CN107452942A - 二次电池 - Google Patents
二次电池 Download PDFInfo
- Publication number
- CN107452942A CN107452942A CN201710221735.0A CN201710221735A CN107452942A CN 107452942 A CN107452942 A CN 107452942A CN 201710221735 A CN201710221735 A CN 201710221735A CN 107452942 A CN107452942 A CN 107452942A
- Authority
- CN
- China
- Prior art keywords
- chemical formula
- lithium
- oxide
- secondary cell
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 55
- 239000000126 substance Substances 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000006182 cathode active material Substances 0.000 claims abstract description 37
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims abstract description 26
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 7
- 229910011125 LiM1O2 Inorganic materials 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- -1 Lithium cobalt oxide Compound Chemical class 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 3
- JEMDLNFQNCQAKN-UHFFFAOYSA-N nickel;oxomanganese Chemical compound [Ni].[Mn]=O JEMDLNFQNCQAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011651 chromium Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 229910016363 Ni0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 3
- 229910004431 Li(Ni0.80Co0.15Al0.05O2) Inorganic materials 0.000 description 3
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910004309 Li(NixCoyAlz)O2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910010023 Li2Mn Inorganic materials 0.000 description 1
- 229910011119 LiM2O2 Inorganic materials 0.000 description 1
- 229910015700 LiMn0.33Ni0.33Co0.33O2 Inorganic materials 0.000 description 1
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013884 LiPF3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DFGMFVYRMVYRRA-UHFFFAOYSA-N [O].CC Chemical compound [O].CC DFGMFVYRMVYRRA-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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Abstract
本发明提供一种包含复合正极活性材料的二次电池,所述复合正极活性材料包含:由化学式1表示的层状锂锰氧化物;和由化学式3表示的含锂的金属氧化物,其中所述层状锂锰氧化物和所述含锂的金属氧化物的混合比在99:1~50:50的重量比范围内,化学式1 a[Li2MnO3]·(1‑a)[LiM1O2]其中0<a<1,且M1为Mn、Ni和Co;以及化学式3 Li(NixCoyAlz)O2其中x、y和z各自独立地选自0<x、y、z<1的范围,0.45≤x≤0.9,0.05≤y≤0.35,0.005≤z≤0.20,且x+y+z=1。所述复合正极活性材料可在宽充电状态(SOC)范围内提供稳定的功率。
Description
本发明专利申请是基于申请日为2012年12月6日,发明名称为“具有改进的功率特性的复合正极活性材料和包含其的二次电池、电池模块和电池组”,申请号为201280012433.8的中国专利申请的分案申请。
技术领域
本发明涉及具有改进的功率特性的复合正极活性材料和包含所述复合正极活性材料的二次电池、电池模块和电池组。
背景技术
近来,已经将锂二次电池用于包括便携式电子装置如移动电话、个人数字助理(PDA)和笔记本电脑的各种领域中。特别地,随着对环境问题关注的增长,已经积极地对作为电动车辆电源的具有高能量密度和放电电压的锂二次电池进行了研究,且某些研究正处于商业化阶段,所述电动车辆能够代替使用化石燃料的车辆如汽油车辆和柴油车辆,且所述使用化石燃料的车辆是空气污染的一个主要原因。
同时,为了将锂二次电池用作电动车辆的电源,锂二次电池必须在宽充电状态(SOC)范围中保持稳定的功率,同时具有高功率。
根据电动车辆的动力源类型,将电动车辆分为典型的电动车辆(EV)、电池电动车辆(BEV)、混合电动车辆(HEV)或插电式混合电动车辆(PHEV)。
然而,由于在上述电动车辆中的典型电动车辆(EV)和串联型PHEV在车辆的驱动方面完全取决于电池而不是发动机,所以与其他类型的电动车辆相比,在可使用的SOC范围内根据电池特性保持稳定的功率对于驱动安全性是非常重要的因素,且需要具有宽的可利用SOC范围的电池。
同时,关于高容量锂二次电池的典型正极材料LiCoO2,在能量密度和功率特性的提高方面已经遇到了实际限制。特别地,当将LiCoO2用于高能量密度应用中时,伴随着高温充电状态中结构的退化,LiCoO2结构中的氧由于LiCoO2的结构不稳定而被排出,与电池中的电解质发生放热反应,由此成为电池爆炸的主要原因。
为了改善LiCoO2的安全限制,已经考虑使用含锂的锰氧化物如层状晶体结构的LiMnO2和尖晶石晶体结构的LiMn2O4以及含锂的镍氧化物(LiNiO2),近来已经对层状结构的锂锰氧化物进行了大量研究,其中以大于其他过渡金属(不包括锂)的量向作为高容量材料的层状锂锰氧化物中添加作为主要过渡金属的锰(Mn)。
所述锂锰氧化物展示相对高的容量,且还在高SOC范围中展示相对高的功率特性。然而,在运行电压极限处即在低SOC范围内电阻会急剧增大,由此功率急剧下降,且初始不可逆容量会变大。
由于在单独使用锂二次电池的典型已知的正极活性材料方面存在这种限制,所以要求使用由其形成的混合物。特别地,为了用作中型和大型装置的电源,迫切需要一种通过在整个SOC范围内展示均匀特性且不会发生快速电压下降而具有改进的安全性并具有高容量的锂二次电池。
发明内容
技术问题
本发明提供一种具有改进的功率特性的复合正极活性材料,其中通过对锂锰氧化物和具有高放电电势的含锂的金属氧化物进行混合可在宽SOC范围内提供稳定的功率。
本发明还提供包含所述复合正极活性材料的二次电池、电池模块和电池组。
技术方案
根据本发明的一个方面,提供一种复合正极活性材料,其包含:由如下化学式1表示的层状锂锰氧化物;和由如下化学式3表示的含锂的金属氧化物,
化学式1
a[Li2MnO3]·(1-a)[LiM1O2]
其中0<a<1,且M1为选自锰(Mn)、镍(Ni)、钴(Co)、铁(Fe)、铬(Cr)、钒(V)、铜(Cu)、锌(Zn)、钛(Ti)、铝(Al)、镁(Mg)和硼(B)中的一种或多种金属;以及
化学式3
Li(NixCoyAlz)O2
其中x、y和z各自独立地选自0<x、y、z<1的范围,且x+y+z=1。
由化学式1表示的层状锂锰氧化物和由化学式3表示的含锂的金属氧化物的混合比可以在99:1~50:50的重量比范围内。
在层状锂锰氧化物的化学式1中的M1可以包括Mn、Ni和Co。
在化学式3中的x、y和z可以分别在0.45~0.90、0.05~0.35和0.005~0.20的范围内。
复合正极活性材料还可包含选自如下物质中的一种或多种物质:锂钴氧化物;锂镍氧化物;锂锰氧化物;锂钴-镍氧化物;锂钴-锰氧化物;锂锰-镍氧化物;锂钴-镍-锰氧化物;以及其中被选自如下中的一种或多种其他元素取代或掺杂的氧化物:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、钙(Ca)、Zn、锆(Zr)、铌(Nb)、钼(Mo)、锶(Sr)、锑(Sb)、钨(W)和铋(Bi)。
根据本发明的另一个方面,提供一种包含所述复合正极活性材料的二次电池。
根据本发明的另一个方面,提供一种包含所述二次电池的电池模块。
根据本发明的另一个方面,提供一种包含所述电池模块的电池组。
所述电池组可以用作选自如下中的一种或多种中型和大型装置的电源:包括电动车辆(EV)、混合电动车辆(HEV)和插电式混合电动车辆(PHEV)的电动车;电动自行车;电动踏板车;电动高尔夫球车;电动卡车;和电动商用车辆。
有益效果
本发明的复合正极活性材料可不仅是无毒的且在成本方面经济,而且还可在宽充电状态(SOC)范围内提供稳定的功率。
此外,通过在二次电池、电池模块和电池组中包含本发明的复合正极活性材料可以改进功率特性。
附图说明
图1是显示功率随实施例1~3和比较例1的电池的各种充电状态(SOC)而变化的图;
图2是显示电阻随实施例1~3和比较例1的电池的各种SOC而变化的图;以及
图3是显示实施例3和比较例1的电池的充电和放电曲线的图。
具体实施方式
根据本发明的一个实施方案的复合正极活性材料包含由如下化学式1表示的层状锂锰氧化物和由如下化学式3表示的含锂的金属氧化物:
化学式1
a[Li2MnO3]·(1-a)[LiM1O2]
其中0<a<1,且M1为选自锰(Mn)、镍(Ni)、钴(Co)、铁(Fe)、铬(Cr)、钒(V)、铜(Cu)、锌(Zn)、钛(Ti)、铝(Al)、镁(Mg)和硼(B)中的一种或多种金属;以及
化学式3
Li(NixCoyAlz)O2
其中x、y和z各自独立地选自0<x、y、z<1的范围,且x+y+z=1。
由于根据本发明的一个实施方案的复合正极活性材料包含由化学式1表示的层状锂锰氧化物和由化学式3表示的含锂的金属氧化物,所以所述复合正极活性材料可以不仅是无毒的且比LiCoO2相对廉价,而且还可在宽的充电状态(SOC)范围内提供稳定的功率。
然而,在将由化学式1表示的层状锂锰氧化物单独用作正极活性材料的情况中,包含所述层状锂锰氧化物的二次电池展示了其中由于在低SOC下电阻的急剧增大而造成功率下降的现象。尽管已经提出了关于这种现象的各种说明,但通常将所述现象解释如下。即,如同在如下反应式中所示,在初始充电期间在基于正极电势为4.5V以上的高压下,两个锂离子和两个电子与源自构成层状结构的锂锰氧化物复合物的Li2MnO3中的氧气一起移出,但在放电期间,仅有一个锂离子和一个电子可逆地插入正极中。
(充电)Li2Mn4+O3→2Li++2e-+1/2O2+Mn4+O2
(放电)Mn4+O2+Li++e-→LiMn3+O2
因此,由化学式1表示的层状锂锰氧化物的初始充电和放电效率会随Li2MnO3的含量(a值)而不同,但会低于典型层状正极活性材料如LiCoO2、LiMn0.5Ni0.5O2或LiMn0.33Ni0.33Co0.33O2的效率。
在此情况中,由于必须超安全标准设计负极的容量以防止在初始循环期间由于化学式1表示的层状锂锰氧化物的大不可逆容量造成锂在负极处沉淀,所以会降低实际可逆容量。此外,关于层状材料,在安全性方面存在限制。
因此,在本发明中,不仅为了致力于解决上述限制并保持由化学式1表示的层状锂锰氧化物的优势,而且为了确保在宽SOC范围内的稳定功率,提供了包括由化学式1表示的层状锂锰氧化物和由化学式3表示的含锂的金属氧化物两者的复合正极活性材料。
根据本发明的实施方案,化学式1中的M1可以包括Mn、Ni和Co以提供经济优势和高容量的二次电池。
根据本发明的实施方案,可以将放电电势比所述层状锂锰氧化物的放电电势更高的化合物用作由化学式3表示的含锂的金属氧化物,从而与由化学式1表示的层状锂锰氧化物混合以整体提高放电电势。
即,关于包含由化学式1表示的层状锂锰氧化物和由化学式3表示的具有高放电电势的含锂的金属氧化物的复合正极活性材料,由于与单独使用由化学式1表示的层状锂锰氧化物的情况相比,可整体提高其放电电势,所以功率可以在宽SOC范围内稳定,并可以减轻在低SOC下电阻急剧增大的现象。
更特别地,由化学式1表示的层状锂锰氧化物的放电电势可以随作为化学式1的M1而选择的金属的类型而不同,但平均为约3.5V。因此,由化学式3表示的含锂的金属氧化物的放电电势可以为3.5V以上,但其放电电势不能限制于此。
在根据本发明实施方案的复合正极活性材料中,由化学式1表示的层状锂锰氧化物和由化学式3表示的含锂的金属氧化物的混合比可以在99:1~50:50的重量比范围内。然而,在以小于1的重量比混合含锂的金属氧化物的情况中,不能在宽SOC范围内确保稳定的功率,且在以大于50的重量比混合含锂的金属氧化物的情况中,包括过量的比层状锂锰氧化物昂贵的含锂的金属氧化物,由此复合正极活性材料在成本方面不适用于大容量装置。
可以将由如下化学式2表示的金属氧化物用作本发明的含锂的金属氧化物,但不能将本发明限制于此。
化学式2
LiM2O2
其中M2是选自Mn、Ni、Co、Fe、Cr、V、Cu、Zn、Ti、Al、Mg和B中的一种或多种金属。
在本发明中,可以使用由化学式3表示的含锂的金属氧化物,其中M2是由化学式2表示的金属氧化物中的Ni、Co和Al。
根据本发明的一个实施方案,在化学式3中的x、y和z可以分别在0.45~0.90、0.05~0.35和0.005~0.20的范围内。在上述范围内,放电电势为3V~4.4V,这相对于由化学式1表示的层状锂锰氧化物的放电电势是足够高的。
如果需要,还可以将选自如下中的一种或多种化合物混合在根据本发明实施方案的复合正极活性材料中:锂钴氧化物;锂镍氧化物;锂锰氧化物;锂钴-镍氧化物;锂钴-锰氧化物;锂锰-镍氧化物;锂钴-镍-锰氧化物;以及其中被其他元素取代或掺杂的氧化物。
所述其他元素可以为选自如下中的一种或多种元素:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、钙(Ca)、Zn、锆(Zr)、铌(Nb)、钼(Mo)、锶(Sr)、锑(Sb)、钨(W)和铋(Bi),但不能将所述其他元素限制于此。
本发明还提供一种包含上述复合正极活性材料的二次电池。
可以将本领域中已知的典型方法用于将本发明实施方案的复合正极活性材料包括在二次电池中的方法,下面将以非限制性实例对包含复合正极活性材料的二次电池的提供进行说明。
二次电池含正极、负极、隔膜和电解质,所述正极包含本发明实施方案的正极活性材料。
可以利用通过将复合正极活性材料、导电剂和粘合剂分散在分散介质中而得到的正极浆料对正极集电器进行涂布,然后干燥以制备包含所述复合正极活性材料的正极。
可以使用本领域中已知的任意一种导电剂、粘合剂、分散介质和集电器,只要所述导电剂、粘合剂、分散介质和集电器可用于锂二次电池中即可。
所述导电剂的非限制性实例可以为选自如下中的一种或多种物质:人造石墨、天然石墨、炭黑、乙炔黑、科琴黑、超导电乙炔炭黑、热裂法炭黑、槽法炭黑、碳纤维、金属纤维、铝、锡、铋、硅、锑、镍、铜、钛、钒、铬、锰、铁、钴、锌、钼、钨、银、金、镧、钌、铂、铱、氧化钛、聚苯胺、聚噻吩、聚乙炔和聚吡咯。
基于100重量份的复合正极活性材料,可以以3重量份~20重量份的量使用导电剂。在导电剂的含量小于5重量份的情况中,电池的电化学性质会退化;在其含量大于20重量份的情况中,单位重量的能量密度下降。
粘合剂的非限制性实例可以为选自如下中的一种或多种物质:聚偏二氟乙烯(PVdF)、聚六氟丙烯-聚偏二氟乙烯共聚物(PVdF/HFP)、聚(乙酸乙烯酯)、聚乙烯醇、聚环氧乙烷、聚乙烯吡咯烷酮、烷基化的聚环氧乙烷、聚乙烯基醚、聚(甲基丙烯酸甲酯)、聚(丙烯酸乙酯)、聚四氟乙烯(PTFE)、聚氯乙烯、聚丙烯腈、聚乙烯基吡啶、苯乙烯-丁二烯橡胶、丙烯腈-丁二烯橡胶、乙烯-丙烯-二烯单体(EPDM)及它们的混合物。
基于100重量份的所述复合正极活性材料,可以以3重量份~15重量份的量使用所述粘合剂。在粘合剂的含量小于3重量份的情况中,电极活性材料与集电器之间的粘附力会不足,且在粘合剂的含量大于15重量份的情况中,粘附力会良好,但电池的容量会下降,这是因为电极活性材料的含量随粘合剂含量的升高而同步下降。
分散介质的非限制性实例可以为N-甲基吡咯烷酮、二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、乙醇、异丙醇、水及它们的混合物。
正极集电器的非限制性实例可以为铂(Pt)、金(Au)、钯(Pd)、铱(Ir)、银(Ag)、钌(Ru)、镍(Ni)、不锈钢(STS)、铝(Al)、钼(Mo)、铬(Cr)、碳(C)、钛(Ti)、钨(W)、铟(In)掺杂的SnO2(ITO)、氟(F)掺杂的SnO2(FTO)及它们的合金;或经C、Ni、Ti或Ag进行过表面处理的不锈钢。
可以使用二次电池中使用的负极、隔膜和电解质而无限制,只要所述负极、隔膜和电解质可用于本领域中即可。
具体地,通过利用负极活性材料如锂金属、锂合金、无定形碳、结晶性碳、碳复合材料和SnO2对负极集电器进行涂布,然后对负极集电器进行干燥和压延,可以制备负极。
更特别地,可以将锂与金属如铝、锌、铋、镉、锑、硅、铅、锡、镓或铟的合金用作所述锂合金。
作为负极集电器,可以使用Pt、Au、Pd、Ir、Ag、Ru、Ni、STS、Cu、Mo、Cr、C、Ti、W、ITO、FTO及它们的合金,还可使用经C、Ni、Ti或Ag进行过表面处理的Cu或不锈钢。
上述正极集电器和负极集电器两者都可以具有诸如箔、膜、片、冲切体、多孔体或发泡体的形式。
隔膜用于防止正极与负极之间的短路并提供锂离子的移动通道。可以将用于二次电池中的已知材料用作隔膜。所使用隔膜的非限制性实例可以为聚烯烃类聚合物如聚丙烯或聚乙烯的层、或其多个层、微孔膜、机织织物和无纺布。
可以将碳酸酯、酯、醚或酮单独或以组合的方式用作电解质。可以将碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲乙酯、碳酸亚乙酯、碳酸亚丙酯或碳酸亚丁酯用作所述碳酸酯,将γ-丁内酯、乙酸甲酯、乙酸乙酯或乙酸丙酯用作所述酯,并可以将二丁醚用作所述醚。然而,不能将本发明限制于此。
还可在电解质中添加锂盐。可以将本领域中已知的锂盐用作所述锂盐,但锂盐的非限制性实例可以为LiBF4、LiPF6、LiAsF6、LiSbF6或LiPF3(CF2CF3)3。
此外,本发明提供一种电池模块,所述电池模块通过根据本领域的典型技术对包含所述复合正极活性材料的二次电池进行串联或并联连接而包括所述二次电池。
包括在电池模块中的二次电池的数量可以根据电池模块的应用和容量进行调节。
此外,本发明提供一种对电池模块进行电连接的电池组。
所述电池组可以用作中型和大型装置的电源,所述中型和大型装置为,例如包括电动车辆(EV)、混合电动车辆(HEV)和插电式混合电动车辆(PHEV)的电动车;电动双轮车辆,包括电动自行车和电动踏板车;电动高尔夫球车;电动卡车;和电动商用车辆,但不能将本发明限制于此。
下文中,将根据具体实例对本发明进行更详细地描述。然而,不能将本发明限制于此。
实施例1
将90重量份的(0.5)[Li2MnO3]·(0.5)[Li(Ni0.33Co0.33Mn0.33O2)]和10重量份的Li(Ni0.80Co0.15Al0.05O2)进行混合以制备复合正极活性材料。
其后,将100重量份的复合正极活性材料、5重量份作为导电剂的炭黑和5重量份作为粘合剂的聚偏二氟乙烯添加至1-甲基-2-吡咯烷酮中以制备用于制备正极的浆料。
接下来,利用所述浆料对铝箔进行涂布,然后干燥以制备正极。通过在110℃下进行热压延并在80℃下的真空烘箱中干燥24小时,形成正极。
将多孔聚乙烯隔膜布置在由此制备的正极与石墨类负极之间,并注入锂电解质以制备聚合物型锂二次电池。
实施例2
除了对80重量份的(0.5)[Li2MnO3]·(0.5)[Li(Ni0.33Co0.33Mn0.33O2)]和20重量份的Li(Ni0.80Co0.15Al0.05O2)进行混合以作为复合正极活性材料之外,以与实施例1相同的方式制备了聚合物型锂二次电池。
实施例3
除了对70重量份的(0.5)[Li2MnO3]·(0.5)[Li(Ni0.33Co0.33Mn0.33O2)]和30重量份的Li(Ni0.80Co0.15Al0.05O2)进行混合以作为复合正极活性材料之外,以与实施例1相同的方式制备了聚合物型锂二次电池。
比较例1
除了使用100重量份的(0.5)[Li2MnO3]·(0.5)[Li(Ni0.33Co0.33Mn0.33O2)]以代替复合正极活性材料之外,以与实施例1相同的方式制备了聚合物型锂二次电池。
实验例
(1)对功率随充电状态的变化进行评价
对功率随根据实施例1~3和比较例1制备的聚合物型锂二次电池的充电状态(SOC)的变化进行了测量,并将其结果示于图1中。
(2)对电阻随充电状态的变化进行测量
对电阻随根据实施例1~3和比较例1制备的聚合物型锂二次电池的SOC的变化进行了测量,并将其结果示于图2中。
(3)对充电和放电电势进行测量
对根据实施例3和比较例1制备的聚合物型锂二次电池的充电和放电电势进行了测量,并将其结果示于图3中。
示于下图1~3中的数据仅是实例,且其具体值可以随电池的规格和周围环境而变化,由此认为功率、电阻和充电和放电电势随各个电池的SOC变化的相对趋势是重要的,而不是其具体值。
参考图1,关于比较例1,测得的功率总体上低于实施例1~3。在SOC低于50%的情况中,功率明显下降,特别地,应理解,根据比较例1和实施例1~3的电池的功率差在20%~40%SOC范围内为10%以上。
参考图2,关于比较例1,测得的电阻值总体上大于实施例1~3,特别地,关于比较例1,可确认在SOC在10%~40%的低范围内的情况中电阻急剧增大。然而,关于实施例1~3,可确认,电阻不会如同比较例1中急剧增大,且其电阻值也小于比较例1的电阻值。
参考图3,比较例1的放电曲线在实施例3的放电曲线下方,由此可理解,实施例3的包含复合正极活性材料的电池的放电电势高于比较例1的包括单种正极活性材料的电池的放电电势。
根据实施例和实验例,包括本发明的复合正极活性材料的电池的电阻在低SOC下不会急剧增大,由此可确认,在宽SOC范围内可确保稳定的功率。
尽管特别显示了本发明并参考其优选实施方案对其进行了说明,但是本领域技术人员应理解,在不背离附属权利要求书所限定的本发明的主旨和范围的条件下可在其中完成形式和细节的各种变化。所述优选实施方案仅理解为描述性意义且不是用于限制的目的。因此,本发明的范围不是由发明的详细说明限定,而是由附属权利要求书限定,在所述范围内的所有差别都应认为包括在本发明内。
Claims (6)
1.一种包含复合正极活性材料的二次电池,所述复合正极活性材料包含:
由下面显示的化学式1表示的层状锂锰氧化物;和
由下面显示的化学式3表示的含锂的金属氧化物,
其中所述由化学式1表示的层状锂锰氧化物和所述由化学式3表示的含锂的金属氧化物的混合比在99:1~50:50的重量比范围内,
化学式1 a[Li2MnO3]·(1-a)[LiM1O2]
其中0<a<1,且M1为Mn、Ni和Co;以及
化学式3 Li(NixCoyAlz)O2
其中x、y和z各自独立地选自0<x、y、z<1的范围,0.45≤x≤0.9,0.05≤y≤0.35,0.005≤z≤0.20,且x+y+z=1。
2.根据权利要求1所述的二次电池,还包含选自如下物质中的一种或多种物质:锂钴氧化物;锂镍氧化物;锂锰氧化物;锂钴-镍氧化物;锂钴-锰氧化物;锂锰-镍氧化物;锂钴-镍-锰氧化物;以及其中被选自如下元素中的一种或多种其他元素取代或掺杂的氧化物:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、钙(Ca)、Zn、锆(Zr)、铌(Nb)、钼(Mo)、锶(Sr)、锑(Sb)、钨(W)和铋(Bi)。
3.根据权利要求1所述的二次电池,其中所述由化学式1表示的层状锂锰氧化物和所述由化学式3表示的含锂的金属氧化物的混合比在90:10~70:30的重量比范围内。
4.根据权利要求1所述的二次电池,其中所述二次电池用于中型和大型装置的电源。
5.根据权利要求4所述的二次电池,其中所述中型和大型装置是选自如下的一种或多种:包括电动车辆(EV)、混合电动车辆(HEV)和插电式混合电动车辆(PHEV)的电动车;电动自行车;电动踏板车;电动高尔夫球车;电动卡车;和电动商用车辆。
6.根据权利要求1所述的二次电池,其中所述复合正极活性材料用于在宽SOC范围内提供稳定的功率。
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WO2013085317A1 (ko) | 2013-06-13 |
KR101515678B1 (ko) | 2015-04-28 |
US20140356715A1 (en) | 2014-12-04 |
EP2662916A4 (en) | 2015-04-29 |
CN103443974A (zh) | 2013-12-11 |
US8840815B2 (en) | 2014-09-23 |
EP2662916A1 (en) | 2013-11-13 |
JP5880989B2 (ja) | 2016-03-09 |
CN107452942B (zh) | 2020-12-01 |
KR20130063699A (ko) | 2013-06-17 |
JP2014517480A (ja) | 2014-07-17 |
EP2662916B1 (en) | 2018-08-08 |
PL2662916T3 (pl) | 2019-05-31 |
US9614219B2 (en) | 2017-04-04 |
US20130228718A1 (en) | 2013-09-05 |
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