KR-102962248-B1 - POSITIVE ELECTRODE ACTIVE MATERIAL, METHOD FOR MANUFACTURING POSITIVE ELECTRODE ACTIVE MATERIAL, AND SECONDARY BATTERY

KR102962248B1KR 102962248 B1KR102962248 B1KR 102962248B1KR-102962248-B1

Abstract

A positive electrode active material with high capacity and excellent cycle performance is provided. The positive electrode active material has a small difference in crystal structure between the charged state and the discharged state. For example, the crystal structure and volume of a positive electrode active material having a layered rock salt crystal structure in the discharged state and a pseudo-spinel crystal structure when charged to a high voltage of about 4.6V have less change due to charging and discharging compared to conventional positive electrode active materials.

Inventors

미카미 마유미
우치다 아야
요네다 유미코
몸마 요헤이
다카하시 마사히로
오치아이 데루아키

Assignees

가부시키가이샤 한도오따이 에네루기 켄큐쇼

Dates

Publication Date: 20260507
Application Date: 20180511
Priority Date: 20170519

Claims (20)

A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and The above fluorine is present in the region in contact with the electrolyte, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 0.5 nm from the surface of the above-mentioned cathode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 1 nm from the surface of the above-mentioned cathode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and The above fluorine is present in the region in contact with the electrolyte, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 0.5 nm from the surface of the above-mentioned cathode active material particles, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle comprises magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 1 nm from the surface of the above-mentioned cathode active material particles, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and The above fluorine is present in the region in contact with the electrolyte, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned positive electrode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 0.5 nm from the surface of the above-mentioned positive electrode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 1 nm from the surface of the above-mentioned cathode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and The above fluorine is present in the region in contact with the electrolyte, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 0.5 nm from the surface of the above-mentioned cathode active material particles, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion of the above-mentioned positive active material particle and the crystal defect or its vicinity each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 1 nm from the surface of the above-mentioned cathode active material particles, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion and the grain boundaries or their vicinity of the above-mentioned positive active material particles each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion and the grain boundaries or their vicinity of the above-mentioned positive active material particles each contain magnesium and fluorine, and The above fluorine is present in the region in contact with the electrolyte, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion and the grain boundaries or their vicinity of the above-mentioned positive active material particles each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned positive electrode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 0.5 nm from the surface of the above-mentioned positive electrode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion and the grain boundaries or their vicinity of the above-mentioned positive active material particles each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and additionally, the peak of fluorine concentration exists up to 1 nm from the surface of the above-mentioned cathode active material particles, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.
A lithium-ion secondary battery comprising a positive electrode, a negative electrode, and an electrolyte, The above anode comprises a plurality of anode active material particles, and The above positive active material particles comprise lithium cobaltate, magnesium, aluminum, and fluorine, and The surface portion and the grain boundaries or their vicinity of the above-mentioned positive active material particles each contain magnesium and fluorine, and In the EDX line analysis of the above-mentioned cathode active material particles, the peak of aluminum concentration is in a deeper region than the peak of magnesium concentration, and A portion of the surface of the above positive active material particles has a rock salt-type crystal structure, The above positive active material particles further have a layered rock salt-type crystal structure in which the crystal orientation substantially matches the rock salt-type crystal structure, and The above cathode includes cathode active material particles, and The above-mentioned cathode active material particles include a carbon material, Lithium-ion secondary battery.

Description

Positive ELECTRODE ACTIVE MATERIAL, METHOD FOR MANUFACTURING POSITIVE ELECTRODE ACTIVE MATERIAL, AND SECONDARY BATTERY One embodiment of the present invention relates to an article, a method, or a method of production. The present invention relates to a process, a machine, a product, or a composition of matter. One embodiment of the present invention relates to a semiconductor device, a display device, a light-emitting device, a capacitor device, a lighting device, an electronic device, or a method of production thereof. In particular, one embodiment of the present invention relates to a positive active material usable in a secondary battery, a secondary battery, and an electronic device comprising a secondary battery. Furthermore, in this specification, the term "energy storage device" refers to any element and/or device having an energy storage function. For example, the category of energy storage devices includes batteries (also referred to as secondary batteries), such as lithium-ion secondary batteries, lithium-ion capacitors, and electric double-layer capacitors. Furthermore, in this specification, the term "electronic device" refers to any device including a storage device, and electro-optical devices including a storage device and information terminal devices including a storage device are all electronic devices. In recent years, various energy storage devices such as lithium-ion secondary batteries, lithium-ion capacitors, and air batteries have been actively developed. In particular, the demand for high-output and high-energy-density lithium-ion secondary batteries for portable information terminals such as mobile phones, smartphones, and laptop computers, portable music players, digital cameras, medical devices, and next-generation clean energy vehicles such as hybrid electric vehicles (HEV), electric vehicles (EV), and plug-in hybrid electric vehicles (PHEV) is rapidly expanding alongside the development of the semiconductor industry. Lithium-ion secondary batteries are essential as rechargeable energy sources in the modern information society. The performance requirements for lithium-ion secondary batteries include, for example, increased energy density, improved cycle performance, safe operation under various environments, and longer-term reliability. Accordingly, research is being conducted on improving the cathode active material to increase the cycle performance and capacity of lithium-ion secondary batteries (Patent Document 1, Patent Document 2, and Non-Patent Document 1). Research is also being conducted on the crystal structure of the cathode active material (Non-Patent Documents 2 to 4). FIG. 1 illustrates the charging depth and crystal structure of a positive electrode active material of one embodiment of the present invention; FIG. 2 illustrates the filling depth and crystal structure of a conventional positive electrode active material; Figure 3 shows the XRD pattern calculated from the crystal structure; Figures 4 (A) and (B) show the crystal structure and magnetism of a positive active material of one embodiment of the present invention; Figures 5 (A) and (B) show the crystal structure and magnetism of a conventional positive active material; Figures 6 (A) and (B) are cross-sectional views of an active material layer containing a graphene compound as a conductive agent; FIG. 7 (A) to (C) illustrate a method for charging a secondary battery; FIGS. 8 (A) to (D) illustrate a method for charging a secondary battery; FIG. 9 shows a discharge method of a secondary battery; Figures 10 (A) to (C) illustrate coin-type secondary batteries; Figures 11 (A) to (D) illustrate a cylindrical secondary battery; Figures 12 (A) and (B) illustrate examples of secondary batteries; (A-1), (A-2), (B-1), and (B-2) of FIG. 13 illustrate examples of secondary batteries; Figures 14 (A) and (B) illustrate examples of secondary batteries; FIG. 15 illustrates an example of a secondary battery; FIG. 16 (A) to (C) illustrates a laminated secondary battery; Figures 17 (A) and (B) illustrate a laminated secondary battery; FIG. 18 is an external view of a secondary battery; FIG. 19 is an external view of a secondary battery; Figures 20 (A) to (C) illustrate a method for manufacturing a secondary battery; (A), (B1), (B2), (C), and (D) of FIG. 21 illustrate a bendable secondary battery; Figures 22 (A) and (B) illustrate a bendable secondary battery; Figures 23 (A) to (H) illustrate examples of electronic devices; Figures 24 (A) to (C) illustrate examples of electronic devices; FIG. 25 illustrates an example of an electronic device; Figures 26 (A) to (C) illustrate examples of electronic devices; FIG. 27 shows the XRD pattern of a positive electrode active material of one embodiment of the present invention of Example 1; FIG. 28 shows the XRD pattern of a positive electrode active material of one embodiment of the present invention of Example 1; FIG. 29 shows the XRD pattern of a positive electrode active material of