TWI461366B - 經碳塗覆之鋰鈦尖晶石 - Google Patents

經碳塗覆之鋰鈦尖晶石 Download PDF

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TWI461366B
TWI461366B TW098132663A TW98132663A TWI461366B TW I461366 B TWI461366 B TW I461366B TW 098132663 A TW098132663 A TW 098132663A TW 98132663 A TW98132663 A TW 98132663A TW I461366 B TWI461366 B TW I461366B
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carbon
titanium oxide
lithium
lithium titanium
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TW201024222A (en
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Jasmin Dollinger
Andreas Pollner
Michael Holzapfel
Nicolas Tran
Norbert Schall
Max Eisgruber
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Sued Chemie Ip Gmbh & Co Kg
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Description

經碳塗覆之鋰鈦尖晶石
本發明係關於經碳塗覆之鈦酸鋰Li4 Ti5 O12 ，以及其製備方法。
不久前，提出了使用鈦酸鋰Li4 Ti5 O12 或簡稱為鋰鈦尖晶石、特別是作為在可充電鋰離子電池中當做陽極材料之石墨的替代品。
在該電池中作為陽極材料的近期概述可在例如Bruce et al.,Angew.Chem.Int.Ed. 2008,47,2930-2946中找到。
和石墨相比，Li4 Ti5 O12 的優點特別是其較佳的循環穩定度、其較佳的熱功率、和較高的操作可靠度。和鋰相比，Li4 Ti5 O12 具有相對固定的1.55V勢能差，且達到數千次電容損失<20%的充電/放電循環。
因此，和之前在可充電鋰離子電池中常被用作為陽極之石墨比起來，鈦酸鋰明顯具有更好的正電位。
然而，較高的正電位也會產生較低的電位差。和石墨的電容372mAh/g(理論值)相比，會導致175mAh/g的電容減少，和以石墨陽極之鋰離子電池相比，此造成明顯較低的能量密度。
然而，Li4 Ti5 O12 具有長的壽命和非毒性，且因此也不會被歸類成對環境造成威脅。
近來，LiFePO4 已在鋰離子電池中被用作陰極材料，且Li4 Ti5 O12 與LiFePO4 結合可達到2V的電位差。
各方面的鈦酸鋰Li4 Ti5 O12 的製備已被詳細敘述。通常，Li4 Ti5 O12 係藉由在鈦化合物，典型為TiO2 ，與鋰化合物，典型為Li2 CO3 之間、於超過750℃之高溫的固態反應方法獲得，如US 5,545,468或EP 1 057 783 A1中所描述。
也有描述製備Li4 Ti5 O12 的溶膠-凝膠方法(DE 103 19 464 A1)。此外，藉由火燄噴銲裂解方式的製備方法係於(Ernst,F.O. et al. Materials Chemistry and Physics 2007,101(2-3,pp. 372-378)中提出，且在無水媒介中所謂的"水熱法"係在(Kalbac,M. et al.,Journal of Solid State Electrochemistry 2003,8(1)pp. 2-6)中提出。
因為作為電極的鈦酸鋰典型地被壓縮至有碳的電極，特別是石墨或碳黑的電極，所以EP 1 796 189 A2建議以移(ex situ)提供複合鋰過渡金屬氧化物，亦即在其與含碳塗層完全合成之後。然而，此方法的一個缺點是獲得產物的大顆粒尺寸，特別是次級粒子的尺寸。再者，在此方法中的碳塗層係位於次級粒子而非初級粒子上，其導致不佳的電化學性質，特別是關於其電容行為。
因此，需要提供另外的鋰鈦氧化物，特別是鈦酸鋰Li4 Ti5 O12 ，其具有特別小的粒子和改良的電化學性質。
根據本發明，此目標係藉由含碳的鋰鈦氧化物達到，該氧化物含有直徑1-80μm的球體(次級)粒子聚集體，其係由以碳塗覆之鋰鈦氧化物初級粒子所組成。
此處德國術語"Partikel"和"Teilchen"係同義地用來表示平均粒徑。
在下文中，鋰鈦氧化物係指鈦酸鋰，其根據本發明包含Li1+x Ti2-x O4 類型的所有鋰鈦尖晶石，其有的空間群Fd3m，且一般也含有任何通式Lix Tiy O(0<x,y<1)的混合鋰鈦氧化物。
如所提到者，根據本發明經碳塗覆的鋰鈦氧化物係由次級粒子所組成，該次級粒子係由塗覆碳的初級粒子所形成。次級粒子係為球體形狀。
根據本發明之次級粒子顆粒尺寸產生的結果為在含有根據本發明經碳塗覆的鋰鈦氧化物材料之電極中的電流密度係特別高的，且和先前技藝的材料、特別是EP 1796 189 A2相比，其具有高的循環穩定度。
令人驚訝地，也發現根據本發明含碳的鋰鈦氧化物具有1-10m2 /g，較佳係<10m2 /g、又更佳係<8m2 /g，且特佳係<5m2 /g的BET表面積(根據DIN 66134測量)。在一特別較佳的具體實例中，典型的值係落在3-5m2 /g的範圍。
典型地，以碳塗覆之初級粒子具有<1μm的尺寸。根據本發明，重要的是初級粒子係小的，且至少部份以碳塗覆，結果是和未經碳塗覆之材料或未均質塗覆之材料相比，或和只有次級粒子有塗覆的材料相比，含有根據本發明鋰鈦氧化物之電極的攜帶電流能力和循環穩定度係特別高的。
在本發明較佳的具體實例中，根據本發明的鋰鈦氧化物的碳含量係0.05到2wt.%，在相當特別的較佳具體實例中為0.05到0.5wt.%。
令人驚訝地，發現相對低的碳含量，即在初級粒子上相對薄的碳塗覆，係足以在含有根據本發明之材料的電極上帶來關於上述的有利效果。
在鋰鈦氧化物中，Li4 Ti5 O12 係較佳的，因為其特別適合用作電極材料。
本發明的目標係進一步藉由製備含碳鋰鈦氧化物的方法來達到，其包括下列步驟：
(a)使鋰鹽、氧化鈦和含碳化合物在溶劑中混合；
(b)使來自步驟a)的混合物乾燥；
(c)鍛燒該乾燥的混合物。
視鋰鹽對氧化鈦的比例而定，可獲得如已描述於上之空間群Fd3m的鋰鈦尖晶石Li1+x Ti2-x O4 或通式Lix Tiy O的混合鋰鈦氧化物。
根據本發明之鋰鈦氧化物的最終碳含量也可在混合時設定。
此處術語"溶劑"係定義為能使起始物質的至少一種成分的至少部分可溶於該溶劑，即，具有至少0.5的溶度積L。溶劑較佳為水。在特別較佳的具體實例中，起始物質的一成分係輕易溶於水的，即，其具有至少10的溶度積L。
特佳地，Li對Ti的原子比為4:5，其結果是特別會得到具有碳塗層的純相Li4 Ti5 O12 。此處純相係指在正常量測準確度的限制內，在金紅石相中藉由XRD量測不會偵測到TiO2 。
較佳地，用於進行根據本發明方法的鋰鹽係選自由下列所組成群組：LiOH、LiNO3 、Li2 CO3 、Li2 O、LiHCO3 、和醋酸鋰，這是因為可讓其他起始化合物加入的水溶液可特別容易地從這些起始化合物製備。
較佳地，TiO2 係以銳鈦礦形式或非結晶形式使用，其有利地不會因為根據本發明方法變成金紅石。
適合用來進行根據本發明方法的含碳化合物係選自例如：烴類，像是多環芳香族物和它們的化合物；苝及其化合物、聚合物和共聚物，像是聚烯烴、粉末形式的聚丙烯共聚物、苯乙烯-聚丁二烯嵌段共聚物、醣類和其衍生物。特佳的聚合物係聚烯烴、聚丁二烯、聚乙烯醇、來自酚的縮合產物、衍生自呋喃甲基的聚合物、苯乙烯衍生物、二乙烯苯衍生物、萘酚非、丙烯腈和醋酸乙烯酯、明膠、織維素、澱粉以及其酯類和醚類與其混合物。
已證明醣類為進行根據本發明的方法特佳的選擇，因為其溶於水的狀況特別好。在醣類中，乳糖、蔗糖(sucrose)和蔗糖(saccharose)係特佳的，乳糖為最佳的。
乾燥步驟b)典型地係以所謂的噴霧乾燥形式進行，其中獲得的混合物係細微地透過噴嘴噴灑且以預產物的形式沉澱。然而，也可使用任何其他方法，其中起始化合物為均質混合且然後導入至氣體流中進行乾燥。除了噴霧乾燥外，這些方法例如為流體化床乾燥、轉動造粒、單獨乾燥或冷凍-乾燥、或其組合。噴霧乾燥係特佳的，且典型地在溫度梯度為90-300℃下進行。
在獲得來自步驟a)之水性混合物的乾燥產物後，其也有利地避免其他先前技術方法的溶劑問題，獲得之噴霧乾燥的預產物係在700到1000℃的溫度鍛燒，較佳在保護的氛圍下以避免在鍛燒期間可能的次級反應，其可能導致不欲的結果，像是例如，碳塗層的氧化。適當的保護氣體例如，氮、氬等或其混合物。
本發明也關於藉由根據本發明之方法獲得的鋰鈦氧化物，其特徵在於如上已描述之特別小的BET表面積和小的初級粒子和從初級粒子形成之次級粒子的顆粒尺寸。
本發明的問題係進一步藉由電極解決，該電極含有根據本發明之經碳塗覆的鋰鈦氧化物。較佳地，該電極係陽極。特別地，發現到這樣的電極具有介於1C和4C之>85%的電容率，且在鋰離子二次電池中於C/10至少165mAh/g的放電能力。
本發明係藉由參考具體實施例和圖式更詳細地描述於下，然而，其並不視為限制。
 具體實施例：
1.概論
LiOH‧H2 O和銳鈦礦形式的TiO2 係在下面用作起始產物。至於在商業可得之LiOH‧H2 O(來自Merck)中，水含量係每批都不同，且係在合成前決定。
LiOH/TiO2 /乳糖的懸浮液係在30-35℃製備，其係首先將LiOH‧H2 O溶於水中，且然後在攪拌下將銳鈦礦形式的TiO2 和乳糖加入：
實施例1：
根據本發明之鈦酸鋰(Li4 Ti5 O12 )的製備
將9.2kg的LiOH‧H2 O溶於45升的水中且然後將20.8kg的TiO2 加入。然後加入不同量的乳糖。進一步改變乳糖的量，使用有30g乳糖/kg LiOH+TiO2 的批料、有60g乳糖/kg LiOH+TiO2 的批料、有90g乳糖/kg LiOH+TiO2 的批料以改變在根據本發明之鈦酸鋰中的碳量。
令人驚訝地發現乳糖具有減少原始懸浮液黏度的效果，結果為相較於在沒有加入乳糖的狀況製備對應懸浮液少用25%的水。然後將混合物在Nubilosa噴霧乾燥器中於大約300℃的起始溫度和100℃的終止溫度下噴霧乾燥。
首先，形成數微米等級的多孔球體聚集體。
然後，將以此方式獲得的產物在800℃於氮氛圍下鍛燒一小時。獲得經聚集之初級粒子(<1μm的初級粒子顆粒尺寸)的大(1-80-μm)聚集體。
圖1顯示有0.2wt.%總碳含量(60g乳糖/kg LiOH+TiO2 )之根據本發明經碳塗覆的鈦酸鋰，而圖5顯示也藉由噴霧乾燥方法獲得之未經塗覆的鈦酸鋰。在根據本發明方法之起始產物中的含碳化合物係作為燒結保溫室且導致有明顯較小的粒子。
比較實施例：
根據實施例1的方法製備未經塗覆的鈦酸鋰，即，沒有添加乳糖。
然後使因此獲得且經鍛燒的鈦酸鋰浸入乳糖溶液3h且在750℃加熱3h(參考EP 1 796 198 A2)。該產物的SEM顯微照係呈現於圖4，且和根據圖1之根據本發明的產物比較，有明顯較粗糙的粒子且同樣由較大的初級粒子燒結在一起，而不是尺寸<1μm的初級粒子。此外，比較實施例的次級粒子具有"沾污的"塗層。碳含量同樣大約0.2wt.%。
然後以根據本發明的材料和比較實施例的材料進行充電/放電循環，該材料即，以相同方法獲得之隨後經塗覆的鈦酸鋰(根據EP 1 796 198 A2)和未經塗覆的鈦酸鋰。
在每個情況中，陽極由85%活性材料、10% Super P碳黑和5% PVDF 21256黏結劑組成。以根據本發明的材料或比較的材料作為半電池中的陽極來進行測量，且和金屬鋰做比較。電極的有效質量含量為2.2mg/cm2 。在循環中涵蓋的範圍為1.0-2.0伏。圖2顯示根據本發明經碳塗覆的鈦酸鋰之充電/放電圖，其中介於1C和4C的電容率為87.5%；在充電和放電期間的電流係相同的。
和未經塗覆的鈦酸鋰做比較，觀察到明顯的穩定度，根據圖6，具有82%的對應電容率。
同樣地，和移地塗覆之鈦酸鋰(圖3)比較，根據本發明的材料係較佳的，其在4C測量到只有75%電容。在充電和放電期間的電流係相同的。
因此，結果顯示經塗覆的原地根據本發明經碳塗覆的鈦酸鋰，和隨後做碳塗覆或未塗覆之鈦酸鋰比較，具有主要優勢為其電容率。
圖12顯示本發明經碳塗覆之Li4 Ti5 O12 的SEM顯微照片；圖2顯示含有根據本發明(原地)經碳塗覆之鈦酸鋰的電極之充電和放電能力的圖表；圖3顯示比較用的移地塗覆之鈦酸鋰的充電和放電能力；圖4顯示隨後(移地)經碳塗覆之Li4 Ti5 O12 的SEM顯微照片；圖5顯示未經塗覆之Li4 Ti5 O12 的SEM顯微照片；圖6顯示未經塗覆之Li4 Ti5 O12 的充電和放電能力；在充電和放電期間的電流相同。

Claims (18)

  1. 一種包含含碳的鋰鈦氧化物之經煅燒球體粒子聚集體，其具有1-80μm的直徑及在1-10m2 /g範圍的BET表面積，其係由以碳塗覆之鋰鈦氧化物初級粒子所組成。
  2. 根據申請專利範圍第1項之聚集體，其初級粒子尺寸<1μm。
  3. 根據申請專利範圍第2項之聚集體，其碳含量為0.05到2wt.%。
  4. 根據申請專利範圍第3項之聚集體，其碳含量為0.05到0.5wt.%。
  5. 根據申請專利範圍第1至4項中任一項之聚集體，其中該鋰鈦氧化物係Li4 Ti5 O12 。
  6. 一種製備根據申請專利範圍第1到5項中任一項之包含含碳鋰鈦氧化物之經煅燒球體粒子聚集體之方法，其含有下列步驟：(a)使鋰鹽、氧化鈦和含碳化合物在溶劑中混合；(b)使來自步驟a)的混合物乾燥；(c)鍛燒該乾燥的混合物。
  7. 根據申請專利範圍第6項之方法，其中該溶劑為水。
  8. 根據申請專利範圍第7項之方法，其中Li/Ti原子比設定為4：5。
  9. 根據申請專利範圍第7或8項之方法，其中該鋰鹽係選自由LiOH、Li2 O、LiNO3 、LiHCO3 、LiCH3 COO所組成 的群組。
  10. 根據申請專利範圍第8項之方法，其中該TiO2 係以銳鈦礦形式或非結晶形式使用。
  11. 根據申請專利範圍第10項之方法，其中該含碳化合物係選自下列組成群組：烴和其衍生物、碳水化合物和其衍生物與聚合物。
  12. 根據申請專利範圍第11項之方法，其中該含碳化合物係選自由下列組成群組的醣類：乳糖、蔗糖(sucrose)、和蔗糖(saccharose)。
  13. 根據申請專利範圍第12項之方法，其中該乾燥係以噴霧乾燥進行。
  14. 根據申請專利範圍第13項之方法，其中該噴霧乾燥係在90-350℃的溫度梯度下進行。
  15. 根據申請專利範圍第6至8項中任一項之方法，其中該煅燒係在700到1000℃的溫度、在保護氛圍下進行。
  16. 一種含有根據申請專利範圍第1至5項中任一項之包含含碳的鋰鈦氧化物之經煅燒球體粒子聚集體的電極。
  17. 一種含有根據申請專利範圍第16項之電極的鋰離子二次電池。
  18. 根據申請專利範圍第17項之鋰離子二次電池，其在C/10具有>165mAh/g的充電/放電能力。
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CN102186775B (zh) 2015-11-25
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