JP2022551946A - 二次電池及び二次電池を備える装置 - Google Patents
二次電池及び二次電池を備える装置 Download PDFInfo
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- JP2022551946A JP2022551946A JP2022522047A JP2022522047A JP2022551946A JP 2022551946 A JP2022551946 A JP 2022551946A JP 2022522047 A JP2022522047 A JP 2022522047A JP 2022522047 A JP2022522047 A JP 2022522047A JP 2022551946 A JP2022551946 A JP 2022551946A
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- Prior art keywords
- secondary battery
- lithium
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- battery according
- organic solvent
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Links
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- 239000003960 organic solvent Substances 0.000 claims abstract description 41
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 26
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 229910001290 LiPF6 Inorganic materials 0.000 claims abstract description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 16
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 10
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
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- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
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- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims 1
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- 238000000034 method Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 3
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- 229910021383 artificial graphite Inorganic materials 0.000 description 3
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- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本願の二次電池において、電解液中の電解質塩が特定の含有量のビスフルオロスルホニルイミドリチウム(LiFSI)及びヘキサフルオロリン酸リチウム(LiPF6)を同時に含み、且つ有機溶媒が特定の含有量のエチレンカーボネート(EC)を含み、これにより、二次電池は、良好な高温サイクル性能及び高温貯蔵性能を両立できる。本願の装置は、前記二次電池を備えるため、少なくとも前記二次電池と同じ利点を有する。
1 電池パック、
2 上部筐体、
3 下部筐体、
4 電池モジュール、
5 二次電池。
正極活性材料(LiNi0.8Co0.1Mn0.1O2)、結着剤 ポリフッ化ビニリデン、及び導電剤 Super Pを、重量比 98:1:1で混合し、N-メチルピロリドン(NMP)を添加し、真空撹拌機の作用下で系が均一な透明状になるまで撹拌して、正極スラリーを得る。正極スラリーをアルミニウム箔に均一に塗布する。室温でアルミニウム箔を乾燥させた後にオーブンに移して乾燥させ、その後に冷間プレス、切断を経て、正極シートを得る。
負極活性材料 人造黒鉛と導電剤 Super P、結着剤 SBRを、質量比 96:2:2で混合し、脱イオン水を添加し、真空撹拌機の作用下で負極スラリーを得る。負極スラリーを負極集電体 銅箔に均一に塗布する。室温で銅箔を乾燥させた後にオーブンに移して乾燥させ、その後に冷間プレス、切断を経て、負極シートを得る。
含水量<10ppmのアルゴンガス雰囲気のグローブボックス内で、各有機溶媒を混合し、次に十分に乾燥後の電解質塩を有機溶媒で溶解させた後、有機溶媒に添加剤(0.5% FEC、1% DTD)を添加し、均一に混合して、電解液を得る。ここで、各電解質塩の体積モル濃度、各有機溶媒の重量比は、表1に示す通りである。表1において、各電解質塩の体積モル濃度は、電解液の総体積に基づいて計算して得られた体積モル濃度であり、各有機溶媒の含有量は、有機溶媒の総重量に基づいて計算して得られた重量百分率である。上記添加剤の含有量は、電解液の総重量に基づいて計算して得られた重量百分率である。
ポリエチレン膜をセパレータとする。
セパレータが正極シートと負極シートの間に位置して隔離の役割を果たすように、正極シート、セパレータ、負極シートを順次に積層した後、巻回により電極アセンブリを得る。電極アセンブリを外装内に置き、上記調製された電解液を乾燥後の二次電池に注入し、真空封止、静置、化成、整形などの工程を経て、二次電池を得る。
正極活性材料(LiNi0.8Co0.1Mn0.1O2)、結着剤 ポリフッ化ビニリデン、及び導電剤 Super Pを、重量比 98:1:1で混合し、N-メチルピロリドン(NMP)を添加し、真空撹拌機の作用下で系が均一な透明状になるまで撹拌して、正極スラリーを得る。正極スラリーをアルミニウム箔上に均一に塗布する。室温でアルミニウム箔を乾燥させた後にオーブンに移して乾燥させ、その後に冷間プレス、切断を経て、正極シートを得る。
負極活性材料 一酸化ケイ素と人造黒鉛を質量比 2:8で混合した後、それと導電剤 Super P、及び結着剤 アクリル酸エステルを、質量比 92:2:6で混合し、脱イオン水を添加し、真空撹拌機の作用下で負極スラリーを得る。負極スラリーを負極集電体 銅箔に均一に塗布する。室温で銅箔を乾燥させた後にオーブンに移して乾燥させ、その後に冷間プレス、切断を経て、負極シートを得る。
含水量<10ppmのアルゴンガス雰囲気のグローブボックス内で、各有機溶媒を混合し、次に十分に乾燥後の電解質塩を有機溶媒で溶解させた後、有機溶媒に添加剤(8% FEC、1% SA、0.8% TMSP)を添加し、均一に混合して、電解液を得る。ここで、各電解質塩の体積モル濃度、各有機溶媒の重量比は、表2に示す通りである。表2において、各電解質塩の体積モル濃度は、電解液の総体積に基づいて計算して得られた体積モル濃度であり、各有機溶媒の含有量は、有機溶媒の総重量に基づいて計算して得られた重量百分率である。上記添加剤の含有量は、電解液の総重量に基づいて計算して得られた重量百分率である。
ポリエチレン膜をセパレータとする。
セパレータが正極シートと負極シートの間に位置して隔離の役割を果たすように、正極シート、セパレータ、負極シートを順次に積層した後、巻回により電極アセンブリを得る。電極アセンブリを外装内に置き、上記調製された電解液を乾燥後の二次電池に注入し、真空封止、静置、化成、整形などの工程を経て、二次電池を得る。
45℃で、二次電池を1Cの定電流で4.25Vまで充電し、さらに4.25Vの定電圧で電流が0.05Cになるまで充電し、5min静置し、次に1Cの定電流でカットオフ電圧の下限まで放電し(表1における各実施例及び比較例は2.8Vを取り、表2における各実施例及び比較例は2.5Vを取る)、これが二次電池の初回充放電サイクルであり、今回の放電容量を二次電池の初回サイクルの放電容量と記し、上記方法に応じて、二次電池に対して、800回の充放電サイクルを行って、二次電池の800回サイクル後の放電容量を得る。
二次電池の45℃で800回サイクル後の容量維持率(%)=(二次電池の800回サイクル後の放電容量/二次電池の初回サイクルの放電容量)×100%
60℃で、二次電池を0.5Cの定電流で4.25Vまで充電し、さらに4.25Vの定電圧で電流が0.05Cになるまで充電し、排水法でこの時のリチウムイオン電池の体積を測定して、V1と記す。その後、二次電池を60℃の恒温箱に入れ、30日間貯蔵した後に取り出し、この時の二次電池の体積を測定して、V2と記す。
二次電池の60℃で30日間貯蔵後の体積膨張率(%)=[(V2-V1)/V1]×100%
2 上部筐体
3 下部筐体
4 電池モジュール
5 二次電池
Claims (15)
- 電解質塩及び有機溶媒を有する電解液を含む二次電池であって、
前記電解質塩は、ビスフルオロスルホニルイミドリチウム(LiFSI)及びヘキサフルオロリン酸リチウム(LiPF6)を含み、
前記電解液におけるビスフルオロスルホニルイミドリチウム(LiFSI)の体積モル濃度は、0.8mol/L~1.2mol/Lであり、
前記電解液におけるヘキサフルオロリン酸リチウム(LiPF6)の体積モル濃度は、0.15mol/L~0.4mol/Lであり、
前記有機溶媒は、エチレンカーボネート(EC)を含み、前記有機溶媒におけるエチレンカーボネート(EC)の質量占有率が≦20%である、
ことを特徴とする二次電池。 - 前記電解液におけるビスフルオロスルホニルイミドリチウム(LiFSI)の体積モル濃度は、0.9mol/L~1.2mol/Lである、
ことを特徴とする請求項1に記載の二次電池。 - 前記電解液におけるヘキサフルオロリン酸リチウム(LiPF6)の体積モル濃度は、0.15mol/L~0.3mol/Lである、
ことを特徴とする請求項1又は2に記載の二次電池。 - ビスフルオロスルホニルイミドリチウム(LiFSI)の体積モル濃度とヘキサフルオロリン酸リチウム(LiPF6)の体積モル濃度の比の値は、3~7:1であり、好ましくは、4~6:1である、
ことを特徴とする請求項1乃至3のいずれか1項に記載の二次電池。 - 前記有機溶媒におけるエチレンカーボネート(EC)の質量占有率が≦15%であり、好ましくは、前記有機溶媒におけるエチレンカーボネート(EC)の質量占有率が≦10%である、
ことを特徴とする請求項1乃至4のいずれか1項に記載の二次電池。 - 前記有機溶媒は、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)のうちの1種類又は複数種類をさらに含む、
ことを特徴とする請求項1乃至5のいずれか1項に記載の二次電池。 - 前記有機溶媒は、エチルメチルカーボネート(EMC)をさらに含み、前記有機溶媒におけるエチルメチルカーボネート(EMC)の質量占有率は、60%~95%であり、好ましくは、75%~95%である、
ことを特徴とする請求項1乃至6のいずれか1項に記載の二次電池。 - 前記電解液は、添加剤をさらに含み、前記添加剤は、フルオロエチレンカーボネート(FEC)、ビニルサルフェート(DTD)、1,3-プロパンスルトン(PS)、1,3-プロペニル-スルトン(PST)、無水コハク酸(SA)、リチウムジフルオロオキサレートボレート(LiDFOB)、リチウムジフルオロビスオキサレートホスフェート(LiDFOP)、トリス(トリメチルシリル)ホスフェート(TMSP)、トリス(トリメチルシリル)ボレート(TMSB)のうちの1種類又は複数種類を含む、
ことを特徴とする請求項1乃至7のいずれか1項に記載の二次電池。 - 前記電解液の25℃での導電率は、6.5mS/cm~9.5mS/cmであり、好ましくは、前記電解液の25℃での導電率は、7.0mS/cm~9.0mS/cmである、
ことを特徴とする請求項1乃至8のいずれか1項に記載の二次電池。 - 前記電解液における前記電解質塩の体積モル濃度は、1.0mol/L~1.4mol/Lであり、好ましくは、1.1mol/L~1.3mol/Lである、
ことを特徴とする請求項1乃至9のいずれか1項に記載の二次電池。 - 前記二次電池は、負極シートを含み、前記負極シートは、負極集電体と、負極集電体の少なくとも一つの表面に配置され且つ負極活性材料を含有する負極フィルムと、を含み、前記負極活性材料は、炭素材料、ケイ素系材料のうちの1種類又は複数種類を含む、
ことを特徴とする請求項1乃至10のいずれか1項に記載の二次電池。 - 前記負極活性材料は、ケイ素系材料を含み、且つ、前記負極活性材料における前記ケイ素系材料の重量占有率が≦40%であり、好ましくは、前記負極活性材料における前記ケイ素系材料の重量占有率は、15%~30%である、
ことを特徴とする請求項11に記載の二次電池。 - 前記二次電池は、正極シートを含み、前記正極シートは、正極集電体と、正極集電体の少なくとも一つの表面に設けられ且つ正極活性材料を含有する正極フィルムと、を含み、前記正極活性材料は、リチウムニッケルコバルトマンガン酸化物、リチウムニッケルコバルトアルミニウム酸化物のうちの1種類又は複数種類を含み、
好ましくは、前記正極活性材料は、一般式 LiaNibCocMdM’eOfAg又は少なくとも一部の表面に被覆層が設けられたLiaNibCocMdM’eOfAgのうちの1種類又は複数種類を含み、ここで、0.8≦a≦1.2、0.5≦b<1、0<c<1、0<d<1、0≦e≦0.1、1≦f≦2、0≦g≦1であり、Mは、Mn、Alから選択される1種類又は複数種類であり、M’は、Zr、Al、Zn、Cu、Cr、Mg、Fe、V、Ti、Bから選択される1種類又は複数種類であり、Aは、N、F、S、Clから選択される1種類又は複数種類である、
ことを特徴とする請求項1乃至12のいずれか1項に記載の二次電池。 - 前記正極活性材料は、リチウムニッケル酸化物、リチウムマンガン酸化物、リン酸鉄リチウム、リン酸マンガンリチウム、リン酸マンガン鉄リチウム、コバルト酸リチウム及びその改質化合物のうちの1種類又は複数種類をさらに含む、
ことを特徴とする請求項13に記載の二次電池。 - 請求項1乃至14のいずれか1項に記載の二次電池を備える、
ことを特徴とする装置。
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