TW201638094A - 用於製備電化學裝置之新系列單離子傳導聚合物的新穎交聯劑及此聚合物 - Google Patents
用於製備電化學裝置之新系列單離子傳導聚合物的新穎交聯劑及此聚合物 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
特定之交聯劑,鹼金屬雙(苯乙烯基磺醯基)醯亞胺單體,係用在為非氟化且非PEO系之單離子性傳導性共聚物之合成中。此共聚物滿足將用作為固體聚合物電解質(SPE)之安全性與成本要求。對於鹼金屬離子電池中之標準液體電解質,它們是有希望的替代品,這是因為它們改善之安全性和可燃性性質。所描述之該共聚物是聚乙烯基磺酸鹽或丙烯酸酯乙烯基磺酸鹽嵌段共聚物。較佳之丙烯酸酯單體為甲基丙烯酸酯而較佳之乙烯基磺酸鹽為苯乙烯磺酸鹽。該共聚物係藉由該乙烯基磺酸鹽與該交聯劑及視需要之該丙烯酸酯之自由基聚合製備,尤其是使用官能化之雙(醯基)磷烷氧化物(BAPO)作為光起始劑之自由基光聚合。亦描述此共聚物作為鋰離子電池中之固體聚合物電解質之用途。
Description
本發明有關適於被使用於傳導共聚物之生產中之交聯劑以及該共聚物,其中該共聚物係適於使用於鋰離子電池。
全電動或混合動力載具的開發已經變成可持續長期開發的迫切需要[1]。在不久的將來最重要的挑戰是找到一種安全、便宜、且有效率的電池技術,其將提供電動載具延長之行駛範圍(>300公里)。於能量密度之相應增加需要活性電極材料和電解質兩者之新化學品的開發[2]。鋰金屬是用來彌補正空氣(O2)或硫陰極以及用來利用這些陰極的高比電容的終極陽極和唯一選擇[3]。儘管如此,使用鋰金屬接觸液體電解質,會導致與再充電期間不規則金屬鋰電極沉積物之形成相關聯的重要安全問題。這將導致樹枝狀結晶(dendrite)的形成,其係爆炸危險之
成因。為了滿足電動載具大量市場的要求,該Li離子電池必須改善相關於熱不穩定性[4]、可燃反應產物之形成、洩漏的可能性、和內部短路的安全問題。固態電解質是減輕該鋰樹枝狀結晶生長的完美解決方案[5]。使用固體聚合物電解質(SPE),其中鋰鹽係與極性聚合物基質相關聯,可以解決大部分的上述安全性問題。再者,使用聚合物電解質,其他相關於電池加工之優點,如層疊(Li金屬、電解質、複合體、陰極)、堆疊和氣密密封將會更容易且有成本效益。
在過去的50年期間,許多聚合物/鋰鹽系統已被視為Li-離子電池中液體電解質的置換物。適當聚合性材料之開發的難度在於設計出合併了高離子性傳導度和良好的機械性質之聚合物的能力[6]。最廣泛經研究和經使用的系統係基於,與輔助離子性傳輸的可撓性大分子結構在一起之溶解在聚環氧乙烷(PEO)無質子聚合物基質中的氟化鹽,該PEO含有使得能夠有鹽之解離之醚配位點。儘管如此,PEO結晶區域的存在會干擾離子傳輸,該離子傳輸需要不定形相[7]。在高溫,高於65℃,大部分基於PEO之聚合物變成黏稠液體,並失去他們的維度穩定性[8]。再者,在該PEO-氟化鹽系統中,鋰離子的運動僅攜帶整體離子性電流的一小部分(1/5),其導致,於電池操作期間,有利於樹枝狀結晶生長之強的濃度梯度形成,其限制了電源輸送[9]。由於這個原因,單離子聚合物係較佳,其中Li+遷移係獨自負責聚合物的離子性傳導。
在過去幾年中,混合不同種類的聚合物或直接共聚合已被廣泛地用於匹配在離子性導電度和SPE聚合物的機械性質方面的要求。共聚物途徑的優點是,藉由建築嵌段之官能化而裁製機械性質如剛性/延展性的可能性,該建築嵌段可能包括新的聚合單元。藉由組合不同官能單元,該鋰傳導度與對鹼金屬之電化學穩定性可經改善。該聚合物鏈之可動性可藉由組合該共聚物與塑化劑而增進,以避免該聚合物之緊密封裝與結晶。
然而,迄今,還沒提供滿意之滿足該機械與傳導度需求之傳導聚合物。因此,本發明之目標為提供具有改善之傳導度及/或機械性質之單體、單體組成物以及單離子固體共聚物電解質。
因此,本發明之一般目標為提供一種交聯劑,其適合作為單離子固體共聚物電解質之生產中的共單體。
現在,為了實施將隨著說明書的進行而變得更加顯而易見之本發明的這些以及又進一步之目的,該交聯劑係藉由下述特徵而表明:其為雙(苯乙烯基磺醯基醯亞胺)鹼金屬鹽,亦即,具如下之式(I)之化合物:
其中,M+為Li+或Na+。
目前較佳之鹽為該鋰鹽。
此交聯劑尤其適合用於單離子傳導聚合物(亦稱為(單離子)傳導(共)聚物或(單離子)導體(共)聚物),或若用於電池應用中,(單離子)傳導(固體)電解質或僅固體電解質)之製備中。
於單離子固體共聚物電解質之生產中,可使用任何自由基起始劑,亦即,熱活化及UV活化自由基起始劑以及熱活化及UV活化自由基起始劑之混合物。此熱活化及/或UV活化起始劑能夠形成一個或較佳兩個自由基。
適合之光起始劑包括α-羥基酮、二苯甲酮、苯甲基衍生物、噻噸酮(thioxanthone)、乙醯基磷烷(acetylphosphane)、或尤其醯基磷烷氧化物(acylphosphane oxide)。乙醯基磷烷及特別是乙醯基磷烷氧化物(acetylphosphane oxide)允許於更高材料深度之高固化速度。目前較佳為乙醯基磷烷種類或醯基磷烷氧化物種類之光起始劑,如他們係描述於例如WO 2006/056541、WO 2011/003772與WO 2014/053455中。這些文件藉由參考他們的整體內容而併入本文中。
醯基磷烷氧化物種類之光起始劑之一般結構係藉下式(II)表示:
於此種光起始劑中:n為從1至6,較佳n為等於1、2、3或4,以及更佳1或2,m為1或2,X為氧或硫,R 1 為-C(R4)3,其中若n=1,所有R 4 係彼此獨立選自下列所組成之群組:- H、- 芳族基、- 烯基及- 脂肪族基,其中該脂肪族基可為未分枝或分枝、未經取代或經下列基團之一或多者取代:芳族基、雜芳族基、雜環狀基、醚(聚乙二醇或聚環氧乙烷)、硒化物、羥基、硫醇、酮、亞胺、羧酸衍生物、碸、亞碸、硫酸鹽、硫鎓、硫亞胺(sulfimine)、磺醯亞胺(sulfoximine)、磺醯胺、胺、銨鹽、腈、硝基、脒、胺基甲酸酯、胍鎓、腙(hydrazone)、醯肼、肼、矽烷、矽氧烷、聚矽氧烷、磷鎓、膦酸酯(phosphinate)、氧化膦或磷酸酯(phosphate)基團。
若n>1,特別是n為從2至6,較佳n為2、3或4,至少一個R 4 為選自上述列表之2至6價取代基,其中前述烷基也可包括位於該鏈中之前述該基團的一、二或更多者,亦即該脂肪族鏈可被前述官能基一次、二次或更
多次中斷(或相連),或經此種基團一次或多次取代,且其中該基團係被至少一個CH2-基團分開R 2 為芳基,較佳2,4,6-三甲基苯基(均三甲苯基)或2,6-二甲氧基苯基,及R 3 為如上面R1中指明之-C(R4)3。
此種光起始劑可與相同類別光起始劑組合使用及/或與其他類別(等)光起始劑組合使用。較佳之起始劑為雙(醯基)磷烷氧化物(BAPO)。此種BAPO可例如與可彌補該BAPO,如α羥基酮、二苯甲酮、苯甲基衍生物、噻噸酮、或其他醯基磷烷氧化物之固化性質之起始劑一起使用。
於目前較佳之實施態樣中,該自由基起始劑為適合用以產生兩個自由基之光起始劑,特別是具上式(II)之光起始劑,其中:n為1,m為2,X為O R 1 為-CH2-CH2(Z),Z為-(CH2)n1-NMe3X’+,其中,其中n1為從1至4,較佳1至3且X’為Cl、Br、或I,較佳Br Z為酯-(CO)OR6,其中R6為於其鏈中包含一個或多個-O-之烷基或該烷基鏈被一個或多個-O-中斷(像聚乙烯基),或攜帶一個或多個矽氧基如-SiR7 y(OR8)3-y,其中y為從0至3,或攜帶一
個或多個銨鹽基如-N(R9)4+X’-,X’係如上定義,其中R7、R8及R9為烷基,較佳C1至C4烷基,以及R2為均三甲苯基或2,6-二甲氧基苯基,更佳均三甲苯基或n為2,m為2,R 1 為-(CO)O-(CH2-CH2-O)x-O(CO)-,其中x係於範圍1至1000,較佳1至10中,最佳x為約100 R 2 為均三甲苯基或2,6-二甲氧基苯基,更佳均三甲苯基。
這些光起始劑將進一步稱為BAPO(雙(醯基)磷烷氧化物)。
通過專利PCT/EP2013/070378(WO 2014/053455)、WO 2006/056541與WO 2011/003772,該BAPO光起始劑(BAPO-1與衍生物BAPO-2、BAPO-3、BAPO-4與BAPO-5與BAPO-6)之合成係可得。
如已於上面指明者,使用於此發明中之目前較佳之光起始劑包括R1要麼為小官能基(BAPO-1、BAPO-3與BAPO-6)要麼為接枝聚合物(BAPO-4與BAPO-5)。BAPO-4為以聚矽氧烷巨分子官能化之光起始劑(例如,藉由聚合BAPO-2而可獲得者),其具有Mn為至高約2400,如本文中所使用BAPO-4之2136。BAPO-5係以聚環氧乙烷(PEO,Mn 6000)官能化,該PEO鍵結在磷原
子,於各端(n=2)。該BAPO之天性可不僅經由所附接之側鏈也經由其之聚合活性干擾該最終聚合物,導致具有不同機械與傳導性質之聚合物。於下述式中,Mes分別為均三甲苯或1,3,5-三甲基苯。
取決於所選擇之該一種或多種自由基起始劑,本發明之交聯劑可單獨與或與丙烯酸酯單體一起與乙烯基磺酸鹽單體,較佳苯乙烯磺酸鹽單體一起使用,以形成共聚物(CP),該CP於添加丙烯酸酯單體之例子中也稱為三嵌段共聚物(TBP)或於沒有丙烯酸酯時也稱為二嵌段共聚物(DBP)。對於鋰離子電池,較佳之鹼金屬為鋰,對於鈉電池,為鈉。
使用該交聯劑與適當之自由基起始劑,如上述的那些,非氟化單離子共聚物電解質可視需要地使用下述作為
進一步之共單體而製備:丙烯酸酯,較佳甲基丙烯酸酯如丙烯酸烷酯,例如甲基丙烯酸甲酯。作為進一步之共單體,使用了鹼金屬磺酸鹽乙烯基單體,較佳鹼金屬苯乙烯磺酸鹽單體,其中該鹼金屬為鈉或鋰。
已發現,使用BAPO-1至BAPO-5中之一者製備之甲基丙烯酸酯、該交聯劑與鋰苯乙烯磺酸鹽單體之共聚物,於至高高於190℃為熱穩定且於60℃提供於10-4 S cm-1範圍之單離子導電度,亦即比單離子聚合物電解質的技術領域狀態中[10]優異一個數量級。
如已於上面描述,該包含(甲基)丙烯酸酯之非氟化單離子傳導共聚物電解質也稱為三嵌段共聚物(TBP),雖然他們真實結構由於缺乏溶解度而不可能被判定。因此,該發明性共聚物電解質可能是三嵌段共聚物一事,僅是基於丙烯酸酯如甲基丙烯酸酯已知為快速均聚合之事實以及基於該所得聚合物之固體含量與經單離產率的假設。僅管如此,本發明仍不以任何方式侷限於此假設或此命名。
類似於TBP,乙烯基磺酸鹽單體與交聯劑之共聚物被稱為二嵌段(共)聚物(DBP),因為-由於莫耳比之差異-至少出現聚乙烯基磺酸鹽嵌段。
該共聚物(TBP)係適合藉由,於水性介質中,自由基起始劑(特別是光起始劑如BAPO)與下列者之經促進聚合而形成:丙烯酸酯,較佳甲基丙烯酸酯,特別甲基丙烯酸甲酯、鹼金屬乙烯基磺酸鹽單體,較佳苯乙烯磺酸鹽
像鋰苯乙烯磺酸鹽與二官能乙烯基單體聯劑,即該鹼基屬(雙(苯乙烯磺醯基)醯亞胺),像鋰(雙(苯乙烯磺醯基)醯亞胺)。藉由使用BAPO1至BAPO6中之一者以及較佳之單體所獲得之最終三嵌段或二嵌段共聚物的一般結構係顯示如下。
取決於所欲特徵,該單體比可於某些範圍內變化。該磺醯基為傳導度所需而於某些具體態樣中,取決所使用之該光起始劑,(甲基)丙烯酸酯為機械穩定性所需。考量這些需求,乙烯基磺酸鹽單體與丙烯酸酯單體之比為1:0至1:4。參考其他單體,亦即該丙烯酸單體與該乙烯基磺酸鹽單體的量,該交聯劑單體可以至高20莫耳%(mol%)之比出現,且較佳以約10mol%之量出現。
於具體實施態樣中,特別是若使用包含酯基於R1之BAPO像BAPO-1至BAPO-5,鹼金屬乙烯基磺酸鹽單體:丙烯酸酯單體之比可於從約1:4至約4:1變化(或另種方式四捨五入該丙烯酸酯單體:鹼金屬磺酸鹽乙烯基單體可從約4:1至約1:4變化),以約1:1之比為目前較佳者。因此,於目前較佳之實施態樣中,(甲基)丙烯酸酯基與磺酸鹽基之莫耳比係約1,且較佳(甲基)丙烯酸酯:乙烯基磺酸鹽:雙(苯乙烯磺醯基)醯亞胺之比為約1:1:0.2。
對於其他BAPO像BAPO-6,該丙烯酸酯可能不為必須者。對於此類聚合物,乙烯基磺酸鹽:(雙(苯乙烯磺醯基)醯亞胺之比可從10:2至10:0.5變化,其中10:1為較佳。
自由基起始劑的最佳量可輕易藉由濃度序列法判定。然而,該光起始劑及/或熱致起始劑通常以總單體的約1mol%出現,該總單體亦即(甲基)丙烯酸酯以及乙烯基磺酸鹽以及雙(苯乙烯磺醯基)醯亞胺。
該最終經交聯聚合物網絡結構促進M+與此陰離子性結構之弱交互作用,提供高解離水平與通過該基質之鹼金屬離子可動性(於60℃,對Li為10-4 S cm-1)。使用BAPO-1至BAPO-5聚合的結果是80-200nm尺寸之聚合物粒子的乳液。使用BAPO-6聚合的結果是水溶性離子傳導聚合物。
於反應期間,含有鹼金屬之表面活性劑(例如鋰十二烷基硫酸鹽)可被添加,其允許對粒子尺寸與該最終乳液之穩定性的有效控制,具有粒子尺寸分布穩定達數週。
雙(醯基)磷烷氧化物係聯結至無機材料如金屬氧化物(參見第1圖)。於單離子傳導聚合物之製備中使用此種經耦合起始劑的意圖為達成鋰離子或鈉離子活性材料與Li離子或Na離子導體聚合物之間的密切接觸。作為概念的證明,於下面描述,於有機溶劑中使用聯結至釩酸鹽之BAPO的MMA(甲基丙烯酸甲酯)聚合。
含有矽氧烷基之BAPO如BAPO-2,可藉由共懸浮反應試劑於適當的有機溶劑像THF中並於惰性氣體中回流適當時間如於氬中4小時(h),而被錨固至材料如電子活性材料像釩酸鹽上。
本發明也有關一種允許加工該SPE乳液而以SPE自支撐膜(self-standing film)為終之乾燥程序。可藉由定位此SPE自支撐膜於陽極與陰極之間而形成電化學單電池(cell),該SPE自支撐膜運作為隔板。本發明也涵蓋藉由溶液澆鑄於電極上之SPE的直接沉積。
也落入本發明之範疇者為添加塑化劑。分別取決於添加時間與量或比,該聚合物膜的特徵可有變化。一般,最小為5重量%(wt%)與最大為20wt%之塑化劑如四乙二醇二甲醚(TEG)可能用於SPE隔板中。
於進一步面向中,本發明有關一種藉由將陰極活性材料(例如LiFePO4或LixHyV3O8,其中,於此式中2<x+y<6.8且0<x<4及0.5<y<6)或如EP 2 755 259(A1)"Self-assembled composite of graphene oxide and H4V3O8")所述之複合釩酸鹽/石墨烯材料與傳導性碳添加劑及上述之該SPE混合所製備之鹼金屬離子電池像鋰離子電池,其中SPE膜隔開金屬鋰製負電極與正電極。於此配置中,該SPE扮演兩種角色,換言之作為隔板與作為電解質。
於此種具體態樣中,用於與該陰極材料及傳導性碳混合之該SPE可具有低機械強度但高傳導度,而該自支撐膜可具有較低傳導度但改善之機械穩定性。
於另一種具體態樣中,該SPE乳液可視需要地與無機填充劑像燻矽(fumed silica)、氧化鈦、氧化鋁、氧化鋯、氧化硼等混合。此種無機奈米尺寸填充劑係特別使用於改善自支撐SPE膜之機械特徵。
於另一種方法中,該活性陰極材料及傳導性碳係塗佈有或混合有該單體與該起始劑,且接著起始聚合或,-於替代性方法中-該起始劑附接至該活性陰極材料,且接著於聚合起始前與該單體組合。由於該單體擴散至該有孔陰
極材料及傳導性碳層,使用熱活化起始劑而非光起始劑可能是有利的。亦,於此實施態樣中,SPE自支撐膜應用作為(額外)隔板可能有需要。
也可能使用兩步驟方法,亦即先使用常用黏結劑或SPE(若有需要)生產陰極,以獲得充分穩定陰極,且接著對此陰極塗佈SPE層。由於該SPE層與該陰極層之密切接觸,該SPE層穩定性相較於分開生產且接著施加之自支撐層係改善。
藉由改變該單體與該填充劑之組成物,該共聚物之特徵可有變化且為大程度適應具體關於傳導度與機械性質之所需。如上所指明者,也可能且經常較佳者為使用SPE之組合,例如具高傳導度且較差機械強度之一層以及具較低傳導度之自支撐膜之組合。
使用SPE層或自支撐膜之優點為預防樹枝狀結晶形成之改善。
該SPE傳導聚合物與該活性陰極材料所製複合膜經設計用以確保該電極與該SPE-隔板之間的最佳介接,提供當設計全電池組電池(full battery cell)時之額外優點。除了該等層之間的良好機械接觸,該電解質聚合物也可增進該電極內部之局部離子傳導。
本發明之SPE不僅可與陰極材料混合也可與陽極材料混合。上述意見分別適用。儘管如此,目前遠較佳之陽極為金屬鋰或鈉。
使用標準的陰極材料,如鋰鐵磷酸鹽(LFP),或新
穎活性材料,如鋰釩酸鹽,其係用於下一代Li離子電池之具有高度吸引力的陰極材料,例如描述在EP 2 755 259 A1中者,已顯示對鋰之電化學穩定性和電化學可行性。該三嵌段聚合性單離子導體(標註為TBP)可適當地藉由為光起始劑所誘發之自由基聚合於水中合成。
因此,除了該具體聯劑與其所製造之固體傳導聚合物之外,本發明其他面向為包含活性電極材料、SPE與可能地傳導填充劑像石墨烯、石墨、傳導碳及其組合之電極,以及使用本發明之SPE作為電解質,較佳與金屬陽極組合而生產之電池。此種電池可藉由包含下列步驟之方法生產,對離型撐體如鋁箔塗佈活性電極材料以及視需要地傳導性填充劑以形成陰極,且接著對該陰極塗佈本發明之固體傳導聚合物之塗層。
當考量下面對其的詳細描述,本發明將得到更好的理解且上述那些之外的其他目的將變得明顯。此說明係參照所附圖式,其中:第1圖:光起始劑BAPO-釩酸鹽之合成。
第2圖:該聯結至釩酸鹽之光起始劑的31P NMR。
第3圖:包埋有從BAPO-釩酸鹽聚合所得之LixHyV3O8纖維之PMMA的SEM影像。
第4圖:該膜聚合物TBP-1之XRD圖案,1a(無LiDS製備)而1b(使用9mM LiDS)。
第5圖:聚合物TBP-1於水中之粒子尺寸分佈。
第6圖:TBP-1之TGA(“A”)與DSC(“B”)曲線。
第7圖:分別使用BAPO-1、BAPO-6作為光起始劑而製備之該三嵌段聚合物(TBP-1至TBP-5與DBP-6)之取決於溫度的傳導度(對數繪製)。
第8圖:於加壓前後LFP複合陰極膜(L1與L2)之SEM影像。
第9圖:釩酸鹽複合陰極膜(V1)之SEM影像。
第10圖:使用該聚合物TBP-1a之複合體L1於60℃與70℃及電流20mA/g(C/8)之循環壽命。
第11圖:複合體L3之比電荷對循環。
第12圖:複合體V1與V2之電壓對比電荷。
第13圖:複合體V1與V2之比電荷對循環。
如上所指明者,本發明有關適於非氟化且非PEO系之單離子性傳導性共聚物之合成的交聯劑。此種共聚物滿足用來作為固體聚合物電解質(SPE)之可靠性(security)與成本要求。他們是Li離子電池或Na離子電池中標準液體電解質的有前景替代品,係因為他們改善之可靠性與不可燃性性質。所述共聚物要麼是經官能化且經交聯之聚乙烯基磺酸鹽要麼是經官能化且經交聯之聚丙
烯酸酯,特別是經官能化且經交聯之甲基丙烯酸酯如經官能化且經交聯之聚甲基丙烯酸甲酯(PMMA),該官能化係以鹼金屬聚乙烯基磺醯基,像鹼金屬聚磺醯基苯乙烯如鋰聚磺醯基苯乙烯(LiPSS)官能化,該交聯係藉由使用該發明性交聯劑,亦即該鹼金屬(像Li)雙(苯乙烯磺醯基)醯亞胺(MBSSI像LiBSSI)單體。本發明之共聚物可藉由自由基聚合,特別是自由基光聚合,較佳使用經官能化之雙(醯基)磷烷氧化物(BAPO)作為光起始劑之光聚合製備。此種共聚物可用來作為鋰離子或鈉離子電池中之固體聚合物電解質。
鋰苯乙烯磺酸鹽購自Tosoh Europe B.V.,The Netherlands(>94%),且係於利用前藉由於雙(2-甲氧基乙基)醚(DME)再結晶且於真空100℃乾燥2天而純化。
甲基丙烯酸甲酯(MMA)購自AldriCH(>99%),且係於使用前蒸餾過。四乙二醇二甲醚(TEG)係藉由蒸餾純化並儲存於分子篩上。
於滴加亞硫醯氯(34.4公克(g),21毫升(mL),289毫莫耳(mmol),8.3當量(eq))之前,將4-乙烯基苯磺酸鈉鹽(7.2g,35mmol,1eq)之二甲基甲醯胺(DMF)(58mL)溶液冷卻至0℃。該亞硫醯氯經除氣但未經純化而使用。於攪拌12h後,該混合物在-4℃放過夜,且接著倒入到冰水中(100mL)並以二乙醚(3×50mL)萃取。該溶液於減壓濃縮而提供淡黃色油(4.4g,66%)。1H-NMR(500.2MHz,CDCl3)δ=7.92(d,J=8.0Hz,2 H,CHAr),7.56(d,J=7.5Hz,2 H,CHAr),6.81(m,1 H,CHolef),5.92(d,J=17.5Hz,1 H,CHolef),5.47(d,J=11.0Hz,1 H,CHolef)ppm。
13C{1H}NMR(75.5MHz,CDCl3):δ=144.9(CH2=CH-C),142.9(CSO2Cl),135.0(CH2=CH),127.6(CHAr),127.2(CHAr),119.5(CH2)ppm。
4-乙烯基苯磺醯氯(2g,9.87mmol,1當量)與氨水溶液(100mL,(25% NH3))反應2h,且接著以醚萃取、以MgSO4乾燥且濃縮而給出呈白色固體之該磺醯胺(1.11g,62%)。
Mp:141℃。
1H-NMR(500.2MHz,CDCl3):δ=7.95(d,J=8.0Hz,2 H,CHAr),7.58(d,J=8.5Hz,2 H,CHAr),6.75(m,1 H,CHolef),5.94(d,J=17.5Hz,1 H,CHolef),5.50(d,J=11.0Hz,1 H,CHolef),3.08(s,2 H,NH2)ppm。
將4-乙烯基苯磺醯氯(323毫克(mg),1.6mmol,1eq)、4-乙烯基苯磺醯胺(293mg,1.6mmol,1eq)與LiH(77mg,3.2mmol,2eq)於THF(5mL)之混合物於Ar室溫(rt)攪拌12h,接著濃縮並以醚清洗而給出白色固體。該固體從MeOH再結晶而給出0.4g,71%產率。
Mp:>250℃ dec.
1H-NMR(500.2MHz,D2O):δ=7.61(m,4H,CHAr),7.46(m,4H,CHAr),6.76(m,2H,CHolef),5.91(d,J=17.5Hz,2H,CHolef),5.36(d,J=11.0Hz,2H,CHolef)。
13C-NMR(75.5MHz,D2O):δ=141.9(CH2=CH-
C),138.9(CSO2N),135.4(CH2=CH),126.7(CHAr),125.8(CHAr),116.4(CH2)ppm。
7Li-MAS NMR δ=0ppm
ATR IR:λ-1(cm-1)=1626 w,1494 m,1424 m,1200 s,1137 m,1093 s,98ws,904 m,839 s,743 m。
EA計算值:C54.0%,H 4.0%;實測值:C53.4%,H4.1%
不同BAPO之一般合成係描述於PCT/EP2013/070378(WO 2014/053455)、WO 2011/003772與WO 2006/056541。對於BAPO-1,參見WO 2014/053455之實施例23,對於BAPO-2,參見2014/053455之實施例12a,對於BAPO-3,參見WO2014/053455之實施例27。BAPO-4係使用BAPO-2以及描述於WO 2011/003772之實施例34之方案製備,且BAPO-5係使用聚乙二醇二丙烯酸酯Mn 6000作為起始材料,根據描述於WO 2014/053455之實施例23製備。
BAPO-6係可溶於水中,且該合成係如專利WO 2006/056541之實施例1所述般使用乙醇中之3-溴丙基三甲基溴化銨用於二烯醇Na[P(COMes)2]χDME}(bisenolate Na[P(COMes)2]χDME})之烷化(步驟d)而實施。
將經矽氧烷基官能化之雙(醯基)磷烷氧化物(BAPO-2)聯結至鋰氫氧化合物釩酸鹽LixHyV3O8(其中2<x+y<6.8且0<x<4及0.5<y<6)(描述於US20130157138 A1中)(第1圖)。
將該BAPO聯結至該釩酸鹽係於氬氣氛於連接至回流濃縮器之100mL舒倫克燒瓶中進行。對LixHyV3O8(1g)之THF(30mL)懸浮液添加BAPO-2(0.05g,0.087mmol)且該混合物於4h期間回流。冷卻該混合物後,將該固體過濾、清洗並於THF(20mL)中超音波震盪兩次,1分鐘。所得綠色固體於50℃真空乾燥24h而給出0.95g。該材料之分析係光譜地(MAS NMR)實施,以確認於該材料中雙(醯基)磷烷)氧化物光活性基之出現(31P NMR)(第2圖)。
MMA之光起始聚合係於氬氣氛於100mL舒倫克燒瓶中進行。係製備該經聯結之光起始劑(0.95g)的THF(30mL)懸浮液且添加該MMA(0.78g,7.8mmol)至該懸浮液中。於照射前,該混合物劇烈攪拌5分鐘。該混合物之照射係以水銀UV燈,於室溫1小時期間劇烈攪拌而實施,其給出凝膠。該綠色固體經懸浮於50mL之
THF、超音波震盪並過濾。該樣本於真空乾燥而給出0.87g綠色固體。此固體之形態藉由SEM分析探究(第3圖)。
TBP-1合成的反應路徑:
該聚合物TBP-1(1b)之合成係於氬氣氛於100mL舒倫克燒瓶中進行。該反應器被填充鋰磺酸鹽苯乙烯(4mmol,760mg)、鋰雙(苯乙烯磺醯基)醯亞胺(0.8mmol,284mg)及蒸餾水(30mL)。於氬氣氛,緩慢添加新鮮蒸餾過之甲基丙烯酸甲酯(MMA)(4mmol,400mg,430μL)以及溶解於DME(二甲氧基乙烷)(5mL)中之光起始劑BAPO-1(R=CH2CH2CO(OCH2CH2)2OEt)(0.08mmol,42mg)至經
攪拌之該混合物中。對該反應混合物添加鋰十二烷基硫酸鹽(9mM)。於22℃以中壓水銀UV燈(254nm)照射1h且同時維持劇烈攪拌(1200rpm)之前,該乳液脫氧20分鐘,而得白色懸浮液。
該聚合物藉由於真空(40℃,20毫巴(mbar))移除溶劑而單離。所得白色黏稠殘質經異丙醇(2×5mL)與四氫呋喃(2×5mL)清洗。回收之聚合物於真空乾燥過夜(25℃,0.1毫巴),而給出945mg(71%產率)。
該聚合物之穩定懸浮液係藉由添加蒸餾水與5%(w/w)四乙二醇二甲醚(TEG)而製備。TEG係添加作為塑化劑以避免該聚合物之緊密封裝。
TBP-2至TBP-5之合成係類似地實施。
對於聚合物TBP-6,鋰苯乙烯磺酸鹽與交聯劑之偏好比為10:1,沒有使用丙烯酸酯或甲基丙烯酸酯。除了此改變與BAPO-6被添加到含有單體之水性溶液中之事實外,其他遵循用於TBP-1之過程。
該聚合物電解質之自支撐膜係藉由澆鑄該TBP懸浮液於具有300-500微米(μm)圓形溝槽之鐵氟龍盤內而製備。這些圓形溝槽具有該電解質膜之傳導度和電池測試(Ø15及17mm)所需尺寸。該聚合物係起先於室溫於
Ar,24h乾燥;接著於50℃,於Ar,於4天期間乾燥,且最終於50℃真空,24h乾燥。該加工產生200-700μm之均勻自支撐膜,使用前其儲存於手套工具箱中2天。
該MAS NMR實驗係使用Bruker Avance 400MHz 9.4T光譜儀實施。使用1.0秒(s)照射頻率脈衝,2.0 s循環延遲,瞬變數600,及7.0千赫茲(kHz)旋轉速率,7Li MAS NMR光譜係於155.50兆赫茲(MHz)紀錄。
粉末X光繞射圖案係於配備有鍺單色器和CuKα1照射(操作於40kV,35mA)之STOE Stadi P繞射儀上獲得。
掃描式電子顯微術(SEM)係於操作於1千伏特(kV)之Zeiss Gemini 1530上實施。
穿透式電子顯微術(TEM)係於CM30ST(FEI;
LaB6陰極)與操作於300kV且具有最大點解析度為約2埃(Å)之TecnaiF30顯微鏡上實施。
阻抗測量係使用50毫伏特(mV)(VMP3,Biologic SAS,France)的激發振幅在500kHz至1赫茲(Hz)的頻率範圍進行。從該電解質膜切割下內直徑為17mm的碟,並將該樣本放置於兩個圓形不銹鋼碟(1.8平方公分(cm2))之間並以溫度穩定膠帶密封之來防空氣和水分。從所獲得線計算體阻抗(R),選擇奈奎斯特(Nyquist)圖中該電解質弧和介接面弧的開端之間的最小值。接著,該聚合物之體阻抗R用於根據方程式1(Eq.1)計算傳導度(σ),其中d為該樣本的厚度而A為於該不鏽鋼碟之間所測量之該樣本面積。此方法學已被廣泛描述用於測量SPE在不同溫度之離子性傳導度[11]。
7Li MAS NMR δ=-0.5ppm
ATR IR:ν(cm-1)=2350 w,1724 s,1456 m,1248 s,1149 s,1085 s,1030 s,985 m,948 m,892 m,758 m,638 s
EA C 52.8%,H 4.0%,N 0.7%
使用XRD繞射,獨立於表面活性劑(LiDS)之添
加,於TBP1沒有發現到清楚的晶度。僅在10°-25°之2θ範圍偵測到非常寬廣的訊號,表明該聚合物含有具有有序鏈之區域,但從該信號寬度,可聲明的是這些有序功能域(domain)非常小或非良好界定者(第4圖)。
另一方面,LiDS之添加對該聚合物粒子尺寸與分佈有影響。所製備之該無LiDS之聚合物展現較劣的穩定性並於數小時後歷經粒子沉降。含LiDS(9毫莫耳濃度(mM))之聚合物懸浮液的ζ尺寸測量顯示約41奈米(nm)粒子尺寸的窄分佈(第5圖)。2週老化後,該尺寸分佈保持不變,並被用於複合膜的製備。
該聚合物之熱穩定性係藉由熱重分析(TGA)評估。至高190℃,TBP1是熱穩定,有可忽略的質量損失(1%)。在290℃有7.6%之增加的質量損失。使用差示掃描量熱法(DSC)定量該聚合物的熔化行為,該聚合物1a之代表曲線表示在第6圖中,其顯示在290℃的吸熱峰。
第7圖顯示TBP-1及使用不同的上述BAPO光起始劑所製備之類似聚合物(TBP2、TBP3、TBP4、TBP5及DBP6)之傳導度對溫度倒數(T-1)。傳導度之線性增加表示該傳導度機制於整個所測量之溫度範圍維持相同。使用聚合性含矽氧烷BAPO(BAPO-4)所獲得之聚合物達成於60℃之最大傳導度0.14毫西門子(mS)/公分(cm)。然而,此樣本於對數傳導度對T-1之圖上展現與該線性增加之偏差。這表示該傳導機制於較高溫度之改變
或第二傳導程序之影響。該聚合物膜對鋰之化學穩定性係藉由將該膜放置在新鮮切割下之鋰上於乾燥氬氣氛測試。於聚合物膜在規則時間間隔(至高3週)提起後,聚合物/Li之介接面維持未改變。
於第一步驟,該陰極活性材料(AM),要麼是經碳塗佈之鋰鐵磷酸鹽(LFP)(2μm,A1100,Alees,Taiwan)要麼是鋰氫氧化合物釩酸鹽LixHyV3O8(其中2<x+y<6.8且0<x<4及0.5<y<6)(描述於US20130157138 A1),係於瑪瑙球磨機中(300rpm,2×10分鐘)與碳黑傳導性添加劑(Super-P,Timcal)預混合及替代地也與石墨(SFG6或KS6,Timcal,Switzerland)預混合。接著添加0.16g/ml濃度之該聚合物TBP-1之水性懸浮液。取決於該固體含量,添加一些額外的去離子水直到達成適當漿黏度。對於LFP與釩酸鹽複合體(L1-L2與V1-V2)之製備,分別使用最佳固體含量為18%與35%附近。為了防止球磨期間之強發泡以及於該陰極膜中產生洞,添加最少量的磷酸三丁酯(>99.0%,Fluka CHemie AG,BuCHs,Switzerland)作為抗發泡劑。於球磨2×30分鐘(300rpm,以反向旋轉方向)後,獲得均勻漿。不同複合體組成物的重量百分比係顯示於表1中。
該漿藉由手術刀澆鑄於標準鋁箔(15μm)上。該膜於室溫通風乾燥1小時,接著於氬氣氛50℃乾燥12h,最終於真空50℃乾燥至少24h,得到40-100μm厚乾膜。對該膜施壓(15噸,5分鐘)以降低該膜中孔洞並改善粒子間之接觸。該LFP系膜的微結構顯示於第9圖中,而該釩酸鹽系膜的相應微結構顯示於第10圖中。
作為製備SPE/AM複合體之替代方式,LFP系陰極係先棒塗佈於鋁箔上且接著滴澆注SPE溶液於該陰極上。
該經塗佈陰極具有組成為88%(LFP)、6%(KS6)及4%(SuperP))。為了確保黏著至該鋁箔,使用2%甲基纖維素鈉(Na-CMC)作為黏結劑。接著滴澆注TBP1之水懸浮液(30wt%)於該LFP陰極上。該複合陰極起先於室溫,於Ar,24h乾燥;接著於50℃,於Ar,於24h期間乾燥,且最終於50℃真空(10mbar),24h乾燥。所得陰極複合體(複合體L3)為100μm厚且含有
17.6mg聚合物/cm2陰極膜之負載。
電化學性能於標準鈕扣單電池(CR2025,Renata,Switzerland)中測試。鋰金屬碟係用作陽極。隨後從該複合陰極膜切割下13mm直徑碟。
對於藉由一步驟路徑製備之複合體(L1-L2 & V1-V2),係將從自支撐SPE膜TBP1來的SPE盤(直徑17mm)放置於該陰極與該陽極間。該測試單電池係於乾燥Ar氣氛(<0.1ppm H2O;<0.1ppm O2)中組裝。對於恆電流實驗,使用20-25毫安培(mA)/g(基於該活性材料)之電流。該LFP窗電壓為3.0-3.9V而對於釩為1.6-4.2V。
該陰極L1(第10圖)顯示接近理論值(於60℃第一循環中,152安時(Ah)/公斤(kg))之電容,且當以電流20mA/g(C/8)循環時,於此溫度所測量之五個循環為穩定。於這五個循環後,將該單電池轉移至另一種用於長時間測量之測量裝置,且將溫度增加至70℃。於此溫度,電容先增加至167Ah/kg。於20個循環後,測量到144Ah/kg。
於第11圖中,該複合體L3(其中該SPE經滴澆注,參見8b)於70℃,3.0-3.9V範圍中以電流20mA/g,經恆電流地循環。於最初6個循環中,觀察到些微的超電容且從第7個循環起再充電效率接近100%。於C/8速率,於第20個循環後,該單電池之性能仍達到高於160mA/g之電容。
第12圖展示使用陰極V1與V2之電池,於70℃第一循環之對Li+/Li(V)之電壓對比電荷(Ah/Kg)。於第13圖中,係顯示這兩種複合體至高到第23個循環之獨立於循環數目之電容。該陰極複合體V1於第一循環展現398Ah/kg之接近理論值之電容,其於第23個循環後下降至148Ah/Kg。該陰極複合體V2於第一循環達到至高419Ah/kg之電容,其於第23個循環後緩慢下降至150Ah/Kg。明顯地,當與V2(僅SuperP作為碳添加劑)相比,複合體V2(Super P與石墨)之庫倫效率被改善。
雖然有顯示和描述目前較佳之本發明具體實施例,但是應當清楚地理解,本發明不限於此,也可於下述申請專利範圍之範疇內以其他方式各式地體現具體實施例及實施。
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Claims (33)
- 一種式(I)之雙(苯乙烯基磺醯基醯亞胺)鹽,
- 如式(I)之雙(苯乙烯基磺醯基醯亞胺)鹽,其中M為鋰。
- 一種如申請專利範圍第1項之雙(苯乙烯基磺醯基醯亞胺)鹽之用途,係作為固體傳導聚合物之生產中之交聯單體。
- 一種如申請專利範圍第1項之雙(苯乙烯基磺醯基醯亞胺)鹽之用途,係作為固體聚合物電解質之生產中之交聯單體。
- 一種藉由將作為交聯單體之如申請專利範圍第1項之雙(苯乙烯基磺醯基醯亞胺)鹽與鹼金屬乙烯基磺酸鹽單體及自由基起始劑共聚合所生產之固體單離子傳導聚合物,該自由基起始劑係選自由光起始劑、熱起始劑及其組合所組成之群組。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中其係固體聚合物電解質。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中係使用丙烯酸酯單體。
- 如申請專利範圍第7項之固體單離子傳導聚合物,其中該丙烯酸酯單體係甲基丙烯酸酯單體。
- 如申請專利範圍第8項之固體單離子傳導聚合物,其中該丙烯酸酯單體係甲基丙烯酸甲酯。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中該乙烯基磺酸鹽單體係苯乙烯磺酸鹽。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中該自由基起始劑係光起始劑或光起始劑與熱起始劑之組合。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中該自由基起始劑包含選自由α-羥基酮、二苯甲酮、二苯基乙二酮(benzil)衍生物、噻噸酮(thioxanthone)、乙醯基磷烷、烷氧基胺和醯基磷烷氧化物所組成之群組之光起始劑。
- 如申請專利範圍第12項之固體單離子傳導聚合物,其中該光起始劑係由下列所組成或含有下列:式(II)之該醯基磷烷氧化物種類之光起始劑,
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中n為1、2、3或4。
- 如申請專利範圍第14項之固體單離子傳導聚合物,其中n為1或2。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中R 2 為2,4,6-三甲基苯基(均三甲苯基)。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中R 2 為2,6-二甲氧基苯基。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中該光起始劑係適於產生二個自由基。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中該光起始劑為式(II),且其中n為1,m為2,X為O,R1為-CH2-CH2(Z),Z為-(CH2)n1-NMe3X’+,其中n1為從1至4,且X’為Cl、Br、或I,Z為酯-(CO)OR6,其中R6為於其鏈中包含一個或多個-O-之烷基或該烷基鏈被一個或多個-O-中斷(像聚乙烯基),或攜帶一個或多個矽氧基如-SiR7 y(OR8)3-y,其中y為從0至3,或攜帶一個或多個銨鹽基如-N(R9)4+X’-,其中R7、R8及R9為烷基,以及R2為均三甲苯基或2,6-二甲氧基苯基,或 n為2,m為2,R1為-(CO)O-(CH2-CH2-O)x-O(CO)-,其中x係於範圍1至1000中,R2為均三甲苯基或2,6-二甲氧基苯基。
- 如申請專利範圍第19項之固體單離子傳導聚合物,其中n1為從1至3。
- 如申請專利範圍第19項之固體單離子傳導聚合物,其中R7、R8及R9為C1至C4烷基。
- 如申請專利範圍第19項之固體單離子傳導聚合物,其中R2為均三甲苯基。
- 如申請專利範圍第19項固體單離子傳導聚合物,其中x為從1至100。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中該光起始劑為下列中之一者:
- 如申請專利範圍第10項之固體單離子傳導聚合物,其中該鹼金屬苯乙烯基磺酸鹽:丙烯酸酯之比例係從約1:0至約1:4。
- 如申請專利範圍第25項之固體單離子傳導聚合物,其中該鹼金屬苯乙烯基磺酸鹽:丙烯酸酯之比例係1:1。
- 如申請專利範圍第7項之固體單離子傳導聚合物,其中參照該丙烯酸酯與磺酸鹽單體的量,該交聯單體係以高達20莫耳%之比例存在。
- 如申請專利範圍第13項之固體單離子傳導聚合物,其中R1為經酯基取代之烷基以及其中該丙烯酸酯:鹼金屬苯乙烯基磺酸鹽:交聯單體之比例係約1:1: 0.2,或其中R1為經銨鹽取代之脂肪族基以及其中該丙烯酸酯:鹼金屬苯乙烯基磺酸鹽:交聯單體之比例係約0:10:1。
- 如申請專利範圍第5項之固體單離子傳導聚合物,其中該光起始劑及/或該熱致起始劑係以總單體之約1mol%存在。
- 一種如申請專利範圍第5項之固體單離子傳導聚合物之用途,係作為鋰離子或鈉離子電池中之電解質。
- 一種包含如申請專利範圍第5項之固體單離子傳導聚合物作為電解質之電池。
- 一種陰極或陽極,其中如申請專利範圍第5項之固體單離子傳導聚合物係密切與陰極或陽極電活性材料及視需要之石墨烯和/或傳導性碳或石墨混合。
- 一種生產如申請專利範圍第31項之電池的方法,其包含下列步驟:以活性電極材料及視需要之傳導性填充劑塗佈釋離性撐體而形成陰極,以及接著對該陰極塗佈如申請專利範圍第5項之固體單離子傳導聚合物之塗層。
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CA2914715A1 (en) | 2016-06-10 |
CA2914715C (en) | 2018-10-02 |
US20160168086A1 (en) | 2016-06-16 |
US9771319B2 (en) | 2017-09-26 |
CN105693566B (zh) | 2018-04-03 |
KR20170140138A (ko) | 2017-12-20 |
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KR20160070701A (ko) | 2016-06-20 |
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