Lithium ion battery using crosslinkable separator
A separator for an electricity storage device comprising a silane-modified polyolefin, wherein silane crosslinking reaction of the silane-modified polyolefin is initiated when it contacts with the electrolyte solution, as well as a method for producing the separator.
1. A separator for an electricity storage device, comprising 5 to 40 weight % of a silane-modified polyolefin and 60 to 95 weight % of a polyolefin other than the silane-modified polyolefin, wherein the storage modulus change ratio (R ΔE′ ) is 1.5 to 20, as defined by the following formula (1):
R ΔE′ =E′ S /E′ j ) (1)
where E′ j is the storage modulus measured at 160° C. to 220° C. for the separator for an electricity storage device before crosslinking reaction of the silane-modified polyolefin, E′ S is the storage modulus measured at 160° C. to 220° C. for the separator for an electricity storage device after crosslinking reaction of the silane-modified polyolefin, and the measuring conditions for the storage modulus E′ (E′ j or E′ S ) are specified by the following (i) to (iv):
(i) the dynamic viscoelasticity measurement is carried out under the following conditions:
Measuring apparatus: RSA-G2 (TA Instruments)
Sample thickness: from 5 μm to 50 μm
Measuring temperature range: −50 to 225° C.
Temperature-elevating rate: 10° C./min
Measuring frequency: 1 Hz
Transform mode: sine wave tension mode (linear tension)
Initial static tensile load: 0.5 N
Initial gap distance (at 25° C.): 25 mm
Auto strain adjustment: Enabled (range: 0.05 to 25% amplitude, 0.02 to 5 N sine wave load);
(ii) the static tensile load is the median value of the maximum stress and minimum stress for each periodic motion, and the sine wave load is the vibrational stress centered on the static tensile load;
(iii) the sine wave tension mode is measurement of the vibrational stress while carrying out periodic motion at a fixed amplitude of 0.2%, wherein in sine wave tension mode, the vibrational stress is measured while varying the gap distance and static tensile load so that the difference between the static tensile load and the sine wave load is within 20%, and when the sine wave load is 0.02 N or lower, the vibrational stress is measured while amplifying the amplitude value so that the sine wave load is no greater than 5 N and the increase in the amplitude value is no greater than 25%; and
(iv) the storage modulus E′ is calculated from the relationship between the obtained sine wave load and amplitude value, and the following formulas:
σ*=σ 0 ·Exp[ i (ω t +δ)],
ε*=ε 0 ·Exp( iωt ),
σ*= E*·ε*
E*=E′+iE″
where σ*: vibrational stress, ε*: strain, i: imaginary number unit, ω: angular frequency, t: time, δ: phase difference between vibrational stress and strain, E*: complex modulus, E′: storage modulus, E″: loss modulus,
vibrational stress: sine wave load/initial cross-sectional area
static tensile load: load at minimum point of vibrational stress for each period (minimum point of gap distance for each period), and
sine wave load: difference between measured vibrational stress and static tensile load.
2. An electricity storage device comprising an electrode, the separator for an electricity storage device according to claim 1 , and a nonaqueous electrolyte solution.
3. A method for producing the separator for an electricity storage device according to claim 1 , wherein the method comprises the following steps:
(1) a sheet-forming step in which a mixture of a silane-modified polyolefin, polyethylene and a plasticizer is extruded, cooled to solidification and cast into a sheet to obtain a sheet;
(2) a stretching step in which the sheet is stretched at least in a uniaxial direction to obtain a stretched sheet;
(3) a porous body-forming step in which the plasticizer is extracted from the stretched sheet in the presence of an extraction solvent, forming pores in the stretched sheet to form a porous body; and
(4) a heat treatment step in which the porous body is subjected to heat treatment.
4. An electricity storage device assembly kit comprising the following two elements:
(1) an exterior body housing a laminated stack or wound body of electrodes and the separator for an electricity storage device according to claim 1 ; and
(2) a container housing a nonaqueous electrolyte solution.
5. The electricity storage device assembly kit according to claim 4 , wherein the nonaqueous electrolyte solution includes a fluorine (F)-containing lithium salt.
6. The electricity storage device assembly kit according to claim 5 , wherein the nonaqueous electrolyte solution includes lithium hexafluorophosphate (LiPF 6 ).
7. The electricity storage device assembly kit according to claim 6 , wherein the nonaqueous electrolyte solution is an acid solution and/or a base solution.
8. The electricity storage device assembly kit according to claim 5 , wherein the nonaqueous electrolyte solution is an acid solution and/or a base solution.
9. The electricity storage device assembly kit according to claim 4 , wherein the nonaqueous electrolyte solution includes lithium hexafluorophosphate (LiPF 6 ).
10. The electricity storage device assembly kit according to claim 9 , wherein the nonaqueous electrolyte solution is an acid solution and/or a base solution.
11. The electricity storage device assembly kit according to claim 4 , wherein the nonaqueous electrolyte solution is an acid solution and/or a base solution.
12. A method for producing an electricity storage device comprising the following steps:
a step of preparing the electricity storage device assembly kit according to claim 4 , and
a step of contacting the separator for an electricity storage device in element (1) of the electricity storage device assembly kit with the nonaqueous electrolyte solution in element (2), to initiate silane crosslinking reaction of the silane-modified polyolefin.
13. The method for producing an electricity storage device according to claim 12 , which further comprises the following steps:
a step of connecting lead terminals to the electrodes of element (1), and
a step of carrying out at least one cycle of charge-discharge.
14. A separator for an electricity storage device, comprising 5 to 40 weight % of a silane-modified polyolefin and 60 to 95 weight % of a polyolefin other than the silane-modified polyolefin, wherein the loss modulus change ratio (R ΔE″ ) is 1.5 to 20, as defined by the following formula (3):
R ΔE″ =E″ S /E″ j (3)
where E″ j is the loss modulus measured at 160° C. to 220° C. for the separator for an electricity storage device before crosslinking reaction of the silane-modified polyolefin, E″s is the loss modulus measured at 160° C. to 220° C. for the separator for an electricity storage device after crosslinking reaction of the silane-modified polyolefin, and the measuring conditions for the loss modulus E″ (E″ j or E″ S ) are specified by the following (i) to (iv):
(i) the dynamic viscoelasticity measurement is carried out under the following conditions:
Measuring apparatus: RSA-G2 (TA Instruments)
Sample thickness: from 5 μm to 50 μm
Measuring temperature range: −50 to 225° C.
Temperature-elevating rate: 10° C./min
Measuring frequency: 1 Hz
Transform mode: sine wave tension mode (linear tension)
Initial static tensile load: 0.5 N
Initial gap distance (at 25° C.): 25 mm
Auto strain adjustment: Enabled (range: 0.05 to 25% amplitude, 0.02 to 5 N sine wave load);
(ii) the static tensile load is the median value of the maximum stress and minimum stress for each periodic motion, and the sine wave load is the vibrational stress centered on the static tensile load;
(iii) the sine wave tension mode is measurement of the vibrational stress while carrying out periodic motion at a fixed amplitude of 0.2%, wherein in sine wave tension mode, the vibrational stress is measured while varying the gap distance and static tensile load so that the difference between the static tensile load and the sine wave load is within 20%, and when the sine wave load is 0.02 N or lower, the vibrational stress is measured while amplifying the amplitude value so that the sine wave load is no greater than 5 N and the increase in the amplitude value is no greater than 25%; and
(iv) the loss modulus E″ is calculated from the obtained sine wave load and amplitude value, and the following formulas:
σ*=σ 0 ·Exp[ i (ω t +δ)],
ε*=ε 0 ·Exp( iωt ),
σ*= E*·ε*
E*=E′+iE″
where σ*: vibrational stress, ε*: strain, i: imaginary number unit, ω: angular frequency, t: time, δ: phase difference between vibrational stress and strain, E*: complex modulus, E″: storage modulus, E″: loss modulus,
vibrational stress: sine wave load/initial cross-sectional area
static tensile load: load at minimum point of vibrational stress for each period (minimum point of gap distance for each period), and
sine wave load: difference between measured vibrational stress and static tensile load.
15. A separator for an electricity storage device, comprising 5 to 40 weight % of a silane-modified polyolefin and 60 to 95 weight % of a polyolefin other than the silane-modified polyolefin, wherein the mixed storage modulus ratio (R E′mix ) is 1.5 to 20, as defined by the following formula (2):
R E′mix =E′ a /E′ 0 (2)
{where E′ a is the storage modulus measured at 160° C. to 220° C. for the separator for an electricity storage device, E′ 0 is the storage modulus measured at 160° C. to 220° C. for a separator for an electricity storage device not containing the silane-modified polyolefin, and the measuring conditions for the storage modulus E′ (E′ a or E′ 0 ) are specified by the following (i) to (iv):
(i) the dynamic viscoelasticity measurement is carried out under the following conditions:
Measuring apparatus: RSA-G2 (TA Instruments)
Sample thickness: from 5 μm to 50 μm
Measuring temperature range: −50 to 225° C.
Temperature-elevating rate: 10° C./min
Measuring frequency: 1 Hz
Transform mode: sine wave tension mode (linear tension)
Initial static tensile load: 0.5 N
Initial gap distance (at 25° C.): 25 mm
Auto strain adjustment: Enabled (range: 0.05 to 25% amplitude, 0.02 to 5 N sine wave load);
(ii) the static tensile load is the median value of the maximum stress and minimum stress for each periodic motion, and the sine wave load is the vibrational stress centered on the static tensile load;
(iii) the sine wave tension mode is measurement of the vibrational stress while carrying out periodic motion at a fixed amplitude of 0.2%, wherein in sine wave tension mode, the vibrational stress is measured while varying the gap distance and static tensile load so that the difference between the static tensile load and the sine wave load is within 20%, and when the sine wave load is 0.02 N or lower, the vibrational stress is measured while amplifying the amplitude value so that the sine wave load is no greater than 5 N and the increase in the amplitude value is no greater than 25%;
(iv) the storage modulus E′ is calculated from the relationship between the obtained sine wave load and amplitude value, and the following formulas:
σ*=σ 0 ·Exp[ i (ω t +δ)],
ε*=ε 0 ·Exp( iωt ),
σ*= E*·ε*
E*=E′+iE″
where σ*: vibrational stress, ε*: strain, i: imaginary number unit, ω: angular frequency, t: time, δ: phase difference between vibrational stress and strain, E*: complex modulus, E′: storage modulus, E″: loss modulus,
vibrational stress: sine wave load/initial cross-sectional area
static tensile load: load at minimum point of vibrational stress for each period (minimum point of gap distance for each period), and
sine wave load: difference between measured vibrational stress and static tensile load.
16. The separator for an electricity storage device according to claim 15 , wherein the separator for an electricity storage device not containing a silane-modified polyolefin is a non-silane-modified polyolefin microporous membrane with a gelation degree of 0% to 10%.
17. A separator for an electricity storage device, comprising 5 to 40 weight % of a silane-modified polyolefin and 60 to 95 weight % of a polyolefin other than the silane-modified polyolefin, wherein the mixed loss modulus ratio (R E″mix ) is 1.5 to 20.0, as defined by the following formula (4):
R E″mix =E″ a /E″ 0 (4)
where E″ a is the loss modulus measured at 160° C. to 220° C. for the separator for an electricity storage device, E″ 0 is the loss modulus measured at 160° C. to 220° C. for a separator for an electricity storage device not containing the silane-modified polyolefin, and the measuring conditions for the loss modulus E″ (E″ a or E″ 0 ) are specified by the following (i) to (iv):
(i) the dynamic viscoelasticity measurement is carried out under the following conditions:
Measuring apparatus: RSA-G2 (TA Instruments)
Sample thickness: from 5 μm to 50 μm
Measuring temperature range: −50 to 225° C.
Temperature-elevating rate: 10° C./min
Measuring frequency: 1 Hz
Transform mode: sine wave tension mode (linear tension)
Initial static tensile load: 0.5 N
Initial gap distance (at 25° C.): 25 mm
Auto strain adjustment: Enabled (range: 0.05 to 25% amplitude, 0.02 to 5 N sine wave load);
(ii) the static tensile load is the median value of the maximum stress and minimum stress for each periodic motion, and the sine wave load is the vibrational stress centered on the static tensile load;
(iii) the sine wave tension mode is measurement of the vibrational stress while carrying out periodic motion at a fixed amplitude of 0.2%, wherein in sine wave tension mode, the vibrational stress is measured while varying the gap distance and static tensile load so that the difference between the static tensile load and the sine wave load is within 20%, and when the sine wave load is 0.02 N or lower, the vibrational stress is measured while amplifying the amplitude value so that the sine wave load is no greater than 5 N and the increase in the amplitude value is no greater than 25%;
(iv) the loss modulus E″ is calculated from the obtained sine wave load and amplitude value, and the following formulas:
σ*=σ 0 ·Exp[ i (ω t +δ)],
ε*=ε 0 ·Exp( iωt ),
σ*= E*·ε*
E*=E′+iE″
where σ*: vibrational stress, ε*: strain, i: imaginary number unit, ω: angular frequency, t: time, δ: phase difference between vibrational stress and strain, E*: complex modulus, E″: storage modulus, E″: loss modulus,
vibrational stress: sine wave load/initial cross-sectional area
static tensile load: load at minimum point of vibrational stress for each period (minimum point of gap distance for each period), and
sine wave load: difference between measured vibrational stress and static tensile load.
18. The separator for an electricity storage device according to claim 17 , wherein the separator for an electricity storage device not containing a silane-modified polyolefin is a non-silane-modified polyolefin microporous membrane with a gelation degree of 0% to 10%.
19. A separator for an electricity storage device comprising 5 to 40 weight % of a silane-modified polyolefin and 60 to 95 weight % of a polyolefin other than the silane-modified polyolefin, wherein the transition temperature is 135° C. to 150° C. for the rubber plateau and the crystal melt flow region, in the temperature-dependent change of the storage modulus of the separator for an electricity storage device.