Method for producing secondary battery including coating on electrode surface

1. A method for producing a secondary battery,

the method comprises

providing a negative electrode, a positive electrode, and an electrolytic solution, and

forming a coating containing S, O, and C on a surface of a negative electrode and/or a positive electrode by performing, on the negative electrode, the positive electrode, and the electrolytic solution, an activation process including step (a), step (b), and step (c) below, or step (a) and step (d) below,

(a) step of performing charging to a second voltage V 2 in step (a-1) or step (a-2) below,

(a-1) step of continuously performing charging at a first rate C 1 to a first voltage V 1 and then performing charging at a second rate C 2 to the second voltage V 2 where V 1 <V 2 , and C 1 <C 2 ,

(a-2) step of performing charging at a constant charging rate C a-2 of 1 C or higher to the second voltage V 2 ,

(b) step of discharging the secondary battery having been subjected to step (a), at a third rate C 3 to a third voltage V 3 or lower,

(c) step of performing charging and discharging at a fourth rate C 4 between the third voltage V 3 and the second voltage V 2 ,

(d) step of keeping the temperature of the secondary battery in a range of 40 to 120° C.,

wherein the electrolytic solution contains a metal salt whose cation is an alkali metal, an alkaline earth metal, or aluminum and whose anion has a chemical structure represented by general formula (1) below, and a linear carbonate represented by general formula (2) below, the linear carbonate being contained by not less than 90 vol % relative to an entire organic solvent, a mole ratio of the linear carbonate relative to the metal salt being 2 to 6,

(R 1 X 1 )(R 2 SO 2 )N  general formula (1)

(R 1 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 2 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 1 and R 2 optionally bind with each other to form a ring,

X 1 is selected from SO 2 , C═O, C═S, R a P═O, R b P═S, S═O, or Si═O,

R a and R b are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R a and R b each optionally bind with R 1 or R 2 to form a ring),

R 20 OCOOR 21   general formula (2)

(R 20 and R 21 are each independently selected from C n H a F b Cl c Br d I e that is a linear alkyl, or C m H f F g Cl h Br i I j that includes a cyclic alkyl in the chemical structure thereof, “n” is an integer not smaller than 1, “m” is an integer not smaller than 3, and “a”, “b”, “c”, “d”, “e”, “f”, “g”, “h”, “i”, and “j” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e and 2m−1=f+g+h+i+j).

2. A method for producing a secondary battery,

providing a negative electrode, a positive electrode, and an electrolytic solution, and

forming a coating containing S, O, and C on a surface of a negative electrode and/or a positive electrode by performing, on the negative electrode, the positive electrode, and the electrolytic solution, an activation process including step (a), step (b), and step (c) below, or step (a) and step (d) below,

(a) step of performing charging to a second voltage V 2 in step (a-1) or step (a-2) below,

(a-1) step of continuously performing charging at a first rate C 1 to a first voltage V 1 and then performing charging at a second rate C 2 to the second voltage V 2 where V 1 <V 2 , and C 1 <C 2 ,

(a-2) step of performing charging at a constant charging rate C a-2 of 2C or higher to the second voltage V 2 ,

(b) step of discharging the secondary battery having been subjected to step (a), at a third rate C 3 to a third voltage V 3 or lower,

(c) step of performing charging and discharging at a fourth rate C 4 between the third voltage V 3 and the second voltage V 2 ,

(d) step of keeping the temperature of the secondary battery in a range of 40 to 120° C.,

wherein the electrolytic solution contains a metal salt whose cation is an alkali metal, an alkaline earth metal, or aluminum and whose anion has a chemical structure represented by general formula (1) below, and a linear carbonate represented by general formula (2) below, the linear carbonate being contained by not less than 90 vol % relative to an entire organic solvent, a mole ratio of the linear carbonate relative to the metal salt being 2 to 6,

(R 1 X 1 )(R 2 SO 2 )N  general formula (1)

(R 1 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 2 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 1 and R 2 optionally bind with each other to form a ring,

X 1 is selected from SO 2 , C═O, C═S, R a P═O, R b P═S, S═O, or Si═O,

R a and R b are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R a and R b each optionally bind with R 1 or R 2 to form a ring),

R 20 OCOOR 21   general formula (2)

(R 20 and R 21 are each independently selected from C n H a F b Cl c Br d I e that is a linear alkyl, or C m H f F g Cl h Br i I j that includes a cyclic alkyl in the chemical structure thereof, “n” is an integer not smaller than 1, “m” is an integer not smaller than 3, and “a”, “b”, “c”, “d”, “e”, “f”, “g”, “h”, “i”, and “j” are each independently an integer not smaller than 0, and satisfy 2 n+1=a+b+c+d+e and 2m−1=f+g+h+i+j).

3. The method for producing the secondary battery according to claim 1 , wherein

a mole ratio of the linear carbonate relative to the metal salt in the electrolytic solution is 3 to 5.

4. The method for producing the secondary battery according to claim 1 , wherein

the chemical structure of the anion of the metal salt is represented by general formula (1-1) below,

(R 3 X 2 )(R 4 SO 2 )N  general formula (1-1)

(R 3 and R 4 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h ,

“n”, “a”, “b”, “c”, “d”, “e”, “f”, “g”, and “h” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e+f+g+h,

R 3 and R 4 optionally bind with each other to form a ring, and in that case, satisfy 2n=a+b+c+d+e+f+g+h,

X 2 is selected from SO 2 , C═O, C═S, R c P═0, R d P═S, S═O, or Si═O,

R c and R d are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R c and R d each optionally bind with R 3 or R 4 to form a ring).

5. The method for producing the secondary battery according to claim 1 , wherein

the chemical structure of the anion of the metal salt is represented by general formula (1-2) below,

(R 5 SO 2 )(R 6 SO 2 )N  general formula (1-2)

(R 5 and R 6 are each independently C n H a F b Cl c Br d I e ,

“n”, “a”, “b”, “c”, “d”, and “e” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e,

R 5 and R 6 optionally bind with each other to form a ring, and, in that case, satisfy 2n=a+b+c+d+e).

6. The method for producing the secondary battery according to claim 1 , wherein

the metal salt is (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, FSO 2 (CF 3 SO 2 )NLi, (SO 2 CF 2 CF 2 SO 2 )NLi, or (SO 2 CF 2 CF 2 CF 2 SO 2 )NLi.

7. The method for producing the secondary battery according to claim 1 , wherein

a relationship among the first rate C 1 , the second rate C 2 , the third rate C 3 , and the fourth rate C 4 is C 1 <C 2 <C 3 <C 4 .

8. The method for producing the secondary battery according to claim 1 , wherein

the charging rate C a-2 in step (a-2) satisfies 1C≤C a-2 ≤13C.

9. The method for producing the secondary battery according to claim 1 , wherein

the temperature in step (c) is in a range of 40 to 120° C.

10. The method for producing the secondary battery according to claim 1 , wherein

step (c) is repeated 5 to 50 times.

11. The method for producing the secondary battery according to claim 1 , wherein

the negative electrode includes a graphite having a BET specific surface area of 0.5 to 15 m 2 /g as a negative electrode active material.

12. The method for producing the secondary battery according to claim 1 , wherein

the negative electrode includes a graphite having a BET specific surface area of 4 to 12 m 2 /g as a negative electrode active material.

13. The method for producing the secondary battery according to claim 11 , wherein

the graphite has a mean particle diameter in a range of 2 to 30 μm.

14. The method for producing the secondary battery according to claim 1 , wherein

the secondary battery includes a polymer having a hydrophilic group as a binding agent.

15. A secondary battery comprising:

an electrolytic solution containing a metal salt whose cation is an alkali metal, an alkaline earth metal, or aluminum and whose anion has a chemical structure represented by general formula (1) below, and a linear carbonate represented by general formula (2) below, the linear carbonate being contained by not less than 90 vol % relative to an entire organic solvent, a mole ratio of the linear carbonate relative to the metal salt being 2 to 6;

a negative electrode;

a positive electrode; and

a coating on a surface of the negative electrode and/or the positive electrode, the coating containing S, O, and C,

when binding energy of elements contained in the coating is measured by using X-ray photoelectron spectroscopy, a peak having a peak top at 528±1.5 eV, a peak having a peak top at 285±1 eV, a peak having a peak top at 169±2 eV, a peak having a peak top at 160±2 eV, or a peak having a peak top at 290±1.5 eV being observed, and a relationship among intensities of these peaks satisfying any one of relational expression 1 to relational expression 4 below,

((intensity of peak having peak top at 528±1.5 eV)/(intensity of peak having peak top at 285±1 eV))≥0.18,  Relational expression 1

(((intensity of peak having peak top at 528±1.5 eV)+(intensity of peak having peak top at 169±2 eV))/(intensity of peak having peak top at 285±1 eV))≥0.21,  Relational expression 2

(((intensity of peak having peak top at 528±1.5 eV)+(intensity of peak having peak top at 160±2 eV))/(intensity of peak having peak top at 285±1 eV))≥0.19,  Relational expression 3

(((intensity of peak having peak top at 528±1.5 eV)+(intensity of peak having peak top at 169±2 eV)+(intensity of peak having peak top at 290±1.5 eV))/(intensity of peak having peak top at 285±1 eV))≥0.33, and  Relational expression 4

a relationship among intensities of these peaks satisfying Relational expression 1, 2 and 3, or a relationship among intensities of these peaks satisfying Relational expression 4,

(R 1 X 1 )(R 2 SO 2 )N  general formula (1)

(R 1 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 2 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 1 and R 2 optionally bind with each other to form a ring,

X 1 is selected from SO 2 , C═O, C═S, R a P═O, R b P═S, S═O, or Si═O,

R a and R b are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R a and R b each optionally bind with R 1 or R 2 to form a ring),

R 20 OCOOR 21   general formula (2)

(R 20 and R 21 are each independently selected from C n H a F b Cl c Br d I e that is a linear alkyl, or C m H f F g Cl h Br i I j that includes a cyclic alkyl in the chemical structure thereof, “n” is an integer not smaller than 1, “m” is an integer not smaller than 3, and “a”, “b”, “c”, “d”, “e”, “f”, “g”, “h”, “i”, and “j” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e and 2m−1=f+g+h+i+j).

16. The secondary battery according to claim 15 , wherein

a mole ratio of the linear carbonate relative to the metal salt in the electrolytic solution is 3 to 5.

17. The secondary battery according to claim 15 , wherein

the chemical structure of the anion of the metal salt is represented by general formula (1-1) below,

(R 3 X 2 )(R 4 SO 2 )N  general formula (1-1)

(R 3 and R 4 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h ,

“n”, “a”, “b”, “c”, “d”, “e”, “f”, “g”, and “h” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e+f+g+h,

R 3 and R 4 optionally bind with each other to form a ring, and in that case, satisfy 2n=a+b+c+d+e+f+g+h,

X 2 is selected from SO 2 , C═O, C═S, R c P═O, R d P═S, S═O, or Si═O,

R c and R d are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R c and R d each optionally bind with R 3 or R 4 to form a ring).

18. The secondary battery according to claim 15 , wherein

the chemical structure of the anion of the metal salt is represented by general formula (1-2) below,

(R 5 SO 2 )(R 6 SO 2 )N  general formula (1-2)

(R 5 and R 6 are each independently C n H a F b Cl c Br d I e ,

“n”, “a”, “b”, “c”, “d”, and “e” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e,

R 5 and R 6 optionally bind with each other to form a ring, and, in that case, satisfy 2n=a+b+c+d+e).

19. The secondary battery according to claim 15 , wherein

the metal salt is (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, FSO 2 (CF 3 SO 2 )NLi, (SO 2 CF 2 CF 2 SO 2 )NLi, or (SO 2 CF 2 CF 2 CF 2 SO 2 )NLi.

20. The secondary battery according to claim 15 , wherein

either the linear alkyl or the cyclic alkyl in R 20 and R 21 of the general formula (2) satisfies a>0 or f>0.

21. The secondary battery according to claim 15 , wherein

the negative electrode includes a graphite having a BET specific surface area of 0.5 to 15 m 2 /g as a negative electrode active material.

22. The secondary battery according to claim 15 , wherein

the negative electrode includes a graphite having a BET specific surface area of 4 to 12 m 2 /g as a negative electrode active material.

23. The secondary battery according to claim 21 , wherein

the graphite has a mean particle diameter in a range of 2 to 30 μm.

24. The secondary battery according to claim 15 , wherein

the secondary battery includes a polymer having a hydrophilic group as a binding agent.

25. A method for producing a secondary battery, the method comprises

providing a negative electrode, a positive electrode, and an electrolytic solution, and

forming a coating a coating containing S, O, and C on a surface of the negative electrode and/or the positive electrode by performing, on the negative electrode, positive electrode, and the electrolytic solution, an activation process including step (a), step (b), and step (c) below,

(a) step of performing charging to a second voltage V 2 in step (a-1) or step (a-2) below,

(a-1) step of performing charging at a first rate C 1 to a first voltage V 1 , and then performing charging at a second rate C 2 to the second voltage V 2 where V 1 <V 2 , and C 1 <C 2 ,

(a-2) step of performing charging at a constant charging rate C a-2 of 0.5C or higher to the second voltage V 2 ,

(b) step of discharging the secondary battery having been subjected to step (a), at a third rate C 3 to a third voltage V 3 or lower, and

(c) step of performing charging and discharging at a fourth rate C 4 between the third voltage V 3 and the second voltage V 2 ,

the electrolytic solution contains a metal salt whose cation is an alkali metal, an alkaline earth metal, or aluminum and whose anion has a chemical structure represented by general formula (1) below, and a linear carbonate represented by general formula (2) below, the linear carbonate being contained by not less than 90 vol % relative to an entire organic solvent, a mole ratio of the linear carbonate relative to the metal salt being 2 to 6,

(R 1 k)(R 2 SO 2 )N  general formula (1)

(R 1 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 2 is selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; CN; SCN; or OCN,

R 1 and R 2 optionally bind with each other to form a ring,

X 1 is selected from SO 2 , C═O, C═S, R a P═O, R b P═S, S═O, or Si═O,

R a and R b are each independently selected from: hydrogen; a halogen; an alkyl group optionally substituted with a substituent group; a cycloalkyl group optionally substituted with a substituent group; an unsaturated alkyl group optionally substituted with a substituent group; an unsaturated cycloalkyl group optionally substituted with a substituent group; an aromatic group optionally substituted with a substituent group; a heterocyclic group optionally substituted with a substituent group; an alkoxy group optionally substituted with a substituent group; an unsaturated alkoxy group optionally substituted with a substituent group; a thioalkoxy group optionally substituted with a substituent group; an unsaturated thioalkoxy group optionally substituted with a substituent group; OH; SH; CN; SCN; or OCN,

R a and R b each optionally bind with R 1 or R 2 to form a ring),

R 20 OCOOR 21   general formula (2)

(R 20 and R 21 are each independently selected from C n H a F b Cl c Br d I e that is a linear alkyl, or C m H f F g Cl h Br i I j that includes a cyclic alkyl in the chemical structure thereof, “n” is an integer not smaller than 1, “m” is an integer not smaller than 3, and “a”, “b”, “c”, “d”, “e”, “f”, “g”, “h”, “i”, and “j” are each independently an integer not smaller than 0, and satisfy 2n+1=a+b+c+d+e and 2m−1=f+g+h+i+j).