KR20230094876A - Electrolyte for secondary battery, manufacturing method thereof, and secondary battery comprising same - Google Patents
Electrolyte for secondary battery, manufacturing method thereof, and secondary battery comprising same Download PDFInfo
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- KR20230094876A KR20230094876A KR1020210184357A KR20210184357A KR20230094876A KR 20230094876 A KR20230094876 A KR 20230094876A KR 1020210184357 A KR1020210184357 A KR 1020210184357A KR 20210184357 A KR20210184357 A KR 20210184357A KR 20230094876 A KR20230094876 A KR 20230094876A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- electrolyte
- formula
- secondary battery
- secondary batteries
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 25
- -1 cycloalkynyl group Chemical group 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005018 aryl alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000005377 alkyl thioxy group Chemical group 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 5
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000006182 cathode active material Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical compound C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 229910013075 LiBF Inorganic materials 0.000 description 5
- 229910052789 astatine Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910003936 Li(Ni0.5Mn0.3Co0.2)O2 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010090 LiAlO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005332 alkyl sulfoxy group Chemical group 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000003974 aralkylamines Chemical group 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 125000005165 aryl thioxy group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- VWBBTLBZDGUKPU-UHFFFAOYSA-N imidazol-1-ylphosphonic acid Chemical compound OP(O)(=O)N1C=CN=C1 VWBBTLBZDGUKPU-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011871 silicon-based negative electrode active material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 이차전지용 전해질에 첨가되어 이차전지의 성능을 향상시킬 수 있는 신규한 전해질 첨가제, 이의 제조방법, 이를 포함하는 전해질 및 이차전지에 관한 것이다.The present invention relates to a novel electrolyte additive that can be added to an electrolyte for a secondary battery to improve the performance of a secondary battery, a method for preparing the same, and an electrolyte and a secondary battery including the same.
전지는 비디오 카메라, 휴대폰, 노트북 컴퓨터 등 휴대용 전자기기의 구동 전원으로 사용된다. 재충전이 가능한 이차전지, 특히 리튬 이차전지는 기존의 납 축전지, 니켈-카드뮴 전지, 니켈수소 전지, 니켈아연 전지 등과 비교하여 단위 중량 당 에너지 밀도가 3배 이상 높고 고속 충전이 가능하다.Batteries are used as power sources for portable electronic devices such as video cameras, mobile phones, and notebook computers. Rechargeable secondary batteries, especially lithium secondary batteries, have three times higher energy density per unit weight than conventional lead storage batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and nickel-zinc batteries, and can be charged at high speed.
이러한 이차전지, 특히 리튬 이차전지의 수요가 급격히 증가하고 있으며, 이에 따라 높은 에너지 밀도와 방전 전압을 갖는 리튬 이차전지에 대해 많은 연구가 행해졌고, 또한 상용화되어 널리 사용되고 있다.Demand for such secondary batteries, particularly lithium secondary batteries, is rapidly increasing, and accordingly, a lot of research has been conducted on lithium secondary batteries having high energy density and discharge voltage, and they have been commercialized and widely used.
리튬 이차전지는 기타 전지와 비교하여 무게가 가볍고, 체적이 작으며, 동작 전압이 높고, 에너지 밀도가 높으며, 출력 전력이 크고, 충전 효율이 높으며, 메모리 효과가 없고 수명이 길다는 등의 장점을 가져서 휴대폰, 노트북 등의 디지털 제품 분야에서 광범위하게 응용되고 있고, 전기자동차, 대형 에너지 저장장치를 위한 최고 선택 중 하나로 여겨지고 있다.Compared to other batteries, lithium secondary batteries have advantages such as light weight, small volume, high operating voltage, high energy density, high output power, high charging efficiency, no memory effect, and long lifespan. It has been widely applied in the field of digital products such as mobile phones and laptops, and is considered one of the best choices for electric vehicles and large-scale energy storage devices.
최근 들어, 전기 자동차와 같은 중대형 리튬 이차전지의 개발이 진행됨에 따라 고전압 및 고용량의 리튬 이차전지를 구현하기 위해 다양한 연구가 진행되고 있는데, 특히 고전압 고용량을 구현하기 위해 양극 활물질의 개발과 이에 적합한 전해질 첨가제가 필요한 상황이다.Recently, as the development of medium and large-sized lithium secondary batteries such as electric vehicles is progressing, various studies are being conducted to realize high voltage and high capacity lithium secondary batteries. This is where additives are needed.
본 발명은 이차전지의 성능을 향상할 수 있는 신규한 이차전지용 전해질 첨가제를 제공하고자 한다. The present invention is intended to provide a novel electrolyte additive for secondary batteries capable of improving the performance of secondary batteries.
본 발명은 종래 문제점을 해결하기 위한 것으로, 음극 및 양극의 안정성 및 내구성이 향상됨으로써 우수한 충방전 특성, 출력 특성, 용량 특성 및 전압 특성을 갖도록 하는 리튬 이차전지용 전해질 첨가제를 제공하고자 한다. The present invention is to solve the conventional problems, and to provide an electrolyte additive for a lithium secondary battery having excellent charge and discharge characteristics, output characteristics, capacity characteristics and voltage characteristics by improving the stability and durability of a negative electrode and a positive electrode.
본 발명의 일 실시예에 의한 이차전지용 전해질 첨가제는 하기 화학식 1로 표시되는 화합물을 포함한다. An electrolyte additive for a secondary battery according to an embodiment of the present invention includes a compound represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서 X는 산소(O) 또는 황(S)이고, A 및 B는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 할로겐; 하이드록시기; 치환 또는 비치환된 탄소수 30이하의 알콕시기 및 아릴옥시기; 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 나이트릴기; 알킬티옥시기; 붕소기; 니트로기; 티올; 아미노기; 히드라진; 아미드기; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염; 중에서 선택된다. In Formula 1, X is oxygen (O) or sulfur (S), A and B are the same as or different from each other and are each independently hydrogen; halogen; hydroxy group; a substituted or unsubstituted alkoxy group and aryloxy group having 30 or less carbon atoms; A substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; nitrile group; Alkyl thioxy group; boron group; nitro group; thiol; amino group; hydrazine; amide group; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof; are selected from
보다 바람직한 일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다. As a more preferred embodiment, the compound represented by Formula 1 may be a compound represented by Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2에서, X는 산소(O) 또는 황(S)이고,In Formula 2, X is oxygen (O) or sulfur (S),
A1 및 B1는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 및 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 중에서 선택된다. A1 and B1 are the same as or different from each other and are each independently hydrogen; And a substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; are selected from
보다 바람직한 일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 3으로 표시되는 화합물일 수 있다. As a more preferred embodiment, the compound represented by Formula 1 may be a compound represented by Formula 3 below.
[화학식 3][Formula 3]
상기 화학식 3에서, X는 산소(O) 또는 황(S)이고, R1 및 R3는 서로 동일하거나 상이하고 각각 독립적으로 치환 또는 비치환된 탄소수 3 이내의 알킬렌기이고, R2 및 R4는 서로 동일하거나 상이하고 각각 독립적으로 수소, 할로겐, 및 치환 또는 비치환된 탄소수 3 이내의 알킬기 중에서 선택된다. In Formula 3, X is oxygen (O) or sulfur (S), R1 and R3 are the same as or different from each other and each independently represents a substituted or unsubstituted alkylene group having 3 or less carbon atoms, and R2 and R4 are the same as or different from each other. They are different and each independently selected from hydrogen, halogen, and a substituted or unsubstituted alkyl group having 3 or less carbon atoms.
보다 바람직한 일 구현예로서, 상기 이차전지용 전해질 첨가제를 제조하는 방법은 반응기에 트라이(1H-이미다졸-1-일)포스핀 옥사이드(Tri(1H-imidazol-1-yl)phosphine oxide) 및 알코올(R1-OH)를 투입하여 반응시키는 단계를 포함할 수 있다. As a more preferred embodiment, the method for preparing the electrolyte additive for a secondary battery includes tri (1H-imidazol-1-yl) phosphine oxide (Tri (1H-imidazol-1-yl) phosphine oxide) and alcohol ( R1-OH) may be added to react.
본 발명의 일 실시예에 의한 이차전지용 전해질은 상기 이차전지용 전해질 첨가제를 포함한다. An electrolyte for a secondary battery according to an embodiment of the present invention includes the electrolyte additive for a secondary battery.
일 구현예로서, 상기 이차전지용 전해질 첨가제는 이차전지용 전해질 전체 대비 0.1 내지 10 중량%로 포함될 수 있다. As an embodiment, the electrolyte additive for a secondary battery may be included in an amount of 0.1 to 10% by weight based on the total amount of the electrolyte for a secondary battery.
일 구현예로서, 상기 이차전지용 전해질은 리튬염; 및 용매;를 더 포함할 수 있다. As an embodiment, the electrolyte for the secondary battery may include a lithium salt; And a solvent; may further include.
일 구현예로서, 상기 이차전지용 전해질은 옥살레이토보레이트계, 옥살레이토포스페이트계, 불소로 치환된 카보네이크계, 비닐리덴 카보네이트계 및 설피닐기 함유 화합물로 이루어진 군으로부터 선택되는 어느 하나 이상의 첨가제를 더 포함할 수 있다. In one embodiment, the secondary battery electrolyte further contains at least one additive selected from the group consisting of oxalate borate-based, oxalatophosphate-based, fluorine-substituted carbonaceous, vinylidene carbonate-based, and sulfinyl group-containing compounds can include
본 발명의 일 실시예에 의한 이차전지는 양극활물질을 포함하는 양극; 음극활물질을 포함하는 음극; 및 양극과 음극 사이에 포함되는 상기 이차전지용 전해질;을 포함한다. A secondary battery according to an embodiment of the present invention includes a cathode including a cathode active material; A negative electrode containing a negative electrode active material; and the secondary battery electrolyte included between the positive electrode and the negative electrode.
본 발명은 이차전지의 성능을 향상할 수 있는 이차전지용 전해질 첨가제 및 이의 제조방법을 제공한다. The present invention provides an electrolyte additive for a secondary battery capable of improving the performance of a secondary battery and a manufacturing method thereof.
본 발명은 음극 및 양극의 안정성 및 내구성이 향상됨으로써 우수한 충방전 특성, 출력 특성, 용량 특성 및 전압 특성을 갖도록 하는 리튬 이차전지용 전해질 첨가제를 제공한다. The present invention provides an electrolyte additive for a lithium secondary battery having excellent charge/discharge characteristics, output characteristics, capacity characteristics and voltage characteristics by improving stability and durability of a negative electrode and a positive electrode.
보다 구체적으로, 본 발명의 선형 포스포네이트(phosphonate) 화합물 구조는 화학적으로 안정하기 때문에, 이를 포함하는 전해액은 전지의 저항을 낮추는 동시에 양극으로부터 용출된 전이금속 이온을 안정화시켜 고온에서 안정할 수 있다.More specifically, since the structure of the linear phosphonate compound of the present invention is chemically stable, an electrolyte containing the same can be stable at high temperatures by stabilizing transition metal ions eluted from the anode while lowering the resistance of the battery. .
본 발명의 기술적 사상의 실시예는, 구체적으로 언급되지 않은 다양한 효과를 제공할 수 있다. Embodiments of the technical idea of the present invention may provide various effects not specifically mentioned.
본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 상세하게 후술되어 있는 실시예를 참조하면 명확해질 것이다. 그러나 본 발명은 여기서 설명되는 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. The advantages and features of the present invention, and how to achieve them, will become clear with reference to the detailed description of the embodiments below. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms.
본 명세서에서 사용되는 "포함하는"은 다른 실시예를 포함할 가능성을 내포하는 개방형 용어(open-ended terms)로 이해되어야 한다.As used herein, “comprising” should be understood as an open-ended term that connotes the possibility of including other embodiments.
본 명세서에서 사용되는 "바람직한" 및 "바람직하게"는 소정 환경 하에서 소정의 이점을 제공할 수 있는 본 발명의 실시 형태를 지칭한다. 그러나, 동일한 환경 또는 다른 환경 하에서, 다른 실시 형태가 또한 바람직할 수 있다. 추가로, 하나 이상의 바람직한 실시 형태의 언급은 다른 실시 형태가 유용하지 않다는 것을 의미하지 않으며, 본 발명의 범주로부터 다른 실시 형태를 배제하고자 하는 것은 아니다.As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Additionally, the recitation of one or more preferred embodiments does not imply that the other embodiments are not useful, nor is it intended to exclude the other embodiments from the scope of the present invention.
본 발명의 한 개의 이미다졸 작용기를 포함하는 선형 포스포네이트(phosphonate) 구조의 이차전지용 전해질 첨가제는 하기 화학식 1로 표시된다. The electrolyte additive for a secondary battery having a linear phosphonate structure including one imidazole functional group according to the present invention is represented by Chemical Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서 X는 산소(O) 또는 황(S)이고, A 및 B는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 할로겐; 하이드록시기; 치환 또는 비치환된 탄소수 30이하의 알콕시기 및 아릴옥시기; 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 나이트릴기; 알킬티옥시기; 붕소기; 니트로기; 티올; 아미노기; 히드라진; 아미드기; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염; 중에서 선택된다. In Formula 1, X is oxygen (O) or sulfur (S), A and B are the same as or different from each other and are each independently hydrogen; halogen; hydroxy group; a substituted or unsubstituted alkoxy group and aryloxy group having 30 or less carbon atoms; A substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; nitrile group; Alkyl thioxy group; boron group; nitro group; thiol; amino group; hydrazine; amide group; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof; are selected from
본 명세서에서 "치환 또는 비치환"은 할로겐기, 니트릴기, 니트로기, 하이드록시기, 카보닐기, 에스테르기, 이미드기, 아미노기, 알콕시기, 아릴옥시기, 알킬티옥시기, 아릴티옥시기, 알킬술폭시기, 아릴술폭시기, 실릴기, 붕소기, 알킬기, 시클로알킬기, 알케닐기, 알키닐기, 아릴기, 아르알킬기, 아르알케닐기, 알킬아릴기, 알킬아민기. 아랄킬아민기, 헤테로아릴아민기, 아릴아민기, 아릴포스핀기, 및 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 것을 의미한다. As used herein, "substituted or unsubstituted" refers to a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, an alkoxy group, an aryloxy group, an alkylthioxy group, an arylthioxy group, an alkyl Sulfoxy group, aryl sulfoxy group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group. It means substituted or unsubstituted with one or more substituents selected from the group consisting of an aralkylamine group, a heteroarylamine group, an arylamine group, an arylphosphine group, and a heterocyclic group.
상기 이차전지는 리튬금속 이차전지, 리튬이온 이차전지, 리튬폴리머 이차전지, 리튬이온 폴리머 이차전지, 리튬황 이차전지, 또는 전고체 전지 등일 수 있으나, 이차전지라면 이에 한정되는 것은 아니다. The secondary battery may be a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion polymer secondary battery, a lithium sulfur secondary battery, or an all-solid-state battery, but the secondary battery is not limited thereto.
또한, 상기 이차전지용 전해질은 고체 전해질, 겔 전해질 및/또는 전해액 등일 수 있으나, 이에 한정되는 것은 아니다. In addition, the secondary battery electrolyte may be a solid electrolyte, a gel electrolyte, and/or an electrolyte solution, but is not limited thereto.
또한, 상기 이차전지용 전해질 첨가제는 전해질에 첨가제로서 투입되는 화합물일 수 있고, 이차전지용 전해질의 용매로서 투입되는 화합물을 총칭하는 의미이다. In addition, the electrolyte additive for a secondary battery may be a compound added as an additive to the electrolyte, and is a generic term for a compound introduced as a solvent of the electrolyte for a secondary battery.
보다 바람직한 일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다. As a more preferred embodiment, the compound represented by Formula 1 may be a compound represented by Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2에서, X는 산소(O) 또는 황(S)이고, A1 및 B1는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 및 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 중에서 선택된다. In Formula 2, X is oxygen (O) or sulfur (S), A1 and B1 are the same as or different from each other and are each independently hydrogen; And a substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; are selected from
본 발명의 선형 포스포네이트(phosphonate) 구조의 전해질 첨가제는 두 개의 알콕시기를 포함하고, 한 개의 이미다졸 작용기를 포함함으로써, 리튬 이차전지의 전기화학적 성능, 반응 속도 및 안정성을 향상시키고 또한 용량유지율과 수명유지율을 충분히 향상시킬 수 있음을 확인하였다. The electrolyte additive having a linear phosphonate structure of the present invention includes two alkoxy groups and one imidazole functional group, thereby improving the electrochemical performance, reaction rate and stability of a lithium secondary battery, and also increasing the capacity retention rate and It was confirmed that the life maintenance rate can be sufficiently improved.
보다 바람직한 일 예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2-1로 표시되는 화합물일 수 있다. As a more preferable example, the compound represented by Formula 1 may be a compound represented by Formula 2-1 below.
[화학식 2-1][Formula 2-1]
상기 화학식 2-1에서, A1 및 B1은 전술한 바와 같다. In Formula 2-1, A1 and B1 are as described above.
또 다른 바람직한 일 예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2-2로 표시되는 화합물일 수 있다. As another preferred example, the compound represented by Formula 1 may be a compound represented by Formula 2-2 below.
[화학식 2-2][Formula 2-2]
상기 화학식 2-2에서, A1 및 B1은 전술한 바와 같다.In Formula 2-2, A1 and B1 are as described above.
일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기와 같을 수 있다. As an embodiment, the compound represented by Chemical Formula 1 may be as follows.
보다 바람직한 일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 3으로 표시되는 화합물일 수 있다. As a more preferred embodiment, the compound represented by Formula 1 may be a compound represented by Formula 3 below.
[화학식 3][Formula 3]
상기 화학식 3에서, X는 산소(O) 또는 황(S)이고, R1 및 R3는 서로 동일하거나 상이하고 각각 독립적으로 치환 또는 비치환된 탄소수 3 이내의 알킬렌기이고, R2 및 R4는 서로 동일하거나 상이하고 각각 독립적으로 수소, 할로겐, 및 치환 또는 비치환된 탄소수 3 이내의 알킬기 중에서 선택된다. In Formula 3, X is oxygen (O) or sulfur (S), R1 and R3 are the same as or different from each other and each independently represents a substituted or unsubstituted alkylene group having 3 or less carbon atoms, and R2 and R4 are the same as or different from each other. They are different and each independently selected from hydrogen, halogen, and a substituted or unsubstituted alkyl group having 3 or less carbon atoms.
가장 바람직한 일 구현예로서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 3-1로 표시되는 화합물 또는 하기 화학식 3-2로 표시되는 화합물일 수 있다. As a most preferred embodiment, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 3-1 or a compound represented by Chemical Formula 3-2.
[화학식 3-1][Formula 3-1]
[화학식 3-2][Formula 3-2]
일 구현예로서, 상기 화학식 2-1로 표시되는 화합물을 제조하는 방법은 다음과 같다. As an embodiment, a method for preparing the compound represented by Chemical Formula 2-1 is as follows.
먼저, 이미다졸(imidazole) 및 클로로트리알킬실란(chlorotrialkylsilane)을 반응시켜, 1-(trialkylsilyl)-1H-imidazole을 제조한다. First, 1-(trialkylsilyl)-1H-imidazole is prepared by reacting imidazole and chlorotrialkylsilane.
[반응식 1][Scheme 1]
상기 반응시, 트리에틸아민을 더 투입하여 반응을 진행하고 반응 완료 후 염산염을 여과함으로써 제거할 수 있다. During the reaction, triethylamine may be further added to proceed with the reaction, and after completion of the reaction, the hydrochloride may be removed by filtering.
다음으로, 상기 제조된 1-(trialkylsilyl)-1H-imidazole 및 phosphoryl trichloride을 반응시켜, Tri(1H-imidazol-1-yl)phosphine oxide을 제조한다. Next, tri(1H-imidazol-1-yl)phosphine oxide is prepared by reacting the prepared 1-(trialkylsilyl)-1H-imidazole and phosphoryl trichloride.
[반응식 2-1][Scheme 2-1]
다음으로, 상기 제조된 Tri(1H-imidazol-1-yl)phosphine oxide 및 Alcohol(R1-0H)을 반응시켜, 두 개의 알콕시가 치환된 하기 화학식 2-1의 화합물을 제조할 수 있다. Next, a compound of Formula 2-1 in which two alkoxy groups are substituted may be prepared by reacting the prepared Tri(1H-imidazol-1-yl)phosphine oxide with Alcohol (R1-0H).
[화학식 2-1][Formula 2-1]
상기 화학식 2-1에서, A1 및 B1은 전술한 바와 같다. In Formula 2-1, A1 and B1 are as described above.
본 발명의 제조방법은 부산물의 생성을 최소화하고 수득률을 높이기 위해 상기 반응식 1 및 반응식 2-1을 거쳐 상기 화학식 2-1의 화합물을 제조할 수 있다. In the production method of the present invention, the compound represented by Chemical Formula 2-1 may be prepared through Reaction Scheme 1 and Reaction Scheme 2-1 in order to minimize the production of by-products and increase the yield.
상기 반응시, 피리딘을 더 투입하여 반응을 진행하고 반응 완료 후 염산염을 여과함으로써 제거할 수 있다. During the reaction, pyridine may be further added to proceed with the reaction, and after completion of the reaction, the hydrochloride may be removed by filtering.
일 구현예로서, 상기 화학식 2-2로 표시되는 화합물을 제조하는 방법은 다음과 같다. As an embodiment, a method for preparing the compound represented by Chemical Formula 2-2 is as follows.
상기 반응식 1에 의해 제조된 1-(trialkylsilyl)-1H-imidazole 및 phosphorothioyl trichloride을 반응시켜, tri(1H-imidazol-1-yl)phosphine sulfide을 제조한다. Tri(1H-imidazol-1-yl)phosphine sulfide is prepared by reacting 1-(trialkylsilyl)-1H-imidazole prepared by Scheme 1 and phosphorothioyl trichloride.
[반응식 2-2][Scheme 2-2]
다음으로, 상기 제조된 tri(1H-imidazol-1-yl)phosphine sulfide 및 Alcohol(R1-0H)을 반응시켜, 두 개의 알콕시가 치환된 하기 화학식 2-2의 화합물을 제조할 수 있다. Next, a compound of Formula 2-2 in which two alkoxy groups are substituted may be prepared by reacting the prepared tri(1H-imidazol-1-yl)phosphine sulfide with Alcohol (R1-0H).
[화학식 2-2][Formula 2-2]
상기 화학식 2-2에서, A1 및 B1은 전술한 바와 같다.In Formula 2-2, A1 and B1 are as described above.
본 발명의 제조방법은 부산물의 생성을 최소화하고 수득률을 높이기 위해 상기 반응식 1 및 반응식 2-2를 거쳐 상기 화학식 2-2 화합물을 제조할 수 있다. In the production method of the present invention, the compound of Formula 2-2 can be prepared through Reaction Scheme 1 and Reaction Scheme 2-2 to minimize the production of by-products and increase the yield.
일 예로서, 상기 반응물은 시약용 및 공업용 모두 사용가능하며, 수분은 낮을수록 좋으나 100 ~ 2000ppm, 바람직하게는 100 ~ 1000ppm, 더욱 바람직하게는 100 ~ 300ppm으로 수분을 제거하여 사용할 수 있다.As an example, the reactants can be used for both reagent and industrial purposes, and the lower the moisture, the better, but may be used after removing the moisture at 100 to 2000 ppm, preferably 100 to 1000 ppm, and more preferably 100 to 300 ppm.
상기 반응은 유기 용매 하에서 진행되며, 유기 용매는 메틸렌클로라이드, 다이클로로 에탄, 다이에틸에테르, 다이아이소프로필 에테르 및 톨루엔 중에서 선택되는 어느 하나 이상일 수 있으며, 이외에도 물과 섞이지 않는 친유성 유기용매에서 합성 가능하나, 이에 한정되는 것은 아니다. The reaction proceeds in an organic solvent, and the organic solvent may be any one or more selected from methylene chloride, dichloroethane, diethyl ether, diisopropyl ether, and toluene. In addition, it can be synthesized in a water-immiscible lipophilic organic solvent. However, it is not limited thereto.
일 예로서, 상기 유기 용매의 수분은 10 ~ 1000ppm, 바람직하게는 10 ~ 700ppm, 더욱 바람직하게는 10 ~ 300ppm의 용매를 사용할 수 있다. As an example, a solvent having a water content of 10 to 1000 ppm, preferably 10 to 700 ppm, and more preferably 10 to 300 ppm of the organic solvent may be used.
일 예로서, 상기 반응 온도는 -5 ~ 100℃, 바람직하게는 -5 ~ 80℃, 더욱 바람직하게는 -5 ~ 50℃일 수 있다. As an example, the reaction temperature may be -5 to 100 °C, preferably -5 to 80 °C, and more preferably -5 to 50 °C.
본 발명의 일 실시예에 의한 이차전지용 전해질은 상기 이차전지용 전해질 첨가제를 포함한다. An electrolyte for a secondary battery according to an embodiment of the present invention includes the electrolyte additive for a secondary battery.
일 예로서, 상기 이차전지용 전해질은 상기 이차전지용 전해질 첨가제가 전체 이차전지용 전해질 전체 대비 0.1 내지 10 중량%, 0.1 내지 5 중량%, 0.1 내지 3 중량%, 0.1 내지 1 중량%, 9 내지 10 중량%, 3 내지 10 중량%, 또는 5 내지 10 중량% 로 포함될 수 있다. As an example, in the secondary battery electrolyte, the secondary battery electrolyte additive is 0.1 to 10% by weight, 0.1 to 5% by weight, 0.1 to 3% by weight, 0.1 to 1% by weight, 9 to 10% by weight, based on the total amount of secondary battery electrolytes. , 3 to 10% by weight, or 5 to 10% by weight.
일 예로서, 상기 이차전지용 전해질은 리튬염; 및 용매;를 더 포함할 수 있다. As an example, the electrolyte for the secondary battery may include a lithium salt; And a solvent; may further include.
일 예로서, 상기 리튬염은 LiPF6, LiBF4, LiB12F12, LiAsF6, LiFSO3, Li2SiF6, LiCF3CO2, LiCH3CO2, LiCF3SO3, LiC4F9SO3, LiCF3CF2SO3, LiCF3(CF2)7SO3, LiCF3CF2(CF3)2CO, Li(CF3SO2)2CH, LiNO3, LiN(CN)2, LiN(FSO2)2, LiN(F2SO2)2, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiC(CF3SO2)3, LiP(CF3)6, LiPF(CF3)5, LiPF2(CF3)4, LiPF3(CF3)3, LiPF4(CF3)2, LiPF4(C2F5)2, LiPF4(CF3SO2)2, LiPF4(C2F5SO2)2, LiBF2C2O4, LiBC4O8, LiBF2(CF3)2, LiBF2(C2F5)2, LiBF2(CF3SO2)2, LiBF2(C2F5SO2)2, LiSbF6, LiAlO4, LiAlF4, LiSCN, LiClO4, LiCl, LiF, LiBr, LiI, LiAlCl4 중에서 선택되는 어느 하나 이상일 수 있으나, 이에 한정되는 것은 아니다.As an example, the lithium salt is LiPF 6 , LiBF 4 , LiB 12 F 12 , LiAsF 6 , LiFSO 3 , Li 2 SiF 6 , LiCF 3 CO 2 , LiCH 3 CO 2 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiCF 3 CF 2 SO 3 , LiCF 3 (CF 2 ) 7 SO 3 , LiCF 3 CF 2 (CF 3 ) 2 CO, Li(CF 3 SO 2 ) 2 CH, LiNO 3 , LiN(CN) 2 , LiN (FSO 2 ) 2 , LiN(F 2 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiP(CF 3 ) 6 , LiPF(CF 3 ) 5 , LiPF 2 (CF 3 ) 4 , LiPF 3 (CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (CF 3 SO 2 ) 2 , LiPF 4 (C 2 F 5 SO 2 ) 2 , LiBF 2 C 2 O 4 , LiBC 4 O 8 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (CF 3 SO 2 ) 2 , LiBF 2 (C 2 F 5 SO 2 ) 2 , LiSbF 6 , LiAlO 4 , LiAlF 4 , LiSCN, LiClO 4 , LiCl, LiF, LiBr, LiI, LiAlCl 4 It may be any one or more selected, but It is not limited.
일 예로서, 상기 용매는 상기 전해질 첨가제가 용해될 수 있는 유기 용매인 것이 바람직하며, 통상적으로 이차전지에 사용될 수 있는 용매는 모두 사용될 수 있으며, 특별히 이에 제한되는 것이 아니다. 일 예로서, 카보네이트계, 에스테르계, 에테르계, 케톤계, 알코올계, 또는 비양성자성 용매 등이 사용될 수 있다. 또한, 일 실시예로서 에틸렌카보네이트(Ethylene carbonate, EC) 및 에틸 메틸 카보네이트(Ethyl methyl carbonate, EMC)를 적어도 어느 하나 이상 포함할 수 있다. As an example, the solvent is preferably an organic solvent in which the electrolyte additive can be dissolved, and all solvents that can be commonly used in secondary batteries may be used, and are not particularly limited thereto. As an example, carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvents may be used. In addition, as an embodiment, at least one or more of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) may be included.
또한, 상기 이차전지용 전해질은 또 다른 첨가제를 더 포함할 수 있다. 일 예로서, 상기 첨가제는 카보네이트 계열의 화합물, 설톤 계열의 화합물 및 포스파젠 계열의 화합물에서 선택되는 어느 하나 이상일 수 있으나, 이에 한정되는 것은 아니다. 보다 바람직하게는, 본 발명의 일 실시예에 의한 상기 선형 포스포네이트(phosphonate) 구조의 전해질은 옥살레이토보레이트계, 옥살레이토포스페이트계, 불소로 치환된 카보네이크계, 비닐리덴 카보네이트계 및 설피닐기 함유 화합물로 이루어진 군으로부터 선택되는 어느 하나 이상의 첨가제를 더 포함하는 경우 보다 이차전지의 음극 및 양극의 안정성 및 내구성을 향상시킬 수 있다. In addition, the electrolyte for a secondary battery may further include another additive. As an example, the additive may be at least one selected from carbonate-based compounds, sultone-based compounds, and phosphazene-based compounds, but is not limited thereto. More preferably, the electrolyte of the linear phosphonate structure according to an embodiment of the present invention is an oxalatoborate-based, oxalatophosphate-based, fluorine-substituted carbonate-based, vinylidene carbonate-based, and sulfyic acid electrolyte. It is possible to improve the stability and durability of the negative electrode and the positive electrode of the secondary battery compared to the case of further including any one or more additives selected from the group consisting of yl group-containing compounds.
본 발명의 일 실시예에 의한 이차전지는 양극활물질을 포함하는 양극, 음극활물질을 포함하는 음극 및 양극과 음극 사이에 포함되는 상기 이차전지용 전해질을 포함한다. A secondary battery according to an embodiment of the present invention includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and the secondary battery electrolyte included between the positive electrode and the negative electrode.
상기 양극은 집전체 및 상기 집전체에 형성되는 양극활물질 층을 포함하며, 상기 양극활물질 층은 양극활물질 이외에도 바인더 또는 도전재를 더 포함할 수 있다. 상기 양극활물질은 이온의 인터칼레이션 및 디인터칼레이션이 가능한 화합물이라면, 이에 특별한 제한은 없다. The cathode includes a current collector and a cathode active material layer formed on the current collector, and the cathode active material layer may further include a binder or a conductive material in addition to the cathode active material. The cathode active material is not particularly limited as long as it is a compound capable of intercalation and deintercalation of ions.
일 예로서, 상기 양극활물질은 LiNixCoyMnzL(1-x-y-z)O2 (0≤x≤1, 0≤y≤1, 0≤z≤1, 및 L은 Al, Sr, Mg, Ti, Nb, V, Ca, Zr, Zn, Sn, Si 및 Fe 중에서 선택된 어느 하나 이상), LiNixCoyAlzL(1-x-y-z)O2 (0≤x≤1, 0≤y≤1, 0≤z≤1 및 L이 Al, Sr, Mg, Ti, Nb, V, Ca, Zr, Zn, Sn, Si 및 Fe 중에서 선택된 어느 하나 이상), wLi2MnO3·(1*?*w)LiMnaNibCocL(1-a-b-c)O2(0<w<1, 0≤a≤1, 0≤b≤1, 0≤c≤1, 및 L은 Al, Sr, Mg, Ti, Nb, V, Ca, Zr, Zn, Sn, Si, Sb 및 Fe 중에서 선택된 어느 하나 이상), Li1.2Mn0.8-aLaO2 (0≤a≤0.8, 및 L은 Al, Sr, Mg, Ca, Ti, V, Cr, Ni, Co, Fe, Cu, Nb, W, Zr, Zn, Sn, Sb 및 Si 중 선택된 어느 하나 이상), LiMPO4 (M은 Fe, Co, Ni, 및 Mn 중에서 선택된 어느 하나 이상), LiMn2-xMxO4 (0≤x<1 및 M은 Ni, Co, Fe, Cr, V, Ti, Nb, Cu, Sn, Sb 및 Si 중에서 선택된 어느 하나 이상), Li2N1-xMxO3 (0≤x<1, N은 Mn, Ni, Sn, Fe, Ru 및 Ir 중 선택된 어느 하나 이상이고, M은 Ti, Mn, Sn, Sb, Ru, 및 Te 중에서 선택된 어느 하나 이상), 및 Li1+xNy-zMzO2 (0≤x≤1, N은 Ti 및 Nb 중에서 선택된 어느 하나 이상이고, M은 V, Ti, Mo 및 W 중에서 선택된 어느 하나 이상) 중에서 선택되는 어느 하나 이상일 수 있으나, 이에 한정되는 것은 아니다. As an example, the cathode active material is LiNi x Co y Mn z L (1-xyz) O 2 (0≤x≤1, 0≤y≤1, 0≤z≤1, and L is Al, Sr, Mg, At least one selected from Ti, Nb, V, Ca, Zr, Zn, Sn, Si and Fe), LiNi x Co y Al z L (1-xyz) O 2 (0≤x≤1, 0≤y≤1 , 0≤z≤1 and L is at least one selected from Al, Sr, Mg, Ti, Nb, V, Ca, Zr, Zn, Sn, Si and Fe), w Li 2 MnO 3 ·(1*?* w ) LiMn a Ni b Co c L (1-abc) O 2 (0<w<1, 0≤a≤1, 0≤b≤1, 0≤c≤1, and L is Al, Sr, Mg, At least one selected from Ti, Nb, V, Ca, Zr, Zn, Sn, Si, Sb, and Fe), Li 1.2 Mn 0.8-a L a O 2 (0≤a≤0.8, and L is Al, Sr, At least one selected from Mg, Ca, Ti, V, Cr, Ni, Co, Fe, Cu, Nb, W, Zr, Zn, Sn, Sb, and Si), LiMPO 4 (M is Fe, Co, Ni, and At least one selected from Mn), LiMn 2-x M x O 4 (0≤x<1 and M is any one selected from Ni, Co, Fe, Cr, V, Ti, Nb, Cu, Sn, Sb and Si or more), Li 2 N 1-x M x O 3 (0≤x<1, N is at least one selected from Mn, Ni, Sn, Fe, Ru and Ir, M is Ti, Mn, Sn, Sb, At least one selected from Ru and Te), and Li 1+x N yz M z O 2 (0≤x≤1, N is at least one selected from Ti and Nb, M is V, Ti, Mo and W Any one or more selected from) may be any one or more selected from, but is not limited thereto.
상기 음극은 집전체 및 상기 집전체 위에 형성된 음극활물질 층을 포함하며, 상기 음극활물질 층은 음극활물질 이외에도 바인더 또는 도전재를 더 포함할 수 있다. The negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer may further include a binder or a conductive material in addition to the negative active material.
상기 음극활물질은 이온을 가역적으로 인터칼레이션 및 디인터칼레이션할 수 있는 물질이라면, 이에 특별한 제한은 없다. 일 예로서, 탄소계 또는 실리콘계 음극활물질이 사용될 수 있다. The negative electrode active material is not particularly limited as long as it is a material capable of reversibly intercalating and deintercalating ions. As an example, a carbon-based or silicon-based negative electrode active material may be used.
상기 이차전지에 분리막이 더 포함되는 경우, 상기 분리막은 다공성 고분자 필름, 예를 들면 에틸렌 단독 중합체, 프로필렌 단독 중합체, 에틸렌/부텐 공중합체, 에틸렌/헥센 공중합체 및 에틸렌/메타크릴레이트 공중합체 등의 폴리올레핀계 고분자로 제조한 다공성 고분자 필름을 단독으로 또는 이들을 적층해 이용해도 되고, 혹은 통상의 다공성 부직포, 예를 들면 고융점의 유리 섬유, 폴리에틸렌 테레프탈레이트 섬유 등의 부직포를 사용할 수 있으나, 이에 한정되는 것은 아니다. When the secondary battery further includes a separator, the separator is a porous polymer film, for example, ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer. Porous polymer films made of polyolefin-based polymers may be used alone or by laminating them, or ordinary porous nonwoven fabrics such as high melting point glass fibers and polyethylene terephthalate fibers may be used, but are limited thereto. It is not.
보다 바람직한 일 예로서, 상기 이차전지는 충전 컷 오프 전압이 4.0 내지 6.0V일 수 있다. As a more preferred example, the secondary battery may have a charge cut-off voltage of 4.0 to 6.0V.
상기 이차전지의 제조방법은 공지의 제조방법에 의한 것으로, 자세한 설명은 생략한다. The manufacturing method of the secondary battery is based on a known manufacturing method, and a detailed description thereof will be omitted.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 한다. 본 발명의 실시예는 여러가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안된다. 본 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, the present invention will be described in more detail through examples. Embodiments of the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. This embodiment is provided to more completely explain the present invention to those skilled in the art.
[전해질 첨가제의 제조][Preparation of Electrolyte Additives]
1-(trimethylsilyl)-1H-imidazole의 제조Preparation of 1-(trimethylsilyl)-1H-imidazole
먼저, 250mL 플라스크에 마그네틱 바, 온도계를 설치하고, 이미다졸(imidazole) 10g을 투입한다. 용매로 수분 100ppm 이하의 톨루엔(toluene) 70ml을 투입한 후 교반하고, 클로로트리메틸실란(chlorotrimethylsilane) 18g을 투입한 후 교반한다. 트리에틸아민(triethylamine) 25g을 저온에서 서서히 적하한다. 상기 적하가 완료되면 2시간 동안 반응을 진행하고 염산염을 여과하여 제거한다. 용액의 용매 제거를 위해 농축한다. 농축한 목적물을 증류하여 1-(trimethylsilyl)-1H-imidazole을 제조한다. 증류 후 63g의 1-(trimethylsilyl)-1H-imidazole을 얻었으며, 이때 수율은 약 80%이다. (1H 7.69ppm, 2H 7.11ppm, 3H M 6.12ppm, 6H 0.15ppm)First, a magnetic bar and a thermometer are installed in a 250mL flask, and 10g of imidazole is added. 70 ml of toluene having a water content of 100 ppm or less as a solvent is added and stirred, and 18 g of chlorotrimethylsilane is added and stirred. 25 g of triethylamine was slowly added dropwise at low temperature. When the dropwise addition is completed, the reaction proceeds for 2 hours, and the hydrochloride salt is removed by filtration. Concentrate the solution to remove the solvent. The concentrated target product is distilled to produce 1-(trimethylsilyl)-1H-imidazole. After distillation, 63 g of 1-(trimethylsilyl)-1H-imidazole was obtained, with a yield of about 80%. (1H 7.69ppm, 2H 7.11ppm, 3H M 6.12ppm, 6H 0.15ppm)
Tri(1H-imidazol-1-yl)phosphine oxide의 제조Preparation of Tri(1H-imidazol-1-yl)phosphine oxide
100mL 플라스크에 마그네틱 바, 온도계를 설치하고, 상기 제조된 1-(trimethylsilyl)-1H-imidazole 13g을 투입한다. 용매로 수분 100ppm 이하의 테트라히드로퓨란(THF) 50ml를 투입한 후 교반하고, 염화 포스포릴(phosphoryl chloride) 4.7g을 무수 테트라히드로퓨란(THF) 20ml에 용해하여, 실온에서 서서히 적가한다. 상기 적가가 완료되면 1시간 동안 반응을 진행하고 염산염을 여과하여 제거한다. 용액의 용매 제거를 위해 농축한다. 농축한 목적물을 Tri(1H-imidazol-1-yl)phosphine oxide을 제조한다. 6.5g의 목적물을 얻었으며, 수율은 약 85%이다. (1H 7.70ppm, 1H 7.22ppm, 1H 7.06ppm) A magnetic bar and a thermometer were installed in a 100mL flask, and 13 g of 1-(trimethylsilyl)-1H-imidazole prepared above was added. After adding 50ml of tetrahydrofuran (THF) with a water content of 100 ppm or less as a solvent, stirring, dissolving 4.7 g of phosphoryl chloride in 20 ml of anhydrous tetrahydrofuran (THF), and slowly adding dropwise at room temperature. When the dropwise addition is completed, the reaction proceeds for 1 hour, and the hydrochloric acid salt is removed by filtration. Concentrate the solution to remove the solvent. Tri(1H-imidazol-1-yl)phosphine oxide is prepared from the concentrated target product. 6.5 g of the target product was obtained, and the yield was about 85%. (1H 7.70ppm, 1H 7.22ppm, 1H 7.06ppm)
di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate의 제조Preparation of di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate
100mL 플라스크에 마그네틱 바, 온도계를 설치하고, 프로파질 알코올 0.98g을 투입한다. 용매로 무수 피리딘(pyridine) 10ml을 투입한 후 교반하고, 상기 제조된 Tri(1H-imidazol-1-yl)phosphine oxide 6.5g을 투입한 후 교반한다. 상기 적하가 완료되면 2시간 동안 반응을 진행하고 염산염을 여과하여 제거한다. 용액의 용매 제거를 위해 농축하여 di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate을 제조한다. 1.7g의 목적물(즉, [화학식 3])을 얻었으며, 이때 수율은 약 86%이다. (1H 7.80ppm, 1H 7.22ppm, 1H 7.01ppm, 4H 4.84, 2H 3.22)Install a magnetic bar and a thermometer in a 100 mL flask, and add 0.98 g of propargyl alcohol. After adding 10 ml of anhydrous pyridine as a solvent, stirring was performed, and 6.5 g of Tri(1H-imidazol-1-yl)phosphine oxide prepared above was added and stirred. When the dropwise addition is completed, the reaction proceeds for 2 hours, and the hydrochloride salt is removed by filtration. Concentrate the solution to remove the solvent to obtain di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate. 1.7 g of the target product (ie, [Formula 3]) was obtained, and the yield at this time is about 86%. (1H 7.80ppm, 1H 7.22ppm, 1H 7.01ppm, 4H 4.84, 2H 3.22)
[전해액의 제조][Preparation of Electrolyte]
[실시예 1] [Example 1]
에틸렌 카보네이트 (EC) 및 에틸메틸 카보네이트(EMC)의 30:70 (vol%)의 용매에 1M의 LiPF6를 혼합하고, 상기 제조한 di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate 2중량% 첨가하여 전해액을 제조하였다. 1M LiPF 6 was mixed in a solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) in a ratio of 30:70 (vol%), and the prepared di(prop-2-yn-1-yl) (1H-imidazol An electrolyte solution was prepared by adding 2% by weight of -1-yl)phosphonate.
[실시예 2] [Example 2]
에틸렌 카보네이트 (EC) 및 에틸메틸 카보네이트(EMC)의 30:70 (vol%)의 용매에 1M의 LiPF6를 혼합하고, 플루오르에틸렌카보네이트(FEC) 1중량% 및 상기 제조한 di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate 1중량% 첨가하여 전해액을 제조하였다.1M LiPF 6 was mixed in a solvent of 30:70 (vol%) of ethylene carbonate (EC) and ethylmethyl carbonate (EMC), 1% by weight of fluoroethylene carbonate (FEC) and the above-prepared di (prop-2- An electrolyte solution was prepared by adding 1% by weight of yn-1-yl) (1H-imidazol-1-yl)phosphonate.
[비교예] [Comparative Example]
상기 실시예 1에서 di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate을 첨가하지 않는 것을 제외하고, 상기 실시예 1과 동일하게 전해액을 제조하였다. An electrolyte solution was prepared in the same manner as in Example 1, except that di(prop-2-yn-1-yl) (1H-imidazol-1-yl)phosphonate was not added in Example 1.
이차전지의 제조Manufacturing of secondary batteries
〈양극의 제조〉<Manufacture of anode>
N-메틸-2-피롤리돈 (NMP) 100 중량부에 양극 활물질로 삼성분계 활물질 (Li(Ni0.5Mn0.3Co0.2)O2), 도전재로 카본 블랙 및 바인더로 폴리비닐리덴플루오라이드 (PVDF)를 90:5:5 (wt%)의 비율로 혼합한 고형분 40 중량부를 첨가하여 양극 활물질 슬러리를 제조하였다. 상기 양극 활물질 슬러리를 두께가 100㎛인 양극 집전체 (Al 박막)에 도포하고, 건조하고 롤 프레스(roll press)를 실시하고, 양극을 제조하였다.A ternary active material (Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 ) as a cathode active material, carbon black as a conductive material, and polyvinylidene fluoride (as a binder) in 100 parts by weight of N-methyl-2-pyrrolidone (NMP). A positive active material slurry was prepared by adding 40 parts by weight of a solid content mixed with PVDF) in a ratio of 90:5:5 (wt%). The positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 100 μm, dried, and subjected to a roll press to prepare a positive electrode.
<음극의 제조〉<Manufacture of cathode>
NMP에 100 중량부에 음극 활물질로 천연 흑연 및 SiOx (0<x<1)와, 바인더로 PVDF, 도전재로 카본 블랙을 90:5:2:3 (wt%)의 비율로 혼합한 고형분 100 중량부를 첨가하여 음극 활물질 슬러리를 제조하였다. 상기 음극 활물질 슬러리를 두께가 90㎛인 음극 집전체 (Cu 박막)에 도포하고, 건조하고 롤 프레스(roll press)를 실시하여 음극을 제조하였다.Solid content of NMP mixed with 100 parts by weight of natural graphite and SiO x (0<x<1) as negative electrode active material, PVDF as binder, and carbon black as conductive material at a ratio of 90:5:2:3 (wt%) An anode active material slurry was prepared by adding 100 parts by weight. The negative electrode active material slurry was coated on a negative electrode current collector (Cu thin film) having a thickness of 90 μm, dried, and subjected to a roll press to prepare a negative electrode.
<이차전지의 제조〉<Manufacture of secondary battery>
상기 제조된 양극, 음극을 폴리에틸렌 다공성 필름과 함께 적층하여 전극조립체를 제조한 다음, 이를 파우치형 전지 케이스에 넣고, 상기 실시예 및 비교예에 의한 이차전지용 전해액을 각각 주액하고 밀봉하였다. An electrode assembly was prepared by laminating the prepared positive and negative electrodes together with a polyethylene porous film, and then placed in a pouch-type "battery" case, injected with the secondary battery electrolytes according to the above examples and comparative examples, respectively, and sealed.
[실험예 1] 용량 유지율(%)의 평가[Experimental Example 1] Evaluation of capacity retention rate (%)
상기 제조된 이차전지를 상온(25℃에서 4.5V까지 1C 충전, 2.75V 1C 방전 후, 4.2V까지 0.5C 충전하여 고온(45℃에서1주 방치 후 4.2V까지 1C 충전, 2.75V 1C 방전 2사이클 진행하여 2사이클째 방전시킨 용량을 측정하여 비교하여, 하기 표 1에 나타내었다. The prepared secondary battery was charged at room temperature (1C charge up to 4.5V at 25°C, discharged at 2.75V 1C, then charged at 0.5C up to 4.2V at high temperature (1C charge up to 4.2V after being left at 45°C for 1 week, discharged at 2.75V 1C 2). After cycle progress, the capacity discharged in the second cycle was measured and compared, and is shown in Table 1 below.
[실험예 2] 고온 수명 유지율(%)의 평가[Experimental Example 2] Evaluation of high temperature life retention rate (%)
상기 제조된 이차전지를 고온(45℃)에서 4.5V까지 1C 충전 후, 2.75V까지 2C 방전하여 초기용량을 측정하고, 이를 500회 반복한 후의 용량을 측정하고, 식 : 수명유지율 = (500회 반복 후 용량/초기용량)*100 으로부터 고온수명유지율을 계산하여 하기 표 2에 나타내었다.After charging the prepared secondary battery at high temperature (45 ° C) to 4.5V by 1C, discharging it by 2C to 2.75V to measure the initial capacity, and measuring the capacity after repeating this 500 times, Formula: Life retention rate = (500 times Capacity after repetition / initial capacity) * 100 The high temperature life retention rate was calculated and shown in Table 2 below.
Claims (9)
이차전지용 전해질 첨가제:
[화학식 1]
상기 화학식 1에서 X는 산소(O) 또는 황(S)이고,
A 및 B는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 할로겐; 하이드록시기; 치환 또는 비치환된 탄소수 30이하의 알콕시기 및 아릴옥시기; 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 나이트릴기; 알킬티옥시기; 붕소기; 니트로기; 티올; 아미노기; 히드라진; 아미드기; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염; 중에서 선택된다.
Including a compound represented by Formula 1 below,
Electrolyte additives for secondary batteries:
[Formula 1]
In Formula 1, X is oxygen (O) or sulfur (S),
A and B are the same as or different from each other and are each independently hydrogen; halogen; hydroxy group; a substituted or unsubstituted alkoxy group and aryloxy group having 30 or less carbon atoms; A substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; nitrile group; Alkyl thioxy group; boron group; nitro group; thiol; amino group; hydrazine; amide group; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof; are selected from
상기 화학식 1로 표시되는 화합물은 하기 화학식 2로 표시되는 화합물인,
이차전지용 전해질 첨가제:
[화학식 2]
상기 화학식 2에서, X는 산소(O) 또는 황(S)이고,
A1 및 B1는 서로 동일하거나 상이하고 각각 독립적으로, 수소; 및 치환 또는 비치환된 탄소수 30 이내의 직쇄 또는 분지쇄로서, 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기, 알카이닐기, 시클로알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기 및 아릴알케닐기; 중에서 선택된다.
According to claim 1,
The compound represented by Formula 1 is a compound represented by Formula 2 below,
Electrolyte additives for secondary batteries:
[Formula 2]
In Formula 2, X is oxygen (O) or sulfur (S),
A1 and B1 are the same as or different from each other and are each independently hydrogen; And a substituted or unsubstituted straight chain or branched chain having up to 30 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, and an arylalkenyl group; are selected from
상기 화학식 1로 표시되는 화합물은 하기 화학식 3으로 표시되는 화합물인,
이차전지용 전해질 첨가제:
[화학식 3]
상기 화학식 3에서, X는 산소(O) 또는 황(S)이고, R1 및 R3는 서로 동일하거나 상이하고 각각 독립적으로 치환 또는 비치환된 탄소수 3 이내의 알킬렌기이고, R2 및 R4는 서로 동일하거나 상이하고 각각 독립적으로 수소, 할로겐, 및 치환 또는 비치환된 탄소수 3 이내의 알킬기 중에서 선택된다.
According to claim 1,
The compound represented by Formula 1 is a compound represented by Formula 3 below,
Electrolyte additives for secondary batteries:
[Formula 3]
In Formula 3, X is oxygen (O) or sulfur (S), R1 and R3 are the same as or different from each other and each independently represents a substituted or unsubstituted alkylene group having 3 or less carbon atoms, and R2 and R4 are the same as or different from each other. They are different and each independently selected from hydrogen, halogen, and a substituted or unsubstituted alkyl group having 3 or less carbon atoms.
반응기에 트라이(1H-이미다졸-1-일)포스핀 옥사이드(Tri(1H-imidazol-1-yl)phosphine oxide) 및 알코올(R1-OH)을 투입하여 반응시키는 단계를 포함하는,
이차전지용 전해질 첨가제 제조방법.
In the method for producing the electrolyte additive for a secondary battery of claim 1,
Including the step of reacting tri (1H-imidazol-1-yl) phosphine oxide (Tri (1H-imidazol-1-yl) phosphine oxide) and alcohol (R1-OH) in a reactor,
Method for manufacturing electrolyte additives for secondary batteries.
이차전지용 전해질.
Comprising the electrolyte additive for a secondary battery of claim 1,
Electrolyte for secondary batteries.
상기 이차전지용 전해질 첨가제는 이차전지용 전해질 전체 대비 0.1 내지 10 중량%로 포함되는,
이차전지용 전해질 첨가제.
According to claim 5,
The electrolyte additive for secondary batteries is included in 0.1 to 10% by weight relative to the total electrolyte for secondary batteries,
Electrolyte additives for secondary batteries.
상기 이차전지용 전해질은 리튬염; 및 용매;를 더 포함하는,
이차전지용 전해질.
According to claim 5,
The electrolyte for the secondary battery may include a lithium salt; And a solvent; further comprising a,
Electrolyte for secondary batteries.
상기 이차전지용 전해질은 옥살레이토보레이트계, 옥살레이토포스페이트계, 불소로 치환된 카보네이크계, 비닐리덴 카보네이트계 및 설피닐기 함유 화합물로 이루어진 군으로부터 선택되는 어느 하나 이상의 첨가제를 더 포함하는,
이차전지용 전해질.
According to claim 5,
The secondary battery electrolyte further comprises at least one additive selected from the group consisting of oxalate borate-based, oxalatophosphate-based, fluorine-substituted carbonaceous, vinylidene carbonate-based, and sulfinyl group-containing compounds,
Electrolyte for secondary batteries.
음극활물질을 포함하는 음극; 및
양극과 음극 사이에 포함되는 제 8 항의 이차전지용 전해질;을 포함하는,
이차전지.
A cathode containing a cathode active material;
A negative electrode containing a negative electrode active material; and
Including, the electrolyte for a secondary battery of claim 8 included between the positive electrode and the negative electrode.
secondary battery.
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