TWI485906B - 含電解質添加物之二次電池 - Google Patents
含電解質添加物之二次電池 Download PDFInfo
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- TWI485906B TWI485906B TW102124692A TW102124692A TWI485906B TW I485906 B TWI485906 B TW I485906B TW 102124692 A TW102124692 A TW 102124692A TW 102124692 A TW102124692 A TW 102124692A TW I485906 B TWI485906 B TW I485906B
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- Prior art keywords
- electrolyte
- secondary battery
- compound
- battery
- battery according
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- 239000002000 Electrolyte additive Substances 0.000 title description 3
- -1 monophosphate compound Chemical class 0.000 claims description 82
- 239000003792 electrolyte Substances 0.000 claims description 71
- 229910019142 PO4 Inorganic materials 0.000 claims description 34
- 239000010452 phosphate Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000005518 polymer electrolyte Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- 239000011244 liquid electrolyte Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000004712 monophosphates Chemical class 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 claims description 2
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- KZMLMFZPKSWYMO-UHFFFAOYSA-N prop-1-ene prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C=CC.C=CC KZMLMFZPKSWYMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- IJTQSYOCOQYXDQ-UHFFFAOYSA-N ethyl carbamate phosphoric acid prop-2-enoic acid Chemical class C(C=C)(=O)O.NC(=O)OCC.P(=O)(O)(O)O IJTQSYOCOQYXDQ-UHFFFAOYSA-N 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 18
- 239000006183 anode active material Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000006182 cathode active material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
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- 230000004913 activation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- 238000004132 cross linking Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
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- 239000002184 metal Substances 0.000 description 4
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- 238000007872 degassing Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000004862 dioxolanes Chemical class 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
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- 238000004880 explosion Methods 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group 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
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Classifications
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
- H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
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- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T10/60—Other road transportation technologies with climate change mitigation effect
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本發明係關於一種二次電池,其包括一電極組,該電極組包括一陰極、一陽極以及一插設於其之間的隔離膜、以及一電解質,其中該陽極包括鋰鈦氧化物(LTO)以作為一陽極活性材料,且該電解質含有一磷酸酯類化合物,以作為一添加物。
行動裝置的科技發展及需求增加快速增加了二次電池的需求。在此類二次電池中,具有高能量密度、高操作電壓、長週期及低自放電率的鋰二次電池係商業上可獲得的並被廣泛地使用。
此外,對環境議題的關注增加了對利用石油燃料的汽車(例如造成空氣汙染主因的汽油車及柴油車)之替代方案的電動車(EV)及混合電動車(HEV)的大量生產之研究。這類電動車通常使用鎳金屬混合(Ni-MH)二次電池作為能源。然而,大量關於使用具有高能量密度、高放電電壓、及穩定輸出的鋰二次電池之研究正如火如荼地進行中,且部分係商業上可獲得的。
依據所利用之電解質的類型,可將鋰二次電池分成含有液態電解質的鋰離子電池、呈膠態之含有液態電解質的鋰離子聚合物電池、以及含有固態電解質的鋰聚合物電池。具體而言,相較於液態電解質電池,由於例如液體洩漏率低之高安全性等的優勢,以及達到輕薄電池的可能性高,鋰離子聚合物或膠態聚合物電池的應用正持續增加。
一鋰離子電池係藉由將含有一鋰鹽的液態電解質注入一電極組中所製造,該電極組包括一陰極及一陽極,各個係藉由將一活性材料塗佈於一集電器上所形成,連同一插設於該陰極及該陽極之間的隔離膜。
用於製造一鋰離子聚合物電池的方法可依據用於電解質注入的基質材料的類型而分為一非交聯聚合物電池的製造方法以及一直接交聯聚合物電池的製造方法。具有高自由基聚合反應性的丙烯酸酯類與甲基丙烯酸酯類材料以及具有高導電性的醚類物質係典型的聚合物基質材料。具體而言,在直接交聯聚合物電池的製造中,一電池係藉由將由電極板及一多孔隔離膜所組成的一膠卷型或堆疊型電極組置入一小袋中,將一熱聚合的聚乙烯氧化物(PEO)類單體或寡聚物交聯劑以及一電解質組成物注入至該小袋中,以及熱固化該些經注入的材料而完成製造。以此方法的電池製造係有優勢的,其中可使用傳統的鋰離子電池之電極板及隔離膜而不用改變。然而,直接交聯聚合物電池的製造具有問題,其中一交聯劑沒有被完整地固化
並且殘留於該電解質中而增加黏度。此使均勻的注入變的困難,藉此大幅地劣化電池性質。
碳類材料係典型地用於鋰二次電池的陽極活性材料。然而,該碳類材料相對於鋰具有0V的低電位因而減少該電解質,產生氣體。具有一相對高電位的鋰鈦氧化物(LTO)亦用以作為一用於鋰二次電池的陽極活性材料以解決這些問題。
然而,當以LTO作為一陽極活性材料時,LTO係作為一種催化劑,在活化及充電/放電製程中產生大量的氫氣,而造成在二次電池安全性上的降低。
因此,亟需提供一種能藉以確保電池安全性同時維持電池性能的技術。
因此,本發明已完成解決上述及其他尚未解決的技術問題。
透過密集的研究及各種不同的實驗之結果,本發明的發明人發現:當二次電池包括鋰鈦氧化物(LTO)以作為一陽極活性材料,且一磷酸酯類化合物作為一電解質添加物時,可達成所欲的功效。基於此發現而完成本發明。
依據本發明,藉由提供一種二次電池,其包括一電極組,該電極組包括一陰極、一陽極以及一插設於其之間的隔離膜、以及一電解質,其中該陽極包括鋰鈦氧化物(LTO)以作為一陽極活性材料,且該電解質含有一磷酸酯類化合物作為一添加物,以完成上述及其他的目的。
在一具體例中,該電解質可為任一液態電解質、一膠態電解質以及一固態電解質,但不限於此。具體來說,該電解質可為一液態電解質或一膠態聚合物電解質。
當該電解質係一液態電解質,藉由該電解質與該陽極活性材料的副反應可促進該電解質的分解,藉此而如上述產生氣體。此種氣體可能造成該二次電池的安全性問題,例如膨脹或爆炸。因此,本發明二次電池係使用一具有一添加至其中的磷酸酯類化合物之液態電解質,以解決此種問題。
當該電解質係一膠態聚合物電解質時,作為該磷酸酯類化合物添加物之一交聯劑係添加至該膠態聚合物電解質中,以提供較佳的循環性質而達成電極介面穩定,因此在高溫儲藏的期間可良好地抑制由產氣所造成的膨脹,亦能大幅增進電池壽命及安全性的效用。
在本發明中,可信的是,由於該磷酸酯類化合物與自由基具有高反應性,能增加聚合反應的程度,藉此增進最終電解質的電化學穩定性。此外,用以作為一陽極活性材料的LTO作用為一催化劑,以促進該磷酸酯類化合物的交聯聚合,藉此最大化上述的效用。
具體而言,當該電解質係一膠態聚合物電解質,在反覆充電/放電的期間下,由於該電解質與該些電極相接觸的區域減少,故會減少該電解質與該些電極的副反應,且由於該電解質係呈一膠態聚合物的形式,因此在氣體壓力上的減少導致亦抑制膨脹。
在一實施例中,該磷酸酯類化合物可包括至少一者擇自由下列所組成之群組:一式(1)之磷酸酯類丙烯酸酯、一式(2)之焦磷酸酯類丙烯酸酯以及一磷酸酯類胺基甲酸酯丙烯酸酯:
其中R1
及R2
係各自獨立地為氫、甲基或F以及n為1至20的整數。
該電解質可更含有一利用該磷酸酯類化合物所聚合的多官能化合物。
當利用該磷酸酯類化合物聚合的多官能化合物附加地用以作為一電解質添加物時,該多官能化合物及該磷酸酯類化合物可補足彼此的電化學及機械特性,藉此進一步增進該電池的整體特性。
具體而言,當一膠態聚合物電解質係使用該磷酸酯類化合物且利用該磷酸酯類化合物所聚合的多官能化合物這兩者而製備,可達成具有更高的彈性之物理性質。亦即,磷酸酯類化合物具有能夠輕易與鋰離子配合的結構,
因而能展現更高的鍵結力,且具有高彈性的多官能化合物係透過一起交聯而聚合,因此能使得該磷酸酯類化合物及該多官能化合物補足彼此的電化學及機械特性。
在一實施例中,該多官能化合物可包括至少一者擇自由下列所組成之群組:一甲基丙烯酸酯類化合物、一不飽和碳酸化合物以及一乙烯基化合物。
該甲基丙烯酸酯類化合物可包括一每分子至少具有兩個丙烯酸酯基團的甲基丙烯酸酯化合物,以及該甲基丙烯酸酯化合物可包括一式(3)之單體或其寡聚物:
其中R3
、R4
及R5
係各自獨立地為氫或經取代或未經取代之C1-C4烷基,以及m為1至20的整數。
此外,該甲基丙烯酸酯類化合物可包括,但不限於,至少一者擇自由下列所組成之群組:二乙二醇二丙烯酸酯(Di(EG)DA)、二乙二醇二甲基丙烯酸酯(Di(EG)DM)、乙二醇二甲基丙烯酸酯(EGDM)、二丙烯二丙烯酸酯(Di(PG)DA)、二丙二醇二甲基丙烯酸酯(Di(PG)DM)、乙二醇二乙烯醚(EGDVE)、乙氧基化的(6)三羥甲基丙烷三丙烯酸酯(ETMPTA)、二乙二醇二乙烯醚(Di(EG)DVE),三乙二醇二甲基丙烯酸酯(Tri(EG)DM)、二季戊四醇戊丙烯酸酯(DPentA)、三羥甲基丙烷三丙烯酸酯(TMPTA)、三羥甲基丙烷三甲基丙烯酸酯(TMPTM)、丙氧酸酯化的(3)三羥甲基丙
烷三丙烯酸酯(PO(3)TMPTA)、丙氧酸酯化的(6)三羥甲基丙烷三丙烯酸酯(PO(6)TMPTA)、聚(乙二醇)二丙烯酸酯(PA1)以及聚(乙二醇)二甲基丙烯酸酯。
該多官能化合物,與該磷酸酯類化合物一起,可形成各種不同類型的共聚物,例如,隨機共聚物、嵌段共聚物以及接枝共聚合物。
以該電解質之總重為基準,該電解質可含有0.1至1wt%,更具體地0.1至0.5wt%之該利用該磷酸酯類化合物所聚合的多官能化合物。
以該電解質之總重為基準,該電解質可含有0.01至30wt%,更具體地0.01至20wt%之該磷酸酯類化合物。
當該電解質係一液態電解質時,若該磷酸酯類化合物的含量過低,則無法完全地達成增強安全性的效用。相對地,若該磷酸酯類化合物的含量過高,雖然安全性增強,但由於鋰鹽的含量相對低可能會劣化整體的電池特性。
當該電解質係一膠態電解質時,若該磷酸酯類化合物的含量過低,則無法輕易地形成膠態聚合物而使得當使用一液態電解質時,該電池的膨脹現象之發生可能更糟,並且形成具有所欲厚度的基板可能會更困難。相對地,若該磷酸酯類化合物的含量過高,膠態聚合物的密度增加而鋰離子傳導率(或導電性)因而減低,造成鋰沉澱,結果電池性能減低。此外,黏性增加,而使得在將該電解質均勻
應用於對應的部分上可能有困難。
將該多官能化合物添加至該磷酸酯類化合物中同樣是如此。因此,以該電解質之總重為基準,該電解質可含有0.01至30%的總量之該磷酸酯類化合物及該多官能化合物,更具體地0.1至5%。
該液態電解質可包括一電解質(塑化劑)及一鋰鹽。當該電解質係一膠態聚合物電解質,則該電解質可更包括一聚合起始劑。
該電解質可作為一塑化劑。該電解質的例子包括非質子有機溶劑,例如N-甲基-2-吡咯啶酮、丙烯碳酸酯(PC)、乙烯碳酸酯(EC)、丁烯碳酸酯(BC)、二甲基碳酸酯(DMC)、二乙基碳酸酯(DEC)、乙基甲基碳酸酯(EMC)、γ-丁內酯、1,2-二甲氧基乙烷、四氫呋喃、2-甲基四氫呋喃、二甲基亞碸、1,3-二噁戊烷、甲醯胺、二甲基甲醯胺、二噁戊烷、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二噁戊烷衍生物、環丁碸、甲基環丁碸、1,3-二甲基-2-四氫咪唑酮、丙烯碳酸酯衍生物、四氫呋喃衍生物、醚、丙酸甲酯以及丙酸乙酯。這些材料可單一使用或作為其兩者以上的混合物。
該鋰鹽係一材料,其於非水性電解質中溶解並解離為鋰離子。該鋰鹽的例子包括LiCl、LiBr、LiI、LiClO4
、LiBF4
、LiB10
Cl10
、LiPF6
、LiCF3
SO3
、LiCF3
CO2
、LiAsF6
、LiSbF6
、LiAlCl4
、CH3
SO3
Li、CF3
SO3
Li、(CF3
SO2
)2
NLi、氯硼烷鋰、低級脂肪族羧酸鋰、四苯硼酸鋰以及亞胺。這些材料可單
一使用或作為其兩者以上的混合物。
以包括在該電解質中的固態成分之總重為基準,該電解質可含有0.01至30wt%,更具體地0.1至20wt%之該鋰鹽。
該聚合起始劑的例子可包括偶氮化合物,例如2,2-偶氮基雙(2-氰基丁烷)、2,2-偶氮基雙(甲基丁腈)、2,2'-偶氮基異丁腈(AIBN)以及偶氮基雙二甲基-戊腈(AMVN);過氧化物,例如過氣化苯甲醯、過氣化乙醯、過氧化二月桂醯、過氧化二-三級丁基、過氧化異丙苯以及過氧化氫;以及氫過氧化物。具體而言,AIBN、2,2'偶氮基雙(2,4-二甲基戊腈)(V65)、二-(4-三級丁基環己烷)-過氧化二碳酸酯(DBC)或諸如此類等可用以作為該聚合起始劑。
該聚合起始劑可於40至80ºC的溫度下分解,以形成自由基,且接著可透過自由基聚合作用而與單體反應,以形成一膠態聚合物電解質。一般而言,自由基聚合作用的進行係藉由序列反應,其包括:一起始反應,涉及具有高反應性或活性位置的瞬時分子(transient molecules)之形成;一增長反應,涉及藉由添加單體以活化鏈末端,而在鏈末端再形成活性位置,一鏈轉移反應,涉及將該些活性位置轉移至其他分子;以及一終止反應,涉及活性鏈中心的破壞。當然,聚合反應亦可進行而不用一聚合起始劑。
此外,為了增進充電/放電特性及耐燃性,例如,吡啶、三乙基亞磷酸酯、三乙醇胺、環狀醚、乙二胺、n-甘醇二甲醚、六磷酸三醯胺、硝基苯衍生物、硫、醌亞胺
染料、N-經取代的噁唑烷酮,N,N-經取代的咪唑啶、乙二醇二烷基醚、銨鹽、吡咯、2-甲氧基乙醇、三氯化鋁或諸如此類等可添加至該電解質中。適當時,為了給予耐燃性,該非水性電解質可更包括含鹵素溶劑,例如四氯化碳或三氯乙烯。再者,為了增進高溫儲藏特性,該非水性電解質可附加地包括二氧化碳氣體。
本發明該的二次電池可為一鋰離子電池。該鋰離子電池的製造可藉由:將一電極組安裝於一電池盒中;將一磷酸酯類化合物、一聚合起始劑、一電解質以及一鋰鹽之混合物注入該電池盒,接著進行密封;以及進行一形成製程以活化該電池並一熟成製程以穩定該經活化的電池。
然而,當該電解質係一膠態聚合物電解質時,一活化製程可在凝膠反應之後進行。當該磷酸酯類化合物用以作為該電解質的一添加物時,可透過加濕及充電/放電來誘導薄膜形成之方法而省略凝膠反應。在一基本方法中,將該電池充電至一程度時,將會發生單體的電化學分解反應,接而進行脫氣。
該形成製程係藉由反覆的充電/放電循環而活化該電池。該熟成製程係藉由使該電池停滯一段特定時間而穩定在該形成製程中經活化的電池的一製程。
該形成製程及該熟成製程進行的條件沒有特別限制並且可在所屬技術領域中所詳知的傳統範圍內調整。
在具體例中,將該混合物注入該電池盒中(首次注入)並且使該電池結構停滯一段特定時間(例如,10小時),而使得該混合物均勻的注入至該電池盒中達成。隨後充電該電池以將其活化。在活化的充電製程中,移除用於陽極之的保護膜時會產生氣體。之後,將該電池再次停滯一段特定時間(例如,12小時)並且為了活化而充電,藉此完成電池製造。
本發明的該二次電池可為一鋰離子聚合物電池。具體而言,該鋰離子聚合物電池的製造可使用一方法,其包括:(a)將一電極組安裝於一電池盒中;(b)將一磷酸酯類化合物、一聚合起始劑、一電解質、以及一鋰鹽之混合物注入該電池盒,接著進行密封;以及(c)將該磷酸酯類化合物進行聚合以形成一膠態聚合物電解質。
具體地,步驟(c)可包括:(c1)將該電池進行熱固化,藉由利用電子束或γ射線的輻射之光固化、或於30至80ºC下進行一安定化反應,以聚合該磷酸酯類化合物;以及(c2)進行一形成製程以活化該電池以及一熟成製程以穩定該經活化的電池。
具體而言,該交聯反應可在惰性條件下進行。由於自由基與作為自由基清除劑的大氣氧氣之反應在惰性氣氛下被根本地阻止,可能可以在實質上沒有無反應的單體存在下來將反應程度增強至一程度。此能防止由大量無反應單體殘留在該電池內部所導致在充電/放電性能上的劣化。
該惰性氣氛條件沒有特別限制,可使用具有低反應性的習知氣體,例如,至少一者擇自由下列所組成之群組:氮氣、氬氣、氦氣以及氙氣可用以作為惰性氣體。
磷酸酯類化合物藉由該交聯反應而結合,以形成具有三維網狀結構之經交聯的聚合物,且該些聚合物接而與該電解質均勻地注入。
該經交聯的聚合物電解質係電化學穩定的能夠穩定存在該電池中,即使在反覆的充電/放電循環之後亦沒有損害。結果,可能可以增進電池安全性並且達成優異的機械性質,例如延伸及彎曲性質。再者,由於透過膠態聚合物電解質之極性鋰離子的連續遷移及轉移可最小化電池性質劣化。
該形成及熟成製程係以如上所述的相同方法來進行。在該形成製程的期間,自用以作為該陰極的鋰金屬氧化物所游離出的鋰離子在該電池充電時遷移並插入作為該陽極的碳電極中。在本發明中,像是Li2
CO3
、LiO及LiOH的化合物,其係藉由高反應性的鋰與碳陽極的反應所產生,在該陽極表面形成一固態電解質介面(SEI)膜。在此情況下,無反應的交聯劑可經歷額外的反應。
在一具體例中,將該混合物注入至該電池盒中(首次注入)並且使該電池結構停滯一段特定時間(例如,3小時),而使得該混合物均勻的注入至該電池盒中達成。隨後,在如上所述的條件下進行熱聚合反應。接而為了活化而充電該電池。在用來活化的充電製程中,移除在形成用於該
陽極的保護膜之期間內所產生的氣體並且將依特性數量的補充混合物第二次地注入至該電池盒中。之後,將該電池再次停滯一段特定時間(例如,12小時)並且為了活化而充電,藉此完成電池製造。
該二次電池的製造通常係藉由將一電解質併入至包括一陰極與一陽極以及一插設於其之間的隔離膜之電極組中。
該陰極的製備係藉由,例如,將一陰極活性材料、一導電材料及一黏結劑塗佈的一混合物於一陰極集電器,繼而乾燥,以及加壓而製備。若有需要可將一填充劑可添加至該混合物中。
該陰極集電器通常製造為3至500μm的厚度。可使用任何的陰極集電器而沒有特別限制,只要提供高導電性而沒有造成在該電池中的化學變化即可。該陰極集電器的例子包括不鏽鋼、鋁、鎳、鈦、燒結碳或表面經碳、鎳、鈦或銀所處理的鋁或不鏽鋼。該陰極集電器可於表面上包括良好的不規則性,俾以增強對該陰極活性材料的附著。此外,該陰極集電器可以各種不同的形式來使用,例如一薄膜、一薄片、一箔、一網、一多孔結構、一發泡體以及一不織布。
該陰極活性材料的例子包括,但不限於,層狀化合物,例如單獨或經一或多個過渡金屬取代的鋰鈷氧化物(LiCoO2
)及鋰鎳氧化物(LiNiO2
);鋰鎂氧化物,像是Li1
+xMn2-x
O4
(其中0x0.33)、LiMnO3
、LiMn2
O3
以及LiMnO2
;
鋰銅氧化物(Li2
CuO2
);釩氧化物,例如LiV3
O8
、LiFe3
O4
、V2
O5
以及Cu2
V2
O7
;由LiNi1-x
Mx
O2
(M=Co、Mn、Al、Cu、Fe、Mg、B或Ga以及0.01x0.3)所表示的Ni-位置類型的鋰鎳氧化物;由LiMn2-x
Mx
O2
(M=Co、Ni、Fe、Cr、Zn或Ta以及0.01x0.1)或Li2
Mn3
MO8
(M=Fe、Co、Ni、Cu或Zn)所表示的鋰鎂複合氧化物;LiMn2
O4
,其中Li部分地由鹼土金屬離子所取代;二硫化合物;以及Fe2
(MoO4
)3
。
以包括該陰極活性材料的混合物之總重為基準,通常添加呈0.01至50wt%的數量之導電材料。可使用任何的導電材料而沒有特別限制,只要提供適當的導電性而沒有造成在電池中的化學變化即可。該導電材料的例子包括石墨,例如天然或人工石墨;碳黑,例如乙炔黑、Ketjen黑、槽黑、爐黑、燈黑以及熱碳黑;導電纖維,例如碳纖維以及金屬纖維;金屬粉末,例如氟化碳、鋁以及鎳粉末;導電晶鬚;例如氧化鋅及鈦酸鉀晶鬚,導電金屬氧化物,例如氧化鈦;以及聚伸苯衍生物。
以包括該陰極活性材料的化合物之總重為基準,該黏結劑係一輔助一活性材料結合至一導電材料及一集電器的組分,通常添加呈1至50wt%的數量之黏結劑。該黏結劑的例子包括多氟亞乙烯、聚乙烯醇、羧甲基纖維素(CMC)、澱粉、羥基丙基纖維素、再生織維素、聚乙烯基吡咯啶酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三聚物(EPDM)、磺酸化EPDM、苯乙烯丁二烯橡膠、氟橡膠以及各種不同的共聚物。
該填充劑係一選擇性地用於抑制陰極膨脹的組分。可使用任何的填充劑而沒有特別限制,只要該填充劑係一不會造成在該電池中的化學變化之纖維材料即可。填充劑的例子包括烯烴類聚合物,例如聚乙烯以及聚丙烯;以及纖維材料,例如玻璃纖維及碳纖維。
例如,該陽極的製備可藉由將一陽極活性材料塗佈至一陽極集電器,繼而乾燥及加壓。若有需要該陽極可更包括如上所述的其他組分。
該陽極集電器通常製造為3至500μm的厚度。可使用任何的陽極集電器而沒有特別限制,只要提供適當的導電性而沒有造成在該電池中的化學變化即可。該陽極集電器的例子包括銅、不鏽鋼、鋁、鎳、鈦、燒結碳或表面經碳、鎳、鈦或銀所處理的鋁或不鏽鋼,或一鋁鎘合金。相似於該陰極集電器,該陽極集電器可包括良好的不規則性於其表面上,俾以增強對該陰極活性材料的鍵結力。此外,該陽極集電器以各種不同的形式來提供,例如一薄膜、一薄片、一箔、一網、一多孔結構、一發泡體以及一不織布。
鋰鈦氧化物可用來作為如上所述的該陽極活性材料。
具體而言,該鋰鈦氧化物可為Li4
Ti5
O12
、LiTi2
O4
或其混合物。更具體而言,該鋰鈦氧化物可為Li4
Ti5
O12
。
該陽極活性材料的例子可包括碳的一混合物,例如非石墨化碳或石墨化碳;金屬複合氧化物,例如
Lix
Fe2
O3
(0x1)、Lix
WO2
(0x1)或Snx
Me1-x
Me'y
Oz
(Me:Mn、Fe、Pb或Ge;Me':Al,B,P,Si,週期表的第I、II及III族元素或鹵素;0<x1,1y3,以及1z8);一鋰金屬;一鋰合金;一矽基合金;一錫基合金;一金屬氧化物,例如SnO、SnO2
、PbO、PbO2
、Pb2
O3
、Pb3
O4
、Sb2
O3
、Sb2
O4
、Sb2
O5
、GeO、GeO2
、Bi2
O3
、Bi2
O4
或Bi2
O5
;一導電纖維,例如聚乙炔;以及一Li-Co-Ni基材料。
本發明的該二次電池可以各種不同的形式所製造。例如,可將該電極組製造為一膠卷結構、一堆疊結構、一堆疊/摺疊結構或諸如此類等。可製造該電池而使得一電極組安裝至一電池盒中,該電池盒由包括一金屬層極一樹脂層的一圓柱罐、一稜柱罐或一積層片所製成。該電池的此種結構在所屬技術領域中廣為知曉的因而其詳細的說明於本發明中省略。
該二次電池可為一鋰二次電池。
該二次電池不僅可作為一用於小型裝置的電源,亦可作為用於如下所述之中型或大型裝置的電源。
本發明亦提供一種電池模組以及一種包括該電池模組的電池組,該電池模組包括該二次電池以作為一單位電池。
該電池組亦可用以作為用於中型或大型裝置的電源,其需要高溫安全性、長壽命以及高速性質。
該中型或大型裝置的具體例包括,但不限於,由電動馬達驅動的動力工具;電動車(EVs),其包括混合電
動車(HEVs)及插入式混合電動車(PHEVs);電動二輪車,其包括電動腳踏車(E-bikes)及電動機踏車(E-scooters);電動高爾夫車;以及電力儲存系統。
由於鋰鈦氧化物(LTO)用以作為一陽極活性材料並且一磷酸酯類化合物用以作為一添加物,本發明的二次電池達成電極介面穩定性,藉此防止氣體及副產品產生。因此,該二次電池不僅展現高度安全性亦展現增進的壽命及高功率特性。
連同隨文所附之圖式的下列詳細說明中將更清楚地理解本發明的上述與其他目的、特徵以及其他優點,其中:圖1係顯示依據試驗例2在一45ºC的箱中之循環特性的比較圖;以及圖2係顯示依據試驗例3在一60ºC的箱中與高溫儲藏壽命有關的氣體產生之程度的比。
現在將透過實施例來更詳細地描述本發明。然而,應注意的是,下列實施例僅供用於例示本發明而沒有限制本發明的範疇。
將一陽極活性材料(Li1.33
Ti1.67
O4
)、一導電材料
(Denka black)以及一黏結劑(PVdF)以95:2.5:2.5的重量比添加至NMP中,繼而進行混合,以製備一陽極混合物。接而將該陽極混合物塗佈於一厚度為20μm的銅箔,以形成厚度為60μm的塗佈層,繼而軋延並乾燥,以製造一陽極。
此外,將作為一陰極活性材料的LiNi0.5
Mn1.5
O4
、一導電材料(Denka black)以及一黏結劑(PVdF)以95:2.5:2.5的重量比添加至NMP中,繼而進行混合,以製備一陰極混合物。接而將該陰極混合物塗佈於一厚度為20μm的銅箔以形成厚度為60μm的塗佈層,繼而軋延並乾燥,以製造一陰極。
接而將作為一隔離膜的一聚乙烯膜(Celgard,thickness:20μm)插設於該陽極及該陰極之間以形成一電極組。將具有的1M LiPF6
一液態電解質以1/2的體積比溶解於一EC/EMC溶劑中,以該電解質之總重為基準,將作為一磷酸酯類材料之一磷酸酯類丙烯酸酯(於式(1)中R1為H以及n為1)以5wt%的數量添加至其中,注入一該電極組固定於其中的小袋中,以製造一袋狀電池。
一袋狀電池係以相同於實施例1的方法所製造,除了一焦磷酸酯類丙烯酸酯(於式(2)中R1為H以及n為1)用以作為一磷酸酯類材料。
一袋狀電池係以相同於實施例1的方法所製造,以該溶劑的重量為基準,除了將作為一多官能化合物之二
季戊四醇戊丙烯酸酯(DPentA)以0.2wt%的數量附加地添加至該電解質中。
一袋狀電池係以相同於實施例2的方法所製造,以該溶劑的重量為基準,除了將作為一多官能化合物之二季戊四醇戊丙烯酸酯(DPentA)以0.2wt%的數量係添加至該電解質中。
一袋狀電池係以相同於實施例1的方法所製造,除了在注入該電解質之後,將作為一聚合起始劑之2,2'-偶氮異丁腈(AIBN)以0.1wt%的數量添加至該電解質中,以該溶劑的重量為基準,並且接而於70ºC的溫度下進行高溫反應歷時5小時以製備一膠態聚合物電解質。
一袋狀電池係以相同於實施例2的方法所製造,除了在注入該電解質之後,以該溶劑的重量為基準,將作為一聚合起始劑之2,2'-偶氮異丁腈(AIBN)以0.1wt%的數量添加至該電解質中,並且接而於70ºC的溫度下進行高溫反應歷時5小時以製備一膠態聚合物電解質。
一袋狀電池係以相同於實施例1的方法所製造,除了使用一不具有磷酸酯類丙烯酸酯(於式(1)中R1為H以及n為1)的電解質添加至其中。
一袋狀電池係以相同於實施例6的方法所製造,除了在將磷酸酯類丙烯酸酯(於式(1)中R1為H以及n為1)以40wt%的數量添加至該電解質中之後,注入該電解質。
將在實施例1至6及比較例1至2中所製造的電池(具有265mAh的預定電容)於2.75V下進行一形成製程。將該電池在一特定的C-速度下且於1.6V及2.75V的範圍內進行充電/放電以證實放電電容。結果顯示於下面表1中。
當電池於一45ºC的箱中,在一5C的C-速度且於1.6V及2.75V的範圍內進行充電/放電,測量在實施例1與3以及比較例1與2中所製造的電池之循環特性。結果顯示於圖1中。
將在實施例1與3以及比較例1與2中所製造的電池(具有265mAh的預定電容)於2.75V下進行一形成製程。將該電池在一特定的C-速度下且於1.6V及2.75V的範圍內進行充電/放電以證實放電電容。在將電池於一60ºC的高溫下儲藏於100%的SOC中之後,測量由副反應所導致的氣體產生。結果顯示於圖2中。
如可於圖1及2中可見,比較例1產生過量的氣體且比較例2顯著地劣化循環特性,然而依據本發明的實施例1至6產生小量的氣體,確保高安全性,並且亦展現較好的循環特性。
如同自上述說明係明顯的,本發明的二次電池具有各種不同的優點,例如,由於鋰鈦氧化物(LTO)用以作為一陽極活性材料且一磷酸酯類化合物用以作為一添加物,故該二次電池達成電極介面穩定性,藉此防止氣體及副產物的產生。因此,該二次電池不僅展現高安全性亦展現增近的壽命及高功率特性。
熟習此技藝者可清楚知悉,在不背離本發明的範疇下可依據上面教示而進行各種不同的修飾及變化。
Claims (20)
- 一種二次電池,包括一電極組,該電極組包括一陰極、一陽極以及插設於其之間的一隔離膜、以及一電解質,其中該陽極包括鋰鈦氧化物(LTO)之一陽極活性材料,且該電解質含有一磷酸酯類化合物,以作為一添加物,其中該磷酸酯類化合物包括至少一者擇自由下列所組成之群組:一式(1)之磷酸酯類丙烯酸酯、一式(2)之焦磷酸酯類丙烯酸酯、以及一磷酸酯類胺基甲酸酯丙烯酸酯:
- 如申請專利範圍第1項所述之二次電池,其中該電解質更含有與該磷酸酯類化合物聚合之一多官能化合物。
- 如申請專利範圍第2項所述之二次電池,其中該多官能化合物包括至少一者擇自由下列所組成之群組:一甲基丙烯酸酯類化合物、一不飽和碳酸化合物以及一乙烯基化合物。
- 如申請專利範圍第3項所述之二次電池,其中該甲基丙烯酸酯類化合物包括一每分子至少具有兩個丙烯酸酯基團的甲基丙烯酸酯化合物。
- 如申請專利範圍第4項所述之二次電池,其中該甲基丙烯酸酯化合物包括一式(3)之單體或其寡聚物:
- 如申請專利範圍第1項所述之二次電池,其中該甲基丙烯酸酯類化合物包括至少一者擇自由下列所組成之群組:二乙二醇二丙烯酸酯(Di(EG)DA)、二乙二醇二甲基丙烯酸酯(Di(EG)DM)、乙二醇二甲基丙烯酸酯 (EGDM)、二丙烯二丙烯酸酯(Di(PG)DA)、二丙二醇二甲基丙烯酸酯(Di(PG)DM)、乙二醇二乙烯醚(EGDVE)、乙氧基化的(6)三羥甲基丙烷三丙烯酸酯(ETMPTA)、二乙二醇二乙烯醚(Di(EG)DVE)、三乙二醇二甲基丙烯酸酯(Tri(EG)DM)、二季戊四醇戊丙烯酸酯(DPentA)、三羥甲基丙烷三丙烯酸酯(TMPTA)、三羥甲基丙烷三甲基丙烯酸酯(TMPTM)、丙氧酸酯化的(3)三羥甲基丙烷三丙烯酸酯(PO(3)TMPTA)、丙氧酸酯化的(6)三羥甲基丙烷三丙烯酸酯(PO(6)TMPTA)、聚(乙二醇)二丙烯酸酯(PA1)以及聚(乙二醇)二甲基丙烯酸酯。
- 如申請專利範圍第2項所述之二次電池,其中,以該電解質之總重為基準,該電解質含有0.1至1wt%之與該磷酸酯類化合物聚合之該多官能化合物。
- 如申請專利範圍第1項所述之二次電池,其中該電解質係一液態電解質或一膠態聚合物電解質。
- 如申請專利範圍第8項所述之二次電池,其中該電解質係一液態電解質。
- 如申請專利範圍第9項所述之二次電池,其中該液態電解質包括作為一塑化劑及一鋰鹽之一電解質。
- 如申請專利範圍第8項所述之二次電池,其中該電解質係一膠態聚合物電解質且該添加物係一交聯劑。
- 如申請專利範圍第11項所述之二次電池,其中該膠態聚合物電解質包括一聚合起始劑、一電解質,以作為一塑化劑、及一鋰鹽。
- 如申請專利範圍第10或12項所述之二次電池,其中以包括在該電解質中的固態成分之總重為基準,該電解質含有0.01至30wt%之該鋰鹽。
- 如申請專利範圍第1項所述之二次電池,其中該二次電池係一鋰離子聚合物電池。
- 一種用於製造如申請專利範圍第14項所述之二次電池的方法,該方法包括:(a)將一電極組安裝於一電池盒中;(b)將一磷酸酯類化合物、一聚合起始劑、一電解質、以及一鋰鹽之混合物注入該電池盒,接著進行密封;以及(c)將該磷酸酯類化合物進行聚合以形成一膠態聚合物電解質。
- 如申請專利範圍第15項所述之二次電池,其中該步驟(c)包括:(c1)將該電池進行熱固化、照射電子束或γ射線之光固化、或於30至80ºC下進行一安定化反應,以聚合該磷酸酯類化合物;以及(c2)進行一成形製程,以活化該電池,並進行一熟化製程,以穩定該經活化的電池。
- 一種電池模組,包括如申請專利範圍第1項所述之二次電池,以作為一單位電池。
- 一種電池組,包括如申請專利範圍第17項所述之電池模組。
- 一種裝置,包括如申請專利範圍第18項所述之電池組。
- 如申請專利範圍第19項所述之裝置,其中該裝置係一電動車、一混合電動車、一插入式混合電動車或一電力儲存系統。
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