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JP-7857479-B2 - Lithium-ion rechargeable battery

JP7857479B2JP 7857479 B2JP7857479 B2JP 7857479B2JP-7857479-B2

Inventors

  • 川上 貴洋
  • 落合 輝明
  • 吉富 修平
  • 廣橋 拓也
  • 元吉 真子
  • 門馬 洋平
  • 後藤 準也

Assignees

  • 株式会社半導体エネルギー研究所

Dates

Publication Date
20260512
Application Date
20250708
Priority Date
20141027

Claims (8)

  1. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a layered rock salt structure. The orientation of the first crystal is different from the orientation of the second crystal. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  2. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the surface of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a layered rock salt structure. The orientation of the first crystal is different from the orientation of the second crystal. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  3. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the cleavage surface of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a layered rock salt structure. The orientation of the first crystal is different from the orientation of the second crystal. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  4. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a spinel-type structure. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  5. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the surface of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a spinel-type structure. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  6. A lithium-ion secondary battery having a positive electrode, The positive electrode comprises a current collector and an active material layer on the current collector. The active material layer comprises a composite oxide containing lithium and manganese, and graphene covering at least a portion of the cleavage surface of the composite oxide. The composite oxide has a first region and a second region, The second region is located on the surface side of the first region and in the surface layer of the composite oxide, The first region and the second region each contain lithium and oxygen, The first region and the second region each contain manganese and an element represented by M, The element represented by M is a metallic element selected from Ni, Ga, Fe, Mo, In, Nb, Nd, Co, Sm, Mg, Al, Ti, Cu, or Zn, Si, or P. The first region has a first crystal which has a layered rock salt structure, The second region has a second crystal which has a spinel-type structure. The ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the second region is smaller than the ratio of the number of oxygen atoms to the sum of the number of manganese atoms and the element represented by M in the first region. The graphene in question is a lithium-ion secondary battery, including multilayer graphene.
  7. In any one of claims 1 to 6 , A lithium-ion secondary battery wherein the graphene contains oxygen, and the proportion of oxygen contained in the graphene is 2 atomic% or more and 20 atomic% or less.
  8. In any one of claims 1 to 7 , A lithium-ion secondary battery in which the thickness of the second region is 0.1 nm or more and 30 nm or less.

Description

The present invention relates to a product, a method, or a method of manufacturing; or to a process, a machine, a manufacture, or a composition of matter. In particular, one aspect of the present invention relates to semiconductor devices, display devices, light-emitting devices, imaging devices, energy storage devices, memory devices, methods for driving them, or methods for manufacturing them. In particular, one aspect of the present invention relates to the structure of an energy storage device and a method for manufacturing the same; in particular to positive electrode active materials for lithium-ion secondary batteries. In recent years, portable electronic devices such as smartphones and tablets have become widespread. Also, With growing concern for environmental issues, hybrid cars and electric vehicles are attracting attention, and the importance of energy storage devices, including rechargeable batteries, is increasing. Examples of rechargeable batteries include nickel-metal hydride batteries, lead-acid batteries, and lithium-ion batteries. Among these, lithium-ion batteries are being actively developed because they offer high capacity and can be made smaller. The basic structure of a secondary battery is one in which an electrolyte is interposed between the positive electrode and the negative electrode. Examples of materials containing the electrolyte include solid electrolytes and electrolyte solutions. The positive and negative electrodes are as follows: Typical configurations include a current collector and an active material layer provided on the current collector. In the case of lithium-ion secondary batteries, materials capable of intercalating and releasing lithium are used as the active materials for the positive and negative electrodes. In lithium-ion secondary batteries, the positive electrode active material is, for example, lithium iron phosphate ( LiFePO₄ ) or lithium manganese phosphate ( LiMnPO₄) , as shown in Patent Document 1. ), lithium cobalt phosphate ( LiCoPO₄ ), lithium nickel phosphate (LiNiP₂) Phosphate compounds having an olivine structure, such as O₄ , which contain lithium (Li) and iron (Fe), manganese (Mn), cobalt (Co), or nickel (Ni), are known. Japanese Patent Application Publication No. 11-25983 A flowchart illustrating the method for producing the active material.A diagram showing particles according to one embodiment of the present invention.A diagram illustrating the crystal structure.A diagram illustrating the crystal structure.A schematic diagram showing electrodes.A diagram illustrating a slim battery.A diagram illustrating a cross-sectional view of an electrode.A diagram illustrating a slim battery.A diagram illustrating a slim battery.A diagram illustrating a slim battery.A diagram illustrating the radius of curvature of a surface.A diagram illustrating the radius of curvature of film.A diagram illustrating a coin-type rechargeable battery.A diagram illustrating a cylindrical storage battery.A diagram illustrating an example of an energy storage device.A diagram illustrating an example of an energy storage device.A diagram illustrating an example of an energy storage device.A diagram illustrating an example of an energy storage device.A diagram illustrating an example of an energy storage device.A diagram illustrating an example of an electronic device.A diagram illustrating an example of an electronic device.A diagram illustrating an example of an electronic device.A diagram illustrating an example of an electronic device.A block diagram illustrating one aspect of the present invention.A conceptual diagram illustrating one aspect of the present invention.A circuit diagram illustrating one aspect of the present invention.A circuit diagram illustrating one aspect of the present invention.A conceptual diagram illustrating one aspect of the present invention.A block diagram illustrating one aspect of the present invention.A flowchart illustrating one aspect of the present invention.A diagram showing the charge and discharge characteristics.A diagram illustrating a particle according to one embodiment of the present invention.A diagram showing the measurement results of EDX.HAADF-STEM observation results.A diagram showing electron diffraction.A diagram showing the charge and discharge characteristics.Cross-sectional view of the electrode and separator.A diagram showing the charge and discharge characteristics.Transmission electron microscope observation results.Results of transmission electron microscopy observation.A diagram showing electron diffraction.A diagram showing the particle size distribution.Scanning electron microscope observation results.Scanning electron microscope observation results.A diagram showing the relationship between the number of charge/discharge cycles and discharge capacity.A diagram showing differential scanning calorimetry curves.A diagram showing the results of EDX measurement.A diagram showing the results of EDX measurement.A diagra