WO2018042945A1 - 二次電池 - Google Patents
二次電池 Download PDFInfo
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- WO2018042945A1 WO2018042945A1 PCT/JP2017/026697 JP2017026697W WO2018042945A1 WO 2018042945 A1 WO2018042945 A1 WO 2018042945A1 JP 2017026697 W JP2017026697 W JP 2017026697W WO 2018042945 A1 WO2018042945 A1 WO 2018042945A1
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- This embodiment relates to a secondary battery.
- the conventional secondary battery does not use an electrolytic solution / rare element and can be made thin, the first electrode / insulator / n-type oxide semiconductor layer / p-type oxide semiconductor layer / second electrode Stacked secondary batteries have been proposed.
- a positive electrode including a positive electrode active material film containing nickel oxide or the like as a positive electrode active material, a solid electrolyte having a water-containing porous structure, and a negative electrode including titanium oxide or the like as a negative electrode active material A secondary battery including a negative electrode including an active material film has been proposed.
- Japanese Patent No. 5508542 Japanese Patent No. 5297809 JP 2015-82445 A JP 2016-82125 A
- This embodiment provides a secondary battery with high energy density, high battery characteristics (storage capacity), and high reliability.
- a first conductivity type first oxide semiconductor layer and a first insulator and a first conductivity type second oxide are disposed on the first oxide semiconductor layer.
- a first charging layer made of a semiconductor, a second conductive type third oxide semiconductor layer disposed on the first charging layer, and between the first charging layer and the third oxide semiconductor layer There is provided a secondary battery including a hydroxide layer disposed and having a metal hydroxide constituting the third oxide semiconductor layer.
- the energy density is improved, the battery characteristics (storage capacity) can be increased, and a highly reliable secondary battery can be provided.
- the secondary battery which concerns on embodiment WHEREIN The scanning electron microscope (SEM) photograph example of the cross section of the sample which produced the 2nd charge layer using the silicone oil.
- FIG. 10 is a SIMS profile example for each element in the secondary battery according to the embodiment shown in FIG.
- the figure which shows the relationship of resistance R (a.u.) and energy density (a.u.) between the 1st electrode and the 2nd electrode with respect to electrical conductivity adjustment material addition amount.
- the secondary battery 30 is disposed on the first conductivity type first oxide semiconductor layer 14 and the first oxide semiconductor layer 14, and includes the first insulator and the first oxide semiconductor layer 14.
- a first charge layer 16 made of a first conductivity type second oxide semiconductor; a second conductivity type third oxide semiconductor layer 24 disposed on the first charge layer 16; a first charge layer 16; and a hydroxide layer 22 having a metal hydroxide that is disposed between the oxide semiconductor layer 24 and the third oxide semiconductor layer 24.
- the secondary battery 30 may include a second charging layer 18 disposed between the first charging layer 16 and the hydroxide layer 22 as shown in FIG.
- the second charge layer 18 may include a second insulator.
- the second charge layer 18 may include a second insulator and a conductivity adjusting material.
- the first charge layer 16 may have a composition different from each other and have at least a two-layer structure.
- the first charge layer 16 may be formed of, for example, silicon oxide (SiO 2 ) / titanium oxide (TiO 2 ). Specifically, it may be formed by a layer structure of SiO 2 / TiO 2, or may be formed by particles bonded structure coated around the TiO 2 particle shape by SiO 2.
- the first charging layer 16, TiO 2 may be provided with a structure mixed with SiO 2 or TiO 2 is wrapped in silicon oxide.
- the composition of titanium oxide and silicon oxide is not limited to TiO 2 and SiO 2, may include a structure in which the composition ratio x of such TiO x or SiO x is changed.
- the n-type oxide semiconductor may be an oxide of titanium (Ti), tin (Sn), zinc (Zn), or magnesium (Mg), SiO 2 and Ti, Sn, Zn, Mg It may be an oxide layer structure, or may be formed by a particle bonding structure in which the periphery of Ti, Sn, Zn, and Mg oxides having a particle shape is covered with SiO 2 . In addition, a structure in which SiO 2 and molecules or molecular groups of Ti, Sn, Zn, and Mg oxides are surrounded by SiO 2 (amorphous) may be provided.
- the first charging layer 16 may have a porous structure.
- the second oxide semiconductor may include at least one oxide selected from the group consisting of oxides of Ti, Sn, Zn, or Mg.
- the conductivity adjusting material may include a first conductivity type semiconductor or metal oxide.
- the conductivity adjusting material may comprise at least one oxide selected from the group consisting of Sn, Zn, Ti, or niobium (Nb) oxide.
- the second insulator may include SiO 2 and the conductivity adjusting material may include SnO x .
- the second insulator may include SiO x formed from silicone oil.
- the first insulator may include SiO 2
- the second oxide semiconductor may include TiO 2 .
- the metal hydroxide is reduced by applying an electric field during charging to convert holes (h + ) into hydrogen ions (H + ), and during discharge, the hydrogen ions are converted into holes. It is a layer to convert to.
- Ni (OH) 2 nickel hydroxide
- NiOOH nickel oxyhydroxide
- the first charging layer 16 is a layer that forms a pair with the hydroxide layer 22 and accumulates hydrogen generated during charging.
- a reaction of M + H 2 O + e ⁇ ⁇ MH + OH ⁇ proceeds during charging, and a reaction of MH + OH ⁇ ⁇ M + H 2 O + e ⁇ proceeds during discharging.
- the efficiency of hydrogen accumulation can be increased.
- hydrogen accumulation and conductivity can be optimized by using a plurality of layers.
- the second oxide semiconductor can be optimized by using an oxide of Ti, Sn, Zn, or Mg.
- the second charge layer 18 is a buffer layer for adjusting the movement of H + and electrons (e ⁇ ). By adding a conductivity adjusting material, the mobility of H + and e ⁇ can be further adjusted. By using an oxide of Sn, Zn, Ti or Nb as the conductivity adjusting material, the second charge layer 18 can be formed thick and electrically with a high breakdown voltage.
- the oxide semiconductor layer 24 forms a pn junction with the n-type semiconductor of the hydroxide layer (NiOOH of the nickel hydroxide layer), and can suppress charge leakage during charging.
- the p-type oxide semiconductor layer 24 is made of NiO, a Ni (OH) 2 layer can be formed by electrical stimulation.
- the n-type first oxide semiconductor layer 14 has an intermediate electrical resistance between the first electrode 12 and the first charging layer 16, and smoothes electrical connection.
- the secondary battery 30 includes a first electrode 12 and a second electrode 26, and the first oxide semiconductor layer 14 includes an n-type first oxide semiconductor layer.
- the second oxide semiconductor includes an n-type second oxide semiconductor
- the third oxide semiconductor layer 24 includes a p-type third oxide semiconductor layer, and the second electrode 26. It may be connected to.
- the third oxide semiconductor layer 24 includes nickel oxide (NiO), and the hydroxide layer 22 includes nickel hydroxide (Ni (OH) 2 ) or At least one of nickel oxyhydroxide (NiOOH) may be provided.
- the third oxide semiconductor layer 24 includes nickel oxide (NiO), and the hydroxide layer 22 includes nickel hydroxide (Ni (OH) 2 ) and nickel oxyhydroxide.
- NiOOH nickel hydroxide
- Ni (OH) 2 nickel hydroxide
- NiOOH nickel oxyhydroxide
- the third oxide semiconductor layer 24 includes nickel oxide (NiO), and the hydroxide layer 22 includes nickel oxyhydroxide (NiOOH) during full charge. At the time of full discharge, nickel hydroxide (Ni (OH) 2 ) is provided.
- Ni (OH) 2 nickel hydroxide
- NiOOH nickel oxyhydroxide
- NiOOH nickel oxyhydroxide
- the hydroxide layer 22 may be formed directly on the second charging layer 18 or, as will be described later, a p-type third oxide semiconductor layer 24 and an n-type first oxide semiconductor layer 14. Alternatively, a pulse voltage may be periodically applied between them.
- a nickel hydroxide (Ni (OH) 2 ) layer is provided between the charge layer (first charge layer 16 + second charge layer 18) 20 and the third oxide semiconductor layer 24.
- the storage capacity can be increased by forming.
- a layer (Ni (OH) x ), Si () containing many OH groups between the second charging layer 18 and the p-type third oxide semiconductor layer 24 is used.
- a configuration in which OH) X is formed and inserted may be adopted. With such a configuration, the storage capacity can be increased and the battery performance can be improved.
- the hydroxide layer 22 is not limited to nickel hydroxide (Ni (OH) 2 ), and is a mixture of layers containing a large amount of OH groups (Ni (OH) x ), Si (OH) x, and the like. It may be formed as a layer. Further, structurally, Ni, Si, O, H, and a compound of an element constituting the second charge layer 18 may be included.
- the p-type third oxide semiconductor layer 24 is nickel oxide (NiO)
- the hydroxide layer 22 is at least one of nickel hydroxide (Ni (OH) 2 ) or nickel oxyhydroxide (NiOOH)
- the charge layer 16 is formed of SiO 2 / TiO 2 and the second charge layer 18 is formed of SiO 2 / SnO will be described.
- FIG. 2A An energy band diagram before charging the secondary battery 30 according to the embodiment is expressed as shown in FIG. 2A, and a schematic configuration of each layer corresponding to FIG. 2A is shown in FIG. It is expressed as shown in Here, E f represents the Fermi level.
- the p-type third oxide semiconductor layer 24 of nickel oxide (NiO) is connected to the second electrode (26) E2, and the first charging layer 16 of SiO 2 / TiO 2 is connected to the first electrode (12) E1. Yes.
- the energy band diagram before charging the secondary battery 30 according to the embodiment is expressed as shown in FIG. 2A, and NiO / Ni (OH) 2 with respect to the vacuum level.
- the conduction band of / SnO / TiO 2 exists at a level of 1.8 eV / 1.47 eV / 4.3 to 4.5 eV / 4.3 eV.
- the band gap energy E g of NiO / Ni (OH) 2 / SnO / TiO 2 is 4.0 eV / 3.7 eV / 3.8 eV / 3.2 eV.
- the band gap energy E g of SiO 2 constituting the charge layer 20 is 8.9 eV.
- the hydroxide layer 22 is nickel hydroxide (Ni (OH) 2 ).
- FIG. 1 An energy band diagram in a state where, for example, about 2.8 V is applied as a charging voltage with the second electrode E2 connected to plus (+) and the first electrode E1 connected to minus ( ⁇ ) is shown in FIG. It is expressed as follows.
- the Fermi level E f in a state where about 2.8 V is applied is expressed as shown in FIG.
- the hydroxide layer 22C being charged generates nickel oxyhydroxide (NiOOH) from nickel hydroxide (Ni (OH) 2 ).
- the layer 22C is represented by a layer structure of nickel hydroxide (Ni (OH) 2 ) / nickel oxyhydroxide (NiOOH) as shown in FIGS. 3 (a) and 3 (b).
- the nickel hydroxide (Ni (OH) 2 ) layer is mainly disposed on the nickel oxide layer (NiO) side, and the nickel oxyhydroxide (NiOOH) layer is disposed on the second charging layer 18 side.
- the energy band diagram in the fully charged state of the secondary battery 30 according to the embodiment is expressed as shown in FIG. 4A, and the schematic configuration of each layer corresponding to FIG. ).
- the conduction band of NiO / NiOOH exists at a level of 1.8 eV + 2.8 eV / ⁇ eV + 2.8 eV.
- the band gap energy E g of NiOOH is 1.75 eV.
- the nickel hydroxide (Ni (OH) 2 ) layer 22 is changed to a nickel oxyhydroxide (NiOOH) layer 22F, and unstable NiOOH Energy is stored as a chemical potential.
- the energy band diagram in the discharge state (connected to the load) of the secondary battery 30 according to the embodiment is expressed as shown in FIG. 5A, and the schematic configuration of each layer corresponding to FIG. This is expressed as shown in FIG. That is, an energy band diagram in a discharge state (connected to the load) in which the load 42 is connected between the second electrode E2 and the first electrode E1 is expressed as shown in FIG.
- the Fermi level E f in a state where approximately 2.8 V is applied gradually increases according to the discharge state, as shown in FIG.
- the reverse reaction of the above charging operation occurs.
- the hydroxide layer 22D during discharge generates nickel hydroxide (Ni (OH) 2 ) from nickel oxyhydroxide (NiOOH).
- the layer 22D is represented by a layer structure of nickel hydroxide (Ni (OH) 2 ) / nickel oxyhydroxide (NiOOH) as shown in FIGS. 5 (a) and 5 (b).
- the nickel hydroxide (Ni (OH) 2 ) layer is mainly formed on the nickel oxide layer (NiO) side, and the nickel oxyhydroxide (NiOOH) layer is formed on the second charge layer 18 side.
- the load 42 is externally connected between the second electrode E2 and the first electrode E1, and therefore, inside the secondary battery 30, electrons e ⁇ are generated from the n-type oxide semiconductor (TiO 2 ) of the charge layer 20.
- the holes h + are emitted from the p-type oxide semiconductor layer (NiO) 24 to the second electrode E2.
- NiOOH nickel oxyhydroxide
- Ni (OH) 2 nickel hydroxide
- the energy band diagram of the secondary battery 30 is expressed as shown in FIG. 6A, where NiO / Ni (OH) 2 / SnO /
- the conduction band of TiO 2 exists at a level of 1.8 eV / 1.47 eV / 4.3 to 4.5 eV / 4.3 eV.
- the band gap energy E g of NiO / Ni (OH) 2 / SnO / TiO 2 is 4.0 eV / 3.7 eV / 3.8 eV / 3.2 eV.
- the band gap energy E g of SiO 2 constituting the charge layer 20 is 8.9 eV.
- the hydroxide layer 22 is nickel hydroxide (Ni (OH) 2 ).
- the manufacturing method of the secondary battery 30 includes the step of forming the first conductivity type first oxide semiconductor layer 14, the first insulator and the first conductivity on the first oxide semiconductor layer 14. Forming a first charge layer 16 made of a second oxide semiconductor of a type, forming a second charge layer 18 on the first charge layer 16, and a second conductivity type on the second charge layer 18. The step of forming the third oxide semiconductor layer 24 and water having a metal hydroxide constituting the third oxide semiconductor layer 24 between the first charge layer 16 and the third oxide semiconductor layer 24. Forming the oxide layer 22.
- -N-type oxide semiconductor layer 14- A TiO 2 film is formed, for example, by sputtering deposition on the first electrode 12 constituting the lower electrode.
- Ti or TiO can be used as a target.
- the film thickness of the n-type oxide semiconductor layer 14 is, for example, about 50 nm to 200 nm.
- a tungsten (W) electrode can be used as the first electrode 12.
- the chemical solution is formed by stirring fatty acid titanium and silicone oil together with a solvent. This chemical solution is applied onto the n-type oxide semiconductor layer 14 using a spin coater. The rotational speed is, for example, about 500 to 3000 rpm. After application, it is dried on a hot plate. The drying temperature on the hot plate is, for example, about 30 ° C.-200 ° C., and the drying time is, for example, about 5-30 minutes. Baking after drying. For the post-drying firing, firing is performed in the air using a firing furnace. The firing temperature is, for example, about 300 ° C. to 600 ° C., and the firing time is, for example, about 10 minutes to 60 minutes.
- the aliphatic acid salt is decomposed to form a fine particle layer of titanium dioxide covered with a silicone insulating film.
- the above manufacturing (manufacturing) method in which titanium dioxide covered with a silicone insulating film is formed is a coating pyrolysis method. Specifically, this layer has a structure in which a metal layer of titanium dioxide coated with silicone is embedded in the silicone layer.
- UV irradiation with a low-pressure mercury lamp is performed.
- the UV irradiation time is, for example, about 10 to 100 minutes.
- -Second charge layer (buffer layer) 18 (Method 1)-
- the chemical solution is formed by stirring fatty acid tin and silicone oil together with a solvent.
- This chemical solution is applied onto the first charging layer 16 using a spin coating device.
- the rotational speed is, for example, about 500 to 3000 rpm.
- After application it is dried on a hot plate.
- the drying temperature on the hot plate is, for example, about 30 ° C.-200 ° C., and the drying time is, for example, about 5-30 minutes.
- firing is performed in the air using a firing furnace.
- the firing temperature is, for example, about 300 ° C.
- the firing time is, for example, about 10 minutes to 60 minutes.
- UV irradiation with a low-pressure mercury lamp is performed.
- the UV irradiation time is, for example, about 10 to 100 minutes.
- the film thickness of the second charging layer (buffer layer) 18 after UV irradiation is, for example, about 100 nm to 300 nm.
- -Second charge layer (buffer layer) 18 (Method 2)-
- the chemical solution is formed by stirring silicone oil with a solvent.
- This chemical solution is applied onto the first charging layer 16 using a spin coating device.
- the rotational speed is, for example, about 500 to 3000 rpm.
- After application it is dried on a hot plate.
- the drying temperature on the hot plate is, for example, about 50 ° C.-200 ° C., and the drying time is, for example, about 5-30 minutes.
- it is fired after drying.
- firing is performed in the air using a firing furnace.
- the firing temperature is, for example, about 300 ° C. to 600 ° C.
- the firing time is, for example, about 10 minutes to 60 minutes.
- UV irradiation with a low-pressure mercury lamp is performed.
- the UV irradiation time is, for example, about 10-60 minutes.
- the film thickness of the second charging layer (buffer layer) 18 after UV irradiation is, for example, about 10 nm-100 nm.
- P-type third oxide semiconductor layer 24 A NiO film is formed on the second charging layer 18 by, for example, sputtering deposition.
- Ni or NiO can be used as a target.
- the film thickness of the p-type oxide semiconductor layer 24 is, for example, about 200 nm to 1000 nm.
- the second electrode 26 as the upper electrode is formed, for example, by depositing Al by sputtering deposition or vacuum deposition. A film can be formed on the p-type third oxide semiconductor layer (NiO) 24 using an Al target.
- a stainless mask may be used, and only the designated region may be formed.
- the second electrode 26 is formed using an electrical stimulation process in which electrical treatment is performed after the formation of the second electrode 26.
- the first electrode 12 is set to the ground potential, and positive and negative voltages are alternately applied to the second electrode 26.
- the atmosphere is air, and the humidity is, for example, about 20% -60%.
- FIG. 7A a schematic circuit configuration of a control system applied to an electrical stimulation process for forming a hydroxide layer between the charging layer 20 and the third oxide semiconductor layer 24 is shown in FIG.
- the circuit connection relationship is represented by a thick line
- the signal flow is represented by a thin line.
- the pulse voltage V A applied to the second electrode 26 of the secondary battery 30 with the first electrode 12 grounded is a voltage via an ammeter 34, a voltmeter 36, and a resistor 38. Supplied from source 32.
- the voltage source 32 can be controlled by the control device 40. Since the values of the ammeter 34 and the voltmeter 36 are fed back to the control device 40, the voltage source 32 controlled by the control device 40 can supply the pulse voltage V A shown in FIG. .
- the pulse voltage V A is, for example, 3V (5 seconds) ⁇ ⁇ 3V (2 seconds) ⁇ 5V (0.5 seconds) ⁇ ⁇ 0.4V (4.5 seconds).
- the Ni (OH) 2 layer 22 can be formed between the second charge layer 18 and the third oxide semiconductor layer (NiO) 24.
- SIMS secondary ion mass spectrometry
- the above-described electrical stimulation step causes a gap between the first charging layer 16 and the third oxide semiconductor layer 24.
- a hydroxide layer can be formed.
- the pulse voltage waveform shown in FIG. 7B is an example, and the voltage, the number of pulses per cycle, the order of positive and negative voltages, and the like can be appropriately selected depending on the configuration of the secondary battery 30. It is also possible to select a pulse waveform with no negative voltage applied.
- the experimental result of the relationship between the energy density and the electrical stimulation time is expressed as shown in FIG.
- the energy density tends to increase as the electrical stimulation time increases. It has been confirmed that the film thickness of the hydroxide (Ni (OH) x ) layer 22 increases as the electrical stimulation time elapses.
- a nickel hydroxide (Ni (OH) 2 ) layer 22 is formed between the charging layer 20 and the third oxide semiconductor layer (NiO) 24, so that Ni (OH) is charged during charging.
- Ni (OH) 2 + h + ⁇ NiOOH + H + proceeds, and during discharge, the reaction of NiOOH + H + ⁇ Ni (OH) 2 + h + proceeds. Therefore, the secondary battery 30 with an increased storage capacity can be provided.
- a hydroxide (Ni (OH) 2 ) layer 22 is formed between the second charging layer (buffer layer) 18 and the third oxide semiconductor layer (NiO) 24 formed only of silicone oil. Yes.
- SIMS analysis In the secondary battery 30 according to the embodiment shown in FIG. 9, the mass analysis of each element was performed while digging from the surface of the third oxide semiconductor layer (NiO) 24, and the SIMS profile for each element was obtained. .
- the region having a Si peak near the depth 5 (au) corresponds to the second charging layer (buffer layer) 18 using only silicone oil.
- a peak of H is observed at the interface between the buffer layer 18 and the third oxide semiconductor layer (NiO) 24 (the depth of the vertical line A).
- the hydroxide (Ni (OH) 2 ) layer 22 is formed electrochemically by an electrical stimulation process. For this reason, there is also the introduction of Si from the SiO x of the underlying second charging layer (buffer layer) 18, and the presence of Si can also be confirmed by the SIMS profile (curve W in FIG. 10).
- the relationship between the resistance R (au) and the energy density (au) between the first electrode and the second electrode with respect to the added amount of the conductivity adjusting material is expressed as shown in FIG.
- the energy density (a.u.) corresponds to the discharge capacity of the secondary battery 30.
- the conductivity adjusting material addition amount corresponds to a value related to the addition amount of SnO x in the second charge layer (buffer layer) 18.
- the values of the resistance R (au) and the energy density (au) between the first electrode and the second electrode are optimal with respect to the values related to the added amount of SnO x in the second charging layer 18. Value exists.
- the second charging layer (buffer layer) 18 is made of an insulator and a conductivity adjusting material, and the energy density can be optimized by controlling the addition amount of the conductivity adjusting material. It is.
- the structure of the secondary battery 30 according to the embodiment is produced in a sheet shape using a stainless steel foil as a substrate. Thereafter, the sheets may be laminated to produce a secondary battery 30 having a necessary capacity.
- the second electrode (upper electrode) of two sheets faces each other, an electrode (thin metal foil) is inserted between them, and the two sheets are stacked in multiple layers to produce a secondary battery with the required capacity. You may do it. After the lamination, sealing may be performed with a laminate or the like.
- the present embodiment includes various embodiments that are not described here.
- the secondary battery according to the present embodiment can be used for various consumer devices and industrial devices, and can be used for communication terminals, secondary batteries for wireless sensor networks, etc. It can be applied to a wide range of application fields such as secondary batteries.
Abstract
Description
実施の形態に係る二次電池の模式的断面構造は、図1に示すように表される。以下、実施の形態に係る二次電池30について、説明する。
水酸化物層22は、充電時、電界印加により、金属水酸化物が還元し、正孔(h+)を水素イオン(H+)に変換し、また、放電時は、水素イオンを正孔に変換する層である。
電界印加により、水酸化ニッケル(Ni(OH)2)がオキシ水酸化ニッケル(NiOOH)に変化する。充電時は、Ni(OH)2+h+→NiOOH+H+の反応が進行し、放電時は、NiOOH+H+→Ni(OH)2+h+の反応が進行する。この反応は、エレクトロクロミズムを伴う。
第1充電層16は、水酸化物層22と対をなし、充電時に発生した水素を蓄積する層である。第1充電層16は、充電時は、M+H2O+e-→MH+OH-の反応が進行し、放電時は、MH+OH-→M+H2O+e-の反応が進行する。多孔質化することで、水素蓄積の効率を増大化可能である。また、複数層とすることで、水素蓄積と導電性を最適化できる。第2酸化物半導体を、Ti、Sn、Zn若しくはMgの酸化物とすることで、最適化可能である。
第2充電層18は、H+及び電子(e-)の移動を調整するためのバッファ層である。導電率調整材を添加することで、さらにH+及びe-の移動度を調整可能である。導電率調整材をSn、Zn、TiまたはNbの酸化物とすることで、第2充電層18を厚く、かつ電気的に高耐圧に形成可能である。
酸化物半導体層24は、水酸化物層のn型半導体(水酸化ニッケル層のNiOOH)に対してpn接合を構成し、充電時の電荷リークを抑制可能である。p型酸化物半導体層24は、NiOとすることで、電気刺激によるNi(OH)2層の形成が可能になる。
n型第1酸化物半導体層14は、第1電極12と第1充電層16の中間の電気抵抗を有し、電気的接合をスムーズにさせる。
以下においては、p型第3酸化物半導体層24は酸化ニッケル(NiO)、水酸化物層22は水酸化ニッケル(Ni(OH)2)若しくはオキシ水酸化ニッケル(NiOOH)の少なくとも一方、第1充電層16はSiO2/TiO2、第2充電層18はSiO2/SnOによって形成される例を説明する。
実施の形態に係る二次電池30の充電前におけるエネルギーバンドダイヤグラムは、図2(a)に示すように表され、図2(a)に対応する各層の模式的構成は、図2(b)に示すように表される。ここで、Efは、フェルミレベルを表す。
実施の形態に係る二次電池30の充電中(順バイアス状態)におけるエネルギーバンドダイヤグラムは、図3(a)に示すように表され、図3(a)に対応する各層の模式的構成は、図3(b)に示すように表される。
実施の形態に係る二次電池30のフル充電状態におけるエネルギーバンドダイヤグラムは、図4(a)に示すように表され、図4(a)に対応する各層の模式的構成は、図4(b)に示すように表される。真空の準位に対して、NiO/NiOOHの伝導帯は、1.8eV+2.8eV/ΔeV+2.8eVのレベルに存在する。また、NiOOHのバンドギャップエネルギーEgは、1.75eVである。
実施の形態に係る二次電池30の放電状態(負荷に接続状態)におけるエネルギーバンドダイヤグラムは、図5(a)に示すように表され、図5(a)に対応する各層の模式的構成は、図5(b)に示すように表される。すなわち、第2電極E2・第1電極E1間に負荷42を接続した放電状態(負荷に接続状態)におけるエネルギーバンドダイヤグラムは、図5(a)に示すように表される。ここで、約2.8Vを印加した状態のフェルミレベルEfは、図5(a)中に示すように、放電状態に応じて、次第に上昇する。実施の形態に係る二次電池30の放電状態(負荷に接続状態)においては、上記の充電動作の逆反応が生じる。
実施の形態に係る二次電池30のフル放電状態におけるエネルギーバンドダイヤグラムは、図6(a)に示すように表され、図6(a)に対応する各層の模式的構成は、図6(b)に示すように表される。
実施の形態に係る二次電池30の製造方法は、第1導電型の第1酸化物半導体層14を形成する工程と、第1酸化物半導体層14上に、第1絶縁物と第1導電型の第2酸化物半導体とからなる第1充電層16を形成する工程と、第1充電層16上に第2充電層18を形成する工程と、第2充電層18上に第2導電型の第3酸化物半導体層24を形成する工程と、第1充電層16と第3酸化物半導体層24との間に、第3酸化物半導体層24を構成する金属の水酸化物を有する水酸化物層22を形成する工程とを有する。
下部電極を構成する第1電極12上にTiO2膜を例えば、スパッタデポジション法で成膜することによって形成する。ここで、TiまたはTiOをターゲットとして使用可能である。n型酸化物半導体層14の膜厚は、例えば、約50nm-200nm程度である。なお、第1電極12は、例えば、タングステン(W)電極などを適用可能である。
薬液は脂肪酸チタンとシリコーンオイルを溶媒と共に攪拌して形成する。この薬液を、スピン塗布装置を用いて、n型酸化物半導体層14上に塗布する。回転数は例えば、約500-3000rpmである。塗布後、ホットプレート上で乾燥させる。ホットプレート上の乾燥温度は、例えば、約30℃-200℃程度、乾燥時間は、例えば約5分-30分程度である。乾燥後焼成する。乾燥後焼成には、焼成炉を用い、大気中で焼成する。焼成温度は例えば、約300℃-600℃程度、焼成時間は例えば、約10分-60分程度である。
薬液は脂肪酸スズとシリコーンオイルを溶媒と共に攪拌して形成する。この薬液を、スピン塗布装置を用いて、第1充電層16上に塗布する。回転数は例えば、約500-3000rpmである。塗布後、ホットプレート上で乾燥させる。ホットプレート上の乾燥温度は例えば、約30℃-200℃程度、乾燥時間は例えば、約5分-30分程度である。さらに、乾燥後焼成する。乾燥後焼成には、焼成炉を用い、大気中で焼成する。焼成温度は例えば、約300℃-600℃程度、焼成時間は例えば、約10分-60分程度である。焼成後、低圧水銀ランプによるUV照射を実施する。UV照射時間は例えば、約10分-100分程度である。UV照射後の第2充電層(バッファ層)18の膜厚は、例えば、約100nm-300nm程度である。
薬液はシリコーンオイルを溶媒と共に攪拌して形成する。この薬液を、スピン塗布装置を用いて、第1充電層16上に塗布する。回転数は例えば、約500-3000rpmである。塗布後、ホットプレート上で乾燥させる。ホットプレート上の乾燥温度は例えば、約50℃-200℃程度、乾燥時間は例えば、約5分-30分程度である。さらに、乾燥後焼成する。乾燥後焼成には、焼成炉を用い、大気中で焼成する。焼成温度は例えば、約300℃-600℃程度、焼成時間は例えば、約10分-60分程度である。焼成後、低圧水銀ランプによるUV照射を実施する。UV照射時間は例えば、約10分-60分程度である。UV照射後の第2充電層(バッファ層)18の膜厚は、例えば、約10nm-100nm程度である。
第2充電層18上にNiO膜を例えば、スパッタデポジション法で成膜することによって形成する。ここで、NiまたはNiOをターゲットとして使用可能である。p型酸化物半導体層24の膜厚は、例えば、約200nm-1000nm程度である。
上部電極としての第2電極26は、例えばAlをスパッタデポジション法若しくは真空蒸着法で成膜することによって形成する。p型第3酸化物半導体層(NiO)24上にAlターゲットを使用して成膜可能である。第2電極26は、例えば、ステンレスマスクを用い、指定領域のみ成膜しても良い。
第2電極26の形成後に電気的処理を行う電気刺激工程を用いて形成する。
実施の形態に係る二次電池30において、エネルギー密度と電気刺激時間との関係の実験結果は、図8に示すように表される。ここで、電気刺激時間とは、1周期TC=12秒のパルス電圧VAを複数サイクル印加する時間に対応している。
実施の形態に係る二次電池30において、第2充電層18をシリコーンオイルのみを用いて作製し、電気刺激工程を経たサンプルの断面SEM写真例は、図9に示すように表される。
図9に示された実施の形態に係る二次電池30において、第3酸化物半導体層(NiO)24の表面より掘りながら、各元素の質量分析を実施し、元素毎のSIMSプロファイルを取得した。
例えば、ステンレス箔を基板として、実施の形態に係る二次電池30の構造をシート状に作製する。その後、このシートを積層し、必要な容量の二次電池30を作製しても良い。
上記のように、いくつかの実施の形態について記載したが、開示の一部をなす論述及び図面は例示的なものであり、限定するものであると理解すべきではない。この開示から当業者には様々な代替実施の形態、実施例及び運用技術が明らかとなろう。
14…第1酸化物半導体層(TiO2層)
16…第1充電層(TiO2/SiO2)
18…第2充電層(バッファ層)
20…充電層(16・18)
22…水酸化物層(Ni(OH)2層)
22C、22D…Ni(OH)2/NiOOH層
22F…NiOOH層
24…第3酸化物半導体層(NiO層)
26…第2電極(E2)
30…二次電池
32…電圧源
34…電流計
36…電圧計
38…抵抗
40…制御装置
42…負荷
VA …パルス電圧
R…第1電極と第2電極間の抵抗
Claims (18)
- 第1導電型の第1酸化物半導体層と、
前記第1酸化物半導体層上に配置され、第1絶縁物と第1導電型の第2酸化物半導体とからなる第1充電層と、
前記第1充電層上に配置された第2導電型の第3酸化物半導体層と、
前記第1充電層と前記第3酸化物半導体層との間に配置され、前記第3酸化物半導体層を構成する金属の水酸化物を有する水酸化物層と
を備えることを特徴とする二次電池。 - 前記第1充電層と前記水酸化物層との間に配置された第2充電層を備えることを特徴とする請求項1に記載の二次電池。
- 前記第2充電層は、第2絶縁物を備えることを特徴とする請求項2に記載の二次電池。
- 前記第2充電層は、第2絶縁物と、導電率調整材とを備えることを特徴とする請求項2に記載の二次電池。
- 前記第1充電層は、多孔質構造を備えることを特徴とする請求項1~4のいずれか1項に記載の二次電池。
- 前記第2酸化物半導体は、Ti、Sn、Zn、若しくはMgの酸化物からなる群から選択された少なくとも1つの酸化物を備えることを特徴とする請求項1~5のいずれか1項に記載の二次電池。
- 前記導電率調整材は、第1導電型の半導体若しくは金属の酸化物を備えることを特徴とする請求項4に記載の二次電池。
- 前記導電率調整材は、Sn、Zn、Ti、若しくはNbの酸化物からなる群から選択された少なくとも1つの酸化物を備えることを特徴とする請求項4または7に記載の二次電池。
- 前記第2絶縁物は、SiO2を備え、前記導電率調整材は、SnOxを備えることを特徴とする請求項4に記載の二次電池。
- 前記第2絶縁物は、シリコーンオイルから成膜したSiOxを備えることを特徴とする請求項4に記載の二次電池。
- 前記第1絶縁物はSiO2を備え、前記第2酸化物半導体はTiO2を備えることを特徴とする請求項1~10のいずれか1項に記載の二次電池。
- 前記導電率調整材の添加量を制御して、エネルギー密度を調整したことを特徴とする請求項4、7~9のいずれか1項に記載の二次電池。
- 前記第3酸化物半導体層は酸化ニッケル(NiO)を備え、
前記水酸化物層は水酸化ニッケル(Ni(OH)2)若しくはオキシ水酸化ニッケル(NiOOH)の少なくとも一方を備えることを特徴とする請求項1~12のいずれか1項に記載の二次電池。 - 前記第3酸化物半導体層は酸化ニッケル(NiO)を備え、
前記水酸化物層は水酸化ニッケル(Ni(OH)2)及びオキシ水酸化ニッケル(NiOOH)の両方が混在する積層構造を備えると共に、前記水酸化ニッケル(Ni(OH)2)は前記第3酸化物半導体層に接し、前記オキシ水酸化ニッケル(NiOOH)は前記第2充電層に接することを特徴とする請求項2~12のいずれか1項に記載の二次電池。 - 前記第3酸化物半導体層は酸化ニッケル(NiO)を備え、
前記水酸化物層は、フル充電時は、オキシ水酸化ニッケル(NiOOH)を備え、フル放電時は、水酸化ニッケル(Ni(OH)2)を備えることを特徴とする請求項13または14に記載の二次電池。 - 充電時において、前記水酸化ニッケル(Ni(OH)2)は、オキシ水酸化ニッケル(NiOOH)に変化することを特徴とする請求項13または14に記載の二次電池。
- 放電時において、前記オキシ水酸化ニッケル(NiOOH)は、水酸化ニッケル(Ni(OH)2)に変化することを特徴とする請求項13または14に記載の二次電池。
- 前記水酸化物層は、前記第3酸化物半導体層と前記第1酸化物半導体層との間にパルス電圧を周期的に印加して形成可能であることを特徴とする請求項1~17のいずれか1項に記載の二次電池。
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EP3509157B1 (en) | 2021-03-03 |
CN109643829B (zh) | 2021-12-14 |
US20190190024A1 (en) | 2019-06-20 |
CA3034996C (en) | 2021-02-16 |
CA3034996A1 (en) | 2018-03-08 |
EP3509157A4 (en) | 2020-05-13 |
KR102144979B1 (ko) | 2020-08-14 |
CN109643829A (zh) | 2019-04-16 |
JP6854100B2 (ja) | 2021-04-07 |
KR20190034271A (ko) | 2019-04-01 |
US11245113B2 (en) | 2022-02-08 |
JP2018037261A (ja) | 2018-03-08 |
TW201813180A (zh) | 2018-04-01 |
TWI635642B (zh) | 2018-09-11 |
EP3509157A1 (en) | 2019-07-10 |
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