Apparatus and method for analyzing chemical state of battery material

Patent metadata

Field	Value
Publication number	US-11378530-B2
Application number	US-201816971518-A
Country	US
Kind code	B2
Filing date	Feb 21, 2018
Priority date	Feb 21, 2018
Publication date	Jul 5, 2022
Grant date	Jul 5, 2022

Abstract

A chemical state analysis apparatus 10 includes: an excitation source 11 configured to irradiate an irradiation region A of a predetermined surface in a sample S containing a battery material with an excitation rays for generating characteristic X-rays of the battery material; an analyzing crystal 13 of a flat plate arranged so as to face the irradiation region A; a slit 12 arranged between the irradiation region A and the analyzing crystal 13, the slit being arranged in parallel to the irradiation region A and a predetermined crystal plane of the analyzing crystal 13; an X-ray linear sensor 15 in which linear detecting elements 151 each having a length in a direction parallel to the slit 12 are arranged in a direction perpendicular to the slit; a wavelength spectrum generation unit 161 configured to generate a wavelength spectrum based on intensity of the characteristic X-rays detected by the X-ray linear sensor 15; a peak wavelength determination unit 162 configured to determine a peak wavelength which is a wavelength in a peak of the wavelength spectrum; and a chemical state specification unit 163 configured to specify a value for specifying a chemical state of the battery material in the sample S from the peak wavelength determined by the peak wavelength determination unit 162 and a standard curve representing a relation between a value representing the chemical state and the peak wavelength.

First claim

The invention claimed is:

1. A chemical state analysis apparatus comprising:
a) an excitation source configured to irradiate an irradiation region of a predetermined surface in a sample containing a battery material with excitation rays for generating characteristic X-rays of the battery material;
b) an analyzing crystal of a flat plate arranged so as to face the irradiation region;
c) a slit arranged between the irradiation region and the analyzing crystal, the slit being arranged in parallel to the irradiation region and a predetermined crystal plane of the analyzing crystal;
d) an X-ray linear sensor in which linear detecting elements each having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit;
e) a wavelength spectrum generation unit configured to generate a wavelength spectrum based on intensity of the characteristic X-rays detected by the X-ray linear sensor;
f) a peak wavelength determination unit configured to determine a peak wavelength which is a wavelength of a peak existing in the wavelength spectrum; and
g) a chemical state specification unit configured to obtain a value for specifying a chemical state of the battery material in the sample, based on the combination of:
the peak wavelength determined by the peak wavelength determination unit; and
a standard curve in which a value representing the chemical state and the peak wavelength are correlated with each other.

2. The chemical state analysis apparatus as recited in claim 1 ,
wherein the standard curve is generated based on the peak wavelength of the wavelength spectrum and valences of ions, the wavelength spectrum is a wavelength spectrum obtained from each of a plurality of standard samples chemically more stable than the battery material of a measurement target, the samples contain the ions of one kind of material contained in the battery material, and the ions are different in valence from each other.

3. The chemical state analysis apparatus as recited in claim 1 ,
wherein the standard curve is generated based on the peak wavelength of the wavelength spectrum and valences of ions, the wavelength spectrum is a wavelength spectrum obtained from each of a plurality of standard samples, the plurality of standard samples is composed of a same kind of elements as a plurality of kinds of elements contained in the battery material of a measurement target and contains the ions of one kind of element among the plurality of elements, the ions being different in valence from each other.

4. The chemical state analysis apparatus as recited in claim 1 ,
wherein the standard curve is generated based on a peak wavelength of the wavelength spectrum when charged to a charge upper limit voltage and a peak wavelength of the wavelength spectrum when discharged to a discharge cut-off voltage in a same kind of secondary batteries.

5. A chemical state analysis method comprising:
irradiating an irradiation region of a predetermined surface in a sample containing a battery material with excitation rays for generating characteristic X-rays of the battery material;
spectrally dispersing the characteristic X-rays generated in the irradiation region by being irradiated with the excitation rays by making the characteristic X-rays incident on an analyzing crystal of a flat plate provided so as to face the irradiation region through a slit parallel to the irradiation region and a predetermined crystal plane of the analyzing crystal, the slit being provided between the irradiation region and the analyzing crystal;
detecting the characteristic X-rays spectrally dispersed by the analyzing crystal with an X-ray linear sensor provided so that linear detecting elements having a length in a direction parallel to the slit are arranged in a direction perpendicular to the slit; and
generating a wavelength spectrum based on intensity of the characteristic X-rays detected by the X-ray linear sensor, obtaining a peak wavelength which is a wavelength of a peak existing in the wavelength spectrum, and obtaining a value for specifying a chemical state of the battery material in the sample based on the combination of: the peak wavelength; and a standard curve in which a value representing a chemical state and the peak wavelength are correlated with each other.

6. The chemical state analysis method as recited in claim 5 ,
wherein the standard curve is generated based on the peak wavelength of the wavelength spectrum and valences of ions, the wavelength spectrum is a wavelength spectrum obtained from each of a plurality of standard samples chemically more stable than the battery material of a measurement target, the samples contain the ions of one kind of material contained in the battery material, and the ions are different in valence from each other.

7. The chemical state analysis method as recited in claim 5 ,
wherein the standard curve is generated based on the peak wavelength of the wavelength spectrum and valences of ions, the wavelength spectrum is a wavelength spectrum obtained from each of a plurality of standard samples, the plurality of standard samples is composed of a same kind of elements as a plurality of kinds of elements contained in the battery material of a measurement target and contains the ions of one kind of element among the plurality of elements, the ions being different in valence from each other.

8. The chemical state analysis method as recited in claim 5 ,
wherein the standard curve is generated based on a peak wavelength of the wavelength spectrum when charged to a charge upper limit voltage and a peak wavelength of the wavelength spectrum when discharged to a discharge cut-off voltage in a same kind of secondary batteries.

9. A chemical state analysis apparatus comprising:
an excitation source configured to irradiate excitation rays to generate characteristic X-rays in a sample containing a metal material;
an analyzing crystal formed when the characteristic X-rays are released;
a slit arranged between the sample and the analyzing crystal;
an X-ray sensor which receives the characteristic X-ray which was dispersed when crystals were formed;
a wavelength spectrum generation unit configured to generate a wavelength spectrum based on intensity of the characteristic X-rays detected by the X-ray linear sensor;
a peak wavelength determination unit configured to determine a peak wavelength which is a wavelength of a peak existing in the wavelength spectrum; and
a chemical state specification unit configured to obtain a value for specifying a chemical state of the metal material in the sample based on the combination of:
the peak wavelength determined by the peak wavelength determination unit; and
a standard curve in which a value representing the chemical state and the peak wavelength are correlated with each other.

10. A chemical state analysis method comprising:
an excitation source configured to irradiate excitation rays to generate characteristic X-rays in a sample containing a metal material;
spectrally dispersing the generated characteristic X-rays through a slit provided between the irradiation region and an analyzing crystal;
detecting the characteristic X-rays spectrally dispersed by the analyzing crystal with an X-ray sensor; and
generating a wavelength spectrum based on intensity of the characteristic X-rays detected by the X-ray sensor, obtaining a peak wavelength which is a wavelength of a peak existing in the wavelength spectrum, and obtaining a value for specifying a chemical state based on the combination of the peak wavelength and a standard curve in which a value representing a chemical state of the metal material in a sample and the peak wavelength are correlated with eac

Assignees

• Shimadzu Corp

Inventors

• Sato Kenji
• Tokuda Satoshi
• Izumi Takuro
• Yoneda Tetsuya
• Adachi Susumu

Classifications

• G01N2223/302

  comparative arrangements · CPC title

• C01G45/1221

  Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof · CPC title

• G01N23/223 Primary

  by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence · CPC title

• G01N2223/076

  X-ray fluorescence · CPC title

• C01P2002/70

  defined by measured X-ray, neutron or electron diffraction data · CPC title