JP2015533020A - リチウム二次電池用電解液及びそれを含むリチウム二次電池 - Google Patents
リチウム二次電池用電解液及びそれを含むリチウム二次電池 Download PDFInfo
- Publication number
- JP2015533020A JP2015533020A JP2015539514A JP2015539514A JP2015533020A JP 2015533020 A JP2015533020 A JP 2015533020A JP 2015539514 A JP2015539514 A JP 2015539514A JP 2015539514 A JP2015539514 A JP 2015539514A JP 2015533020 A JP2015533020 A JP 2015533020A
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- Japan
- Prior art keywords
- secondary battery
- carbonate
- solvent
- lithium secondary
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 17
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 10
- 239000010450 olivine Substances 0.000 claims description 10
- 229910052609 olivine Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003660 carbonate based solvent Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 claims description 2
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910015044 LiB Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium 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
- -1 glyme solvent Chemical class 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- 239000011163 secondary particle Substances 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- 239000010409 thin film Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
Description
Claims (20)
- リチウム塩及び非水系溶媒を含むリチウム二次電池用電解液において、前記非水系溶媒は、エーテル系溶媒及びグリム(glyme)系溶媒を含み、前記エーテル系溶媒:グリム(glyme)系溶媒は、非水系溶媒の全体積を基準として20:80〜60:40であることを特徴とする、リチウム二次電池用電解液。
- 前記グリム(glyme)系溶媒は、エチレングリコールジメチルエーテル{CH3OCH2CH2OCH3:グリム}、ジエチレングリコールジメチルエーテル{CH3(OCH2CH2)2OCH3:ジグリム}、ジエチレングリコールジエチルエーテル{C2H5(OCH2CH2)2OC2H5}、トリエチレングリコールジメチルエーテル{CH3(OCH2CH2)3OCH3}、トリエチレングリコールジエチルエーテル{C2H5(OCH2CH2)3OC2H5}からなる群から選択される1つ以上であることを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 前記エーテル系溶媒は、テトラヒドロフラン、2−メチルテトラヒドロフラン、ジメチルエーテル及びジブチルエーテルから選択される1つ以上であることを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 前記グリム(glyme)系溶媒は、ジエチレングリコールジメチルエーテル{CH3(OCH2CH2)2OCH3:ジグリム}であることを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 前記エーテル系溶媒:グリム(glyme)系溶媒は、非水系溶媒の全体積を基準として25:75〜65:45であることを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 前記電解液は、追加的にカーボネート系溶媒を含むことを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 前記グリム(glyme)系溶媒とエーテル系溶媒の体積(A):カーボネート系溶媒の体積(B)は、電解液全体の重量比を基準として、A:Bは15:85〜85:15であることを特徴とする、請求項6に記載のリチウム二次電池用電解液。
- 前記カーボネート系溶媒は、環状カーボネートであり、前記環状カーボネートは、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、1,2−ブチレンカーボネート、2,3−ブチレンカーボネート、1,2−ペンチレンカーボネート、及び2,3−ペンチレンカーボネートのうちの1つ以上であることを特徴とする、請求項6に記載のリチウム二次電池用電解液。
- 前記カーボネート系溶媒は、追加的に線状カーボネートを含み、前記線状カーボネートは、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、ジプロピルカーボネート(DPC)、エチルメチルカーボネート(EMC)、メチルプロピルカーボネート(MPC)及びエチルプロピルカーボネート(EPC)のうちの1つ以上であり、環状カーボネートと線状カーボネートは、カーボネート系溶媒の体積比を基準として1:4〜4:1の割合で混合比を有することを特徴とする、請求項8に記載のリチウム二次電池用電解液。
- 前記リチウム塩は、LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiPF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、クロロボランリチウム、4フェニルホウ酸リチウム及びイミドからなる群から選択された1つ以上であり、濃度は、電解液内で0.5〜3Mであることを特徴とする、請求項1に記載のリチウム二次電池用電解液。
- 請求項1に記載のリチウム二次電池用電解液を含むことを特徴とする、リチウム二次電池。
- 前記リチウム二次電池は、
(i)正極活物質として下記化学式1のリチウム金属リン酸化物を含む正極と、
Li1+aM(PO4−b)Xb(1)
上記式中、Mは、第2族〜第12族の金属からなる群から選択される1種以上であり、Xは、F、S及びNから選択された1種以上であり、−0.5≦a≦+0.5、0≦b≦0.1である。
(ii)負極活物質として非晶質カーボンを含む負極とを含んでいることを特徴とする、請求項11に記載のリチウム二次電池。 - 前記リチウム金属リン酸化物は、下記化学式2のオリビン結晶構造のリチウム鉄リン酸化物であることを特徴とする、請求項12に記載のリチウム二次電池:
Li1+aFe1−xM’x(PO4−b)Xb(2)
上記式中、
M’は、Al、Mg、Ni、Co、Mn、Ti、Ga、Cu、V、Nb、Zr、Ce、In、Zn及びYから選択された1種以上であり、
Xは、F、S及びNから選択された1種以上であり、
−0.5≦a≦+0.5、0≦x≦0.5、0≦b≦0.1である。 - 前記オリビン結晶構造のリチウム鉄リン酸化物はLiFePO4であることを特徴とする、請求項13に記載のリチウム二次電池。
- 前記オリビン結晶構造のリチウム鉄リン酸化物は、伝導性カーボンでコーティングされていることを特徴とする、請求項14に記載のリチウム二次電池。
- 前記非晶質カーボンは、ハードカーボン及び/又はソフトカーボンであることを特徴とする、請求項12に記載のリチウム二次電池。
- 請求項11に記載のリチウム二次電池を単位電池として含むことを特徴とする、電池モジュール。
- 請求項17に記載の電池モジュールを含むことを特徴とする、電池パック。
- 請求項18に記載の電池パックを含むことを特徴とする、デバイス。
- 前記デバイスは、ハイブリッド電気自動車、プラグインハイブリッド電気自動車、または電力貯蔵用システムであることを特徴とする、請求項19に記載のデバイス。
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PCT/KR2013/010706 WO2014081252A1 (ko) | 2012-11-23 | 2013-11-22 | 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지 |
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KR20180001997A (ko) * | 2016-06-28 | 2018-01-05 | 주식회사 엘지화학 | 리튬-설퍼 전지용 전해액 및 이를 포함하는 리튬-설퍼 전지 |
US11605081B2 (en) | 2016-11-21 | 2023-03-14 | Samsung Electronics Co., Ltd. | Method and device applying artificial intelligence to send money by using voice input |
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CN108847502A (zh) * | 2018-05-08 | 2018-11-20 | 东风商用车有限公司 | 一种磷酸铁锂电池高低温电解液 |
KR20200005466A (ko) * | 2018-07-06 | 2020-01-15 | 주식회사 엘지화학 | 전도성 물질의 비표면적 측정 방법 |
KR102621697B1 (ko) * | 2018-08-16 | 2024-01-04 | 현대자동차주식회사 | 전고체 전지용 바인더 용액, 이를 포함하는 전극 슬러리 및 이를 사용한 전고체 전지의 제조방법 |
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CN109273759A (zh) * | 2018-09-27 | 2019-01-25 | 中山大学 | 一种二次电池用的电解液及含有其的二次电池 |
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