be obtained.
- a negative electrode current collector for a sodium battery wherein the negative electrode current collector is made of aluminum and has a zinc coating formed on the aluminum surface.
- Claim 2 is An aluminum oxide layer is formed on the aluminum surface where the zinc coating is not formed, An aluminum oxide layer is not formed at the interface between the zinc coating and the aluminum, or is formed at a portion where the zinc coating is not formed at the interface between the zinc coating and the aluminum. 2.
- Claim 3 is A method for producing a negative electrode current collector for a sodium battery, wherein a zinc coating is formed on an aluminum surface by a zincate treatment.
- the zincate treatment dissolves the Al oxide film to form a Zn film, so that the thickness of the aluminum oxide layer present at the interface can be reduced.
- the present inventor further examined the zincate treatment and found that when the double zincate treatment was adopted, the coverage of the Zn coating was further improved, the overvoltage was further reduced, and the voltage efficiency was further improved.
- the double zincate treatment refers to a treatment in which a zinc coating once formed by the zincate treatment is dissolved using, for example, nitric acid and then the zincate treatment is performed again.
- Claim 5 is A sodium battery negative electrode current collector according to claim 1 or 2, wherein the sodium battery negative electrode current collector is used.
- the negative electrode current collector Al with a Zn film formed directly on the surface through a thin Al oxide film or without an Al oxide film is used, so that the overvoltage is small as described above. At the same time, the wettability with Na is improved, and a sufficiently high voltage efficiency negative electrode can be obtained.
- a sodium battery negative electrode wherein sodium is deposited on a surface of the sodium battery negative electrode current collector according to claim 1.
- the negative electrode active material Na is deposited on the surface of the Al negative electrode current collector with the Zn coating formed directly on the surface through the thin Al oxide film or without the Al oxide film. Thereby, the volume change at the time of charging / discharging becomes small, and the cycling characteristics of a sodium battery can be improved.
- Na is deposited (electrodeposited) by charging after assembling a battery using a Na compound capable of occluding and desorbing Na, such as NaCrO 2 , as the positive electrode active material.
- a Na compound capable of occluding and desorbing Na such as NaCrO 2
- This method is preferable because it is easy to handle because it is possible to precipitate highly reactive Na without touching the outside air.
- the invention of this claim is not limited to the Na deposition after the battery assembly described above, but a method of precipitating Na before the battery assembly by an electrodeposition or vapor deposition under an inert atmosphere or vacuum. It can also be used.
- the invention according to claim 7 The sodium battery negative electrode of Claim 5 or Claim 6 is used, It is a sodium battery characterized by the above-mentioned.
- the negative electrode current collector Al with a Zn film formed directly on the surface through a thin Al oxide film or without an Al oxide film is used. A sufficiently high voltage efficiency can be obtained. And since the wettability with Na can be sufficiently secured by forming the Zn coating, unlike the alloy-based negative electrode, a negative electrode in which Na as a negative electrode active material is sufficiently precipitated on the surface of the Al negative electrode current collector is provided. It is possible to provide a sodium battery that can be formed, has a small volume change during charge and discharge, and has excellent cycle characteristics.
- Negative electrode current collector (1) Zincate treatment of Al
- the negative electrode current collector according to the present invention is produced by subjecting Al to a zincate treatment. Specifically, for example, the zincate treatment is performed by etching the surface of the Al foil and then performing Zn substitution plating. At this time, a portion such as a tab lead that is a connection portion with an external electrode is masked so that a Zn film is not formed.
- an oxide layer of several to several nanometers is formed on the Al surface, and a thicker oxide layer may be formed in some cases.
- an Al layer including an Al oxide film on the surface is formed by zincate treatment. It elutes and is replaced with a Zn film having a low electric resistance, and the Zn film is slowly oxidized.
- the zincate treatment since the Al oxide film on the surface is eluted, the thickness of the oxide layer at the interface can be further reduced or eliminated as compared with the case where it is formed by other methods such as a vapor phase method. For this reason, it is possible to obtain a smaller overvoltage.
- FIG. 3 shows an example of an electron micrograph showing a cross section in the vicinity of the surface of the zincate-treated Al foil. As shown in FIG. 3, a uniform Zn film having a thickness of about 100 nm is formed on the surface of the Al foil.
- Double zincate treatment When the zinc coating formed by the above zincate treatment is eluted using, for example, concentrated nitric acid having a concentration of about 60%, and the zincate treatment is performed again, the coverage with the Zn coating is improved. In addition, since a denser and thinner Zn film can be formed, it is preferable that the overvoltage can be further reduced.
- FIG. 4 is a diagram schematically showing the configuration of the sodium battery negative electrode according to one embodiment of the present invention.
- reference numeral 7 denotes a tab lead attached to the Al foil 1.
- 2 is a Zn film formed by the zincate treatment, and 5 is Na deposited on the Zn film.
- the negative electrode for sodium batteries of the present invention is constituted by depositing Na5 on the surface of the Zn coating 2 of the negative electrode current collector.
- the negative electrode current collector As a specific method for depositing Na5 on the surface of the negative electrode current collector, it may be deposited at any point before or after the battery assembly, as described above.
- a sodium battery using the sodium battery negative electrode is produced by assembling a positive electrode in which a positive electrode active material is provided on a positive electrode current collector, an electrolytic solution, and a separator in addition to the negative electrode for a sodium battery.
- Positive electrode (b) Positive electrode current collector An Al foil is used as the positive electrode current collector.
- Positive electrode active material examples include NaCrO 2 , NaFeO 2 , and Na 2/3 Fe 1/3 Mn 2/3 O 2. Among these, NaCrO 2 is preferably used. . In order to suppress a decrease in capacity due to the charge / discharge cycle, charge / discharge is performed within the range where x is 0 ⁇ x ⁇ 0.4 when expressed as Na desorption amount, that is, Na 1-x CrO 2. Is called.
- Electrolytic Solution As the electrolytic solution, an electrolytic solution in which an electrolyte (supporting salt) shown below is dissolved in an organic solvent or an electrolytic solution made of a molten salt (ionic liquid) is preferably used.
- electrolyte (a) electrolyte (supporting salt) in which an electrolyte (supporting salt) is dissolved in an organic solvent the following may be mentioned.
- NaFSA sodium bis (fluorosulfonyl) amide
- NaPF 6 sodium bis (fluorosulfonyl) amide
- NaAsF 6 NaSbF 6
- NaBF 4 NaCF 3 SO 3
- Carbonates propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di (methoxy Carbonyloxy) ethane, etc.
- Ethers 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.
- esters methyl formate, methyl acetate, ⁇ -butyrolactone, etc.
- Nitriles acetonitrile, butyronitrile, etc.
- Electrolytic solution made of molten salt examples include the following.
- An ionic liquid comprising a mixture of NaFSA and KFSA (potassium bis (fluorosulfonyl) amide), for example, in a molar ratio of 56:44
- An ionic liquid containing organic cations such as quaternary ammonium ions, imidazolium ions, pyrrolidinium ions, piperidinium ions, morpholinium ions, and phosphonium ions in addition to NaFSA
- Evaluation of Negative Electrode in Sodium Battery can be performed by Na precipitation dissolution and charge / discharge evaluation.
- Precipitation / dissolution evaluation of Na The precipitation / dissolution evaluation of Na can be evaluated by overvoltage at the time of charging / discharging of the assembled sodium battery. That is, the voltage required for the precipitation and dissolution of Na is indicated as the magnitude of the overvoltage. For this reason, if the overvoltage is small, it is determined that the battery performance is good and the voltage efficiency is good.
- Etching treatment Etching solution: “Top Alsoft 108” manufactured by Okuno Pharmaceutical Co., Ltd. 50 g / L aqueous solution ⁇ Etching conditions: Temperature: 50 ° C., Time: 30 seconds
- a battery similar to the above was assembled using an Al foil (thickness 20 ⁇ m) that has not been subjected to zincate treatment as a negative electrode current collector, and the same measurement was performed.
- FIG. 5 The measurement results are shown in FIG. In FIG. 5, it is shown that Na is dissolved above the voltage of 0 V, and Na is precipitated below.
- the solid line indicates the case of the Al foil that has been subjected to the zincate process
- the broken line indicates the case of the Al foil that has not been subjected to the zincate process
- the vertical axis indicates the voltage (V)
- the horizontal axis indicates the energization time (minutes). Show.
- FIG. 5 shows that the voltage fluctuation is small and the overvoltage is reduced by applying the zincate process.
- Example of Configuration of Battery Assembly A sodium battery having high voltage efficiency and good cycle characteristics is particularly advantageous when it is an battery assembly.
- 7A and 7B show a configuration example of the assembled battery. 7A is a top view and FIG. 7B is a side view.
- the positive electrode and the negative electrode indicated by bold lines are alternately arranged via separators.
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Abstract
Stably provided is a sodium battery which has a sufficiently high voltage efficiency when Al is used for the negative electrode collector, and in which Na is deposited uniformly. Also provided is a negative electrode collector for sodium batteries, wherein: a zinc coating is formed on a surface of aluminium; an aluminium oxide layer is formed on the surface of the aluminium upon which the zinc coating has not been formed; and an aluminium oxide layer is not formed on the interface between the zinc coating and the aluminium, or, an aluminium oxide layer, which is thinner than the aluminium oxide layer formed on the section upon which the zinc coating has not been formed, is formed on the interface between the zinc coating and the aluminium. Also provided is a method for producing the negative electrode collector for sodium batteries, in which the zinc coating is formed on the surface of the aluminium using zincate treatment.
Description
本発明は、ナトリウムイオン(Na+)が伝導するナトリウム電池用負極集電体とその製造方法、ナトリウム電池用負極およびナトリウム電池に関する。
TECHNICAL FIELD The present invention relates to a negative electrode current collector for sodium batteries that conducts sodium ions (Na + ), a method for producing the same, a negative electrode for sodium batteries, and a sodium battery.
車載用や低炭素電力供給システム等の新エネルギー用の分野等においては、エネルギー密度に優れた蓄電デバイスが強く求められている。このような蓄電デバイスとしては、リチウムイオン電池(Liイオン電池)、ナトリウム硫黄電池(NAS電池)などのナトリウム電池などがあるが、近年、ナトリウム電池の内でも、特に、電解液に溶融塩を用いた溶融塩電解液電池に関する技術開発が種々行われている(例えば特許文献1、非特許文献1)。
In the field of new energy such as in-vehicle and low-carbon power supply systems, there is a strong demand for energy storage devices with excellent energy density. Examples of such power storage devices include sodium batteries such as lithium ion batteries (Li ion batteries) and sodium sulfur batteries (NAS batteries). Recently, among sodium batteries, in particular, molten salts are used for the electrolyte. Various technical developments related to molten salt electrolyte batteries have been made (for example, Patent Document 1 and Non-Patent Document 1).
即ち、Naはクラーク数が2.64とLiの0.006に比べて圧倒的に大きく、材料の調達を安定して容易に行うことができる。
That is, Na has an overwhelmingly large Clark number of 2.64 and 0.006 of Li, and materials can be procured stably and easily.
そして、Liイオン電池の場合には、冷却効率を上げて熱暴走を防ぐために充分なスペース(空隙)を設けて配置する必要があるため、組電池の体積が大きくなる。また、NAS電池の場合も、安全対策上、防火砂が充填された断熱容器内に配置する必要があり、組電池の体積が大きくなる。これに対して、溶融塩電解液電池の場合には、これらの配慮が不要であるため、組電池の体積をLiイオン電池の約1/2、NAS電池の約1/4とコンパクト化することができる。
In the case of a Li-ion battery, it is necessary to provide a sufficient space (air gap) to increase the cooling efficiency and prevent thermal runaway, so that the volume of the assembled battery increases. Also, in the case of a NAS battery, it is necessary to arrange it in a heat insulating container filled with fireproof sand for safety measures, and the volume of the assembled battery increases. On the other hand, in the case of a molten salt electrolyte battery, these considerations are unnecessary, so the volume of the assembled battery should be reduced to about 1/2 of the Li ion battery and about 1/4 of the NAS battery. Can do.
このようなナトリウム電池の負極として、従来は、金属Naと錫(Sn)等との合金からなる合金系負極が用いられていた。しかしながら、このような合金系負極は、活物質であるNaを吸蔵、脱離する際に、大きな体積変化(膨張収縮)が繰り返し起こるため、容量の劣化やサイクル特性の悪化を招く恐れがあった。
Conventionally, an alloy-based negative electrode made of an alloy of metal Na and tin (Sn) or the like has been used as the negative electrode of such a sodium battery. However, such an alloy-based negative electrode repeatedly causes large volume changes (expansion and shrinkage) when the active material Na is occluded and desorbed, which may cause deterioration of capacity and cycle characteristics. .
このため、Naを吸蔵、脱離する際の膨張収縮(体積変化)が小さく、容量の劣化やサイクル特性の悪化を招く恐れがないナトリウム電池用負極が望まれており、上記のNaを吸蔵、脱離する合金系負極に替わる負極の検討が行われている。
For this reason, there is a demand for a negative electrode for sodium batteries that has a small expansion and contraction (volume change) when storing and desorbing Na, and that does not cause deterioration in capacity and cycle characteristics. A negative electrode that replaces the alloy-based negative electrode to be detached has been studied.
そして、そのような負極として、金属集電体の上でNaを溶解、析出させる負極が検討され、その結果、負極集電体としてアルミニウム(Al)が好適であることが分かった。
And, as such a negative electrode, a negative electrode in which Na was dissolved and deposited on a metal current collector was studied, and as a result, it was found that aluminum (Al) was suitable as the negative electrode current collector.
即ち、例えば、銅(Cu)は、導電性に優れ、過電圧を抑制することが期待できるが、Naと合金化するため、ナトリウム電池の負極集電体として用いることには問題がある。
また、ニッケル(Ni)はNaと合金化しないが、Cuと比較して電気抵抗率が4倍以上高く、過電圧が大きくなる可能性がある。これに対し、Alは、Naと合金化することがない。また、AlはCuの1.5倍程度の電気抵抗率で、導電性に優れているためNiほど過電圧が大きくならず、高い電圧効率のナトリウム電池が期待できる。さらに、Alは軽量、低コストである。 That is, for example, copper (Cu) is excellent in conductivity and can be expected to suppress overvoltage. However, since it is alloyed with Na, there is a problem in using it as a negative electrode current collector of a sodium battery.
Nickel (Ni) does not alloy with Na, but its electrical resistivity is four times higher than Cu, which may increase the overvoltage. On the other hand, Al does not alloy with Na. In addition, Al has an electrical resistivity of about 1.5 times that of Cu and is excellent in conductivity. Therefore, Ni does not increase the overvoltage as much as Ni, and a high voltage efficiency sodium battery can be expected. Furthermore, Al is light and low cost.
また、ニッケル(Ni)はNaと合金化しないが、Cuと比較して電気抵抗率が4倍以上高く、過電圧が大きくなる可能性がある。これに対し、Alは、Naと合金化することがない。また、AlはCuの1.5倍程度の電気抵抗率で、導電性に優れているためNiほど過電圧が大きくならず、高い電圧効率のナトリウム電池が期待できる。さらに、Alは軽量、低コストである。 That is, for example, copper (Cu) is excellent in conductivity and can be expected to suppress overvoltage. However, since it is alloyed with Na, there is a problem in using it as a negative electrode current collector of a sodium battery.
Nickel (Ni) does not alloy with Na, but its electrical resistivity is four times higher than Cu, which may increase the overvoltage. On the other hand, Al does not alloy with Na. In addition, Al has an electrical resistivity of about 1.5 times that of Cu and is excellent in conductivity. Therefore, Ni does not increase the overvoltage as much as Ni, and a high voltage efficiency sodium battery can be expected. Furthermore, Al is light and low cost.
しかし、Alを負極集電体に用いたナトリウム電池においては、過電圧が大きくなり、期待通りの高い電圧効率を得ることができない場合があった。また、Alのみの負極集電体とし、充電時にAl上に直接Naを析出させる場合には、Naとの濡れ性(密着性)が悪く、均一にNaが析出しない場合があった。
However, in the sodium battery using Al as the negative electrode current collector, the overvoltage becomes large, and there is a case where high voltage efficiency as expected cannot be obtained. Further, when a negative electrode current collector made of only Al was used and Na was deposited directly on Al during charging, the wettability (adhesiveness) with Na was poor and Na could not be deposited uniformly.
このため、Alを負極集電体に用いた電圧効率が充分に高く、また、均一にNaが析出するナトリウム電池を安定的に提供することができる技術が望まれていた。
For this reason, there has been a demand for a technique capable of stably providing a sodium battery in which the voltage efficiency using Al as a negative electrode current collector is sufficiently high and Na is uniformly deposited.
本発明者は、上記課題の解決について検討を行った結果、従来のAl負極集電体の場合、表面に電気抵抗が大きなAl酸化膜が形成され易く、Al酸化膜が形成されると過電圧が大きくなり、充分に高い電圧効率を得ることができないと共に、Naとの濡れ性が悪くなることが分かった。
As a result of studying the solution of the above problems, the present inventor has found that in the case of a conventional Al negative electrode current collector, an Al oxide film having a large electric resistance is easily formed on the surface, and when the Al oxide film is formed, overvoltage is generated. It became large and it was found that a sufficiently high voltage efficiency could not be obtained and the wettability with Na deteriorated.
そして、このようなAl酸化膜の形成を抑制する手段につき、さらに検討を行った結果、Al基材へのめっき密着性を得るための前処理として行われる亜鉛(Zn)被膜の形成が有効であり、Zn被膜を形成する手法としては、種々の方法を採用することができるが、ジンケート処理が特に好ましいことが分かった。
Further, as a result of further investigation on means for suppressing the formation of such an Al oxide film, formation of a zinc (Zn) film performed as a pretreatment for obtaining plating adhesion to an Al base material is effective. In addition, various methods can be adopted as a method for forming the Zn film, but it has been found that the zincate treatment is particularly preferable.
即ち、ジンケート処理によりAl表面のAl酸化膜がZn被膜に置換された場合、このZn被膜はAl酸化膜に比べ電気抵抗を小さくすることができ、小さな過電圧、及び期待通りの高い電圧効率を得ることができる。
That is, when the Al oxide film on the Al surface is replaced with the Zn film by the zincate treatment, the Zn film can reduce the electric resistance as compared with the Al oxide film, and obtain a small overvoltage and high voltage efficiency as expected. be able to.
具体的には、このジンケート処理は、図1のAに示すように、Al酸化膜を溶かしてAl3+を形成させることにより露出したAl表面にZnを析出させて(Zn置換めっき)、Al基材へのめっき密着性を得る手法である。そして図1のBに示すように、表面の全てがZnに置換されてAlが露出した部分がなくなると反応が終了する。このとき、Alの表面にはZn薄膜が形成されているため、その後のAl酸化物の形成が抑制され、Naとの濡れ性が維持される。
Specifically, as shown in FIG. 1A, this zincate treatment is performed by precipitating Zn on the exposed Al surface by dissolving an Al oxide film to form Al 3+ (Zn displacement plating). This is a technique for obtaining plating adhesion to a material. And as shown to B of FIG. 1, reaction will complete | finish, when all the surfaces are substituted by Zn and there is no part which Al exposed. At this time, since a Zn thin film is formed on the surface of Al, the subsequent formation of Al oxide is suppressed and wettability with Na is maintained.
次に、図2Aおよび図2Bに、Al箔を負極集電体に用いて、その上に負極活物質であるNaを析出させる際(充電時)のNa+と電子(e-)の移動を説明する図を示し、過電圧につき説明する。
Next, FIG. 2A and FIG. 2B show the movement of Na + and electrons (e − ) when an Al foil is used as a negative electrode current collector and Na as a negative electrode active material is deposited thereon (during charging). The figure to explain is shown and it explains per overvoltage.
図2Aはジンケート処理されていないAl箔を負極集電体とした場合を、図2Bはジンケート処理されたAl箔を負極集電体とした場合を示している。そして、図2Aまたは図2Bにおいて、1はAl箔、2はジンケート処理によって形成されたZn被膜、3はAl箔1の表面に生成したAl酸化物被膜、4はZn被膜2の表面に生成したZn酸化物被膜、5は析出したNa、6は電解液である。
FIG. 2A shows a case where an Al foil not subjected to zincate treatment is used as a negative electrode current collector, and FIG. 2B shows a case where an Al foil subjected to zincate treatment is used as a negative electrode current collector. 2A or 2B, 1 is an Al foil, 2 is a Zn film formed by zincate treatment, 3 is an Al oxide film formed on the surface of the Al foil 1, and 4 is formed on the surface of the Zn film 2. Zn oxide film, 5 is deposited Na, and 6 is an electrolytic solution.
充電時には、電解液6からNa+が、Al箔1側からe-が供給されて、Na5が析出されるが、図2Aに示すように、ジンケート処理されていないAl箔の場合には、Al箔1の表面にAl酸化物被膜3が形成されており、このAl酸化物被膜3は厚みが数nmであっても電気抵抗が大きいため、過電圧が大きくなる。この結果、充分に高い電圧効率を得ることができない。また、Al酸化物被膜3は濡れ性が悪いため、Naを均一に析出させることができない。
At the time of charging, Na + is supplied from the electrolytic solution 6 and e − is supplied from the Al foil 1 side, and Na 5 is deposited. However, as shown in FIG. 2A, in the case of an Al foil not subjected to zincate treatment, Al An Al oxide film 3 is formed on the surface of the foil 1, and even if the Al oxide film 3 has a thickness of several nanometers, the electric resistance is large, so that the overvoltage increases. As a result, a sufficiently high voltage efficiency cannot be obtained. Moreover, since the Al oxide film 3 has poor wettability, Na cannot be deposited uniformly.
これに対して、図2Bに示すように、ジンケート処理されたAl箔の場合には、表面に形成されたZn被膜2はAl酸化物被膜に比べ電気抵抗が遙かに小さい。そして、Zn被膜2の酸化(Zn酸化物被膜4の形成)は、Alの酸化に比べて遅く、一旦酸化されても生成されるZnOの密度が小さく体積が大きいため、バリア性が高く、酸化の進行を抑制する効果が大きく、表面酸素量を少なくすることができる。また、Zn酸化物被膜4の電気抵抗はAl酸化物被膜に比べ小さく、Naとの濡れ性がよい。このため、ジンケート処理されたAl箔の表面にNaを析出させる場合には、過電圧が小さくなり、充分に高い電圧効率を得ることができる。
On the other hand, as shown in FIG. 2B, in the case of an Al foil treated with zincate, the Zn coating 2 formed on the surface has much lower electrical resistance than the Al oxide coating. The oxidation of the Zn film 2 (formation of the Zn oxide film 4) is slower than the oxidation of Al, and the density of ZnO generated even once oxidized is small and the volume is large. The effect of suppressing the progress of the growth is great, and the amount of surface oxygen can be reduced. Further, the electrical resistance of the Zn oxide film 4 is smaller than that of the Al oxide film, and the wettability with Na is good. For this reason, when Na is deposited on the surface of the zincate-treated Al foil, the overvoltage is reduced and sufficiently high voltage efficiency can be obtained.
本発明は、上記の知見に基づいてなされたものであり、請求項1に記載の発明は、
アルミニウムからなり、該アルミニウム表面に、亜鉛被膜が形成されていることを特徴とするナトリウム電池用負極集電体である。 The present invention has been made based on the above findings, and the invention according toclaim 1
A negative electrode current collector for a sodium battery, wherein the negative electrode current collector is made of aluminum and has a zinc coating formed on the aluminum surface.
アルミニウムからなり、該アルミニウム表面に、亜鉛被膜が形成されていることを特徴とするナトリウム電池用負極集電体である。 The present invention has been made based on the above findings, and the invention according to
A negative electrode current collector for a sodium battery, wherein the negative electrode current collector is made of aluminum and has a zinc coating formed on the aluminum surface.
そして、請求項2に記載の発明は、
前記亜鉛被膜が形成されていないアルミニウム表面には、アルミニウム酸化層が形成されており、
前記亜鉛被膜と前記アルミニウムとの界面には、アルミニウム酸化層が形成されていないこと、または
前記亜鉛被膜と前記アルミニウムとの界面には、前記亜鉛被膜が形成されていない部分に形成されている前記アルミニウム酸化層よりも薄いアルミニウム酸化層が形成されていること
を特徴とする請求項1に記載のナトリウム電池用負極集電体である。 And the invention ofClaim 2 is
An aluminum oxide layer is formed on the aluminum surface where the zinc coating is not formed,
An aluminum oxide layer is not formed at the interface between the zinc coating and the aluminum, or is formed at a portion where the zinc coating is not formed at the interface between the zinc coating and the aluminum. 2. The negative electrode current collector for a sodium battery according toclaim 1, wherein an aluminum oxide layer thinner than the aluminum oxide layer is formed.
前記亜鉛被膜が形成されていないアルミニウム表面には、アルミニウム酸化層が形成されており、
前記亜鉛被膜と前記アルミニウムとの界面には、アルミニウム酸化層が形成されていないこと、または
前記亜鉛被膜と前記アルミニウムとの界面には、前記亜鉛被膜が形成されていない部分に形成されている前記アルミニウム酸化層よりも薄いアルミニウム酸化層が形成されていること
を特徴とする請求項1に記載のナトリウム電池用負極集電体である。 And the invention of
An aluminum oxide layer is formed on the aluminum surface where the zinc coating is not formed,
An aluminum oxide layer is not formed at the interface between the zinc coating and the aluminum, or is formed at a portion where the zinc coating is not formed at the interface between the zinc coating and the aluminum. 2. The negative electrode current collector for a sodium battery according to
そして、請求項3に記載の発明は、
アルミニウム表面に、亜鉛被膜をジンケート処理によって形成することを特徴とするナトリウム電池用負極集電体の製造方法である。 And the invention ofClaim 3 is
A method for producing a negative electrode current collector for a sodium battery, wherein a zinc coating is formed on an aluminum surface by a zincate treatment.
アルミニウム表面に、亜鉛被膜をジンケート処理によって形成することを特徴とするナトリウム電池用負極集電体の製造方法である。 And the invention of
A method for producing a negative electrode current collector for a sodium battery, wherein a zinc coating is formed on an aluminum surface by a zincate treatment.
ジンケート処理は、前記したように、Al酸化膜を溶かしてZn被膜を形成させるものであるため、界面に存在するアルミニウム酸化層の厚みを薄くすることができる。
As described above, the zincate treatment dissolves the Al oxide film to form a Zn film, so that the thickness of the aluminum oxide layer present at the interface can be reduced.
本発明者は、前記ジンケート処理についてさらに検討を行い、ダブルジンケート処理を採用した場合、Zn被膜の被覆率がより向上して、一層過電圧が低減され、電圧効率がより向上することが分かった。ここで、ダブルジンケート処理とは、ジンケート処理によって一旦形成されたZn被膜を、例えば硝酸等を用いて溶解させた後、再度ジンケート処理を行う処理を指す。
The present inventor further examined the zincate treatment and found that when the double zincate treatment was adopted, the coverage of the Zn coating was further improved, the overvoltage was further reduced, and the voltage efficiency was further improved. Here, the double zincate treatment refers to a treatment in which a zinc coating once formed by the zincate treatment is dissolved using, for example, nitric acid and then the zincate treatment is performed again.
請求項4に記載の発明は、上記の知見に基づいてなされたものであり、
前記亜鉛被膜の形成をジンケート処理によって行った後、形成された亜鉛被膜を溶解させ、再度ジンケート処理によって亜鉛被膜を形成することを特徴とする請求項3に記載のナトリウム電池用負極集電体の製造方法である。 Invention of Claim 4 was made | formed based on said knowledge,
4. The negative electrode current collector for a sodium battery according toclaim 3, wherein the zinc coating is formed by zincate treatment, the formed zinc coating is dissolved, and the zinc coating is formed again by zincate treatment. 5. It is a manufacturing method.
前記亜鉛被膜の形成をジンケート処理によって行った後、形成された亜鉛被膜を溶解させ、再度ジンケート処理によって亜鉛被膜を形成することを特徴とする請求項3に記載のナトリウム電池用負極集電体の製造方法である。 Invention of Claim 4 was made | formed based on said knowledge,
4. The negative electrode current collector for a sodium battery according to
そして、請求項5に記載の発明は、
請求項1または請求項2に記載のナトリウム電池用負極集電体が用いられていることを特徴とするナトリウム電池用負極である。 And the invention ofClaim 5 is
A sodium battery negative electrode current collector according to claim 1 or 2, wherein the sodium battery negative electrode current collector is used.
請求項1または請求項2に記載のナトリウム電池用負極集電体が用いられていることを特徴とするナトリウム電池用負極である。 And the invention of
A sodium battery negative electrode current collector according to
負極集電体として、薄く形成されたAl酸化膜を介して、あるいはAl酸化膜を介さずに直接に表面にZn被膜が形成されたAlを用いているため、前記したように、過電圧が小さいと共に、Naとの濡れ性が向上し、充分に高い電圧効率の負極を得ることができる。
As the negative electrode current collector, Al with a Zn film formed directly on the surface through a thin Al oxide film or without an Al oxide film is used, so that the overvoltage is small as described above. At the same time, the wettability with Na is improved, and a sufficiently high voltage efficiency negative electrode can be obtained.
そして、請求項6に記載の発明は、
請求項1または請求項2に記載のナトリウム電池用負極集電体の表面に、ナトリウムが析出されていることを特徴とするナトリウム電池用負極である。 And invention ofClaim 6 is the following.
A sodium battery negative electrode, wherein sodium is deposited on a surface of the sodium battery negative electrode current collector according toclaim 1.
請求項1または請求項2に記載のナトリウム電池用負極集電体の表面に、ナトリウムが析出されていることを特徴とするナトリウム電池用負極である。 And invention of
A sodium battery negative electrode, wherein sodium is deposited on a surface of the sodium battery negative electrode current collector according to
薄く形成されたAl酸化膜を介して、あるいはAl酸化膜を介さずに直接に表面にZn被膜が形成されたAl負極集電体の表面に負極活物質であるNaを析出させて負極とすることにより、充放電に際しての体積変化が小さくなり、ナトリウム電池のサイクル特性を向上させることができる。
The negative electrode active material Na is deposited on the surface of the Al negative electrode current collector with the Zn coating formed directly on the surface through the thin Al oxide film or without the Al oxide film. Thereby, the volume change at the time of charging / discharging becomes small, and the cycling characteristics of a sodium battery can be improved.
Naを析出させる具体的な方法としては、例えば、正極活物質にNaCrO2等のNaを吸蔵脱離可能なNa化合物を用いて電池を組立てた後に充電することによりNaを析出(電析)させる方法を挙げることができる。
As a specific method for depositing Na, for example, Na is deposited (electrodeposited) by charging after assembling a battery using a Na compound capable of occluding and desorbing Na, such as NaCrO 2 , as the positive electrode active material. A method can be mentioned.
この方法は、反応性に富むNaを外気に触れさせることなく析出させることができる方法であるため、取り扱いが容易となり好ましい。
This method is preferable because it is easy to handle because it is possible to precipitate highly reactive Na without touching the outside air.
しかし、本請求項の発明は、上記した電池組立後のNa析出に限定されるものではなく、不活性雰囲気や真空下での電析や蒸着などにより電池組立前に予めNaを析出させる方法を用いることもできる。
However, the invention of this claim is not limited to the Na deposition after the battery assembly described above, but a method of precipitating Na before the battery assembly by an electrodeposition or vapor deposition under an inert atmosphere or vacuum. It can also be used.
また、請求項7に記載の発明は、
請求項5または請求項6に記載のナトリウム電池用負極が用いられていることを特徴とするナトリウム電池である。 The invention according toclaim 7
The sodium battery negative electrode ofClaim 5 or Claim 6 is used, It is a sodium battery characterized by the above-mentioned.
請求項5または請求項6に記載のナトリウム電池用負極が用いられていることを特徴とするナトリウム電池である。 The invention according to
The sodium battery negative electrode of
負極集電体として、薄く形成されたAl酸化膜を介して、あるいはAl酸化膜を介さずに直接に表面にZn被膜が形成されたAlを用いているため、前記したように、過電圧が小さく、充分に高い電圧効率を得ることができる。そして、Zn被膜の形成により、Naとの濡れ性を充分に確保することができるため、合金系負極と異なり、Al負極集電体表面に負極活物質であるNaを充分に析出させた負極を形成することができ、充放電に際しての体積変化が小さく、サイクル特性に優れたナトリウム電池を提供することができる。
As the negative electrode current collector, Al with a Zn film formed directly on the surface through a thin Al oxide film or without an Al oxide film is used. A sufficiently high voltage efficiency can be obtained. And since the wettability with Na can be sufficiently secured by forming the Zn coating, unlike the alloy-based negative electrode, a negative electrode in which Na as a negative electrode active material is sufficiently precipitated on the surface of the Al negative electrode current collector is provided. It is possible to provide a sodium battery that can be formed, has a small volume change during charge and discharge, and has excellent cycle characteristics.
本発明によれば、Alを負極集電体に用いた電圧効率が充分に高く、また、均一にNaが析出するナトリウム電池を安定的に提供することができる。
According to the present invention, it is possible to stably provide a sodium battery in which voltage efficiency using Al as a negative electrode current collector is sufficiently high and Na is uniformly deposited.
以下、実施の形態に基づき本発明を具体的に説明する。
Hereinafter, the present invention will be specifically described based on embodiments.
1.負極集電体
(1)Alのジンケート処理
本発明に係る負極集電体は、Alにジンケート処理を施すことによって作製される。具体的には、例えば、Al箔の表面をエッチング処理し、その後、Zn置換めっきを施すことにより、ジンケート処理が行われる。なお、この際、タブリードなど外部電極との接続部となる部分には、マスキングなどして、Zn被膜が形成されないようにする。 1. Negative electrode current collector (1) Zincate treatment of Al The negative electrode current collector according to the present invention is produced by subjecting Al to a zincate treatment. Specifically, for example, the zincate treatment is performed by etching the surface of the Al foil and then performing Zn substitution plating. At this time, a portion such as a tab lead that is a connection portion with an external electrode is masked so that a Zn film is not formed.
(1)Alのジンケート処理
本発明に係る負極集電体は、Alにジンケート処理を施すことによって作製される。具体的には、例えば、Al箔の表面をエッチング処理し、その後、Zn置換めっきを施すことにより、ジンケート処理が行われる。なお、この際、タブリードなど外部電極との接続部となる部分には、マスキングなどして、Zn被膜が形成されないようにする。 1. Negative electrode current collector (1) Zincate treatment of Al The negative electrode current collector according to the present invention is produced by subjecting Al to a zincate treatment. Specifically, for example, the zincate treatment is performed by etching the surface of the Al foil and then performing Zn substitution plating. At this time, a portion such as a tab lead that is a connection portion with an external electrode is masked so that a Zn film is not formed.
通常、Al表面には数Å~数nm程度の酸化層が形成され、場合によりさらに厚い酸化層が形成され得るが、前記したように、ジンケート処理により、表面のAl酸化膜を含むAl層が溶出して電気抵抗が小さいZn被膜に置換され、さらにZn被膜は酸化が遅い。
そして、ジンケート処理の場合には、表面のAl酸化膜を溶出するため、気相法など他の方法で形成した場合に比べて界面の酸化層の厚みを一層薄くする、あるいは無くすことができる。このため、一層小さな過電圧を得ることが可能となる。 Usually, an oxide layer of several to several nanometers is formed on the Al surface, and a thicker oxide layer may be formed in some cases. However, as described above, an Al layer including an Al oxide film on the surface is formed by zincate treatment. It elutes and is replaced with a Zn film having a low electric resistance, and the Zn film is slowly oxidized.
In the case of the zincate treatment, since the Al oxide film on the surface is eluted, the thickness of the oxide layer at the interface can be further reduced or eliminated as compared with the case where it is formed by other methods such as a vapor phase method. For this reason, it is possible to obtain a smaller overvoltage.
そして、ジンケート処理の場合には、表面のAl酸化膜を溶出するため、気相法など他の方法で形成した場合に比べて界面の酸化層の厚みを一層薄くする、あるいは無くすことができる。このため、一層小さな過電圧を得ることが可能となる。 Usually, an oxide layer of several to several nanometers is formed on the Al surface, and a thicker oxide layer may be formed in some cases. However, as described above, an Al layer including an Al oxide film on the surface is formed by zincate treatment. It elutes and is replaced with a Zn film having a low electric resistance, and the Zn film is slowly oxidized.
In the case of the zincate treatment, since the Al oxide film on the surface is eluted, the thickness of the oxide layer at the interface can be further reduced or eliminated as compared with the case where it is formed by other methods such as a vapor phase method. For this reason, it is possible to obtain a smaller overvoltage.
図3に、ジンケート処理されたAl箔の表面近傍の断面を示す電子顕微鏡写真の一例を示す。図3に示すように、Al箔の表面には、厚み100nm程度の均一なZn被膜が形成されている。
FIG. 3 shows an example of an electron micrograph showing a cross section in the vicinity of the surface of the zincate-treated Al foil. As shown in FIG. 3, a uniform Zn film having a thickness of about 100 nm is formed on the surface of the Al foil.
(2)ダブルジンケート処理
上記のジンケート処理によって形成されたZn被膜を、例えば濃度が60%程度の濃硝酸を用いて溶出させた後、再度ジンケート処理を行った場合、Zn皮膜による被覆率が向上し、一層緻密で薄いZn被膜を形成させることができるため、より過電圧を小さくすることができ好ましい。 (2) Double zincate treatment When the zinc coating formed by the above zincate treatment is eluted using, for example, concentrated nitric acid having a concentration of about 60%, and the zincate treatment is performed again, the coverage with the Zn coating is improved. In addition, since a denser and thinner Zn film can be formed, it is preferable that the overvoltage can be further reduced.
上記のジンケート処理によって形成されたZn被膜を、例えば濃度が60%程度の濃硝酸を用いて溶出させた後、再度ジンケート処理を行った場合、Zn皮膜による被覆率が向上し、一層緻密で薄いZn被膜を形成させることができるため、より過電圧を小さくすることができ好ましい。 (2) Double zincate treatment When the zinc coating formed by the above zincate treatment is eluted using, for example, concentrated nitric acid having a concentration of about 60%, and the zincate treatment is performed again, the coverage with the Zn coating is improved. In addition, since a denser and thinner Zn film can be formed, it is preferable that the overvoltage can be further reduced.
(3)タブリード
集電体には、必要に応じて適宜タブリードが設けられる。図4は、本発明の一実施の形態のナトリウム電池用負極の構成を模式的に示す図である。図4において、7がAl箔1に取付けられたタブリードである。なお、2はジンケート処理によって形成されたZn被膜であり、5はZn被膜上に析出させたNaである。 (3) Tab lead The current collector is appropriately provided with a tab lead as required. FIG. 4 is a diagram schematically showing the configuration of the sodium battery negative electrode according to one embodiment of the present invention. In FIG. 4,reference numeral 7 denotes a tab lead attached to the Al foil 1. In addition, 2 is a Zn film formed by the zincate treatment, and 5 is Na deposited on the Zn film.
集電体には、必要に応じて適宜タブリードが設けられる。図4は、本発明の一実施の形態のナトリウム電池用負極の構成を模式的に示す図である。図4において、7がAl箔1に取付けられたタブリードである。なお、2はジンケート処理によって形成されたZn被膜であり、5はZn被膜上に析出させたNaである。 (3) Tab lead The current collector is appropriately provided with a tab lead as required. FIG. 4 is a diagram schematically showing the configuration of the sodium battery negative electrode according to one embodiment of the present invention. In FIG. 4,
2.ナトリウム電池用負極
次に、上記負極集電体を用いたナトリウム電池用負極について説明する。図4に示すように、本発明のナトリウム電池用負極は、負極集電体のZn被膜2の表面にNa5を析出させて構成されている。 2. Next, a negative electrode for sodium batteries using the negative electrode current collector will be described. As shown in FIG. 4, the negative electrode for sodium batteries of the present invention is constituted by depositing Na5 on the surface of theZn coating 2 of the negative electrode current collector.
次に、上記負極集電体を用いたナトリウム電池用負極について説明する。図4に示すように、本発明のナトリウム電池用負極は、負極集電体のZn被膜2の表面にNa5を析出させて構成されている。 2. Next, a negative electrode for sodium batteries using the negative electrode current collector will be described. As shown in FIG. 4, the negative electrode for sodium batteries of the present invention is constituted by depositing Na5 on the surface of the
負極集電体表面にNa5を析出させる具体的な方法としては、前記したように、電池組立前、電池組立後のいずれの時点で析出させてもよい。
As a specific method for depositing Na5 on the surface of the negative electrode current collector, it may be deposited at any point before or after the battery assembly, as described above.
3.ナトリウム電池
次に、上記ナトリウム電池用負極を用いたナトリウム電池について説明する。ナトリウム電池は、上記のナトリウム電池用負極の他に、正極集電体上に正極活物質が設けられた正極、電解液およびセパレータを組立てることにより作製される。 3. Next, a sodium battery using the sodium battery negative electrode will be described. A sodium battery is produced by assembling a positive electrode in which a positive electrode active material is provided on a positive electrode current collector, an electrolytic solution, and a separator in addition to the negative electrode for a sodium battery.
次に、上記ナトリウム電池用負極を用いたナトリウム電池について説明する。ナトリウム電池は、上記のナトリウム電池用負極の他に、正極集電体上に正極活物質が設けられた正極、電解液およびセパレータを組立てることにより作製される。 3. Next, a sodium battery using the sodium battery negative electrode will be described. A sodium battery is produced by assembling a positive electrode in which a positive electrode active material is provided on a positive electrode current collector, an electrolytic solution, and a separator in addition to the negative electrode for a sodium battery.
(1)正極
(イ)正極集電体
正極集電体としては、Al箔が用いられる。 (1) Positive electrode (b) Positive electrode current collector An Al foil is used as the positive electrode current collector.
(イ)正極集電体
正極集電体としては、Al箔が用いられる。 (1) Positive electrode (b) Positive electrode current collector An Al foil is used as the positive electrode current collector.
(ロ)正極活物質
正極活物質としては、NaCrO2、NaFeO2、Na2/3Fe1/3Mn2/3O2等を挙げることができるが、これらの内でもNaCrO2が好ましく用いられる。なお、充放電サイクルによる容量低下を抑制するため、Naの脱離量、即ちNa1-xCrO2で表したときのxが0≦x≦0.4を満足する範囲内において充放電が行われる。 (B) Positive electrode active material Examples of the positive electrode active material include NaCrO 2 , NaFeO 2 , and Na 2/3 Fe 1/3 Mn 2/3 O 2. Among these, NaCrO 2 is preferably used. . In order to suppress a decrease in capacity due to the charge / discharge cycle, charge / discharge is performed within the range where x is 0 ≦ x ≦ 0.4 when expressed as Na desorption amount, that is, Na 1-x CrO 2. Is called.
正極活物質としては、NaCrO2、NaFeO2、Na2/3Fe1/3Mn2/3O2等を挙げることができるが、これらの内でもNaCrO2が好ましく用いられる。なお、充放電サイクルによる容量低下を抑制するため、Naの脱離量、即ちNa1-xCrO2で表したときのxが0≦x≦0.4を満足する範囲内において充放電が行われる。 (B) Positive electrode active material Examples of the positive electrode active material include NaCrO 2 , NaFeO 2 , and Na 2/3 Fe 1/3 Mn 2/3 O 2. Among these, NaCrO 2 is preferably used. . In order to suppress a decrease in capacity due to the charge / discharge cycle, charge / discharge is performed within the range where x is 0 ≦ x ≦ 0.4 when expressed as Na desorption amount, that is, Na 1-x CrO 2. Is called.
(2)電解液
電解液としては、以下に示す電解質(支持塩)を有機溶媒に溶解させた電解液、または溶融塩(イオン液体)からなる電解液が好ましく用いられる。 (2) Electrolytic Solution As the electrolytic solution, an electrolytic solution in which an electrolyte (supporting salt) shown below is dissolved in an organic solvent or an electrolytic solution made of a molten salt (ionic liquid) is preferably used.
電解液としては、以下に示す電解質(支持塩)を有機溶媒に溶解させた電解液、または溶融塩(イオン液体)からなる電解液が好ましく用いられる。 (2) Electrolytic Solution As the electrolytic solution, an electrolytic solution in which an electrolyte (supporting salt) shown below is dissolved in an organic solvent or an electrolytic solution made of a molten salt (ionic liquid) is preferably used.
(イ)電解質(支持塩)を有機溶媒に溶解させた電解液
(a)電解質(支持塩)としては、以下のものを挙げることができる。
NaFSA(ナトリウムビス(フルオロスルフォニル)アミド)、NaClO4、NaPF6、NaAsF6、NaSbF6、NaBF4、NaCF3SO3、NaN(SO2CF3)2等 (A) As an electrolyte (a) electrolyte (supporting salt) in which an electrolyte (supporting salt) is dissolved in an organic solvent, the following may be mentioned.
NaFSA (sodium bis (fluorosulfonyl) amide), NaClO 4 , NaPF 6 , NaAsF 6 , NaSbF 6 , NaBF 4 , NaCF 3 SO 3 , NaN (SO 2 CF 3 ) 2 and the like
(a)電解質(支持塩)としては、以下のものを挙げることができる。
NaFSA(ナトリウムビス(フルオロスルフォニル)アミド)、NaClO4、NaPF6、NaAsF6、NaSbF6、NaBF4、NaCF3SO3、NaN(SO2CF3)2等 (A) As an electrolyte (a) electrolyte (supporting salt) in which an electrolyte (supporting salt) is dissolved in an organic solvent, the following may be mentioned.
NaFSA (sodium bis (fluorosulfonyl) amide), NaClO 4 , NaPF 6 , NaAsF 6 , NaSbF 6 , NaBF 4 , NaCF 3 SO 3 , NaN (SO 2 CF 3 ) 2 and the like
(b)有機溶媒としては、以下のものを挙げることができる。
(B) As an organic solvent, the following can be mentioned.
・カーボネート類:プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、イソプロピルメチルカーボネート、ビニレンカーボネート、4-トリフルオロメチル-1,3-ジオキソラン-2-オン、1,2-ジ(メトキシカルボニルオキシ)エタン等
Carbonates: propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di (methoxy Carbonyloxy) ethane, etc.
・エーテル類:1,2-ジメトキシエタン、1,3-ジメトキシプロパン、ペンタフルオロプロピルメチルエーテル、2,2,3,3-テトラフルオロプロピルジフルオロメチルエーテル、テトラヒドロフラン、2-メチルテトラヒドロフラン等
Ethers: 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.
・エステル類:蟻酸メチル、酢酸メチル、γーブチロラクトン等
・ Esters: methyl formate, methyl acetate, γ-butyrolactone, etc.
・ニトリル類:アセトニトリル、ブチロニトリル等
Nitriles: acetonitrile, butyronitrile, etc.
・アミド類:N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等
Amides: N, N-dimethylformamide, N, N-dimethylacetamide, etc.
(ロ)溶融塩(イオン液体)からなる電解液
溶融塩(イオン液体)からなる電解液としては、以下のものを挙げることができる。 (B) Electrolytic solution made of molten salt (ionic liquid) Examples of the electrolytic solution made of molten salt (ionic liquid) include the following.
溶融塩(イオン液体)からなる電解液としては、以下のものを挙げることができる。 (B) Electrolytic solution made of molten salt (ionic liquid) Examples of the electrolytic solution made of molten salt (ionic liquid) include the following.
・NaFSAとKFSA(カリウムビス(フルオロスルフォニル)アミド)の例えばモル比で56:44の混合物からなるイオン液体
An ionic liquid comprising a mixture of NaFSA and KFSA (potassium bis (fluorosulfonyl) amide), for example, in a molar ratio of 56:44
・NaFSAに加え、カチオンとして、4級アンモニウムイオン、イミダゾリウムイオン、ピロリジニウムイオン、ピペリジニウムイオン、モルホリニウムイオン、フォスフォニウムイオン等の有機カチオンを含むイオン液体
An ionic liquid containing organic cations such as quaternary ammonium ions, imidazolium ions, pyrrolidinium ions, piperidinium ions, morpholinium ions, and phosphonium ions in addition to NaFSA
4.ナトリウム電池における負極の評価
組立てられたナトリウム電池における負極の評価は、Naの析出溶解評価、および充放電評価により行うことができる。 4). Evaluation of Negative Electrode in Sodium Battery Evaluation of the negative electrode in an assembled sodium battery can be performed by Na precipitation dissolution and charge / discharge evaluation.
組立てられたナトリウム電池における負極の評価は、Naの析出溶解評価、および充放電評価により行うことができる。 4). Evaluation of Negative Electrode in Sodium Battery Evaluation of the negative electrode in an assembled sodium battery can be performed by Na precipitation dissolution and charge / discharge evaluation.
(1)Naの析出溶解評価
Naの析出溶解評価は、組立てられたナトリウム電池の充放電時の過電圧により評価することができる。即ち、Naの析出、溶解に必要な電圧が過電圧の大きさとして示される。このため、過電圧が小さければ、電池性能が良く電圧効率も良いと判断される。 (1) Precipitation / dissolution evaluation of Na The precipitation / dissolution evaluation of Na can be evaluated by overvoltage at the time of charging / discharging of the assembled sodium battery. That is, the voltage required for the precipitation and dissolution of Na is indicated as the magnitude of the overvoltage. For this reason, if the overvoltage is small, it is determined that the battery performance is good and the voltage efficiency is good.
Naの析出溶解評価は、組立てられたナトリウム電池の充放電時の過電圧により評価することができる。即ち、Naの析出、溶解に必要な電圧が過電圧の大きさとして示される。このため、過電圧が小さければ、電池性能が良く電圧効率も良いと判断される。 (1) Precipitation / dissolution evaluation of Na The precipitation / dissolution evaluation of Na can be evaluated by overvoltage at the time of charging / discharging of the assembled sodium battery. That is, the voltage required for the precipitation and dissolution of Na is indicated as the magnitude of the overvoltage. For this reason, if the overvoltage is small, it is determined that the battery performance is good and the voltage efficiency is good.
(2)充放電評価
充放電評価は、電圧効率により評価することができる。 (2) Charge / Discharge Evaluation Charge / discharge evaluation can be evaluated by voltage efficiency.
充放電評価は、電圧効率により評価することができる。 (2) Charge / Discharge Evaluation Charge / discharge evaluation can be evaluated by voltage efficiency.
電圧効率は、容量の50%充放電の時の放電電圧と充電電圧の比率として下式のように定義されるものであり、充電量に対してどれだけ放電できるかを示している。90%以上であると好ましく、95%以上であるとより好ましい。
電圧効率(%)=(放電電圧/充電電圧)×100% The voltage efficiency is defined as the ratio of the discharge voltage and the charge voltage at the time of 50% charge / discharge of the capacity as shown in the following formula, and indicates how much discharge can be performed with respect to the charge amount. It is preferably 90% or more, and more preferably 95% or more.
Voltage efficiency (%) = (discharge voltage / charge voltage) × 100%
電圧効率(%)=(放電電圧/充電電圧)×100% The voltage efficiency is defined as the ratio of the discharge voltage and the charge voltage at the time of 50% charge / discharge of the capacity as shown in the following formula, and indicates how much discharge can be performed with respect to the charge amount. It is preferably 90% or more, and more preferably 95% or more.
Voltage efficiency (%) = (discharge voltage / charge voltage) × 100%
以下、実施例に基づき本発明をさらに具体的に説明する。
Hereinafter, the present invention will be described more specifically based on examples.
1.負極集電体の作製
厚み20μmのAl箔を用意し、以下に示すエッチング処理およびZn置換めっき処理によりAl箔表面にジンケート処理を施し、負極集電体を作製した。 1. Production of Negative Electrode Current Collector An Al foil having a thickness of 20 μm was prepared, and the surface of the Al foil was subjected to a zincate treatment by etching treatment and Zn displacement plating treatment described below to produce a negative electrode current collector.
厚み20μmのAl箔を用意し、以下に示すエッチング処理およびZn置換めっき処理によりAl箔表面にジンケート処理を施し、負極集電体を作製した。 1. Production of Negative Electrode Current Collector An Al foil having a thickness of 20 μm was prepared, and the surface of the Al foil was subjected to a zincate treatment by etching treatment and Zn displacement plating treatment described below to produce a negative electrode current collector.
(1)エッチング処理:
・エッチング液 :奥野製薬社製「トップアルソフト108」
50g/L 水溶液
・エッチング条件:温度:50℃、時間:30秒 (1) Etching treatment:
Etching solution: “Top Alsoft 108” manufactured by Okuno Pharmaceutical Co., Ltd.
50 g / L aqueous solution ・ Etching conditions: Temperature: 50 ° C., Time: 30 seconds
・エッチング液 :奥野製薬社製「トップアルソフト108」
50g/L 水溶液
・エッチング条件:温度:50℃、時間:30秒 (1) Etching treatment:
Etching solution: “Top Alsoft 108” manufactured by Okuno Pharmaceutical Co., Ltd.
50 g / L aqueous solution ・ Etching conditions: Temperature: 50 ° C., Time: 30 seconds
(2)Zn置換めっき
・めっき液 :奥野製薬社製「サブスターZN-1」
180cc/L 水溶液
・めっき条件 :温度:25℃、時間:30秒 (2) Zn displacement plating Plating solution: “Substar ZN-1” manufactured by Okuno Pharmaceutical Co., Ltd.
180cc / L aqueous solution ・ Plating conditions: Temperature: 25 ° C., Time: 30 seconds
・めっき液 :奥野製薬社製「サブスターZN-1」
180cc/L 水溶液
・めっき条件 :温度:25℃、時間:30秒 (2) Zn displacement plating Plating solution: “Substar ZN-1” manufactured by Okuno Pharmaceutical Co., Ltd.
180cc / L aqueous solution ・ Plating conditions: Temperature: 25 ° C., Time: 30 seconds
2.Naの析出溶解評価
(1)ナトリウム電池の組立
上記で作製されたジンケート処理が施されたAl箔(厚み20μm)を負極集電体、金属Naを正極、厚み200μmのガラス不織布をセパレータ、ナトリウムビス(フルオロスルフォニル)アミド(NaFSA)とカリウムビス(フルオロスルフォニル)アミド(KFSA)との混合物(モル比56:44)からなる溶融塩を電解液として、ナトリウム電池を組立てた。 2. Evaluation of precipitation and dissolution of Na (1) Assembly of sodium battery The above-prepared zincate-treated Al foil (thickness 20 μm) was used as the negative electrode current collector, metal Na as the positive electrode, glass nonwoven fabric with a thickness of 200 μm as the separator, sodium bis A sodium battery was assembled using a molten salt composed of a mixture (molar ratio 56:44) of (fluorosulfonyl) amide (NaFSA) and potassium bis (fluorosulfonyl) amide (KFSA) as an electrolyte.
(1)ナトリウム電池の組立
上記で作製されたジンケート処理が施されたAl箔(厚み20μm)を負極集電体、金属Naを正極、厚み200μmのガラス不織布をセパレータ、ナトリウムビス(フルオロスルフォニル)アミド(NaFSA)とカリウムビス(フルオロスルフォニル)アミド(KFSA)との混合物(モル比56:44)からなる溶融塩を電解液として、ナトリウム電池を組立てた。 2. Evaluation of precipitation and dissolution of Na (1) Assembly of sodium battery The above-prepared zincate-treated Al foil (
(2)Naの析出溶解評価
作製されたナトリウム電池に、温度90℃、電流密度0.1mA/cm2で通電を行い、Al箔上でNaを析出、溶解させたときの負極側の電圧の時間経過に伴う変化を測定した。 (2) Precipitation / dissolution evaluation of Na The manufactured sodium battery was energized at a temperature of 90 ° C. and a current density of 0.1 mA / cm 2 , and the voltage on the negative electrode side when Na was precipitated and dissolved on the Al foil was measured. Changes with time were measured.
作製されたナトリウム電池に、温度90℃、電流密度0.1mA/cm2で通電を行い、Al箔上でNaを析出、溶解させたときの負極側の電圧の時間経過に伴う変化を測定した。 (2) Precipitation / dissolution evaluation of Na The manufactured sodium battery was energized at a temperature of 90 ° C. and a current density of 0.1 mA / cm 2 , and the voltage on the negative electrode side when Na was precipitated and dissolved on the Al foil was measured. Changes with time were measured.
比較のために、ジンケート処理が施されていないAl箔(厚み20μm)を負極集電体として、上記と同様の電池を組立て、同様の測定を行った。
For comparison, a battery similar to the above was assembled using an Al foil (thickness 20 μm) that has not been subjected to zincate treatment as a negative electrode current collector, and the same measurement was performed.
測定結果を図5に示す。図5において、電圧0Vより上ではNaが溶解、下ではNaが析出していることを示している。そして、図5において、実線はジンケート処理が施されたAl箔、破線はジンケート処理が施されていないAl箔の場合であり、縦軸は電圧(V)、横軸は通電時間(分)を示している。
The measurement results are shown in FIG. In FIG. 5, it is shown that Na is dissolved above the voltage of 0 V, and Na is precipitated below. In FIG. 5, the solid line indicates the case of the Al foil that has been subjected to the zincate process, the broken line indicates the case of the Al foil that has not been subjected to the zincate process, the vertical axis indicates the voltage (V), and the horizontal axis indicates the energization time (minutes). Show.
図5より、ジンケート処理を施すことにより、電圧の揺れが小さく、過電圧が低減されていることが分かる。
FIG. 5 shows that the voltage fluctuation is small and the overvoltage is reduced by applying the zincate process.
これは、上述したように、ジンケート処理により、Al箔の表面に電気抵抗が小さなZn被膜が形成されており、バリア層となるAl酸化膜が形成されていないために過電圧が低減されたものと考えられる。
This is because, as described above, a zinc film having a small electric resistance is formed on the surface of the Al foil by the zincate process, and an Al oxide film serving as a barrier layer is not formed, so that the overvoltage is reduced. Conceivable.
3.充放電評価
(1)ナトリウム電池の組立
上記で作製されたジンケート処理Al箔(厚み20μm)の負極集電体と、Al箔(厚み20μm)上に正極活物質としてNaCrO2を厚み50μmでコートした正極と、ガラス不織布セパレータ(厚み200μm)とを用いて、NaFSAとKFSAとの混合物(モル比56:44)からなる溶融塩を電解液として、ナトリウム電池を組立てた。 3. Charge / Discharge Evaluation (1) Assembly of Sodium Battery The negative electrode current collector of the zincate-treated Al foil (thickness 20 μm) prepared above and NaCrO 2 as a positive electrode active material were coated on the Al foil (thickness 20 μm) with a thickness of 50 μm. Using a positive electrode and a glass nonwoven fabric separator (thickness 200 μm), a sodium battery was assembled using a molten salt composed of a mixture of NaFSA and KFSA (molar ratio 56:44) as an electrolyte.
(1)ナトリウム電池の組立
上記で作製されたジンケート処理Al箔(厚み20μm)の負極集電体と、Al箔(厚み20μm)上に正極活物質としてNaCrO2を厚み50μmでコートした正極と、ガラス不織布セパレータ(厚み200μm)とを用いて、NaFSAとKFSAとの混合物(モル比56:44)からなる溶融塩を電解液として、ナトリウム電池を組立てた。 3. Charge / Discharge Evaluation (1) Assembly of Sodium Battery The negative electrode current collector of the zincate-treated Al foil (
(2)充放電評価
作製されたナトリウム電池を用いて、温度90℃、充放電レート0.1Cで充放電を行い、充電および放電における負極の電圧変化を測定した。結果を図6に示す。図6において、50%放電時および50%充電時の電圧はそれぞれ3.18Vと3.22Vであり、電圧効率が99%と極めて高く、従来のナトリウム電池における電圧効率95%を大きく上回っていることが分かる。 (2) Charging / discharging evaluation Using the produced sodium battery, charging / discharging was performed at a temperature of 90 ° C. and a charging / discharging rate of 0.1 C, and voltage change of the negative electrode during charging and discharging was measured. The results are shown in FIG. In FIG. 6, the voltages at 50% discharge and 50% charge are 3.18 V and 3.22 V, respectively, and the voltage efficiency is extremely high at 99%, which is much higher than the voltage efficiency of 95% in the conventional sodium battery. I understand that.
作製されたナトリウム電池を用いて、温度90℃、充放電レート0.1Cで充放電を行い、充電および放電における負極の電圧変化を測定した。結果を図6に示す。図6において、50%放電時および50%充電時の電圧はそれぞれ3.18Vと3.22Vであり、電圧効率が99%と極めて高く、従来のナトリウム電池における電圧効率95%を大きく上回っていることが分かる。 (2) Charging / discharging evaluation Using the produced sodium battery, charging / discharging was performed at a temperature of 90 ° C. and a charging / discharging rate of 0.1 C, and voltage change of the negative electrode during charging and discharging was measured. The results are shown in FIG. In FIG. 6, the voltages at 50% discharge and 50% charge are 3.18 V and 3.22 V, respectively, and the voltage efficiency is extremely high at 99%, which is much higher than the voltage efficiency of 95% in the conventional sodium battery. I understand that.
これは、ジンケート処理により負極の過電圧が低減し、電圧効率が向上したためと考えられる。
This is thought to be because the overvoltage of the negative electrode was reduced by the zincate treatment, and the voltage efficiency was improved.
(3)ナトリウム電池のサイクル特性
次に、充電深度65%の充放電を100サイクル行い、容量低下などの劣化を測定した。その結果、容量低下などの劣化は見られず、良好なサイクル特性を有していることが確認できた。 (3) Cycle characteristics of sodium battery Next, charge / discharge at a charge depth of 65% was performed 100 cycles, and deterioration such as capacity reduction was measured. As a result, no deterioration such as a decrease in capacity was observed, and it was confirmed that the battery had good cycle characteristics.
次に、充電深度65%の充放電を100サイクル行い、容量低下などの劣化を測定した。その結果、容量低下などの劣化は見られず、良好なサイクル特性を有していることが確認できた。 (3) Cycle characteristics of sodium battery Next, charge / discharge at a charge depth of 65% was performed 100 cycles, and deterioration such as capacity reduction was measured. As a result, no deterioration such as a decrease in capacity was observed, and it was confirmed that the battery had good cycle characteristics.
5.組電池の構成例
このように電圧効率が高くサイクル特性も良好なナトリウム電池は、組電池とした場合に特に優位性が発揮される。図7Aおよび図7Bに組電池の一構成例を示す。なお、図7Aは上面図、図7Bは側面図である。 5. Example of Configuration of Battery Assembly A sodium battery having high voltage efficiency and good cycle characteristics is particularly advantageous when it is an battery assembly. 7A and 7B show a configuration example of the assembled battery. 7A is a top view and FIG. 7B is a side view.
このように電圧効率が高くサイクル特性も良好なナトリウム電池は、組電池とした場合に特に優位性が発揮される。図7Aおよび図7Bに組電池の一構成例を示す。なお、図7Aは上面図、図7Bは側面図である。 5. Example of Configuration of Battery Assembly A sodium battery having high voltage efficiency and good cycle characteristics is particularly advantageous when it is an battery assembly. 7A and 7B show a configuration example of the assembled battery. 7A is a top view and FIG. 7B is a side view.
図7Aの右図に示すように、素電池単体においては、太線で示す正極及び負極がセパレータを介して交互に配置されている。
As shown in the right figure of FIG. 7A, in the unit cell unit, the positive electrode and the negative electrode indicated by bold lines are alternately arranged via separators.
そして、図7Bに示すように、電圧3Vの素電池単体が4個隙間を設けず直列に配置されて、12Vの電圧が得られるようになっており、Liイオン電池やNAS電池に比べてコンパクト化されていることが分かる。
Then, as shown in FIG. 7B, four unit cells with a voltage of 3V are arranged in series without any gaps, so that a voltage of 12V can be obtained, which is more compact than Li-ion batteries and NAS batteries. It can be seen that
以上、本発明を実施の形態に基づいて説明したが、本発明は上記の実施の形態に限定されるものではない。本発明と同一および均等の範囲内において、上記の実施の形態に対して種々の変更を加えることができる。
As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to said embodiment. Various modifications can be made to the above-described embodiments within the same and equivalent scope as the present invention.
1 Al箔
2 Zn被膜
3 Al酸化物被膜
4 Zn酸化物被膜
5 Na
6 電解液
7 タブリード 1Al foil 2 Zn coating 3 Al oxide coating 4 Zn oxide coating 5 Na
6Electrolyte 7 Tab lead
2 Zn被膜
3 Al酸化物被膜
4 Zn酸化物被膜
5 Na
6 電解液
7 タブリード 1
6
Claims (7)
- アルミニウム表面に、亜鉛被膜が形成されていることを特徴とするナトリウム電池用負極集電体。 A negative electrode current collector for sodium batteries, characterized in that a zinc coating is formed on the aluminum surface.
- 前記亜鉛被膜が形成されていないアルミニウム表面には、アルミニウム酸化層が形成されており、
前記亜鉛被膜と前記アルミニウムとの界面には、アルミニウム酸化層が形成されていないこと、または
前記亜鉛被膜と前記アルミニウムとの界面には、前記亜鉛被膜が形成されていない部分に形成されている前記アルミニウム酸化層よりも薄いアルミニウム酸化層が形成されていること
を特徴とする請求項1に記載のナトリウム電池用負極集電体。 An aluminum oxide layer is formed on the aluminum surface where the zinc coating is not formed,
An aluminum oxide layer is not formed at the interface between the zinc coating and the aluminum, or is formed at a portion where the zinc coating is not formed at the interface between the zinc coating and the aluminum. 2. The negative electrode current collector for a sodium battery according to claim 1, wherein an aluminum oxide layer thinner than the aluminum oxide layer is formed. - アルミニウム表面に、亜鉛被膜をジンケート処理によって形成することを特徴とするナトリウム電池用負極集電体の製造方法。 A method for producing a negative electrode current collector for sodium batteries, wherein a zinc coating is formed on an aluminum surface by a zincate treatment.
- 前記亜鉛被膜の形成をジンケート処理によって行った後、形成された亜鉛被膜を溶解させ、再度ジンケート処理によって亜鉛被膜を形成することを特徴とする請求項3に記載のナトリウム電池用負極集電体の製造方法。 4. The negative electrode current collector for a sodium battery according to claim 3, wherein the zinc coating is formed by zincate treatment, the formed zinc coating is dissolved, and the zinc coating is formed again by zincate treatment. 5. Production method.
- 請求項1または請求項2に記載のナトリウム電池用負極集電体が用いられていることを特徴とするナトリウム電池用負極。 A sodium battery negative electrode current collector according to claim 1 or 2, wherein the sodium battery negative electrode current collector is used.
- 請求項1または請求項2に記載のナトリウム電池用負極集電体の表面に、ナトリウムが析出されていることを特徴とするナトリウム電池用負極。 A sodium battery negative electrode, wherein sodium is deposited on the surface of the sodium battery negative electrode current collector according to claim 1 or 2.
- 請求項5または請求項6に記載のナトリウム電池用負極が用いられていることを特徴とするナトリウム電池。 A sodium battery, wherein the sodium battery negative electrode according to claim 5 or 6 is used.
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JP2014235912A (en) * | 2013-06-03 | 2014-12-15 | 住友電気工業株式会社 | Sodium molten salt battery and method for manufacturing the same |
WO2018014164A1 (en) * | 2016-07-18 | 2018-01-25 | 宁德时代新能源科技股份有限公司 | Method for supplementing sodium ion battery with sodium and electrode sheet and battery obtained by preparation |
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JP6369251B2 (en) * | 2014-09-11 | 2018-08-08 | 住友電気工業株式会社 | Positive electrode for sodium molten salt battery and sodium molten salt battery using the same |
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WO2010110465A1 (en) * | 2009-03-25 | 2010-09-30 | 住友化学株式会社 | Sodium ion battery |
WO2011108716A1 (en) * | 2010-03-05 | 2011-09-09 | 住友電気工業株式会社 | Process for production of negative electrode precursor material for battery, negative electrode precursor material for battery, and battery |
WO2011111566A1 (en) * | 2010-03-12 | 2011-09-15 | 住友電気工業株式会社 | Negative electrode material for battery, negative electrode precursor material for battery, and battery |
JP2011228211A (en) * | 2010-04-22 | 2011-11-10 | Sumitomo Electric Ind Ltd | Molten-salt battery and method of manufacturing the same |
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WO2010110465A1 (en) * | 2009-03-25 | 2010-09-30 | 住友化学株式会社 | Sodium ion battery |
WO2011108716A1 (en) * | 2010-03-05 | 2011-09-09 | 住友電気工業株式会社 | Process for production of negative electrode precursor material for battery, negative electrode precursor material for battery, and battery |
WO2011111566A1 (en) * | 2010-03-12 | 2011-09-15 | 住友電気工業株式会社 | Negative electrode material for battery, negative electrode precursor material for battery, and battery |
JP2011228211A (en) * | 2010-04-22 | 2011-11-10 | Sumitomo Electric Ind Ltd | Molten-salt battery and method of manufacturing the same |
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JP2014235912A (en) * | 2013-06-03 | 2014-12-15 | 住友電気工業株式会社 | Sodium molten salt battery and method for manufacturing the same |
WO2018014164A1 (en) * | 2016-07-18 | 2018-01-25 | 宁德时代新能源科技股份有限公司 | Method for supplementing sodium ion battery with sodium and electrode sheet and battery obtained by preparation |
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