TW201908239A - 矽-碳複合材料粉末 - Google Patents
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Abstract
本發明係有關矽-碳複合材料粉末,其中 a) Si與C分佈整個粒子,及 b) 在粒子表面上的(C/Si)表面
之重量比率大於在整個粒子內的(C/Si)總
之重量比率。 該矽-碳複合材料粉末係利用下列方式來產生:將SiH4
、Si2
H6
、Si3
H8
與/或有機矽烷的氣流與至少一種選自由乙烯、乙烷、丙烷與乙炔所組成之群組的烴之氣流同時進料至反應器,並利用電漿增強化學氣相沉積法使該氣流反應。
Description
本發明係關於矽-碳複合材料粉末、其製造的方法及其在鋰離子電池上之用途。
已知在鋰的合金化/去合金化期間,大幅體積膨脹/收縮導致鋰離子電池中的裂縫形成,接著導致活性質量粒子粉碎及永久性電容量衰減。 已經利用各種方式以克服該大幅體積變化,從而獲得對Si陽極更佳之電容量保持率與循環壽命。其中,最有希望的方式係形成奈米複合材料結構,其中奈米Si粒子被活性外殼(較佳為碳殼)包圍。 此外,由於在循環期間該以Si為基礎之陽極所遭受的該大幅體積變化所引起之裂縫導致該電極表面暴露於電解質。這導致厚固體電解質界面(SEI)層不斷形成。該SEI的過度成長造成該電極之低庫倫效率、較高的離子傳輸阻力及低電子導電率,最後導致電池變乾。奈米Si粒子被碳殼包圍之複合材料已被證明亦有利於抑制該SEI的形成[Dimitrijevic et al., J. Power Sources 206(2012)343]。 已經利用各種方法來製備矽-碳複合材料。方法包含球磨法或機械研磨法、熱分解法、化學/熱氣相沉積法、及凝膠的化學反應。 在WO2013078645A1中主張一種矽-碳複合材料,其包含中孔矽粒子與配置在該矽粒子上的碳塗層,其中該矽粒子具有2至4 nm與20至40 nm的二種孔徑分佈。該碳塗層厚度是5至10 nm,且以該複合材料總重量為基準計,該碳占10至50重量%的量。還主張一種製備該矽-碳複合材料的方法,其包含下列步驟:在球磨情況下透過在SiCl4
與Li13
Si4
之間的機械化學反應來製備中孔矽粒子與接著進行熱處理與清洗程序;及用化學氣相沉積法以碳塗覆該中孔矽粒子。 在Angew. Chem., Int. Ed. 2006, 45, 6896中,Ng等人揭露利用在400℃下於空氣中的噴霧熱分解程序之經碳塗覆的Si奈米複合材料。在此奈米複合材料中之碳最可能是非晶質的。儘管有可能是小量之非晶質矽,然而該矽的主要部分相應於奈米晶質Si。該矽被厚度約10 nm之非晶質或部分非晶質碳層包圍。 在J. Phys. Chem. C 2007, 111, 11131中,Ng等人另外揭露低溫噴霧熱分解法以產生可在可充電鋰離子電池中作為陽極材料之Si奈米複合材料。<100 nm的奈米Si粒子在檸檬酸/乙醇溶液中被進一步噴霧熱分解,導致在球形Si奈米粒子表面上形成均質碳塗層。 在Electrochemistry Communications 28(2013)40中,Yang等人揭露含有被埋入碳基質中的Si之複合材料。矽-碳奈米複合材料粉末係藉由噴霧熱分解法製得。包含可形成新奈米複合材料中的Si與C二者之活性有機矽烷的氣溶膠在管式爐中於900℃下反應。估計Si之重量分率是40%。重要地,該方法產生均勻尺寸的粒子,其中碳與非晶質Si分佈良好。 在Nanoscale, 2013, 5, 5384中,Zhang等人報告在鋰離子電池中作為陽極材料之非晶質矽-碳奈米球的製備。這些奈米球係利用作為Si與C二者的前驅物之甲基三氯矽烷(CH3
SiCl3
)在900℃下藉由化學氣相沉積法來合成。據發現,該Si-C奈米球是由約60重量%之非晶質C與約40重量%的Si組成,其具有400至600 nm之直徑與43.8 m2
/g的表面積。 在ACS Appl. Mater. Interfaces 2015, 7, 6637中,Sorice等人報告藉由在二級雷射熱分解反應器中的一步驟的連續程序來形成經碳覆蓋之矽奈米粒子。在第一階段中所形成的結晶化矽核心在第二階段中被主要由碳組成之連續殼覆蓋。在Si/C界面不存在碳化矽。在第一階段中,雷射光束與導致矽奈米粒子合成的SiH4
流相互作用。Ar載體氣流將其轉移到第二階段,其中乙烯(C2
H4
)被同軸地插入。利用二面鏡子把該雷射光束傳輸到該第二階段並散焦以便使該C2
H4
流與該矽核心之間的相互作用時間最大化。此第二相互作用導致碳殼沉積於小矽奈米粒子積聚物周圍。矽奈米粒子直徑被調整成約30 nm。雷射功率與聚焦被調整以有利於該矽核心的結晶結構。 在Ind. Eng. Chem. Res. 2014, 53, 12697中,Yu等人報告藉由動態化學氣相沉積(CVD)法以甲苯或乙炔作為碳源以在晶質Si奈米粒子上形成均勻碳塗層。 在ACS Appl. Mater. Interfaces 2014, 6, 19026中,Chaukulkar等人報告經碳塗覆的矽奈米粒子之電漿合成法。在管式石英反應器中,在50 W的射頻(rf)功率下將SiH4
自上游注入。C2
H2
係在該SiH4
注入點之石英管的下游注入。 儘管這些方法皆提供比純Si陽極具有更佳的循環效能之矽-碳複合材料陽極,然而仍需要改善電容量衰減。 據報告,當電壓變成少於50 mV時,在矽的鋰化期間形成晶質Lix
Si(x≥3.75)。在鋰化期間轉變成Lix
Si(x≥3.75)相會導致高內應力,導致粒子破裂與電池衰減,如在J. Electrochemical Soc. 2016, 163, A255中Iaboni與Obrovac所報告。 防止Lix
Si(x≥3.75)形成之方法中的一者係將含有Si之電極的循環電壓限制在50 mV以上。然而,這導致電池能量密度顯著減少。除了具有較低能量密度外,高密度合金電極亦可能與石墨或碳的其他型態混合,因此限制該含有Si之電極的電壓可能不實用。在這樣之電極中,必須使合金相循環至低電壓,使得石墨或碳仍是活性的。因此,最好在不限制該電壓下防止Lix
Si(x≥3.75)形成。 Lix
Si(x≥3.75)形成之抑制可以在包含活性Si相與非活性基質相的粒子中實現,比如可在含有Si之合金與Si/SiOx
(x≤2)複合材料中發現。然而,非活性相會使材料之比電容量減少,因此是非所欲的。
本發明之標的是矽-碳複合材料粉末,其中 a) Si與C分佈整個粒子,及 b) 在粒子表面上的(C/Si)表面
之重量比率大於在整個粒子內的(C/Si)總
之重量比率。 在此矽-碳複合材料粉末中,由電壓對電容量的測量證實了Lix
Si(x≥3.75)之形成被抑制。此外,在此矽-碳複合材料粉末表面的較高含C量在防止SEI過度成長上是有優勢的。 本發明之矽-碳複合材料粉末具有不展現出能由穿透式電子顯微鏡(TEM)偵測到核殼結構之出人意料的性質。 在粒子表面上的(C/Si)表面
之重量比率與(C/Si)總
之重量比率都藉由穿透式電子顯微鏡(TEM)的能量色散X射線分析(EDX)測得。 在一個優選實施方式中,比率(C/Si)表面
/(C/Si)總
係為3≤(C/Si)表面
/(C/Si)總
≤130。在另一個優選實施方式中,比率(C/Si)表面
/(C/Si)總
係為10≤(C/Si)表面
/(C/Si)總
≤50。 (C/Si)總
之重量比率較佳為0.01≤(C/Si)總
≤3,更佳為0.3≤(C/Si)總
≤1。 與先前技術形成對比,在本發明之粉末中,Si與C分佈整個粒子。藉由穿透式電子顯微鏡(TEM)不會偵測到核殼結構。此外,在本發明的粉末中不會偵測到碳化矽。 本發明的粉末之Si與C可為晶質或非晶質的。對其作為鋰離子電池之一部分的新用途而言,優選為Si與C是非晶質的。 本發明之粉末的粒子可為單離形式或聚集形式。較佳地平均粒徑是300 nm或以下,更佳為20至100 nm。 本發明另外提供一種用於製造該矽-碳複合材料粉末之方法,其中將SiH4
、Si2
H6
、Si3
H8
與/或有機矽烷的氣流與至少一種選自由乙烯、乙烷、丙烷與乙炔所組成之群組的烴之氣流同時進料至反應器,其中利用電漿增強化學氣相沉積法使該氣流反應。 烴對SiH4
與/或有機矽烷的比率可在寬範圍下被選定。較佳地該比率是0.01至3。 該有機矽烷可能選自由下列所組成之群組:CH3
SiH3
、(CH3
)2
SiH2
、(CH3
)3
SiH、C2
H5
SiH3
、 (C2
H5
)2
SiH2
、(C2
H5
)3
SiH、(CH3
)4
Si、(C2
H5
)4
Si、 C3
H7
SiH3
、(C3
H7
)4
Si、C4
H9
SiH3
、(C4
H9
)2
SiH2
、 (C4
H9
)3
SiH、(C4
H9
)4
Si、C5
H11
SiH3
、(C5
H11
)2
SiH2
、 (C5
H11
)3
SiH、(C5
H11
)4
Si、C6
H13
SiH3
、(C6
H13
)4
Si、 (C7
H15
)SiH3
、(C7
H15
)2
SiH2
、(C7
H15
)3
SiH、(C7
H15
)4
Si。CH3
SiH3
、(CH3
)2
SiH2
與(CH3
)3
SiH為最優選。 乙烯、乙烷與丙烷是優選的烴。乙炔是反應性較高之起始原料且必須小心謹慎避免SiC形成。也就是說,或者使用低乙炔濃度或者改變用於電漿增強化學氣相沉積的裝置。 包含該矽烷與該烴的反應混合物之平均滯留時間可用來影響平均粒徑。減少在電漿中的滯留時間通常使粒徑減少。因此,4 s之滯留時間產生300 nm的平均粒徑,1 s之短滯留時間導致低於100 nm的平均粒徑。使用0.5 s之滯留時間導致獲得具有低於50 nm的平均粒徑之粉末。 本發明之另一個標的是該矽-碳複合材料粉末在製造鋰離子電池上的用途。
實施例1 (根據本發明) 將射頻(RF)非熱電漿應用於化學氣相沉積(CVD)法以產生粉末材料。裝置包括RF電漿源、管式石英反應器、泵、製程氣體入口、排氣與粉末收集室。把石英管反應器抽空到10至100 mbar的基礎壓力。該電漿源頻率是13.56 MHz且該RF功率被設定為50至200 W。透過質量流控制器將經Ar稀釋之SiH4
與乙烯同時注入。在氣體混合物中的矽烷濃度是20體積%。比率CHx
/SiH4
是0.16。氣體流率與壓力用於調整在電漿中的滯留時間。 4 s之長滯留時間導致獲得具有低於300 nm的平均粒徑之粉末。1 s的短滯留時間導致獲得具有低於100 nm之平均粒徑的粉末。使用0.5 s之滯留時間導致獲得一級粒子平均粒徑低於50 nm的粉末。 在所獲得之矽-碳複合材料粉末中,Si與C分佈整個粒子。在粒子表面上的(C/Si)表面
之重量比率是3.5,及在整個粒子內的(C/Si)總
之重量比率是1.0,其係利用穿透式電子顯微鏡(TEM)的能量色散X射線分析(EDX)測得。在該矽-碳複合材料粉末中該比率(C/Si)表面
/(C/Si)總
是3.5。 實施例2至4:另外的實施方式是用在實施例1中所描述之條件來進行。不同於實施例1的是,在實施例2至4中,根據表中列示的內容改變碳前驅物氣體CHx
的類型。在該表中給出該矽-碳複合材料粉末參數之變化。 實施例5 (比較例):另外的實施方式是用在實施例1中所描述之條件來進行。不同於實施例1的是,只將SiH4
引進該石英管反應器中。不使用碳前驅物氣體。所獲得之粉末只含有矽。據此在粒子表面上的(C/Si)表面
之重量比率及在整個粒子內的(C/Si)總
之重量比率是零。 在實施例5中的矽粉末與在實施例1至4中的矽-碳複合材料粉末之間的差異亦可在圖1 (x軸=2θ(度);y軸=強度(a.u.))中所示之X射線繞射(XRD)圖案中顯而易見的。在實施例5(A)中所製成之矽粉末的XRD圖案特徵為奈米晶Si之接近28.4°的較尖銳之譜峰、及非晶質Si之較寬的譜峰(非晶質鹵基)。根據定量相分析,晶質矽的量是20體積%。 和矽粉末(A)相比較,在矽-碳複合材料粉末(B)之XRD圖案中的非晶質鹵基強度減少並稍微位移到較高之繞射角。接近28.4°的較尖銳之譜峰是由於奈米晶Si,其在矽-碳複合材料粉末(B)中係以4體積%之量存在。非晶質鹵基強度減少與鹵基位移表示形成具有分佈整個粒子的Si與C之矽-碳複合材料粉末,亦即該非晶質鹵基係由Si與C混合物產生。 在球磨機中製備含有根據比較的實施例5所製得之矽粉末、苯乙烯-丁二烯橡膠之水溶液與奈米碳管的電極漿料,隨後塗到銅箔上並乾燥。將粉末塗料衝壓成片並加到具有Li金屬相對電極與1 M LiPF6
的碳酸伸乙酯/碳酸二甲酯溶液電解質之硬幣型電池內。圖2 (x軸=電容量(mAh/g);y軸=電壓(V))顯示根據比較的實施例5的矽-碳複合材料粉末之電化學電池研究的結果。由於Lix
Si(x≥3.75)相之去鋰化而形成之特徵電壓坪是存在的。相比之下,在含有根據實施例1至4所製得之矽-碳複合材料粉末的電極中,對電極穩定性有害的相Lix
Si(x≥3.75)之形成被有效地抑制,此可由在圖3中缺乏特有電壓坪所證實。在圖2與3中數字1、2、3、20、50代表第一、第二…個負載循環。在圖2中“*”代表與Lix
Si(x≥3.75)化合物之去鋰化有關的電壓坪。 實施例6 (比較例):另外的實施方式是用在實施例1中所描述之條件來進行。不同於實施例1的是,將乙炔加到石英管反應器中作為碳前驅物氣體CHx
,且CHx
/SiH4
比率是1。比較的實施例6的反應產物主要是非晶質SiC,而非所欲之大致晶質的Si僅佔一小部分。根據在TEM中之EDX分析,在C/Si比率中沒有顯著差異(參照表):在粒子表面上的(C/Si)表面
之重量比率及在整個粒子內的(C/Si)總
之重量比率是1.3。比較的實施例6(C)的材料之XRD圖案中的非晶質鹵基位移到較高的繞射角,顯示非晶質SiC形成。這類型材料對電池應用是較不利的。
圖1表示實施例1至6的矽-碳複合材料粉末之X射線繞射圖。 圖2表示實施例5的矽-碳複合材料粉末之電化學電池研究結果。 圖3表示實施例1至4的矽-碳複合材料粉末之電化學電池研究結果。
Claims (10)
- 一種矽-碳複合材料粉末,其中 a) Si與C分佈整個粒子,及 b) 在粒子表面上的(C/Si)表面 之重量比率大於在整個粒子內的(C/Si)總 之重量比率。
- 如請求項1之矽-碳複合材料粉末,其中3≤(C/Si)表面 /(C/Si)總 ≤130。
- 如請求項1或2之矽-碳複合材料粉末,其中0.01≤ (C/Si)總 ≤3。
- 如請求項1至3之矽-碳複合材料粉末,其中Si與C是非晶質的。
- 如請求項1至4之矽-碳複合材料粉末,其平均直徑是300 nm或更少。
- 一種用於製造如請求項1至5之矽-碳複合材料粉末的方法,其中 將SiH4 、Si2 H6 、Si3 H8 與/或有機矽烷的氣流與至少一種選自由乙烯、乙烷、丙烷與乙炔所組成之群組的烴之氣流同時進料至反應器,其中利用電漿增強化學氣相沉積法使該氣流反應。
- 如請求項6之方法,其中烴對SiH4 與/或有機矽烷的比率是0.01至3。
- 如請求項6或7之方法,其中該烴是乙烯、乙烷或丙烷。
- 如請求項6至8之方法,其中該有機矽烷是CH3 SiH3 、(CH3 )2 SiH2 或(CH3 )3 SiH。
- 一種如請求項1至5之矽-碳複合材料粉末的用途,其係用於製造鋰離子電池。
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