TW201402458A - 乾式硏磨微粒材料的方法 - Google Patents

乾式硏磨微粒材料的方法 Download PDF

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TW201402458A
TW201402458A TW102117000A TW102117000A TW201402458A TW 201402458 A TW201402458 A TW 201402458A TW 102117000 A TW102117000 A TW 102117000A TW 102117000 A TW102117000 A TW 102117000A TW 201402458 A TW201402458 A TW 201402458A
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graphene
metal
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In-Hwan Do
Michael Knox
Scott L Murray
Robert M Privette
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In-Hwan Do
Michael Knox
Scott L Murray
Robert M Privette
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Abstract

藉由介質球磨研磨製造之石墨烯具有極小粒子尺寸、相對較高之表面積及獨特縱橫比。其獨特地適合於藉由塗佈或混合其他微粒製造奈米複合物或塗層。可用該高表面積且相對較低縱橫比的石墨烯塗佈金屬或金屬氧化物或一起形成複合物。若所添加之微粒大於該石墨烯，則其經石墨烯塗佈，且若其具有大致相同的尺寸，則形成奈米複合物。該等奈米複合物適用於製造電極，尤其適用於電池及超級電容器應用。

Description

乾式研磨微粒材料的方法
敬啟者：在此特告知：吾人，即居住於密歇根州英厄姆縣東蘭辛市之韓國公民Inhwan Do、居住於密歇根州英厄姆縣東蘭辛市之美國公民Michael Knox、居住於密歇根州英厄姆縣東蘭辛市之美國公民Scott Murray及居住於密歇根州英厄姆縣東蘭辛市之美國公民Robert M.Privette發明了一種新且新穎的乾式研磨微粒材料的方法，下文是說明書。
本發明涉及具有金屬或金屬氧化物之石墨烯片晶奈米複合物及塗佈有金屬或金屬氧化物之奈米石墨烯片晶。該等經塗佈及複合之微粒適用作電極且適用於電應用。
石墨係由呈高度結構化片晶之許多層碳形成。此等片晶在與石墨上部結構分離時總稱為石墨烯。石墨烯具有引人關注之化學、物理及電特性。此等特性使石墨烯成為評價極高的產物。如微粒直徑、微粒寬度及表面積所界定之石墨烯之品質決定其工業效用。宜用金屬微粒塗佈或複合石墨烯以用於電應用。
總部設於密歇根州蘭辛(Lansing,Michigan)之Xg Sciences公司藉由高能量的以塑膠為介質的乾式機械研磨方法製造一種「C」級石墨烯。等級型號特性使其獨特地適合於用奈米微粒塗佈或與奈米微粒混合以 形成適用於電極之材料。
申請人知道，如顯示用矽處理石墨烯之濕式方法之2011年5月12日公開之美國專利公開案2011/0111303 A1。
此外，專利權人知道，闡述用於研磨微粒材料之濕式方法的在Peukert等人名下之EP2275385，其中研磨介質為釔穩定二氧化鋯。
藉由介質球磨研磨製造之石墨烯具有極小粒子尺寸及相對較高的表面積。其獨特地適合於藉由塗佈或混合其他微粒來製造奈米複合物或塗層。可用高表面積且相對較低縱橫比的石墨烯塗佈金屬或金屬氧化物或一起形成複合物。本文中，發明者咸信，本發明之材料具有獨特縱橫比。與矽混合之磨碎的石墨之縱橫比十分接近1，來自GO方法之石墨烯、外延生長石墨烯或來自夾層加熱方法之石墨烯均具有極高縱橫比。本發明之中等縱橫比石墨烯較佳塗佈1至4μm的微粒且較佳與甚至更小的奈米微粒混合。
基於縱橫比、粒子尺寸及/或表面積之拉曼光譜(Raman spectroscopy)，本發明提供獨特的石墨烯。
基於由拉曼光譜及量測峰高度計算之下表，產生下表。
天然石墨具有極高G/D比率。磨碎成非晶形粉末之石墨具有如下G/D比率，本發明之材料的G/D比率起始時較高且隨著材料之加工程度愈高愈接近於2。非晶形石墨亦具有至2000cm-1之G峰紅移。雖然本發明之材料可具有較小紅移，但根據數據之品質，很難確定。極高表面積及縱橫比證實其主要為石墨烯奈米片晶。
機械剝落石墨烯不同於磨碎的石墨，不同之處在於其維持強結晶sp2結構。因為石墨磨碎成非晶形，所以G與D拉曼譜線之比率接近於2，且G線由1560cm-1紅移至2000cm1。G峰稱為石墨烯峰。D峰稱為擾亂峰。石墨磨碎的程度愈高，G峰降低愈多且D峰增強愈多。
若所添加之微粒大於石墨烯，則其用石墨烯塗佈，且若其約有大致相同的尺寸，則形成奈米複合物。奈米複合物適用於製造電極，尤其適用於電池及電容器應用。
【發明詳述】
因此，在一個具體實例中，提供一種乾式研磨微粒材料的方法，，其中至少一種微粒材料為層狀材料，該方法係在非層狀材料存在下以獲得組成物，其中層狀材料剝落且其中非層狀材料與剝落之材料複合。
剝落之材料的粒子尺寸10μm×5nm厚或更小。另外，除控制研磨介質之硬度外，乾式研磨藉由控制研磨介質之表面能來控制。
在一個第二具體實例中，提供一種乾式研磨微粒材料的方法，其中至少一種微粒材料為層狀材料，該方法係在選自由i.陶瓷、ii.玻璃及iii.石英組成之群的微粒材料存在下以獲得組成物，其中層狀材料剝落且其中微粒材料經剝落之材料塗佈。
剝落之材料的粒子尺寸為500nm更小。另外，除控制研磨介質之硬度外，乾式研磨藉由控制研磨介質之表面能來控制。
在一個第四具體實例中，存在一種藉由第一具體實例獲得之複合產物及一種藉由第二具體實例獲得之經塗佈產物。
藉由本發明方法製造之石墨烯之縱橫比相對較窄但大於石 墨。就本發明而言，大於5且小於200之縱橫比較佳，且大於10且小於25之縱橫比更佳。
小(亦即厚度為1至5奈米且直徑為50至100奈米)、高表面積(大於500 BET)、中等縱橫比石墨烯具有對用小金屬或金屬氧化物微粒塗佈而言獨特之尺寸。
適用於本發明之金屬為類金屬矽及金屬錫、鐵、鎂、錳、鋁、鉛、金、銀、鈦、鉑、鈀、釕、銅、鎳、銠及任何以上金屬之混合物。
適用於本發明之塑膠研磨介質之按布氏硬度量表(Brinell Scale)之硬度在3至100之範圍內。塑膠研磨介質係選自基本上由以下組成之群：聚縮醛、聚丙烯酸酯(諸如甲基丙烯酸甲酯)、聚碳酸酯、聚苯乙烯、聚丙烯、聚乙烯、聚四氟乙烯、聚乙烯-醯亞胺、聚氯乙烯、聚胺-醯亞胺、酚醛樹脂及基於甲醛之熱固性樹脂及任何所指定塑膠之混合物。
適用於本發明之微粒金屬氧化物為選自以下之金屬氧化物：矽、錫、鐵、鎂、錳、鋁、鉛、金、銀、鈦、鉑、鈀、釕、銅、鎳、銠、鎢、鈷、鉬及任何上文所指定金屬氧化物之混合物，其中該等金屬及金屬氧化物粒子之尺寸為100μm或更小。粒子尺寸較佳為10μm或更小，且粒子尺寸最佳為5μm或更小。
金屬碳化物、金屬氮化物以及非層狀材料均適用於本發明。
適用於本發明之石墨烯之厚度較佳為5nm或更小。
圖1為Si/石墨烯電池效能圖(200-250m2/g，100分鐘加工時間)。
實施例1
將2g天然石墨及1g微米級Si(1至4μm)裝載至65ml不鏽鋼研磨容器中且在24g聚甲基丙烯酸甲酯球存在下進行研磨。聚甲基丙烯酸甲酯球由兩種不同尺寸組成，亦即直徑為1/4吋及3/8吋。高能量研磨機在<1500rpm下運轉且其夾持速度為每分鐘1060個循環。聚甲基丙烯 酸甲酯球可用聚碳酸酯、聚苯乙烯、聚丙烯、聚乙烯、聚四氟乙烯、聚乙烯亞胺、聚氯乙烯及聚醯胺亞胺替換以控制固定研磨時間之研磨效率、石墨烯尺寸、孔隙分佈及表面積、Si與石墨烯表面之間的接觸品質。所製造之Si/石墨烯複合物之表面積可視研磨時間(60至500分鐘)及Si/石墨烯組成及球材料之類型而定，在100m2/g至700m2/g不等。
對Si/石墨烯(200至250m2/g，100分鐘加工)樣品作為鋰離子電池之陽極的電池效能之結果繪製在下文中。Si/石墨烯在100mA/g下經35個循環顯示高電容量(>800mAh/g，電極負載)，由此支持以低成本、簡單、節省時間、環保、可撓性的方式來製造用於能量應用之高效能之基於石墨烯的複合材料。一些容量波動係歸因於溫度變化。
實施例2
將2g天然石墨及1g奈米級金屬氧化物(Fe2O3、NiO、CoO3、MnO3)裝載於65ml不鏽鋼研磨容器中且在24g聚甲基丙烯酸甲酯球存在下研磨。產物可用作鋰電池之陽極材料及超級電容器之電極。

Claims (41)

  1. 一種乾式研磨微粒材料之方法，其中至少一種該等微粒材料為層狀材料，該方法係在非層狀材料存在下進行以獲得組成物，其中該層狀材料剝落且其中該非層狀材料與該剝落之材料複合，該剝落之材料的粒子尺寸為10μm×5nm厚或更小，且其中除控制該研磨介質之硬度外，該乾式研磨係藉由控制該研磨介質之表面能來控制。
  2. 如申請專利範圍第1項之方法，其中該非層狀材料係選自基本上由以下組成之群：i.微粒金屬，及ii.微粒金屬氧化物。
  3. 如申請專利範圍第1項之方法，其中該層狀材料為石墨。
  4. 如申請專利範圍第1項之方法，其中該研磨介質之表面能基本上等於該層狀材料之表面能。
  5. 如申請專利範圍第1項之方法，其中該研磨介質之按布氏硬度量表(Brinell Scale)計之硬度在3至100之範圍內。
  6. 如申請專利範圍第1項之方法，其中該剝落之材料之縱橫比大於約25。
  7. 如申請專利範圍第1項之方法，其中該剝落之材料之縱橫比為5至200。
  8. 如申請專利範圍第1項之方法，其中該剝落之材料之尺寸在50nm至10μm之範圍內。
  9. 如申請專利範圍第1項之方法，其中該剝落之材料之厚度為1nm至5nm。
  10. 如申請專利範圍第1項之方法，其中該研磨介質為塑膠材料。
  11. 如申請專利範圍第10項之方法，其中該塑膠係選自基本上由以下組成之群：i.聚甲基丙烯酸甲酯， ii.聚碳酸酯，iii.聚苯乙烯，iv.聚丙烯，v.聚乙烯，vi.聚四氟乙烯，vii.聚乙烯亞胺，viii.聚氯乙烯，ix.聚胺-醯亞胺，及x. i至ix中任一者之合金。
  12. 如申請專利範圍第2項之方法，其中該等微粒金屬係選自基本上由以下組成之群：i.矽，ii.錫，iii.鐵，iv.鎂，v.錳，vi.鋁，vii.鉛，viii.金，ix.銀，x.鈦，xi.鉑，xii.鈀，xiii.釕，xiv.銅， xv.鎳，xvi.銠，及xvii. i至xvi中任一者之合金。
  13. 如申請專利範圍第2項之方法，其中該等微粒金屬氧化物係選自基本上由以下者之氧化物組成之群：i.矽，ii.錫，iii.鐵，iv.鎂，v.錳，vi.鋁，vii.鉛，viii.金，ix.銀，x.鈦，xi.鉑，xii.鈀，xiii.釕，xiv.銅，xv.鎳，xvi.銠，及xvii. i至xvi中任一者之合金。
  14. 如申請專利範圍第1項之方法，其中該微粒非層狀材料之尺寸小於100μm。
  15. 如申請專利範圍第1項之方法，其中該等微粒為金屬碳化物。
  16. 如申請專利範圍第1項之方法，其中該等微粒材料為金屬氮化物。
  17. 一種產物，其係由如申請專利範圍第1項之方法製造。
  18. 一種電極，其係由如申請專利範圍第17項之產物製造。
  19. 一種催化劑，其係由如申請專利範圍第17項之產物製造。
  20. 一種塗層，其係由如申請專利範圍第17項之產物製造。
  21. 一種電子組件，其係由如申請專利範圍第17項之產物製造。
  22. 一種導熱組件，其係由如申請專利範圍第17項之產物製造。
  23. 一種乾式研磨微粒材料之方法，其中至少一種該等微粒材料為層狀材料，該方法係在選自由i.陶瓷、ii.玻璃及iii.石英組成之群的微粒材料存在下進行以獲得組成物，其中該層狀材料剝落且其中該微粒材料經該剝落之材料塗佈，該剝落之材料的粒子尺寸為500nm或更小，且其中除控制該研磨介質之硬度外，該乾式研磨係藉由控制該研磨介質之表面能來控制。
  24. 一種乾式研磨微粒材料之方法，其中至少一種該等微粒材料為層狀材料，該方法係在選自由i.陶瓷、ii.玻璃及iii.石英組成之群的微粒材料存在下進行以獲得組成物，其中該層狀材料剝落且其中該微粒材料經該剝落之材料塗佈，該剝落之材料的粒子尺寸為10μm或更大且其中除控制該研磨介質之硬度外，該乾式研磨係藉由控制該研磨介質之表面能來控制。
  25. 一種包含與石墨烯複合之微粒的物質之組成物，其中該等粒子係選自基本上由金屬粒子及金屬氧化物粒子組成之群，其中該等金屬及金屬氧化物粒子之尺寸為100μm或更小。
  26. 如申請專利範圍第25項之物質之組成物，其中該等金屬及金屬氧化物粒子之尺寸為100μm或更小。
  27. 如申請專利範圍第25項之物質之組成物，其中該等金屬及金屬氧化物 粒子之尺寸為10μm或更小。
  28. 如申請專利範圍第25項之物質之組成物，其中該等金屬及金屬氧化物粒子之尺寸為1μm或更小。
  29. 如申請專利範圍第25項之物質之組成物，其中該石墨烯之厚度小於5nm。
  30. 如申請專利範圍第25項之物質之組成物，其中該石墨烯為單層厚度。
  31. 如申請專利範圍第25項之物質之組成物，其中該石墨烯之氧含量為10原子量%或更小。
  32. 如申請專利範圍第25項之物質之組成物，其中該金屬係選自基本上由鐵、鎂、鈷、鉬及鉛組成之群。
  33. 如申請專利範圍第25項之物質之組成物，其中該金屬氧化物係選自基本上由氧化鐵、氧化鎂、氧化鈷、氧化鉬及氧化鉛組成之氧化物的群。
  34. 如申請專利範圍第25項之物質之組成物，其中該石墨烯粒子之尺寸小於5μm。
  35. 如申請專利範圍第25項之物質之組成物，其中該石墨烯之表面積大於約300m2/g BET。
  36. 如申請專利範圍第25項之物質之組成物，其中該等金屬粒子大於與其複合之石墨烯。
  37. 如申請專利範圍第25項之物質之組成物，其中該金屬粒子之尺寸與其所組合之石墨烯基本上相同。
  38. 如申請專利範圍第25項之物質之組成物，其為奈米複合物。
  39. 一種電極，其係由如申請專利範圍第25項之組成物製造。
  40. 一種電池，其包含至少一個如申請專利範圍第39項之電極。
  41. 一種電容器，其包含如申請專利範圍第39項之電極。
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US20160256873A1 (en) 2016-09-08
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CN104582855A (zh) 2015-04-29
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