KR101612351B1 - 비수계 전해액 및 비수계 전해액 2 차 전지 - Google Patents
비수계 전해액 및 비수계 전해액 2 차 전지 Download PDFInfo
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- KR101612351B1 KR101612351B1 KR1020137032037A KR20137032037A KR101612351B1 KR 101612351 B1 KR101612351 B1 KR 101612351B1 KR 1020137032037 A KR1020137032037 A KR 1020137032037A KR 20137032037 A KR20137032037 A KR 20137032037A KR 101612351 B1 KR101612351 B1 KR 101612351B1
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- South Korea
- Prior art keywords
- active material
- mass
- negative electrode
- carbonate
- lithium
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 39
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 160
- 229910052751 metal Inorganic materials 0.000 claims abstract description 97
- 239000002184 metal Substances 0.000 claims abstract description 90
- 229910013870 LiPF 6 Inorganic materials 0.000 claims abstract description 75
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 125000004429 atom Chemical group 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
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- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 229910052698 phosphorus Chemical group 0.000 claims abstract description 9
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 90
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- 229910017052 cobalt Inorganic materials 0.000 claims 2
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- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- KZEXVNKGDKTRPC-UHFFFAOYSA-N triethyl(2-methoxyethyl)phosphanium Chemical compound CC[P+](CC)(CC)CCOC KZEXVNKGDKTRPC-UHFFFAOYSA-N 0.000 description 1
- LDCGCIDVVXHEAM-UHFFFAOYSA-N triethyl(heptyl)phosphanium Chemical compound CCCCCCC[P+](CC)(CC)CC LDCGCIDVVXHEAM-UHFFFAOYSA-N 0.000 description 1
- GCRCSLNXFKCFHB-UHFFFAOYSA-N triethyl(hexyl)azanium Chemical compound CCCCCC[N+](CC)(CC)CC GCRCSLNXFKCFHB-UHFFFAOYSA-N 0.000 description 1
- CUIGTYKJLRVARY-UHFFFAOYSA-N triethyl(hexyl)phosphanium Chemical compound CCCCCC[P+](CC)(CC)CC CUIGTYKJLRVARY-UHFFFAOYSA-N 0.000 description 1
- QCLVFLIIJODTJU-UHFFFAOYSA-N triethyl(octyl)phosphanium Chemical compound CCCCCCCC[P+](CC)(CC)CC QCLVFLIIJODTJU-UHFFFAOYSA-N 0.000 description 1
- NFRBUOMQJKUACC-UHFFFAOYSA-N triethyl(pentyl)azanium Chemical compound CCCCC[N+](CC)(CC)CC NFRBUOMQJKUACC-UHFFFAOYSA-N 0.000 description 1
- RGXJWHBYXNYHML-UHFFFAOYSA-N triethyl(pentyl)phosphanium Chemical compound CCCCC[P+](CC)(CC)CC RGXJWHBYXNYHML-UHFFFAOYSA-N 0.000 description 1
- ARUIMKUOHIINGI-UHFFFAOYSA-N trifluoro(methylsulfonyl)methane Chemical compound CS(=O)(=O)C(F)(F)F ARUIMKUOHIINGI-UHFFFAOYSA-N 0.000 description 1
- QRBLCSZZIDXRBY-UHFFFAOYSA-N triheptyl(octyl)phosphanium Chemical compound CCCCCCCC[P+](CCCCCCC)(CCCCCCC)CCCCCCC QRBLCSZZIDXRBY-UHFFFAOYSA-N 0.000 description 1
- HSQNIIUDNMPIJI-UHFFFAOYSA-N trihexyl(methyl)azanium Chemical compound CCCCCC[N+](C)(CCCCCC)CCCCCC HSQNIIUDNMPIJI-UHFFFAOYSA-N 0.000 description 1
- UULWDDRUAOVYLH-UHFFFAOYSA-N trihexyl(propyl)phosphanium Chemical compound CCCCCC[P+](CCC)(CCCCCC)CCCCCC UULWDDRUAOVYLH-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- ACZOGADOAZWANS-UHFFFAOYSA-N trimethyl(pentyl)azanium Chemical compound CCCCC[N+](C)(C)C ACZOGADOAZWANS-UHFFFAOYSA-N 0.000 description 1
- IIVDETMOCZWPPU-UHFFFAOYSA-N trimethylsilyloxyboronic acid Chemical compound C[Si](C)(C)OB(O)O IIVDETMOCZWPPU-UHFFFAOYSA-N 0.000 description 1
- DURXHUNJSOGLRO-UHFFFAOYSA-N tripentyl(propyl)phosphanium Chemical compound CCCCC[P+](CCC)(CCCCC)CCCCC DURXHUNJSOGLRO-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- LJHXAZLYJUNWIS-UHFFFAOYSA-N tris(trimethoxysilyl) phosphate Chemical compound CO[Si](OC)(OC)OP(=O)(O[Si](OC)(OC)OC)O[Si](OC)(OC)OC LJHXAZLYJUNWIS-UHFFFAOYSA-N 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
M(FSO3)x (1)
[식 (1) 중, M 은 금속 원자, N(R)4 또는 P(R)4 (여기서, R 은, 탄소수 1 ∼ 12 인 유기기 또는 수소 원자이고 (단, 4 개의 R 전부가 수소 원자일 필요는 없다), 서로 동일하거나 상이해도 되며, 4 개의 R 의 일부 또는 전부는, 그것들이 결합되어 있는 질소 원자 또는 인 원자와 함께 고리를 형성해도 된다) 이고, M 이 금속 원자인 경우, x 는 금속 원자 M 의 가수로서 1 이상의 정수이며, M 이 N(R)4 또는 P(R)4 인 경우, x 는 1 이다]
Description
Claims (15)
- 비수 용매; LiPF6; 및 식 (1) :
M(FSO3)x
[식 (1) 중,
M 은 금속 원자, N(R)4 또는 P(R)4 (여기서 R 은 탄소수 1 ∼ 12 인 유기 기 또는 수소 원자이고 (단, 4 개의 R들 전부가 수소 원자는 아니다), R 들은 동일하거나 또는 상이하고, 그리고 4 개의 R들의 일부 또는 전부는, R들이 결합되어 있는 질소 원자 또는 인 원자와 함께 고리를 형성해도 된다) 이고;
M 이 금속 원자인 경우, x 는 금속 원자 M 의 가수로서 1 이상의 정수이며; 그리고 M 이 N(R)4 또는 P(R)4 인 경우, x 는 1 이다]
로 나타내는 플루오로술폰산염을 함유하고,
또한 불소 원자를 갖는 고리형 카보네이트, 탄소-탄소 불포화 결합을 갖는 고리형 카보네이트, 고리형 술폰산에스테르 화합물, 시아노기를 갖는 화합물, 디이소시아네이트 화합물, LiPF6 이외의 플루오로인산리튬염, 리튬이미드염류, 및 옥살산기를 갖는 리튬염류로 이루어지는 군으로부터 선택되는 적어도 1종을 함유하는, 비수계 전해액으로서,
상기 비수계 전해액 중의 FSO3 의 몰 함유량이 0.0005 ㏖/L ∼ 0.5 ㏖/L 인, 비수계 전해액. - 삭제
- 제 1 항에 있어서,
상기 식 (1) 로 나타내는 플루오로술폰산염이 플루오로술폰산리튬인, 비수계 전해액. - 제 1 항에 있어서,
상기 불소 원자를 갖는 고리형 카보네이트를 상기 비수계 전해액 중에 0.001 ∼ 85 질량% 의 양으로 함유하는, 비수계 전해액. - 제 1 항에 있어서,
상기 탄소-탄소 불포화 결합을 갖는 고리형 카보네이트를 상기 비수계 전해액 중에 0.001 ∼ 10 질량% 의 양으로 함유하는, 비수계 전해액. - 제 1 항에 있어서,
상기 고리형 술폰산에스테르를 상기 비수 전해액 중에 0.001 ∼ 10 질량% 의 양으로 함유하는, 비수계 전해액. - 제 1 항에 있어서,
상기 시아노기를 갖는 화합물을 상기 비수 전해액 중에 0.001 ∼ 10 질량% 의 양으로 함유하는, 비수계 전해액. - 제 1 항에 있어서,
상기 디이소시아네이트 화합물을 상기 비수 전해액 중에 0.001 ∼ 5 질량% 의 양으로 함유하는, 비수계 전해액. - 제 1 항에 있어서,
상기 LiPF6 이외의 플루오로인산리튬염 및 리튬이미드염류, 및 상기 옥살산기를 갖는 리튬염류로부터 선택되는 적어도 1 종의 상기 비수계 전해액 중의 농도가 0.0005 ∼ 0.5 ㏖/L 인, 비수계 전해액. - 리튬 이온들을 흡장 및 방출 가능한 부극 및 정극; 그리고 제 1 항에 기재된 비수계 전해액을 포함하는, 비수계 전해액 2 차 전지.
- 제 10 항에 있어서,
상기 부극은 집전체 및 상기 집전체 상에 배치된 부극 활물질층을 포함하며, 상기 부극 활물질층은 규소의 단체 금속, 합금 및 화합물, 그리고 주석의 단체 금속, 합금 및 화합물로부터 선택되는 적어도 1 종을 함유하는 부극 활물질을 포함하는, 비수계 전해액 2 차 전지. - 제 10 항에 있어서,
상기 부극은 집전체 및 상기 집전체 상에 배치된 부극 활물질층을 포함하며, 상기 부극 활물질층은 탄소질 재료를 함유하는 부극 활물질을 포함하는, 비수계 전해액 2 차 전지. - 제 10 항에 있어서,
상기 부극은 집전체 및 집전체 상에 배치된 부극 활물질층을 포함하며, 상기 부극 활물질층은 리튬티탄 복합 산화물을 함유하는 부극 활물질을 포함하는, 비수계 전해액 2 차 전지. - 제 10 항에 있어서,
상기 정극은 집전체 및 집전체 상에 배치된 정극 활물질층을 포함하며, 상기 정극 활물질층은 리튬·코발트 복합 산화물, 리튬·망간 복합 산화물, 리튬·코발트·망간 복합 산화물, 리튬·니켈 복합 산화물, 리튬·코발트·니켈 복합 산화물, 리튬·니켈·망간 복합 산화물, 및 리튬·니켈·코발트·망간 복합 산화물로 이루어지는 군에서 선택된 1 종을 함유하는, 비수계 전해액 2 차 전지. - 제 10 항에 있어서,
상기 정극은 집전체 및 집전체 상에 배치된 정극 활물질층을 포함하며, 상기 정극 활물질층은 LixMPO4 (M 은 주기표의 제 4 주기에 속하는 4 족 ∼ 11 족의 천이 금속들로 이루어지는 군으로부터 선택된 1 종의 원소이고, 그리고 x 는 0 < x < 1.2 를 만족한다) 를 함유하는, 비수계 전해액 2 차 전지.
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