WO2022254975A1 - 電池 - Google Patents
電池 Download PDFInfo
- Publication number
- WO2022254975A1 WO2022254975A1 PCT/JP2022/017746 JP2022017746W WO2022254975A1 WO 2022254975 A1 WO2022254975 A1 WO 2022254975A1 JP 2022017746 W JP2022017746 W JP 2022017746W WO 2022254975 A1 WO2022254975 A1 WO 2022254975A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- positive electrode
- solid electrolyte
- battery
- electrolyte layer
- Prior art date
Links
- 239000000463 material Substances 0.000 claims abstract description 125
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 106
- 239000007774 positive electrode material Substances 0.000 claims abstract description 74
- 239000003792 electrolyte Substances 0.000 claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
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- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 25
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- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 229910005578 NiBi Inorganic materials 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 7
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- 229910015730 LixMnyO2 Inorganic materials 0.000 abstract 1
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- 239000011572 manganese Substances 0.000 description 8
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- 159000000002 lithium salts Chemical class 0.000 description 7
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Images
Classifications
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- H—ELECTRICITY
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- C01F17/00—Compounds of rare earth metals
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- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- This disclosure relates to batteries.
- US Pat. No. 5,300,000 discloses using a product obtained by mixing and sintering LiOH and MnO 2 as a positive electrode active material.
- Examples of Patent Document 1 disclose a battery using the positive electrode active material and a LiPb alloy as a negative electrode active material.
- Non-Patent Document 1 reveals that the product obtained by mixing and firing LiOH and MnO 2 is a composite of Li 2 MnO 3 and MnO 2 .
- Patent Document 2 discloses an all-solid battery using a halide solid electrolyte.
- the present disclosure is operable with Li x Mn y O 2 (0 ⁇ x ⁇ 1.05, 0.9 ⁇ y ⁇ 1.1) as a positive electrode active material and an alloy containing Bi and Ni as a negative electrode active material.
- Li x Mn y O 2 (0 ⁇ x ⁇ 1.05, 0.9 ⁇ y ⁇ 1.1) as a positive electrode active material and an alloy containing Bi and Ni as a negative electrode active material.
- the battery of the present disclosure is a positive electrode; a negative electrode; an electrolyte layer positioned between the positive electrode and the negative electrode; with the positive electrode comprises a positive electrode material;
- the positive electrode material includes a positive electrode active material and a first solid electrolyte material,
- the positive electrode active material contains a material represented by the following compositional formula (1), Li x Mn y O 2 Formula (1) where 0 ⁇ x ⁇ 1.05 and 0.9 ⁇ y ⁇ 1.1 are satisfied,
- the negative electrode includes an alloy containing Ni and Bi as a negative electrode active material.
- Li x Mn y O 2 (0 ⁇ x ⁇ 1.05, 0.9 ⁇ y ⁇ 1.1) was used as the positive electrode active material, and an alloy containing Ni and Bi was used as the negative electrode active material.
- a novel battery is provided that is operable.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a battery 2000 according to Embodiment 1.
- FIG. FIG. 2 is a cross-sectional view showing a schematic configuration of battery 3000 according to the second embodiment.
- 3 is a graph showing an X-ray diffraction pattern of NiBi produced on nickel foil in Example 1.
- FIG. 4 is a graph showing charge-discharge curves of the battery of Example 1.
- the battery according to the first aspect of the present disclosure includes a positive electrode; a negative electrode; an electrolyte layer positioned between the positive electrode and the negative electrode; with
- the positive electrode includes a positive electrode active material and a first solid electrolyte material,
- the positive electrode active material contains a material represented by the following compositional formula (1), Li x Mn y O 2 Formula (1) where 0 ⁇ x ⁇ 1.05 and 0.9 ⁇ y ⁇ 1.1 are satisfied,
- the negative electrode includes an alloy containing Ni and Bi as a negative electrode active material.
- Li x Mn y O 2 (0 ⁇ x ⁇ 1.05, 0.9 ⁇ y ⁇ 1.1) is used as the positive electrode active material, and an alloy containing Ni and Bi is used as the negative electrode active material.
- a novel battery is provided that is operable with
- the composition formula (1) may satisfy 0 ⁇ x ⁇ 1.
- the positive electrode active material sufficiently absorbs and releases Li.
- the positive electrode active material more sufficiently absorbs and releases Li, charging and discharging at deep depths can be possible.
- the positive electrode active material more sufficiently absorbs and releases Li, charging and discharging at deep depths can be possible.
- the negative electrode may contain an alloy containing Ni and Bi as main components of the negative electrode active material.
- the discharge flatness of the negative electrode is improved, and the battery operates better.
- the alloy containing Ni and Bi may be represented by the following compositional formula (2).
- the a satisfies 0 ⁇ a ⁇ 3.
- the discharge flatness of the negative electrode is improved.
- the battery operates better.
- the negative electrode may contain a material represented by the following compositional formula (3).
- Li z Bi formula (3) Here, z satisfies 0 ⁇ z ⁇ 3.
- the negative electrode sufficiently absorbs and releases Li.
- Li is sufficiently absorbed and released at the positive and negative electrodes.
- the battery according to any one of the first to ninth aspects further includes a negative electrode current collector electrically connected to the negative electrode, the negative electrode current collector comprising: It may contain Ni.
- the battery according to the tenth aspect can stably extract electricity.
- the negative electrode may be a plated layer.
- the battery according to the eleventh aspect has improved capacity.
- the first solid electrolyte material is selected from the group consisting of Li, a metal element other than Li, and a metalloid element It may contain at least one selected and at least one selected from the group consisting of Cl and Br.
- the battery according to the twelfth aspect has improved capacity.
- the first solid electrolyte material may include a material represented by compositional formula (4) below.
- ⁇ 4, ⁇ 4, and ⁇ 4 are values greater than 0
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements
- X is Cl and Br. is at least one element selected from the group consisting of
- the ionic conductivity of the first solid electrolyte material can be increased.
- the resistance resulting from the movement of Li ions can be reduced, and an increase in the internal resistance of the battery during charging can be suppressed.
- the ionic conductivity of the first solid electrolyte material can be further increased.
- the resistance resulting from the movement of Li ions can be further reduced, and an increase in the internal resistance of the battery during charging can be more effectively suppressed.
- the electrolyte layer includes a first electrolyte layer and a second electrolyte layer, and the first electrolyte layer is It may be located between the positive electrode and the negative electrode, and the second electrolyte layer may be located between the first electrolyte layer and the negative electrode.
- the battery according to the fifteenth aspect can suppress an increase in internal resistance during charging.
- FIG. 1 is a cross-sectional view showing a schematic configuration of battery 2000 according to Embodiment 1 of the present disclosure.
- Battery 2000 includes a positive electrode 201 , a negative electrode 203 , and an electrolyte layer 202 positioned between positive electrode 201 and negative electrode 203 .
- Cathode 201 includes cathode material 1000 .
- Cathode material 1000 includes cathode active material 110 and first solid electrolyte material 100 .
- the positive electrode active material 110 contains a material represented by the following compositional formula (1). Li x Mn y O 2 Formula (1) where 0 ⁇ x ⁇ 1.05 and 0.9 ⁇ y ⁇ 1.1 are satisfied.
- the negative electrode 203 contains an alloy containing Ni and Bi as a negative electrode active material.
- cathode 201 has cathode material 1000 .
- Cathode material 1000 includes cathode active material 110 and first solid electrolyte material 100 .
- the positive electrode active material 110 includes a material represented by the following compositional formula (1). Li x Mn y O 2 Formula (1) Here, 0 ⁇ x ⁇ 1.05 and 0.9 ⁇ y ⁇ 1.1.
- composition formula (1) 0 ⁇ x ⁇ 1 may be satisfied.
- compositional formula (1) is inexpensive because it does not contain Co. With the configuration described above, the cost of the battery 2000 can be reduced.
- the positive electrode active material 110 may consist of only the material represented by the compositional formula (1).
- the cathode active material 110 may consist of LiMnO 2 only.
- the first solid electrolyte material 100 may contain Li, at least one selected from the group consisting of metal elements other than Li and metalloid elements, and at least one selected from the group consisting of Cl and Br. .
- Simetallic elements are B, Si, Ge, As, Sb, and Te.
- Metallic element means all elements contained in Groups 1 to 12 of the periodic table except hydrogen, and B, Si, Ge, As, Sb, Te, C, N, P, O, S, and It is an element contained in all Groups 13 to 16 except Se. In other words, it is a group of elements that can become cations when a halogen compound and an inorganic compound are formed.
- the positive electrode material 1000 has high oxidation resistance. Therefore, an increase in internal resistance during charging of the battery 2000 can be suppressed.
- the first solid electrolyte material 100 may be represented by the following compositional formula (4).
- ⁇ 4, ⁇ 4, and ⁇ 4 are values greater than 0
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements
- X is Cl and Br. is at least one element selected from the group consisting of
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 can be further reduced.
- M may contain Y. That is, the first solid electrolyte material 100 may contain Y as a metal element.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 can be further reduced.
- composition formula (4) 1 ⁇ 4 ⁇ 4, 0 ⁇ 4 ⁇ 2, and 3 ⁇ 4 ⁇ 7 may be satisfied.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased. Thereby, the resistance resulting from movement of Li ions in the positive electrode material 1000 can be further reduced.
- the first solid electrolyte material 100 containing Y may be, for example, a compound represented by the composition formula Li a Me b Y c X 6 .
- Me is at least one element selected from the group consisting of metal elements excluding Li and Y and metalloid elements.
- m' is the valence of Me.
- At least one element selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb may be used as Me.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 in the battery can be further reduced.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A1). Li 6-3d Y d X 6 Formula (A1) Here, in the composition formula (A1), X is a halogen element and contains Cl. Also, 0 ⁇ d ⁇ 2 is satisfied.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased. Thereby, the resistance resulting from movement of Li ions in the positive electrode material 1000 can be further reduced.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A2). Li 3 YX 6 Formula (A2) Here, in the composition formula (A2), X is a halogen element and contains Cl.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 in the battery can be further reduced.
- the first solid electrolyte material 100 may contain Li3YBr2Cl4 .
- the first solid electrolyte material 100 may be Li3YBr2Cl4 .
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A3). Li 3-3 ⁇ Y 1+ ⁇ Cl 6 Formula (A3) Here, 0 ⁇ 0.15 is satisfied in the composition formula (A3).
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 in the battery can be further reduced.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A4).
- Me is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. Also, ⁇ 1 ⁇ 2, 0 ⁇ a4 ⁇ 3, 0 ⁇ (3 ⁇ 3 ⁇ +a4), 0 ⁇ (1+ ⁇ a4), and 0 ⁇ x4 ⁇ 6 are satisfied.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased.
- the resistance resulting from movement of Li ions in the positive electrode material 1000 in the battery can be further reduced.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A5).
- Me is at least one element selected from the group consisting of Al, Sc, Ga, and Bi.
- ⁇ 1 ⁇ 1, 0 ⁇ a5 ⁇ 2, 0 ⁇ (1+ ⁇ a5), and 0 ⁇ x5 ⁇ 6 are satisfied.
- the ionic conductivity of the first solid electrolyte material 100 can be further increased. Thereby, the resistance resulting from movement of Li ions in the positive electrode material 1000 can be further reduced.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A6).
- Me is at least one element selected from the group consisting of Zr, Hf, and Ti.
- ⁇ 1 ⁇ 1, 0 ⁇ a6 ⁇ 1.5, 0 ⁇ (3 ⁇ 3 ⁇ a6), 0 ⁇ (1+ ⁇ a6), and 0 ⁇ x6 ⁇ 6 are satisfied.
- the first solid electrolyte material 100 may be a material represented by the following compositional formula (A7).
- Me is at least one element selected from the group consisting of Ta and Nb.
- ⁇ 1 ⁇ 1, 0 ⁇ a7 ⁇ 1.2, 0 ⁇ (3 ⁇ 3 ⁇ 2a7), 0 ⁇ (1+ ⁇ a7), and 0 ⁇ x7 ⁇ 6 are satisfied.
- Examples of the first solid electrolyte material 100 include Li3YX6 , Li2MgX4 , Li2FeX4 , Li(Al, Ga , In) X4 , Li3 (Al, Ga, In ) X6 , and the like. can be used.
- X includes Cl.
- this notation indicates at least one element selected from the parenthesized element group. That is, "(Al, Ga, In)” is synonymous with "at least one selected from the group consisting of Al, Ga and In". The same is true for other elements.
- the first solid electrolyte material 100 may not contain sulfur.
- the first solid electrolyte material 100 may contain a sulfide solid electrolyte.
- sulfide solid electrolytes include Li 2 SP 2 S 5 , Li 2 S—SiS 2 , Li 2 S—B 2 S 3 , Li 2 S—GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 10 GeP 2 S 12 , Li 6 PS 5 Cl, etc. may be used.
- LiX, Li2O , MOq , LipMOq , etc. may be added to these.
- X is at least one element selected from the group consisting of F, Cl, Br and I.
- M is at least one element selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn.
- p and q are each independently a natural number.
- the first solid electrolyte material 100 may contain lithium sulfide and phosphorus sulfide.
- the sulfide solid electrolyte may be at least one selected from the group consisting of Li 2 SP 2 S 5 and Li 6 PS 5 Cl.
- the shape of the first solid electrolyte material 100 is not particularly limited.
- the first solid electrolyte material 100 is a powder material, its shape may be acicular, spherical, oval, or the like, for example.
- the shape of the first solid electrolyte material 100 may be particulate.
- the median diameter of the first solid electrolyte material 100 may be 100 ⁇ m or less.
- positive electrode active material 110 and first solid electrolyte material 100 can form a good dispersion state in positive electrode material 1000 . Therefore, the charge/discharge characteristics of the battery 2000 are improved.
- the median diameter of the first solid electrolyte material 100 may be 10 ⁇ m or less. According to the above configuration, in the positive electrode material 1000, the positive electrode active material 110 and the first solid electrolyte material 100 can form a good dispersed state.
- the median diameter of first solid electrolyte material 100 may be smaller than the median diameter of positive electrode active material 110 . According to the above configuration, in the positive electrode, the first solid electrolyte material 100 and the positive electrode active material 110 can form a better dispersed state.
- the median diameter of the positive electrode active material 110 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the median diameter of the positive electrode active material 110 is 0.1 ⁇ m or more, the positive electrode active material 110 and the first solid electrolyte material 100 can form a good dispersion state in the positive electrode material 1000 . Therefore, the charge/discharge characteristics of the battery using the positive electrode material 1000 are improved.
- the median diameter of the positive electrode active material 110 is 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material 110 is improved. Therefore, battery 2000 can operate at high power.
- the median diameter of the positive electrode active material 110 may be larger than the median diameter of the first solid electrolyte material 100 . Thereby, the positive electrode active material 110 and the first solid electrolyte material 100 can form a good dispersed state.
- volume diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
- the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
- the positive electrode material 1000 may further contain a positive electrode active material other than the positive electrode active material 110.
- a positive electrode active material includes a material that has the property of absorbing and releasing metal ions (eg, lithium ions).
- positive electrode active materials other than the positive electrode active material 110 include lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, or transition metal oxysulfides. nitrides, etc. may be used.
- Examples of lithium-containing transition metal oxides include Li(Ni, Co, Al) O2 , Li(Ni, Co, Mn) O2 , LiCoO2 , and the like. In particular, when a lithium-containing transition metal oxide is used, the manufacturing cost of the positive electrode material 1000 can be reduced, and the average discharge voltage can be increased.
- the positive electrode material 1000 in the battery 2000 of Embodiment 1 may include multiple first solid electrolyte materials 100 and multiple positive electrode active materials 110 .
- the content of the first solid electrolyte material 100 and the content of the positive electrode active material 110 in the positive electrode material 1000 may be the same or different.
- the first solid electrolyte material 100 and the cathode active material 110 may contact each other.
- the volume ratio "v1:100-v1" between the positive electrode active material 110 and the first solid electrolyte material 100 contained in the positive electrode 201 may satisfy 30 ⁇ v1 ⁇ 98.
- v1 represents the volume ratio of the positive electrode active material 110 when the total volume of the positive electrode active material 110 and the first solid electrolyte material 100 contained in the positive electrode 201 is 100.
- 30 ⁇ v1 is satisfied, a sufficient battery energy density can be ensured.
- v1 ⁇ 98 battery 2000 can operate at high output.
- At least part of the surface of the positive electrode active material 110 may be covered with a coating material.
- Coating materials include sulfide solid electrolytes, oxide solid electrolytes, and halide solid electrolytes.
- sulfide solid electrolytes As the sulfide solid electrolyte used for the coating material, the same materials as those exemplified for the first solid electrolyte material 100 may be used.
- the oxide solid electrolyte used as the coating material includes Li--Nb--O compounds such as LiNbO 3 , Li--B--O compounds such as LiBO 2 and Li 3 BO 3 , Li--Al--O compounds such as LiAlO 2 , Li—Si—O compounds such as Li 4 SiO 4 , Li—Ti—O compounds such as Li 2 SO 4 and Li 4 Ti 5 O 12 , Li—Zr—O compounds such as Li 2 ZrO 3 , Li 2 MoO 3 Li-Mo-O compounds such as LiV 2 O 5 Li-VO compounds such as Li-WO compounds such as Li 2 WO 4 Li-P-O compounds such as Li 3 PO 4 .
- the halide solid electrolyte may be free of sulfur.
- the thickness of the positive electrode 201 may be 10 ⁇ m or more and 500 ⁇ m or less. When the thickness of the positive electrode 201 is 10 ⁇ m or more, a sufficient energy density of the battery can be secured. When the thickness of positive electrode 201 is 500 ⁇ m or less, battery 2000 can operate at high output.
- Electrolyte layer 202 is positioned between positive electrode 201 and negative electrode 203 .
- the electrolyte layer 202 contains an electrolyte material.
- the electrolyte material is, for example, a solid electrolyte material.
- the electrolyte layer 202 may be a solid electrolyte layer.
- electrolyte layer 202 may include the same material as first solid electrolyte material 100 .
- a halide solid electrolyte As the solid electrolyte material contained in the electrolyte layer 202, a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used.
- the oxide solid electrolyte contained in the electrolyte layer 202 includes, for example, a NASICON solid electrolyte represented by LiTi 2 (PO 4 ) 3 and its element-substituted products, a (LaLi)TiO 3 -based perovskite solid electrolyte, Li 14 LISICON solid electrolytes typified by ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 and element-substituted products thereof, garnet-type solid electrolytes typified by Li 7 La 3 Zr 2 O 12 and element-substituted products thereof, and Li 3 glasses or glass - ceramics based on PO4 and its N-substituted products, and Li--B--O compounds such as LiBO2 and Li3BO3 , to which Li2SO4 , Li2CO3 , etc. are added; can be used.
- NASICON solid electrolyte represented by LiTi 2 (PO 4 ) 3 and its element
- a compound of a polymer compound and a lithium salt can be used as the polymer solid electrolyte contained in the electrolyte layer 202.
- the polymer compound may have an ethylene oxide structure.
- a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt. Therefore, the ionic conductivity can be further increased.
- Lithium salts include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN( SO2CF3 ) 2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 ) ( SO2C4F9 ), and LiC( SO2CF3 ) 3 , etc. may be used .
- One lithium salt selected from the exemplified lithium salts can be used alone. Alternatively, mixtures of two or more lithium salts selected from the exemplified lithium salts can be used.
- the complex hydride solid electrolyte contained in the electrolyte layer 202 for example, LiBH 4 --LiI, LiBH 4 --P 2 S 5 or the like can be used.
- the electrolyte layer 202 may contain a solid electrolyte material as a main component. That is, the electrolyte layer 202 may contain a solid electrolyte material, for example, at a mass ratio of 50% or more (that is, 50% by mass or more) with respect to the entire electrolyte layer 202 .
- the charge/discharge characteristics of the battery can be improved.
- the electrolyte layer 202 may contain a solid electrolyte material, for example, at a mass ratio of 70% or more (that is, 70% by mass or more) with respect to the entire electrolyte layer 202 .
- the charge/discharge characteristics of the battery 2000 can be further improved.
- the electrolyte layer 202 contains a solid electrolyte material as a main component, and may further contain unavoidable impurities, starting materials, by-products, decomposition products, etc. used when synthesizing the solid electrolyte material. good.
- the electrolyte layer 202 may contain a solid electrolyte material, for example, 100% by mass (ie, 100% by mass) of the entire electrolyte layer 202, excluding impurities that are unavoidably mixed.
- the charge/discharge characteristics of the battery 2000 can be further improved.
- the electrolyte layer 202 may be composed only of the solid electrolyte material.
- the electrolyte layer 202 may contain two or more of the materials listed as solid electrolyte materials.
- electrolyte layer 202 may include a halide solid electrolyte and a sulfide solid electrolyte.
- the thickness of the electrolyte layer 202 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of the electrolyte layer 202 is 1 ⁇ m or more, the short circuit between the positive electrode 201 and the negative electrode 203 is less likely to occur. When the thickness of electrolyte layer 202 is 300 ⁇ m or less, battery 2000 can operate at high output.
- the electrolyte material contained in the electrolyte layer 202 may be an electrolytic solution.
- the electrolyte layer 202 may be composed of a separator and an electrolytic solution impregnated in the separator.
- Negative electrode 203 includes a material that has the property of intercalating and deintercalating metal ions (eg, lithium ions). That is, the negative electrode 203 contains a negative electrode active material. The negative electrode 203 contains an alloy containing Ni and Bi as a negative electrode active material.
- Bi is a metal element that alloys with lithium.
- an alloy containing Ni reduces the load on the crystal structure of the negative electrode active material when lithium atoms are desorbed and inserted during charging and discharging, and the capacity retention rate of the battery is reduced. It is presumed that the decrease in For example, when the negative electrode active material is NiBi, lithium is occluded by forming an alloy with lithium during charging. That is, a lithium-bismuth alloy is produced in the negative electrode 203 when the battery 2000 is charged.
- the lithium-bismuth alloy produced contains, for example, at least one selected from the group consisting of LiBi and Li 3 Bi.
- the negative electrode 203 contains at least one selected from the group consisting of LiBi and Li 3 Bi, for example. Upon discharge of battery 2000, lithium is released from the lithium bismuth alloy and the lithium bismuth alloy reverts to NiBi.
- the negative electrode 203 may contain an alloy containing Ni and Bi as main components of the negative electrode active material.
- the negative electrode 203 contains an alloy containing Ni and Bi as main components of the negative electrode active material” means “in the negative electrode 203, an alloy containing Ni and Bi as the negative electrode active material with the highest molar ratio. It means “there is”.
- the negative electrode 203 may contain only an alloy containing Ni and Bi as a negative electrode active material.
- NiBi a formula (2)
- a satisfies 0 ⁇ a ⁇ 3.
- the negative electrode 203 may contain NiBi as a negative electrode active material.
- the negative electrode 203 may contain NiBi as a main component of the negative electrode active material.
- the negative electrode 203 may contain only NiBi as a negative electrode active material.
- the negative electrode 203 may contain a material represented by the following compositional formula (3).
- Li z Bi formula (3) Here, z satisfies 0 ⁇ z ⁇ 3.
- the negative electrode 203 may contain at least one selected from the group consisting of LiBi and Li 3 Bi.
- the negative electrode 203 may contain a material other than an alloy containing Ni and Bi as a negative electrode active material.
- a metal material, a carbon material, an oxide, a nitride, a tin compound, a silicon compound, or the like can be used as the negative electrode active material.
- the metal material may be a single metal.
- the metal material may be an alloy.
- metallic materials include lithium metal or lithium alloys.
- Examples of carbon materials include natural graphite, coke, ungraphitized carbon, carbon fiber, spherical carbon, artificial graphite, or amorphous carbon. From the point of view of capacity density, silicon, tin, silicon compounds, or tin compounds can be used.
- the negative electrode 203 may not contain an electrolyte.
- the negative electrode 203 may be a layer made of a material represented by compositional formula (2).
- the negative electrode 203 may be in the form of a thin film.
- the negative electrode 203 may be a plated layer.
- the negative electrode 203 may be a plated layer formed by depositing an alloy containing Ni and Bi by plating.
- the thickness of the negative electrode 203 is not particularly limited, and may be, for example, 1 ⁇ m or more and 500 ⁇ m or less.
- the thickness of the negative electrode 203 may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the negative electrode 203 is 1 ⁇ m or more, a sufficient energy density of the battery 2000 can be secured.
- the thickness of negative electrode 203 is 500 ⁇ m or less, battery 2000 can operate at high output.
- the negative electrode 203 may further contain a conductive material.
- Conductive materials include carbon materials, metals, inorganic compounds, and conductive polymers.
- Carbon materials include graphite, acetylene black, carbon black, ketjen black, carbon whiskers, needle coke, and carbon fibers.
- Graphite includes natural graphite and artificial graphite.
- Natural graphite includes massive graphite and flake graphite.
- Metals include copper, nickel, aluminum, silver, and gold.
- Inorganic compounds include tungsten carbide, titanium carbide, tantalum carbide, molybdenum carbide, titanium boride, and titanium nitride. These materials may be used alone, or a mixture of multiple types may be used.
- a current collector electrically connected to the positive electrode 201 or the negative electrode 203 may be provided. That is, the battery 2000 may further include a positive current collector and a negative current collector.
- the negative electrode 203 may be arranged in direct contact with the surface of the negative electrode current collector.
- the negative electrode 203 may be a plated layer formed by depositing an alloy containing Ni and Bi on the negative electrode current collector by plating.
- the negative electrode 203 may be a plated layer of an alloy containing Ni and Bi provided in direct contact with the surface of the negative electrode current collector.
- the negative electrode 203 When the negative electrode 203 is a plated layer provided in direct contact with the surface of the negative electrode current collector, the negative electrode 203 adheres to the negative electrode current collector. As a result, it is possible to suppress the deterioration of current collection characteristics of the negative electrode that occurs when the negative electrode 203 repeatedly expands and contracts. Therefore, the charge/discharge characteristics of battery 2000 are further improved. Furthermore, when the negative electrode 203 is a plated layer, the negative electrode 203 contains an alloy containing Ni and Bi, which are active materials, at a high density, so that a further increase in capacity can be realized.
- the material of the negative electrode current collector is, for example, a single metal or alloy. More specifically, it may be a single metal or alloy containing at least one selected from the group consisting of copper, chromium, nickel, titanium, platinum, gold, aluminum, tungsten, iron, and molybdenum.
- Current collector 205 may be stainless steel. These materials can also be used as materials for the positive electrode current collector.
- the negative electrode current collector may contain nickel (Ni).
- the negative electrode current collector may be a metal foil or a metal foil containing Ni.
- metal foils containing Ni include Ni foils and Ni alloy foils.
- the Ni content in the metal foil may be 50% by mass or more, or may be 80% by mass or more.
- the metal foil may be a Ni foil containing substantially only Ni as metal.
- the negative electrode 203 may be NiBi synthesized by electroplating Bi on the surface of a negative electrode current collector containing Ni.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
- a binder is used to improve the binding properties of the material that constitutes the electrode.
- Binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, and carboxymethyl cellulose, and the like.
- Binders include tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and Copolymers of two or more materials selected from the group consisting of hexadiene can be used. A mixture of two or more selected from these may also be used.
- At least one of the positive electrode 201 and the negative electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include graphites such as natural graphite or artificial graphite, carbon blacks such as acetylene black and Ketjen black, conductive fibers such as carbon fibers and metal fibers, carbon fluoride, metals such as aluminum Powders, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymeric compounds such as polyaniline, polypyrrole, and polythiophene, and the like can be used. Cost reduction can be achieved when a carbon conductive aid is used as the conductive aid.
- Shapes of the battery 2000 in Embodiment 1 include, for example, a coin shape, a cylindrical shape, a rectangular shape, a sheet shape, a button shape, a flat shape, and a laminated shape.
- a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by a known method. It may also be manufactured by making laminated laminates.
- Embodiment 2 (Embodiment 2) Embodiment 2 will be described below. Descriptions overlapping those of the first embodiment are omitted as appropriate.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 3000 according to Embodiment 2.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 3000 according to Embodiment 2.
- a battery 3000 according to Embodiment 2 includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
- Electrolyte layer 202 is positioned between positive electrode 201 and negative electrode 203 .
- Electrolyte layer 202 includes first electrolyte layer 301 and second electrolyte layer 302 .
- the first electrolyte layer 301 is positioned between the positive electrode 201 and the negative electrode 203
- the second electrolyte layer 302 is positioned between the first electrolyte layer 301 and the negative electrode 203 .
- FIG. 2 shows an example of a configuration of a battery 3000 in which a first electrolyte layer 301 is in contact with a positive electrode 201 and a second electrolyte layer 302 is in contact with a negative electrode 203 .
- the first electrolyte layer 301 and the second electrolyte layer 302 may be solid electrolyte layers.
- the reduction potential of the solid electrolyte material included in the second electrolyte layer 302 may be lower than the reduction potential of the solid electrolyte material included in the first electrolyte layer 301 .
- the solid electrolyte material contained in the first electrolyte layer 301 can be used without being reduced. Thereby, the charge/discharge efficiency of the battery 3000 can be improved.
- the second electrolyte layer 302 may contain a sulfide solid electrolyte.
- the reduction potential of the sulfide solid electrolyte contained in the second electrolyte layer 302 is lower than the reduction potential of the solid electrolyte material contained in the first electrolyte layer 301 .
- the solid electrolyte material contained in the first electrolyte layer 301 can be used without being reduced. Thereby, the charge/discharge efficiency of the battery 3000 can be improved.
- the thickness of the first electrolyte layer 301 and the second electrolyte layer 302 may be 1 ⁇ m or more and 300 ⁇ m or less. When the thickness of first electrolyte layer 301 and second electrolyte layer 302 is 1 ⁇ m or more, short circuit between positive electrode 201 and negative electrode 203 is less likely to occur. When the thickness of first electrolyte layer 301 and second electrolyte layer 302 is 300 ⁇ m or less, battery 3000 can operate at high output.
- a mixed solution was prepared by mixing benzophenone and methyl ethyl carbonate. The concentration of benzophenone in the mixed solution was 1 mol/liter.
- a lithium solution was prepared by dissolving Li metal in the mixed solution to a saturation concentration. The concentration of lithium in the lithium solution was 1 mol/liter.
- ⁇ - ⁇ -MnO 2 was immersed in the prepared lithium solution for 1.8 days. Thereafter, the lithium solution was removed, washed with methyl ethyl carbonate, and vacuum dried to obtain a positive electrode active material Li x Mn y O 2 (0 ⁇ x ⁇ 1.05, 0.9 ⁇ y ⁇ 1.1). rice field.
- a nickel foil (10 cm ⁇ 10 cm, thickness: 10 ⁇ m) was preliminarily degreased with an organic solvent, masked on one side, and immersed in an acidic solvent for degreasing and activation of the nickel foil surface.
- a plating bath was prepared by adding bismuth methanesulfonate as a soluble bismuth salt to 1.0 mol/L of methanesulfonic acid so that Bi 3+ ions would be 0.18 mol/L.
- the activated nickel foil was immersed in the plating bath after being connected to a power source so that current could be applied.
- Bi was electroplated to a thickness of approximately 3 ⁇ m on the unmasked nickel foil surface.
- the nickel foil was recovered from the acid bath, removed from the masking, washed with pure water, and dried.
- the nickel foil electroplated with Bi was heat-treated at 400° C. for 60 hours in an electric furnace in an argon atmosphere.
- the X-ray diffraction measurement of the heat-treated nickel foil was performed using an X-ray diffractometer (MiNi Flex, manufactured by RIGAKU) using Cu-K ⁇ rays with wavelengths of 1.5405 ⁇ and 1.5444 ⁇ as X-rays using the ⁇ -2 ⁇ method.
- NiBi which has a monoclinic crystal structure and can be assigned to the space group C2/m, was formed on the nickel foil.
- 3 is a graph showing an X-ray diffraction pattern of NiBi produced on nickel foil in Example 1.
- FIG. After that, by punching to a size of ⁇ 0.92 cm, a negative electrode was obtained as a plating layer made of NiBi on a current collector made of nickel foil.
- a battery of Example 1 was produced by the following procedure.
- the negative electrode was laminated so that the Bi-plated surface was in contact with the solid electrolyte layer.
- a pressure of 720 MPa a laminate composed of a positive electrode, a solid electrolyte layer, and a negative electrode was produced.
- the battery was placed in a constant temperature bath at 25°C.
- Constant current charging was performed at a current value of 86 ⁇ A, which is 0.05C rate (20 hour rate) for the theoretical capacity of the battery.
- the charge termination voltage was set to 3.9V.
- constant current discharge was performed with a final discharge voltage of 0.5V.
- FIG. 4 is a graph showing the charge-discharge curve of the battery of Example 1.
- FIG. The battery of Example 1 was charged and discharged as shown in FIG.
- the battery of the present disclosure can be used, for example, as an all-solid lithium ion secondary battery.
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Abstract
Description
正極と、
負極と、
前記正極と前記負極との間に位置する電解質層と、
を備え、
前記正極は、正極材料を含み、
前記正極材料は、正極活物質と、第1固体電解質材料と、を含み、
前記正極活物質は下記の組成式(1)で表される材料を含み、
LixMnyO2・・・式(1)
ここで、0≦x≦1.05、および、0.9≦y≦1.1が満たされ、
前記負極は、負極活物質としてNiとBiとを含む合金を含む。
本開示の第1態様に係る電池は、
正極と、
負極と、
前記正極と前記負極との間に位置する電解質層と、
を備え、
前記正極は、正極活物質と、第1固体電解質材料と、を含み、
前記正極活物質は下記の組成式(1)で表される材料を含み、
LixMnyO2・・・式(1)
ここで、0≦x≦1.05、および、0.9≦y≦1.1が満たされ、
前記負極は、負極活物質としてNiとBiとを含む合金を含む。
NiBia・・・式(2)
ここで、前記aは、0<a≦3を満たす。
LizBi・・・式(3)
ここで、zは、0<z≦3を満たす。
Liα4Mβ4Xγ4・・・式(4)
ここで、α4、β4、およびγ4は、0より大きい値であり、Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1種であり、Xは、ClおよびBrからなる群より選択される少なくとも1種の元素である。
2.5≦α4≦3、
1≦β4≦1.1、
γ4=6
を満たしてもよい。
図1は、本開示の実施の形態1における電池2000の概略構成を示す断面図である。
LixMnyO2・・・式(1)
ここで、0≦x≦1.05、および、0.9≦y≦1.1が満たされる。
上述のとおり、正極201は、正極材料1000を有する。正極材料1000は、正極活物質110と、第1固体電解質材料100とを含む。正極活物質110は、下記の組成式(1)で表される材料を含む。
LixMnyO2・・・式(1)
ここで、0≦x≦1.05、0.9≦y≦1.1である。
Liα4Mβ4Xγ4 ・・・式(4)
ここで、α4、β4、およびγ4は、0より大きい値であり、Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1種であり、Xは、ClおよびBrからなる群より選択される少なくとも1種の元素である。
Li6-3dYdX6・・・式(A1)
ここで、組成式(A1)において、Xは、ハロゲン元素であり、かつ、Clを含む。また、0<d<2、が満たされる。
Li3YX6・・・式(A2)
ここで、組成式(A2)において、Xは、ハロゲン元素であり、かつ、Clを含む。
Li3-3δY1+δCl6・・・式(A3)
ここで、組成式(A3)において、0<δ≦0.15、が満たされる。
Li3-3δ+a4Y1+δ-a4Mea4Cl6-x4Brx4・・・式(A4)
ここで、組成式(A4)において、Meは、Mg、Ca、Sr、Ba、およびZnからなる群より選択される少なくとも1つの元素である。また、-1<δ<2、0<a4<3、0<(3-3δ+a4)、0<(1+δ-a4)、および0≦x4<6、が満たされる。
Li3-3δY1+δ-a5Mea5Cl6-x5Brx5・・・式(A5)
ここで、組成式(A5)において、Meは、Al、Sc、Ga、およびBiからなる群より選択される少なくとも1つの元素である。また、-1<δ<1、0<a5<2、0<(1+δ-a5)、および0≦x5<6、が満たされる。
Li3-3δ-a6Y1+δ-a6Mea6Cl6-x6Brx6・・・式(A6)
ここで、組成式(A6)において、Meは、Zr、Hf、およびTiからなる群より選択される少なくとも1つの元素である。また、-1<δ<1、0<a6<1.5、0<(3-3δ-a6)、0<(1+δ-a6)、および0≦x6<6、が満たされる。
Li3-3δ-2a7Y1+δ-a7Mea7Cl6-x7Brx7・・・式(A7)
ここで、組成式(A7)において、Meは、Ta、およびNbからなる群より選択される少なくとも1つの元素である。また、-1<δ<1、0<a7<1.2、0<(3-3δ-2a7)、0<(1+δ-a7)、および0≦x7<6、が満たされる。
電解質層202は、正極201と負極203との間に配置される。
負極203は、金属イオン(例えば、リチウムイオン)を吸蔵かつ放出する特性を有する材料を含む。すなわち、負極203は、負極活物質を含む。負極203は、負極活物質としてNiとBiとを含む合金を含む。
NiBia・・・式(2)
ここで、aは、0<a≦3を満たす。
LizBi・・・式(3)
ここで、zは、0<z≦3を満たす。
以下、実施の形態2が説明される。実施の形態1と重複する説明は、適宜、省略される。
[第1固体電解質材料の作製]
アルゴン雰囲気中で、原料粉LiBr、YBr3、LiCl、およびYCl3を、モル比でLiBr:YBr3:LiCl:YCl3=1:1:5:1となるように、秤量した。その後、遊星型ボールミル(フリッチュ製、P-7型)を用い、25時間、600rpmでミリング処理することで、第1固体電解質材料としてLi3YBr2Cl4の粉末を得た。
ベンゾフェノンとメチルエチルカーボネートとを混合して混合溶液を調製した。混合溶液におけるベンゾフェノンの濃度は、1mol/リットルであった。混合溶液に飽和濃度までLi金属を溶解させてリチウム溶液を調製した。リチウム溶液におけるリチウムの濃度は、1mol/リットルであった。調製したリチウム溶液に、γ-β-MnO2を1.8日間浸漬した。その後、リチウム溶液を除去し、メチルエチルカーボネートで洗浄後、真空乾燥することで正極活物質LixMnyO2(0<x≦1.05、0.9≦y≦1.1)を得た。
得られた正極活物質と、第1固体電解質材料と、導電助剤としての気相法炭素繊維(VGCF(昭和電工株式会社製))とを、正極活物質:第1固体電解質材料:VGCF=27.75:64.75:7.5の質量比率となるように秤量し、乳鉢で混合することで、実施例1の正極材料を作製した。なお、VGCFは、昭和電工株式会社の登録商標である。
前処理として、ニッケル箔(10cm×10cm、厚み:10μm)を有機溶剤により予備脱脂した後、片面をマスキングして酸性溶剤に浸漬することで脱脂を行い、ニッケル箔表面を活性化させた。メタンスルホン酸1.0mol/Lに、可溶性ビスマス塩としてメタンスルホン酸ビスマスをBi3+イオンが0.18mol/Lとなるように加えて、めっき浴が作製された。活性化させたニッケル箔は、電流を印加できるように電源に接続した後、めっき浴内に浸漬させた。その後、電流密度を2A/dm2に制御することにより、マスキングをしていないニッケル箔表面におよそ3μmの厚みとなるようにBiを電気めっきした。電気めっき後に、ニッケル箔を酸性浴から回収し、マスキングを外した後に純水により洗浄、乾燥した。その後、アルゴン雰囲気とした電気炉内でBiを電気めっきしたニッケル箔を400℃で60時間熱処理した。熱処理したニッケル箔のX線回折測定を、X線回折装置(RIGAKU製、MiNi Flex)を用いて、波長1.5405Åおよび1.5444ÅであるCu-Kα線をX線として用いたθ-2θ法で行ったところ、得られたX線回折パターンから、ニッケル箔上に、結晶構造が単斜晶で空間群C2/mに帰属可能なNiBiが生成していることを確認した。図3は、実施例1においてニッケル箔上に作製されたNiBiのX線回折パターンを示すグラフである。その後、φ0.92cmの大きさに打ち抜くことによって、ニッケル箔からなる集電体上に、NiBiからなるめっき層である負極が得られた。
実施例1の電池を以下の手順で作製した。
上述の実施例1の電池を用いて、以下の条件で、充電試験が実施された。
Claims (15)
- 正極と、
負極と、
前記正極と前記負極との間に位置する電解質層と、
を備え、
前記正極は、正極材料を含み、
前記正極材料は、正極活物質と、第1固体電解質材料と、を含み、
前記正極活物質は下記の組成式(1)で表される材料を含み、
LixMnyO2・・・式(1)
ここで、0≦x≦1.05、および、0.9≦y≦1.1が満たされ、
前記負極は、負極活物質としてNiとBiとを含む合金を含む、
電池。 - 前記組成式(1)は、0≦x≦1を満たす、
請求項1に記載の電池。 - 前記組成式(1)は、x=1を満たす、
請求項2に記載の電池。 - 前記組成式(1)は、y=1を満たす、
請求項1から3のいずれか一項に記載の電池。 - 前記負極は、負極活物質の主成分として前記NiとBiとを含む合金を含む、
請求項1から4のいずれか一項に記載の電池。 - 前記NiとBiとを含む合金は、下記の組成式(2)で表される、
請求項1から5のいずれか一項に記載の電池。
NiBia・・・式(2)
ここで、前記aは、0<a≦3を満たす。 - 前記組成式(2)は、a=1を満たす、
請求項6に記載の電池。 - 前記負極は、下記の組成式(3)で表される材料を含む、
請求項1から7のいずれか一項に記載の電池。
LizBi・・・式(3)
ここで、zは、0<z≦3を満たす。 - 前記組成式(1)は、x=0、および、y=1を満たし、前記組成式(3)は、z=3を満たす、
請求項8に記載の電池。 - 前記負極に電気的に接続された負極集電体をさらに含み、
前記負極集電体は、Niを含む、
請求項1から9のいずれか一項に記載の電池。 - 前記負極は、めっき層である、
請求項1から10のいずれか一項に記載の電池。 - 前記第1固体電解質材料は、Liと、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1種と、ClおよびBrからなる群より選択される少なくとも1種とを含む、
請求項1から11のいずれか一項に記載の電池。 - 前記第1固体電解質材料は、下記の組成式(4)により表される材料を含む、
請求項1から12のいずれか一項に記載の電池。
Liα4Mβ4Xγ4・・・式(4)
ここで、α4、β4、およびγ4は、0より大きい値であり、
Mは、Li以外の金属元素および半金属元素からなる群より選択される少なくとも1種であり、
Xは、ClおよびBrからなる群より選択される少なくとも1種の元素である。 - 前記組成式(4)は、
2.5≦α4≦3、
1≦β4≦1.1、
γ4=6
を満たす、
請求項13に記載の電池。 - 前記電解質層は、第1電解質層および第2電解質層を含み、
前記第1電解質層は、前記正極と前記負極との間に位置し、
前記第2電解質層は、前記第1電解質層と前記負極との間に位置する、
請求項1から14のいずれか一項に記載の電池。
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JP2000173586A (ja) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2000173585A (ja) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
US20200083556A1 (en) * | 2015-03-06 | 2020-03-12 | Pu Chen | Battery, battery pack, and uninterruptible power supply |
JP2020524359A (ja) * | 2017-05-30 | 2020-08-13 | ナノテク インストゥルメンツ, インコーポレイテッドNanotek Instruments, Inc. | 導電性の変形可能な準固体ポリマー電極を有する形状適合性のアルカリ金属電池 |
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JP2000173586A (ja) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
JP2000173585A (ja) * | 1998-12-02 | 2000-06-23 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
US20200083556A1 (en) * | 2015-03-06 | 2020-03-12 | Pu Chen | Battery, battery pack, and uninterruptible power supply |
JP2020524359A (ja) * | 2017-05-30 | 2020-08-13 | ナノテク インストゥルメンツ, インコーポレイテッドNanotek Instruments, Inc. | 導電性の変形可能な準固体ポリマー電極を有する形状適合性のアルカリ金属電池 |
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