TWI461555B - 一種多層膜矽／石墨烯複合材料陽極結構 - Google Patents
一種多層膜矽／石墨烯複合材料陽極結構 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 68
- 229910021389 graphene Inorganic materials 0.000 title claims description 61
- 239000002131 composite material Substances 0.000 title claims description 45
- PYTMYKVIJXPNBD-UHFFFAOYSA-N clomiphene citrate Chemical compound [H+].[H+].[H+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.C1=CC(OCCN(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C(Cl)C1=CC=CC=C1 PYTMYKVIJXPNBD-UHFFFAOYSA-N 0.000 title 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 238000005566 electron beam evaporation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000002427 irreversible effect Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 229910052732 germanium Inorganic materials 0.000 description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- 239000010405 anode material Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000003303 ruthenium Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KCFIHQSTJSCCBR-UHFFFAOYSA-N [C].[Ge] Chemical compound [C].[Ge] KCFIHQSTJSCCBR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Description
本發明係揭示一種具高電化學特性之多層膜矽/石墨烯複合材料陽極結構。
於2012年Ji等人(Nano Energy 2012,1,164)將石墨烯(graphene)溶液透過抽氣過濾形成薄膜，並將其轉印至銅箔電流收集器上，另於其表面藉電漿輔助化學氣相沉積(plasma-enhanced chemical vapor deposition；PECVD)形成矽薄膜，重複數次該製程即可成功製備矽/石墨烯多層膜複合材料做為電池之陽極，其中五層之矽/石墨烯結構樣品其電化學特性最佳，然而以50 mA/g電流密度下進行充放電測試，該五層之矽/石墨烯結構樣品於第30循環之放電電容量衰退至第1循環之59.5%。
同年Zhang等人(Electrochem.Commun.2012,23,17)於銅箔電流收集器上分別藉電化學沉積(electrophoretic deposition；EPD)與射頻磁控濺鍍(RF magnetron sputter)，依序製備碳/石墨烯多層膜複合材料做為電池之陽極，於840 mA/g電流密度下進行充放電測試，其第一循環放電電容量可達3150 mAh/g，但該研究所計算之克電容量並未考慮碳材重量，故其實際電容量遠較此值為低。更重要的是，該碳/石墨烯多層膜複合材料的充放電第1循環之庫倫效率(coulombic efficiency)僅71.9%，充放電第2循環之放電電容量即衰退至約2000 mAh/g，故可逆電容量(reversible capacity)僅為63.5%。
而2012年Kim等人亦於美國專利(US 8168328)提出碳/矽多層膜複合材料陽極結構，然該碳/矽多層膜複合材料陽極結構必須利用退火(annealing)方式於其碳矽多層膜間形成一所謂之穩定界面矽化(silicide)層。
本發明提出以電子束蒸鍍技術製備具高電化學特性之矽/石墨烯多層膜複合材料陽極結構，藉石墨烯高導電性之優點改善矽薄膜之電化學特性，並將石墨烯薄膜及矽薄膜厚度皆控制於50 nm以下以降低於充放電過程中陽極材料之體積變化。
首先於銅箔電流收集器表面沉積一石墨烯薄膜以形成該結構之底表面，可避免該電流收集器與該矽薄膜之導電度差異過大而造成電化學表現不佳，為防止該矽薄膜因接觸空氣而氧化成不具活性之二氧化矽，故最後以一石墨烯薄膜形成該結構之表面。
該陽極材料由一矽上層薄膜與一石墨烯下層薄膜構成一單元層，重複此單元層達所需之層數後最終再沉積一石墨烯薄膜做為表面，即完成製備矽/石墨烯多層膜複合陽極材料，其中以重複七層單元層之矽/石墨烯多層膜複合陽極材料(7L)之電化學表現較佳，其第1循環之庫倫效率可達80%以上，而第2循環之不可逆電容量可降低至20%以下，此外經過30個充放電循環後，其放電電容量仍可維持於第1循環的65%以上。
截至目前為止並無任何研究揭示具高電容量且不含穩定界面矽化(silicide)層之矽/石墨烯多層膜複合材料陽極結構，而可達成上述電化學性能。
本發明提供另一種製備高電化學特性之矽/石墨烯多層膜複
合材料陽極結構之方法，該方法採直接連續式鍍膜且不含穩定界面矽化(silicide)層，更不須經繁雜之退火(annealing)步驟，該製備技術乃電子束蒸鍍，其腔體之壓力維持在4~10 Pa；將基材之溫度控制於200℃；電子束轟擊石墨靶材形成第一層石墨烯薄膜，設定該石墨烯薄膜之鍍率為1000 nm/h；於該第一層石墨烯薄膜表面，亦藉電子束轟擊矽靶材沉積一矽薄膜，設定該矽薄膜之鍍率為500 nm/h；於該矽薄膜表面再接續沉積第二層石墨烯薄膜，依序交替重複以形成本發明之結構。
11‧‧‧矽
12‧‧‧石墨烯
13‧‧‧銅箔
第1圖係本發明之實施例矽/石墨烯多層膜複合材料陽極結構之結構圖，其中一矽層及一石墨烯層構成一單元層。
第2圖係本發明之實施例以電子束蒸鍍技術製備矽/石墨烯多層膜複合材料陽極結構其X光粉末繞射圖譜，由上而下，9L、7L、5L、3L、1L、及Cu列分別代表9層單元層、7層單元層、5層單元層、3層單元層、1層單元層及銅箔的繞射圖譜。
第3圖係本發明之實施例以電子束蒸鍍技術製備矽/石墨烯多層膜複合材料陽極結構之穿透式電子顯微鏡影像。
第4圖係本發明之實施例以電子束蒸鍍技術製備的7單元層的矽/石墨烯多層膜複合材料陽極結構之拉曼圖譜。
第5圖係本發明之實施例與比較例之1單元層矽/石墨烯多層膜複合材料陽極結構之(a)充放電測試圖與(b)循環壽命圖。
第6圖係本發明之實施例與比較例之3單元層矽/石墨烯多層膜複合材料
陽極結構之(a)充放電測試圖與(b)循環壽命圖。
第7圖係本發明之實施例與比較例之5單元層矽/石墨烯多層膜複合材料陽極結構之(a)充放電測試圖與(b)循環壽命圖。
第8圖係本發明之實施例與比較例之7單元層矽/石墨烯多層膜複合材料陽極結構之(a)充放電測試圖與(b)循環壽命圖。
第9圖係本發明之實施例與比較例之9單元層矽/石墨烯多層膜複合材料陽極結構之(a)充放電測試圖與(b)循環壽命圖。
第10圖係本發明之實施例與比較例之矽/石墨烯多層膜複合材料陽極結構之層數與第一循環放電電容量關係圖。
第11圖係本發明之實施例與比較例之矽/石墨烯多層膜複合材料陽極結構之層數與第一循環庫倫效率關係圖。
第12圖係本發明之實施例與比較例之矽/石墨烯多層膜複合材料陽極結構之層數與第二循環可逆電容量關係圖。
以電子束蒸鍍技術，於銅箔電流收集器表面連續沉積數層矽/石墨烯複合陽極材料，而沉積腔體之壓力維持於4~10Pa，基材之溫度則控制於150~250℃，且石墨烯薄膜與矽薄膜其鍍率則分別固定約為1000 nm/h與500 nm/h。於製備步驟中，銅箔電流收集器表面首先沉積石墨烯薄膜，接續以矽、石墨烯、矽、石墨烯之順序交互沉積，且最上一層之薄膜皆固定為石墨烯薄膜。而此材料之電化學測試乃將其與鋰金屬組裝為鈕扣電池(coin cell)，使用六氟磷酸鋰(lithium hexafluorophosphate；LiPF6
)溶於碳酸乙烯酯(ethylene carbonate；EC)與二甲基碳酸酯(dimethyl carbonate；DMC)做為電解
液，並於100 mA/g電流密度下進行充放電測試。
參考第1圖所示為本發明之實施例與比較例以電子束蒸鍍製備之矽/石墨烯多層膜複合材料陽極結構其結構圖，製程皆固定以沉積石墨烯薄膜做為起始與結束，可降低矽薄膜及銅箔間導電度差異與防止矽薄膜接觸空氣而氧化。
參考第3圖所示為本發明之矽/石墨烯多層膜複合材料陽極結構其穿透式電子顯微鏡影像，薄膜材料厚度皆控制於50 nm以下，避免於充放電過程中體積劇烈變化。
參考第4圖所示為本發明所製備之矽/石墨烯多層膜複合材料陽極結構其拉曼圖譜，可於505 cm-1
發現矽之拉曼訊號，此外亦可分別於1339cm-1
、1569cm-1
與2697cm-1
分別發現石墨烯其D band、G band與2D band之拉曼訊號，D band之存在指出石墨烯結構中具少部分缺陷，而有助於鋰離子進行嵌入與嵌出。
參考第5圖所示為本發明之1單元層矽/石墨烯多層膜複合材料陽極結構(a)充放電測試圖與(b)循環壽命圖，其第一循環放電電容量與庫倫效率分別為552 mAh/g與53.8%，而其第二循環可逆電容量則為48.3%。
參考第6圖所示為本發明之3單元層矽/石墨烯多層膜複合材料陽極結構(a)充放電測試圖與(b)循環壽命圖，其第一循環放電電容量與庫倫效率分別為1090 mAh/g與76.3%，而其第二循環可逆電容量則為73.3%。
參考第7圖所示為本發明之5單元層矽/石墨烯多層膜複合材料陽極結構(a)充放電測試圖與(b)循環壽命圖，其第一循環放電電容量與庫倫效率分別為1110 mAh/g與79.8%，而其第二循環可逆電容量則為77.7%。
參考第8圖所示為本發明之7單元層矽/石墨烯多層膜複合材料陽極結構(a)充放電測試圖與(b)循環壽命圖，其第一循環放電電容量與庫倫效率分別為1660 mAh/g與82.3%，而其第二循環可逆電容量則為84.3%。
參考第9圖所示為本發明之9單元層矽/石墨烯多層膜複合材料陽極結構(a)充放電測試圖與(b)循環壽命圖，其第一循環放電電容量與庫倫效率分別為1719 mAh/g與81.0%，而其第二循環可逆電容量則為65.4%。
參考第10圖所示為本發明之矽/石墨烯多層膜複合材料陽極結構其層數與第一循環放電電容量關係，可得知層數提升至7層時電容量可達飽和。
參考第11圖所示為本發明之矽/石墨烯多層膜複合材料陽極結構其層數與第一循環庫倫效率關係，可得知層數為7層具最高庫倫效率。
參考第12圖所示為本發明之矽/石墨烯多層膜複合材料陽極結構其層數與第二循環可逆電容量關係，可得知層數為7層具最高可逆電容量。
11‧‧‧矽
12‧‧‧石墨烯
13‧‧‧銅箔
Claims (8)
- 一種多層膜複合材料陽極結構，係利用一電子束蒸鍍技術沉積於一陽極基材之上，其包含：由一非晶相結構之矽上層薄膜與一石墨烯下層薄膜堆疊形成一矽/石墨烯單元層，且至少一該矽/石墨烯單元層亦相互堆疊於該陽極基材之上，而最上層的該非晶相結構之矽上層薄膜上另沉積一石墨烯薄膜。
- 如申請專利範圍第1項所示之該非晶相結構之矽/石墨烯單元層最佳為7層。
- 如申請專利範圍第1項所示之陽極基材為一銅箔。
- 如申請專利範圍第2項所示至少具一非晶相結構之矽/石墨烯單元層，其中各薄膜層之最佳厚度為50 nm。
- 如申請專利範圍第2項所示之多層膜複合材料陽極結構為7層複合結構，並以一石墨烯薄膜做為多層膜複合材料陽極結構之頂表面。
- 如申請專利範圍第5項所示之多層膜複合材料陽極結構以小於100 mAh/g之一電流密度進行測試，且該多層膜複合材料陽極結構之一電容量大於1000 mAh/g。
- 如申請專利範圍第6項所示之多層膜複合材料陽極結構之一第1充放電循環之庫倫效率大於80%，該多層膜複合材料陽極結構之第2充放電循環不可逆電容量小於20%，且經過 30個充放電循環，該矽/石墨烯多層膜複合材料陽極結構之放電電容量大於第1循環之65%。
- 一種電極結構之製備方法，其步驟包含：提供一電子束蒸鍍腔體；使該腔體之壓力維持在4~10 Pa；在150~250℃下，沈積一石墨烯膜；以及在150~250℃下，沈積一矽膜於該石墨烯膜上。
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| US14/314,895 US20150004494A1 (en) | 2013-06-26 | 2014-06-25 | Multilayer Si/Graphene Composite Anode Structure |
| CN201410298530.9A CN104253266B (zh) | 2013-06-26 | 2014-06-26 | 一种多层膜硅/石墨烯复合材料阳极结构 |
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| CN108666566B (zh) * | 2017-03-31 | 2021-08-31 | 华为技术有限公司 | 一种制备电极材料的方法、电极材料及电池 |
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| CN110197895A (zh) * | 2018-02-26 | 2019-09-03 | 华为技术有限公司 | 一种复合材料及其制备方法 |
| CN110197896A (zh) * | 2018-02-26 | 2019-09-03 | 华为技术有限公司 | 一种复合材料及其制备方法 |
| CN108807840A (zh) * | 2018-05-28 | 2018-11-13 | 云南大学 | 热处理工艺制备碳硅负极材料的方法 |
| CN108807883A (zh) * | 2018-05-28 | 2018-11-13 | 云南大学 | 硅碳薄膜负极材料及其制备方法 |
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| CN104253266B (zh) | 2017-05-03 |
| US20150004494A1 (en) | 2015-01-01 |
| TW201500568A (zh) | 2015-01-01 |
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