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US-20260125275-A1 - LITHIUM-CONTAINING OXIDE, ELECTRODE, AND BATTERY

US20260125275A1US 20260125275 A1US20260125275 A1US 20260125275A1US-20260125275-A1

Abstract

A lithium-containing oxide having a cationic-disordered rock salt-type structure, in which, when a solid 7 Li-NMR spectrum has been measured, a signal 1 having a half width of more than 0 ppm and 40 ppm or less and a signal 2 having a half width of more than 100 ppm and 2000 ppm or less are observed in a range of a chemical shift of −3000 to 3000 ppm for which a peak of a 1 mol/L LiCl aqueous solution is set to 0 ppm, and an integrated intensity of the signal 1 relative to a total of integrated intensities of the signal 1 and the signal 2 is more than 0% and 60% or less.

Inventors

  • Tsutomu YAMABAYASHI
  • Hiroshi Kageyama

Assignees

  • SUMITOMO CHEMICAL COMPANY, LIMITED
  • KYOTO UNIVERSITY

Dates

Publication Date
20260507
Application Date
20230519
Priority Date
20220530

Claims (10)

  1. 1 . A lithium-containing oxide having a cationic-disordered rock salt-type structure, wherein, when a solid 7 Li-NMR spectrum has been measured, a signal 1 having a half width of more than 0 ppm and 40 ppm or less and a signal 2 having a half width of more than 100 ppm and 2000 ppm or less are observed in a range of a chemical shift of −3000 to 3000 ppm for which a peak of a 1 mol/L LiCl aqueous solution is set to 0 ppm, and an integrated intensity of the signal 1 relative to a total of integrated intensities of the signal 1 and the signal 2 is more than 0% and 60% or less.
  2. 2 . The lithium-containing oxide according to claim 1 represented by a formula: in the formula, 1<x≤1.40, 0.55≤a≤0.90, 0.05≤b≤0.22, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is Si or two or more elements of Si and at least one element selected from P, S, V and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.
  3. 3 . The lithium-containing oxide according to claim 1 represented by a formula: in the formula, 1<x≤1.30, 0.4≤a≤0.85, 0.05≤b≤0.30, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is V or two or more elements of V and at least one element selected from P, S, Si and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.
  4. 4 . The lithium-containing oxide according to claim 1 represented by a formula: in the formula, 1<x≤1.40, 0.55≤a≤0.90, 0.05≤b≤0.22, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is Ge or two or more elements of Ge and at least one element selected from P, S, Si and V, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.
  5. 5 . The lithium-containing oxide according to claim 1 represented by a formula: in the formula, 1<x≤1.30, 0.4≤a≤0.85, 0.05≤b≤0.30, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is at least two or more selected from the group consisting of Si, P, S, V and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.
  6. 6 . The lithium-containing oxide according to claim 1 , wherein, in powder X-ray diffraction measurement using a CuKα ray at 25° C., a half width of a peak that is observed in a 2θ range of 42° to 46° is 0.5° to 5°.
  7. 7 . A lithium-containing oxide comprising: 8 to 12 mass % of Li; 35 to 56 mass % of M′ that is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu; and more than 0 mass % and 15 mass % or less of M″ that is at least one element selected from the group consisting of Si, P, S, V and Ge, wherein, in powder X-ray diffraction measurement using a CuKα ray at 25° C., a diffraction pattern derived from a cationic-disordered rock salt-type structure is observed, when a solid 7 Li-NMR spectrum has been measured, a signal 1 having a half width of more than 0 ppm and 40 ppm or less and a signal 2 having a half width of more than 100 ppm and 2000 ppm or less are observed in a range of a chemical shift of −3000 to 3000 ppm for which a peak of a 1 mol/L LiCl aqueous solution is set to 0 ppm, and an integrated intensity of the signal 1 relative to a total of integrated intensities of the signal 1 and the signal 2 is more than 0% and 60% or less.
  8. 8 . An electrode comprising: the lithium-containing oxide according to claim 1 .
  9. 9 . A battery comprising: the electrode according to claim 8 .
  10. 10 . The lithium-containing oxide according to claim 1 having an amorphous phase.

Description

TECHNICAL FIELD The present disclosure relates to a lithium-containing oxide, an electrode, and a battery. BACKGROUND ART Secondary batteries performing charging and discharging by migrating alkali metal ions between the positive electrode and the negative electrode are known. Among such secondary batteries, lithium ion secondary batteries are typical, have been already put into practical use as small power supplies for mobile phones or laptops, and furthermore, can be used as large power supplies such as automotive power supplies for electric vehicles or hybrid vehicles or power supplies for distributed energy storage, and the demand thereof is increasing. As positive electrode materials of lithium ion secondary batteries, lithium-containing oxides such as Li1.2Mn0.4Ti0.4O2 or Li1.3Mn0.4Nb0.3O2 having a cationic-disordered rock salt-type crystal structure are known. Compared with conventional lithium-containing lamellar oxides such as LiCoO2, cationic-disordered lithium-containing compositions enable an increase in the lithium content proportion in the composition and become positive electrode materials having a high energy density. In addition, cationic-disordered lithium-containing oxides and oxyfluorides in which a low-valency transition metal such as Mn2+ and a high-valency transition metal such as V4+ are combined together, and furthermore, cationic-disordered lithium-containing oxides into which a lithium salt such as Li2SO4 has been introduced are also known (Non Patent Literature 1 and Patent Literature 1 to 3). CITATION LIST Patent Literature [Patent Literature 1] Japanese Unexamined Patent Application Publication No. 2018-92958[Patent Literature 2] Japanese Unexamined Patent Application Publication No. 2020-534234[Patent Literature 3] WO 2017/169599 Non Patent Literature [Non Patent Literature 1] Nature Communications 7, Article Number: 13814 (2016) SUMMARY OF INVENTION Technical Problem Here, conventional cationic-disordered lithium-containing oxides have a large voltage hysteresis or irreversible capacity between charging and discharging and have a low energy efficiency between charging and discharging. The present disclosure has been made in consideration of the above circumstance, and an objective of the present disclosure is to provide a cationic-disordered lithium-containing oxide having a high energy efficiency and an electrode and a battery in which the cationic-disordered lithium-containing oxide is used. Solution to Problem The present disclosure includes the following embodiments [1] to [11]. [1] A lithium-containing oxide having a cationic-disordered rock salt-type structure, in which, when a solid 7Li-NMR spectrum has been measured, a signal 1 having a half width of more than 0 ppm and 40 ppm or less and a signal 2 having a half width of more than 100 ppm and 2000 ppm or less are observed in a range of a chemical shift of −3000 to 3000 ppm for which a peak of a 1 mol/L LiCl aqueous solution is set to 0 ppm, andan integrated intensity of the signal 1 relative to a total of integrated intensities of the signal 1 and the signal 2 is more than 0% and 60% or less.[2] The lithium-containing oxide of [1] represented by a formula: LixM′aM″bZcO2-eXd, in the formula, 1<x≤1.40, 0.55≤a≤0.90, 0.05≤b≤0.22, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is Si or two or more elements of Si and at least one element selected from P, S, V and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.[3] The lithium-containing oxide of [1] represented by a formula: LixM′aM″bZcO2-eXd, in the formula, 1<x≤1.30, 0.4≤a≤0.85, 0.05≤b≤0.30, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is V or two or more elements of V and at least one element selected from P, S, Si and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.[4] The lithium-containing oxide of [1] represented by a formula: LixM′aM″bZcO2-eXd, in the formula, 1<x≤1.40, 0.55≤a≤0.90, 0.05≤b≤0.22, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is Ge or two or more elements of Ge and at least one element selected from P, S, Si and V, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.[5] The lithium-containing oxide of [1] represented by a formula: LixM′aM″bZcO2-eXd, in the formula, 1<x≤1.30, 0.4≤a≤0.85, 0.05≤b≤0.30, 1.8≤x+a+b≤2.2, 0≤c≤0.20, 0≤d<0.70, 0≤e<0.70, M′ is at least one element selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, M″ is at least two or more selected from the group consisting of Si, P, S, V and Ge, Z is an element except Li, O, M′, M″ and halogen, and X is a halogen element.[6] The lithium-containing oxide of any one of [1] to [5], in which, in powder X-ray diffract