Secondary battery-use active material, secondary battery-use electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus
A secondary battery includes: a cathode; an anode; and an electrolytic solution. The cathode contains an active material capable of inserting and extracting an electrode reactant. A ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry. Since a secondary battery according to the present invention has an intensity ratio IS/IF of 0.04 or more as obtained by a negative ion analysis of the active material using time-of-flight secondary ion mass spectrometry, the secondary battery is able to achieve excellent battery characteristics.
1. A secondary battery comprising:
a cathode;
an anode; and
an electrolytic solution, wherein
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
2. The secondary battery according to claim 1 , wherein
the compound represented by the formula (1) contains one or more of compounds represented by the following formulas (1-1) to (1-13),
the compound represented by the formula (2) contains one or more of compounds represented by the following formulas (2-1) to (2-11),
the compound represented by the formula (3) contains one or more of compounds represented by the following formulas (3-2) to (3-11), and
the compound represented by the formula (4) contains one or more of compounds represented by the following formulas (4-1) to (4-11).
3. The secondary battery according to claim 1 , wherein
the active material contains a lithium composite oxide, and
the lithium composite oxide contains lithium (Li) and one or more transition metal elements as constituent elements.
4. The secondary battery according to claim 3 , wherein the lithium composite oxide contains cobalt (Co) as the transition metal element, and has a layered rock-salt crystal structure.
5. The secondary battery according to claim 3 , wherein the lithium composite oxide contains, on its surface, one or more elements different from the transition metal element.
6. The secondary battery according to claim 1 , wherein
an upper limit of a charging voltage is from 4.2 V to 4.8 V both inclusive, and
a lower limit of a discharging voltage is from 2.0 V to 3.3 V both inclusive.
7. The secondary battery according to claim 1 , wherein the secondary battery is a lithium secondary battery.
8. A secondary battery comprising:
a cathode;
an anode; and
an electrolytic solution, wherein
the cathode contains an active material capable of inserting and extracting an electrode reactant, and wherein a ratio IN/IF of a peak intensity IN derived from SNO 2 − and the peak intensity IF derived from LiF 2 − is 0.03 or more, the peak intensity IN and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ) and a nitrogen bond (>N—),
the compound having the sulfonyl group and the nitrogen bond contains one or more of compounds represented by the following formulas (1) and (2),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group having more than 6 carbon atoms, an oxygen-containing hydrocarbon group having more than 6 carbon atoms, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another, and
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element.
9. The secondary battery according to claim 8 , wherein
the compound represented by the formula (1) contains one or more of compounds represented by the following formulas (1-1) to (1-9), (1-11), and (1-13), and
the compound represented by the formula (2) contains one or more of compounds represented by the following formulas (2-1) to (2-11)
10. A secondary battery-use electrode comprising an active material capable of inserting and extracting an electrode reactant, wherein
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
11. A secondary battery-use active material, wherein
the secondary battery-use active material is capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
12. A battery pack comprising:
a secondary battery;
a control section configured to control a usage state of the secondary battery; and
a switch section configured to switch the usage state of the secondary battery according to an instruction of the control section, wherein
the secondary battery includes a cathode, an anode, and an electrolytic solution,
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
13. An electric vehicle comprising:
a secondary battery;
a conversion section configured to convert electric power supplied from the secondary battery into drive power;
a drive section configured to operate according to the drive power; and
a control section configured to control an usage state of the secondary battery, wherein
the secondary battery includes a cathode, an anode, and an electrolytic solution,
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
14. An electric power storage system comprising:
a secondary battery;
one or more electric devices configured to be supplied with electric power from the secondary battery; and
a control section configured to control the supplying of the electric power from the secondary battery to the one or more electric devices, wherein
the secondary battery includes a cathode, an anode, and an electrolytic solution,
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
15. An electric power tool comprising:
a secondary battery; and
a movable section configured to be supplied with electric power from the secondary battery, wherein
the secondary battery includes a cathode, an anode, and an electrolytic solution,
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.
16. An electronic apparatus comprising an secondary battery as an electric power supply source, wherein
the secondary battery includes a cathode, an anode, and an electrolytic solution,
the cathode contains an active material capable of inserting and extracting an electrode reactant, and
a ratio IS/IF of a peak intensity IS derived from SO 2 − and a peak intensity IF derived from LiF 2 − is 0.04 or more, the peak intensity IS and the peak intensity IF being obtained by negative ion analysis on the active material with use of time-of-flight secondary ion mass spectrometry, the active material includes a central section and a coating section, the central section being capable of inserting and extracting the electrode reactant, and the coating section being provided on the central section, and the coating section contains a compound having a sulfonyl group (>SO 2 ),
the compound having the sulfonyl group contains one or more of compounds represented by the following formulas (1) to (4),
where each of R1 to R4 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R1 to R4 are optionally bound to one another,
where each of R5 and R6 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R5 and R6 are optionally bound to each other, and M is a metal element,
where each of R7 to R12 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, R7 to R12 are not all hydrogen groups, and any two or more of R7 to R12 are optionally bound to one another, and
where each of R13 to R16 is one of a hydrogen group, a hydrocarbon group, an oxygen-containing hydrocarbon group, a halogen group, a halogenated hydrocarbon group, a halogenated oxygen-containing hydrocarbon group, and a group obtained by binding two or more thereof, and any two or more of R13 to R16 are optionally bound to one another.