CN101310408B - 用于改善低温性质的锂二次电池电解质和包含该电解质的二次电池 - Google Patents
用于改善低温性质的锂二次电池电解质和包含该电解质的二次电池 Download PDFInfo
- Publication number
- CN101310408B CN101310408B CN2006800427335A CN200680042733A CN101310408B CN 101310408 B CN101310408 B CN 101310408B CN 2006800427335 A CN2006800427335 A CN 2006800427335A CN 200680042733 A CN200680042733 A CN 200680042733A CN 101310408 B CN101310408 B CN 101310408B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- battery
- lithium
- secondary battery
- active material
- 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.)
- Active
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003792 electrolyte Substances 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- -1 lithium manganese metal oxide Chemical class 0.000 claims abstract description 22
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000011149 active material Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 10
- 229910015645 LiMn Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 claims description 5
- 229910014689 LiMnO Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052698 phosphorus Chemical group 0.000 claims description 4
- 239000011574 phosphorus Chemical group 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006183 anode active material Substances 0.000 abstract 1
- 239000006182 cathode active material Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 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
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012047 Li4SiO4-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012075 Li4SiO4-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012057 Li4SiO4—LiI—LiOH Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 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
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910012573 LiSiO Inorganic materials 0.000 description 1
- 229910012346 LiSiO4-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012345 LiSiO4-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012348 LiSiO4—LiI—LiOH Inorganic materials 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供了锂二次电池,其使用锂锰金属氧化物作为阴极活性材料及非石墨碳材料作为阳极活性材料,且基于该电解质的总重量,在含锂盐的非水电解质中,包含0.1至20重量%的式I所表示的盐:R4X+YZn -(I),其中R、X、Y、Z和n如说明书所定义。本发明的锂二次电池能够凭借电池在低温下充电/放电在阴极-阳极界面形成电荷双层,通过增加锂离子-电极反应性和降低电极-界面电阻而改善电池的低温性质,并因此能优选用于中/大型电池体系中,例如需要在严苛条件下操作的电动车(EVs)或混合电动车(HEVs)的电源。
Description
技术领域
本发明涉及用于锂二次电池的电解质和包含该电解质的二次电池。更具体而言,本发明是涉及用于锂二次电池的电解质,其凭借电池在低温下充电/放电在阴极-阳极界面形成电荷双层,通过增加锂离子-电极反应性和降低电极界面电阻而能够改善电池的低温性质,并因此能够用于中/大型电池系统中,作为不得不在严苛条件下操作的电动车(EVs)或混合电动车(HEVs)的电源。
背景技术
对于机动设备的技术发展及需求增加导致二次电池作为能源的需求快速增加。特别是,大量的研究及调查也集中于具有高能量密度和高放电电压的锂二次电池。这些锂二次电池也可市售并广泛使用。
再者,环境关心的增加吸引了大量对电动车(EVs)和混合电动车(HEVs)的深入研究,所述电动车(EVs)和混合电动车(HEVs)能够取代化石燃料驱动车辆,诸如汽油机辆和柴油机车,主要原因之一在于空气污染。虽然镍氢(Ni-H2)电池被大量用作EVs和HEVs的电源,但是大量研究已经积极进行,以使用具有高能量密度和高放电电压的锂二次电池,因此有一定的商业化结果。
一般而言,锂离子二次电池使用碳材料作为阳极活性材料和金属氧化物诸如锂钴氧化物或锂锰氧化物作为阴极活性材料,并通过在阳极和阴极之间放置多孔聚烯烃隔膜及添加包含诸如LiPF6的锂盐的非水电解质来制备。随着电池充电,锂离子离开阴极活性材料并迁移进入该阳极的碳层。相反,随着放电,锂离子离开碳层并迁移进入阴极活性材料。在此,非水电解质作为介质,锂离子通过它在阳极与阴极之间迁移。如此的非水电解质在电池的操作电压范围中必需稳定,并且必需具备以充分高的速率转移离子的能力。
含锂离子的非水电解质可以溶液的形式使用,其中锂盐,诸如LiPF6,在非水电解质中易溶,溶解在环状碳酸酯溶剂中。当这样的非水电解质仅仅使用能够充分离解锂离子的高度极性的环状碳酸酯时,这可能造成与电解质粘度增加并因而降低离子导电性有关的的问题。
因此,为了降低非水电解质的粘度,使用极性小但粘度低的线性碳酸酯的混合电解质的技术是本领域已知的。这类线性碳酸酯的代表性范例可包括碳酸二甲基酯(DMC)、碳酸二乙基酯(DEC)及碳酸乙基甲基酯(EMC)。在这些材料中,EMC具有最低的凝固点-55℃,当其被使用时发挥出优异的低温和寿命性能。作为环状碳酸酯的范例,可以提及的是可由碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和碳酸亚丁酯(BC)所制得。尤其是,PC具有低凝固点-49℃,且因此发挥出良好的低温性能。然而,当使用体积大的石墨化碳作为阳极,PC在充电过程中与阳极急剧反应,因此难以使用大量的PC。为此原因,主要使用在阳极形成稳定保护膜的EC。
如同上述所讨论,为了加强电池的低温性能,传统的锂离子二次电池通过使用低沸有机溶剂作为构成非水电解质的有机溶剂,应用其中LiPF6盐混合于线性或环状碳酸酯中的非水电解质和其混合物。已知具有这样组成的非水电解质在室温和高温下均表现出最稳定的电池性质。
然而,LiPF6,其通常用作非水电解质中的锂盐,其在低温下经历Li离子和PF6阴离子解离程度的降低。因此,使用LiPF6作为锂盐的二次电池会遭遇诸如内部电池电阻急剧增加并因此降低电力输出的缺点。
另一方面,当锂二次电池用于EVs及HEVs时,该电池必须可操作,即便是在诸如冬季的低温条件下也是如此,并因此需要在低温下的优良电力输出性质。
因此,为了防止电池低温性能的恶化,同时保持传统非水电解质在室温及高温下均显现出稳定的电池性质的组成,需要进行倾向于向电解质添加隔离材料的研究及调查。此外,为了改善电池的低温性能,其优选致力于防止电池在低温下电阻增加及防止伴随的电力输出性质的恶化。
关于改善二次电池或电容器的低温性质,日本专利特开公布No.2001-85058建议使用具有不对称结构的氟化溶剂,诸如HCF2(CF2)3COOEt、HCF2(CF2)3CH2I、FC(CF3)2(CF2)4(CF3)2CF、H(CF2)2OCH3等等。然而,这些溶剂在用其大量生产二次电池时,由于相当高的生产成本,以及由于比碳酸酯基溶剂的极性小引起的锂离子的解离度低,而遭到了根本的限制。
因此,本领域还需要开发一种二次电池的制备技术,其能够发挥出色的操作性能,同时实现低生产成本。
发明内容
因此,进行本发明用于解决尚未解决的上述问题及其它技术问题。
作为解决上述问题的各种广泛而深入的研究和实验的结果,本发明的发明者发现,当通过向锂二次电池的电解质中选择性添加某种具有庞大结构的盐来制造锂二次电池时,凭借电池在低温下充电/放电在阴极-阳极界面形成电荷双层,通过增加锂离子-电极反应性和降低电极-界面电阻而改善了该电池的低温性质。本发明已经基于这些发现而完成。
更具体而言,本发明提供了锂二次电池的电解质,其表现出优良的低温性质并因此即使当其在严苛条件下,特别是于低温下,使用在诸如电动车(EVs)及混合电动车(HEVs)时,能够提供优良的性质。
具体实施方式
依据本发明的一个方面,上述及其它目标可通过对使用锂锰金属氧化物作为阴极活性材料及非石墨碳材料作为阳极活性材料的锂二次电池提供含锂盐的非水电解质来完成,基于电解质的总重量,所述电解质包含量为0.1至20重量%的下式I所表示的盐:
R4X+YZn - (I)
其中:
R为C3-C10烷基;
X为氮或磷;
Y为硼或磷;
X和Y不相同;
Z为C3-C10烷基,C4-C10环状或芳香基,或卤素;以及
n为4或6,并根据选择的X及Y而确定Y的氧化数。
利用本发明的电解质的锂二次电池中,使用锂锰金属氧化物作为阴极活性材料对于改善电池的安全性有贡献。锂锰金属氧化物的范例可包括锂锰氧化物,诸如式Li1+xMn2-xO4(0≤x≤0.33)的化合物、LiMnO3、LiMn2O3和LiMnO2;式LiMn2-xMxO2(M=Co、Ni、Fe、Cr、Zn、Ta或其任意组合,且0.01≤x≤0.1)、或式Li2Mn3MO8(M=Fe、Co、Ni、Cu、Zn或其任意组合)的锂锰复合氧化物;及其中部分Li被碱土金属离子所取代的LiMn2O4。其中,LiMn2O4、LiNi0.5Mn0.5O2或LiNi1/3Mn1/3Co1/3O2更为优选,且LiNi1/3Mn1/3Co1/3O2就电池耐用性而言特别优选(日历寿命性质)。
如上所述,本发明采用非石墨碳材料作为阳极活性材料。该非石墨碳材料能够使用碳酸亚丙酯(PC),所述碳酸亚丙酯(PC)作为电解质溶剂在低温下表现出相对低的粘度,同时具有高介电常数。
在锂二次电池中用作阳极活性材料的碳材料的种类,可分为软质炭黑,其具有高石墨化碳的层状结晶结构(石墨烯结构:碳原子以六边形蜂巢状排列的平面层),及硬质炭黑,其具有这样的层状结晶结构及无定形结构的混合结构。此外,具有完全层状结晶结构的碳,诸如天然石墨,也单独分类为石墨。亦即,作为阳极活性材料的碳材料种类可以广义区分为石墨、软质炭黑及硬质炭黑。
用在这里,术语“非石墨碳材料”通常指碳材料含有超过50%非石墨碳材料且因此不能被视为石墨碳材料的情况。因此,本发明的阳极材料包括其中混合了低于50%石墨碳材料的阳极材料。
在一个优选实施方式中,非石墨碳材料可以是基于重量比率,含有超过50%硬质炭黑的阳极材料。
由于作为阳极活性材料的上述碳材料的特征,包括石墨和软质炭黑的锂二次电池大量采用了碳酸亚乙酯(EC)作为电解质溶剂。然而,非石墨碳可使用碳酸亚丙酯(PC)作为电解质溶剂。依据本发明的发明人进行的实验,证实碳酸亚丙酯(PC)由于比碳酸亚乙酯(EC)的凝固点低,被优选用作需要在低温操作的电池的材料。
当适当时,为了增加锂离子的导电性及确保反应稳定性,除了PC之外,包含诸如碳酸二乙酯(DEC)、碳酸二甲酯(DMC)等的线性碳酸酯的混合溶剂也可被使用。
式I的盐,其混合于含锂盐的非水电解质中,是在电解质溶剂中表现出高解离度并且解离的阳离子和阴离子与锂电池内的阴极和阳极没有反应性的化合物,并且能够在阴极和阳极的界面处形成电荷双层。亦即,式I的化合物能够凭借电池在低温下充电/放电在阴极-阳极界面处形成电荷双层,通过增加锂离子-电极反应性并因此降低电极-界面电阻和从而改善能量输出性能,而改善电池的低温性质。依据本发明的发明人进行的实验,证实相对于传统的锂二次电池,使用式I的化合物在-20至-30℃的低温下,提供了内部电池电阻降低超过约40%以及增加电力输出超过40%。
在式I中,R优选为C3-C10烷基,更优选为丁基。
作为式I的盐的特别优选的范例,可提及(C4H9)4NB(C4H9)4、(C4H9)4NBF4、(C4H9)4NB(C6H5)4、(C4H9)4NPF6、(C4H9)4PBF4及其任意组合。
式I的盐优选基于电解质的总重量,以0.1至20重量%的量添加。如果该盐的含量过低,则难以获得添加该盐想获得的效果。相反地,如果该盐的含量过高,则可能不理想地导致问题,诸如电解质粘度增加和电池内部电阻增加。
给定量的锂盐添加至含锂盐的非水电解质。可用于本发明的锂盐的范例包括但不限于LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂肪族羧酸锂、四苯基硼酸锂及酰亚胺。
此外,为了改善充电/放电特性及阻燃性,可向非水电解质添加例如吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正-甘醇二甲醚、六磷酸三酰胺、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。
依据本发明的另一方面,其提供了包含上述电解质的锂二次电池。该锂二次电池一般由阴极、阳极、隔膜及含锂盐非水电解质所组成。
阴极通过向阴极集流器施加上述作为阴极活性材料的锂锰金属氧化物、导电材料及粘合剂的混合物来构造。假若需要,可进一步向混合物中添加填料。
阴极集流器通常构造成厚度为3至500μm。对于阴极集流器的材料并没有特殊限制,只要它们具有高导电性,而不会造成所构造电池中的化学变化。对于阴极集流器的材料的范例,可以提到不锈钢、铝、镍、钛、烧结碳、以及用碳、镍、钛或银进行表面处理的铝或不锈钢。阴极集流器可构造成在其表面上具有微细的不规则性,藉以增强与阴极活性材料的粘合强度。此外,阴极集流器可采取多种型式,包括薄膜、板、箔、网、多孔结构、泡沫及无纺织物。
导电材料基于包含有阴极活性材料的混合物的总重量,添加1至50重量%的量。对于导电材料并无特定限制,只要它具有适当的导电性,而不会造成所构造的电池的化学变化。导电材料的范例,可提到的导电材料包括石墨,例如天然或人工石墨;炭黑,例如炭黑、乙炔黑、Ketjen黑、槽黑、炉黑、灯黑及热裂黑;导电纤维,例如碳纤维及金属纤维;金属粉末,例如碳氟化物粉末、铝粉及镍粉;导电丝,例如氧化锌及钛酸钾;导电金属氧化物,例如氧化钛;及聚苯烯衍生物。
粘合剂是辅助活性材料与该导电材料之间粘合以及与集流器结合的成分。基于包括阴极活性材料的混合物的总重量,通常添加量为1至50重量%的粘合剂。作为结合剂的范例,可提到的有聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生的纤维素、聚乙烯基吡咯啶酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元聚合物(EPDM)、磺化EPDM、苯乙烯-丁二烯橡胶、含氟橡胶及各种共聚物。
填料为用于抑制阴极膨胀的任选成分。对于填料并没有特殊限制,只要其不会造成制造的电池中的化学变化,并且是纤维材料。作为填料的范例,可使用烯烃聚合物,例如聚乙烯及聚丙烯;及纤维材料,如玻璃纤维及碳纤维。
阳极是通过向阳极集流器施加上文提及的非石墨碳材料,随后干燥而制成。类似于阴极混合物,如果需要的话,可以进一步包括其它成分,包括上述导电材料、结合剂和填料。
阳极集流器通常构造成厚度为3至500μm。对于阳极集流器的材料并没有特殊限制,只要它们具有适当的导电性,而不会造成所制造电池中的化学变化。对于阳极集流器的材料的范例,可以提到的有铜、不锈钢、铝、镍、钛、烧结碳、表面用碳、镍、钛或银处理的铜或不锈钢、和铝镉合金。类似于阴极集流器,也可加工阳极集流器以在其表面上形成微细的不规则状,藉此增进与阳极活性材料的粘合强度。此外,可使用多种形式的阳极集流器,包括薄膜、板、箔、网、多孔结构、泡沫及无纺织物。
隔膜插入到阴极与阳极之间。作为隔膜,使用具有高离子渗透性与机械强度的绝缘薄膜。隔膜通常具有0.01至10μm的孔径,且厚度为5至300μm。作为隔膜,使用由烯烃聚合物如聚丙烯和/或玻璃纤维或聚乙烯所制成的板或无纺织物,这些具有耐化学性及疏水性。当使用固态电解质如聚合物做为该电解质时,该固态电解质亦可同时做为隔膜与电解质。
作为含锂盐的非水电解质,固态电解质、无机固态电解质等可被使用。
关于用于本发明的有机固体电解质的实例,可举出聚乙烯衍生物、聚乙烯氧化物衍生物、聚丙烯氧化物衍生物、磷酸酯聚合物、聚合搅拌赖氨酸(poly agitation lysine)、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯、及含离子性解离基的聚合物。
作为用于本发明的无机固体电解质的实例,可举出锂的氮化物、卤化物及硫酸盐,例如Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH及Li3PO4-Li2S-SiS2。
依据本发明的锂二次电池可优选用作单元电池,用于高电力、大容量电池或电池组,特别是作为即使在低温条件下也需要高能输出的车辆诸如电动车(EVs)及混合电动车(HEVs)的电力来源。
[实施例]
现在,本发明将参照以下实施例而更详尽地描述。这些实施例仅用来例示本发明且不应解释成限制本发明的范围及精神。
[实施例1]
LiNi1/3Mn1/3Co1/3O2作为阴极活性材料,Super-P作为导电材料且聚偏二氟乙烯(PVDF)作为粘合剂,以重量比85∶10∶5混合在溶剂(N-甲基吡咯烷酮)中以制备浆料。得到的浆料均匀地施加于铝箔上,在对流炉中于130℃干燥,并在预定的压力下加压以制备阴极。
无定型碳作为阳极活性材料且聚偏二氟乙烯(PVDF)作为粘合剂,以重量比95∶5混合于溶剂(N-甲基吡咯烷酮)中以制备浆料。产生的浆料均匀地施加于铜箔上,在对流炉中于130℃干燥,并在预定的压力下加压以制备阳极。
含锂盐的非水电解质通过向PC/DMC(体积比=70∶30)的混合溶剂中添加1M LiPF6,接着添加基于该电解质总重量的3重量%(C4H9)4NB(C4H9)4而制备。
接着,多孔聚乙烯膜(CelgardTM)作为隔膜被插入如上所制备的阳极及阴极之间,且上述制备的含锂盐非水电解质于氩气氛下在干燥盒中添加于得到的电极组件,从而制备锂离子聚合物电池。
[实施例2]
锂离子聚合物电池的制备与实施例1的方式相同,除了向电解质添加2重量%的(C4H9)4NB(C4H9)4。
[实施例3]
锂离子聚合物电池的制备与实施例1的方式相同,除了向电解质添加1重量%的(C4H9)4NB(C4H9)4。
[实施例4]
锂离子聚合物电池的制备与实施例1的方式相同,除了向电解质添加等量的(C4H9)4NB(C6H5)4,以代替(C4H9)4NB(C4H9)4。
[比较例1]
锂离子聚合物电池的制备与实施例1的方式相同,除了不向电解质添加(C4H9)4NB(C4H9)4。
[比较例2]
锂离子聚合物电池的制备与实施例1的方式相同,除了使用天然石墨作为阳极活性材料,以代替无定型碳。
[比较例3]
锂离子聚合物电池的制备与实施例1的方式相同,除了向电解质添加(C2H3)4NB(C4H9)4,以代替(C4H9)4NB(C4H9)4。
[试验例1]
测量实施例1至4及比较例1至3制备的电池在-20℃下的电池电力输出。这样获得的结果在下表1示出,取比较例1的电池的电力输出作为100%的值。
表1
实施例号 | 低温下的电力输出 | 实施例号 | 低温下的电力输出 |
实施例1 | 113% | 比较例1 | 100% |
实施例2 | 110% | 比较例2 | 88% |
实施例3 | 108% | 比较例3 | 103% |
实施例4 | 107% | - | - |
自表1可看出,依据本发明的实施例1至4的电池在低温下相较于没有添加盐的比较例1的电池,表现出优越的电力输出。
此外,与实施例2中使用无定型碳的电池相比较,比较例2中使用天然石墨作为阳极活性材料的电池,尽管添加了依据本发明的盐,仍表现出较低的低温性质。
再者,比较例3中使用具有非大体积取代基的(C2H3)4NB(C4H9)4盐的电池,在盐的含量相同时,相较于实施例1的电池,表现出低温性质明显不同。
工业实用性
从以上描述明显可见,依据本发明的锂二次电池,凭借电池在低温下充电/放电在阴极-阳极界面形成电荷双层,通过增加锂离子-电极反应性和降低电极界面电阻而能改善电池的低温性质,并因此能够优选用于中/大型电池系统中,作为迫使在严苛条件下操作的电动车(EVs)或混合电动车(HEVs)的电源。
虽然为了举例说明的目的,已经披露了本发明的优选实施方式,但本领域技术人员应体会在不背离所附权利要求所公开的发明范围与精神之下可进行各种修改、增加与取代。
Claims (10)
1.一种使用锂锰金属氧化物作为阴极活性材料和非石墨碳材料作为阳极活性材料的锂二次电池的含锂盐非水电解质,所述电解质基于该电解质的总重量,含有量为0.1至20重量%的式I表示的盐:
R4X+YZn - (I)
其中:
R为C3-C10烷基;
X为氮或磷;
Y为硼或磷;
X和Y不相同;
Z为C3-C10烷基,C4-C10环状基团或C4-C10芳香基,或卤素;以及
n为4或6,并根据选择的X和Y而确定Y的氧化数。
2.如权利要求1所述的电解质,其中所述锂锰金属氧化物为式Li1+xMn2-xO4(0≤x≤0.33)的锂锰氧化物、LiMnO3、LiMn2O3或LiMnO2;式LiMn2-xMxO2(M=Co、Ni、Fe、Cr、Zn、Ta或其任何组合,且0.01≤x≤0.1)、或式Li2Mn3MO8(M=Fe、Co、Ni、Cu、Zn或其任何组合)的锂锰复合氧化物;或其中一部分Li用碱土金属离子取代的LiMn2O4。
3.如权利要求1所述的电解质,其中所述锂锰金属氧化物为LiMn2O4、LiNi0.5Mn0.5O2或LiNi1/3Mn1/3Co1/3O2。
4.如权利要求3所述的电解质,其中所述锂锰金属氧化物为LiNi1/3Mn1/3Co1/3O2。
5.如权利要求1所述的电解质,其中所述非石墨碳材料为硬质炭黑。
6.如权利要求1所述的电解质,其中碳酸亚丙酯或碳酸亚丙酯与线性碳酸酯的混合溶剂被用作电解质的溶剂。
7.如权利要求1所述的电解质,其中式I的R为丁基。
8.如权利要求1所述的电解质,其中式I的盐选自(C4H9)4NB(C4H9)4、(C4H9)4NBF4、(C4H9)4NB(C6H5)4、(C4H9)4NPF6、(C4H9)4PBF4及其任意组合。
9.一种包括权利要求1至8中任一项所述的电解质的锂二次电池。
10.如权利要求9所述的电池,其中所述电池被用作电动车(EV)或混合电动车(HEV)的电源。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020050108843A KR100908571B1 (ko) | 2005-11-15 | 2005-11-15 | 안전성과 저온 출력 특성이 우수한 리튬 이차전지 |
KR10-2005-0108843 | 2005-11-15 | ||
PCT/KR2006/004721 WO2007058445A1 (en) | 2005-11-15 | 2006-11-13 | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101310408A CN101310408A (zh) | 2008-11-19 |
CN101310408B true CN101310408B (zh) | 2010-10-06 |
Family
ID=38041246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006800427335A Active CN101310408B (zh) | 2005-11-15 | 2006-11-13 | 用于改善低温性质的锂二次电池电解质和包含该电解质的二次电池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8067114B2 (zh) |
EP (1) | EP1949486B1 (zh) |
KR (1) | KR100908571B1 (zh) |
CN (1) | CN101310408B (zh) |
TW (1) | TWI353074B (zh) |
WO (1) | WO2007058445A1 (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100893228B1 (ko) * | 2006-09-11 | 2009-04-16 | 주식회사 엘지화학 | 저온 특성이 향상된 리튬 이차전지용 전해질 및 이를포함하고 있는 이차전지 |
US9893337B2 (en) | 2008-02-13 | 2018-02-13 | Seeo, Inc. | Multi-phase electrolyte lithium batteries |
WO2009103029A2 (en) * | 2008-02-13 | 2009-08-20 | Seeo, Inc | Electrodes with solid polymer electrolytes |
US9356281B2 (en) * | 2008-05-20 | 2016-05-31 | GM Global Technology Operations LLC | Intercalation electrode based on ordered graphene planes |
WO2011057074A2 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene-composite materials in a graphite network |
KR102193243B1 (ko) | 2011-04-11 | 2020-12-28 | 미쯔비시 케미컬 주식회사 | 플루오로술폰산리튬의 제조 방법, 플루오로술폰산리튬, 비수계 전해액, 및 비수계 전해액 2 차 전지 |
US8551650B2 (en) * | 2011-05-12 | 2013-10-08 | Northwestern University | Graphene materials having randomly distributed two-dimensional structural defects |
KR101423595B1 (ko) * | 2011-07-13 | 2014-07-25 | 주식회사 엘지화학 | 저온 특성이 우수한 전지셀을 포함하는 이차전지 팩 |
KR101538428B1 (ko) * | 2013-06-20 | 2015-07-22 | 순천향대학교 산학협력단 | 탄산 프로필렌계 용액에서 흑연 내부에 리튬 이온의 삽입방법 |
EP3108534B1 (en) * | 2014-02-18 | 2019-10-23 | Robert Bosch GmbH | A graphene/he-ncm composite for lithium ion battery, a method for preparing said composite, and an electrode material and a lithium ion battery comprising said composite |
US9634315B2 (en) | 2014-08-01 | 2017-04-25 | SiNode Systems, Inc. | Carbon containing binderless electrode formation |
EP3276732B1 (en) * | 2015-03-24 | 2020-07-08 | Nec Corporation | Lithium-ion secondary cell and method for manufacturing same |
US9923245B2 (en) | 2015-04-03 | 2018-03-20 | Seeo, Inc. | Fluorinated alkali ion electrolytes with urethane groups |
WO2016164505A1 (en) | 2015-04-07 | 2016-10-13 | Seeo, Inc. | Fluorinated alkali ion electrolytes with cyclic carbonate groups |
WO2016200559A1 (en) | 2015-06-09 | 2016-12-15 | Seeo, Inc. | Peo-based graft copolymers with pendant fluorinated groups for use as electrolytes |
US10115998B2 (en) | 2015-06-22 | 2018-10-30 | SiNode Systems, Inc. | Cathode additives to provide an excess lithium source for lithium ion batteries |
KR20190005894A (ko) | 2016-05-10 | 2019-01-16 | 시오 인코퍼레이티드 | 니트릴 기를 갖는 플루오르화된 전해질 |
US11171325B2 (en) | 2016-07-11 | 2021-11-09 | Nanograf Corporation | Optimized electrode design for graphene based anodes |
EP3712998A4 (en) * | 2017-11-22 | 2021-08-04 | GS Yuasa International Ltd. | SECONDARY LITHIUM-ION BATTERY |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4522901A (en) * | 1983-03-16 | 1985-06-11 | Allied Corporation | Secondary battery containing organoborate electrolyte |
CN1280711A (zh) * | 1997-10-10 | 2001-01-17 | 波利普拉斯电池有限公司 | 液体电解质锂-硫电池 |
CN1430306A (zh) * | 2001-12-28 | 2003-07-16 | 三井化学株式会社 | 非水电解液和使用这种电解液的锂二次电池 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139681A (en) * | 1978-03-02 | 1979-02-13 | Exxon Research & Engineering Co. | Electrochemical cells having alkali metal anodes and electrolyte salt complex compositions including haloorganometallic alkali metal salt complexes |
JPH02224910A (ja) * | 1989-02-23 | 1990-09-06 | Oomi Kogyo Kk | ガイドローラ付き切削具 |
JPH02239571A (ja) * | 1989-03-14 | 1990-09-21 | Hitachi Maxell Ltd | 有機電解液電池 |
JP3242430B2 (ja) * | 1991-11-14 | 2001-12-25 | ニチコン株式会社 | 電解コンデンサ |
JP2619845B2 (ja) * | 1992-01-28 | 1997-06-11 | 鐘紡株式会社 | 有機電解質電池 |
JP2001085058A (ja) | 1999-09-20 | 2001-03-30 | Hitachi Ltd | 非水電解液及びこれを用いたリチウム1次電池及びリチウム2次電池及び電気化学キャパシタ及び高分子電解質及びこれを用いたポリマ2次電池 |
US6316141B1 (en) * | 1999-10-18 | 2001-11-13 | Bar Ilan University | High-energy, rechargeable, electrochemical cells with non-aqueous electrolytes |
SG103298A1 (en) * | 2000-06-16 | 2004-04-29 | Nisshin Spinning | Polymer battery and method of manufacture |
EP1184918B1 (en) * | 2000-08-28 | 2009-10-14 | Nissan Motor Co., Ltd. | Rechargeable lithium ion battery |
WO2003054986A1 (fr) * | 2001-12-21 | 2003-07-03 | Sanyo Electric Co.,Ltd. | Accumulateur secondaire a electrolyte non aqueux |
JP4281895B2 (ja) * | 2001-12-28 | 2009-06-17 | 三井化学株式会社 | 非水電解液およびそれを用いたリチウム二次電池 |
JP4056278B2 (ja) * | 2002-03-28 | 2008-03-05 | 三洋電機株式会社 | 非水電解質電池 |
JP2004234879A (ja) * | 2003-01-28 | 2004-08-19 | Nissan Motor Co Ltd | 真性ポリマー電解質を備える二次電池用電極およびその製造方法、ならびに、二次電池 |
JP4513280B2 (ja) * | 2003-06-12 | 2010-07-28 | 三菱化学株式会社 | 非水系電解液二次電池用電解液および非水系電解液二次電池 |
JP2005203131A (ja) * | 2004-01-13 | 2005-07-28 | Hitachi Ltd | エネルギーデバイス |
-
2005
- 2005-11-15 KR KR1020050108843A patent/KR100908571B1/ko active IP Right Grant
-
2006
- 2006-11-13 CN CN2006800427335A patent/CN101310408B/zh active Active
- 2006-11-13 EP EP06812554A patent/EP1949486B1/en active Active
- 2006-11-13 WO PCT/KR2006/004721 patent/WO2007058445A1/en active Application Filing
- 2006-11-14 TW TW095142097A patent/TWI353074B/zh active
- 2006-11-15 US US11/559,943 patent/US8067114B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4522901A (en) * | 1983-03-16 | 1985-06-11 | Allied Corporation | Secondary battery containing organoborate electrolyte |
CN1280711A (zh) * | 1997-10-10 | 2001-01-17 | 波利普拉斯电池有限公司 | 液体电解质锂-硫电池 |
CN1430306A (zh) * | 2001-12-28 | 2003-07-16 | 三井化学株式会社 | 非水电解液和使用这种电解液的锂二次电池 |
Non-Patent Citations (1)
Title |
---|
JP 2005-5153 A,全文. |
Also Published As
Publication number | Publication date |
---|---|
EP1949486A4 (en) | 2010-01-20 |
TWI353074B (en) | 2011-11-21 |
US20070111106A1 (en) | 2007-05-17 |
TW200803012A (en) | 2008-01-01 |
US8067114B2 (en) | 2011-11-29 |
KR100908571B1 (ko) | 2009-07-22 |
KR20070051383A (ko) | 2007-05-18 |
EP1949486A1 (en) | 2008-07-30 |
WO2007058445A1 (en) | 2007-05-24 |
EP1949486B1 (en) | 2011-05-11 |
CN101310408A (zh) | 2008-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101310408B (zh) | 用于改善低温性质的锂二次电池电解质和包含该电解质的二次电池 | |
KR101320381B1 (ko) | 수계 바인더를 포함하는 음극을 구비한 리튬 이차전지 | |
KR100801637B1 (ko) | 양극 활물질 및 그것을 포함하고 있는 리튬 이차전지 | |
KR101451196B1 (ko) | 양극 활물질 및 그것을 포함한 리튬 이차전지 | |
KR20070106821A (ko) | 저온 출력 특성이 개선된 리튬 이차전지 | |
CN103109401B (zh) | 正极活性材料和包含所述正极活性材料的锂二次电池 | |
CN104969400A (zh) | 新型二次电池 | |
KR101617415B1 (ko) | 리튬 이차전지의 제조방법 및 이를 사용하여 제조되는 리튬 이차전지 | |
CN102714314B (zh) | 正极活性材料和包含所述正极活性材料的锂二次电池 | |
US9608259B2 (en) | Positive electrode for secondary battery | |
EP2713427B1 (en) | Positive electrode active material for a secondary battery having improved rate characteristics | |
KR100783294B1 (ko) | 양극 활물질 및 그것을 포함하고 있는 리튬 이차전지 | |
US20130295455A1 (en) | Method for preparing electrode mix and the electrode mix prepared by using the same | |
KR100893228B1 (ko) | 저온 특성이 향상된 리튬 이차전지용 전해질 및 이를포함하고 있는 이차전지 | |
KR20130117392A (ko) | 우수한 성능의 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
KR20110124145A (ko) | 이차전지용 양극 활물질 | |
KR101616722B1 (ko) | 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
US20130313470A1 (en) | Cathode active material and lithium secondary battery comprising the same | |
KR20130002750A (ko) | 고전압용 이차전지 | |
EP2613384A2 (en) | Cathode active material for secondary battery | |
KR101605680B1 (ko) | 음극 합제의 제조방법 및 이를 이용하여 제조되는 이차전지 | |
KR20160035286A (ko) | 수명특성이 향상된 고전압 리튬 이차전지 | |
KR101447484B1 (ko) | 이차전지용 양극 활물질 | |
KR20130118273A (ko) | 리튬 이차전지용 전극의 제조 방법 및 이를 사용하여 제조되는 전극 | |
KR20130116824A (ko) | 전극 합제의 제조방법 및 이를 사용하여 제조되는 전극 합제 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20211125 Address after: Seoul, South Kerean Patentee after: LG Energy Solution,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |