石墨烯-金屬氧化物復合物鋰離子電池負極

1、© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 5136 X iaolin L i , W en Q i , D onghai M ei , M aria L. S ushko , I lhan A ksay , a nd J un L iu * Functionalized Graphene Sheets as Molecular Templates for Controlled Nucleation and Self-Assembly of Metal Oxide-Graphene NanocompositesD r.

2、X. L. Li, Dr. D. Mei, Dr. M. L. Sushko, Dr. J. LiuPaci c Northwest National LaboratoryRichland, WA 99352, USAE -mail: J un.L W . QiDepartment of Materials Science and EngineeringTianjin UniversityTianjin 300072, ChinaD r. I. AksayDepartment of Chemical EngineeringPrinceton UniversityPrince

3、ton, NJ 08544, USAD OI: 10.1002/adma.201202189 S ince its discovery, 1 graphene has been widely studied forelectronics, 14 energy, 512 catalysis, 1316 and sensing applica-tions. 17 , 18 Functionalized graphene sheets (FGS (or chemicallyderived graphene sheets, 1921 along with other graphene mate-ria

4、ls including pristine graphene and graphene oxide (GO, 4 , 22 , have been explored extensively because of their good electrical conductivity and tunable functional groups that are either retained after the chemical/physical reduction of graphene oxide or introduced during the exfoliation of graphite

5、/expand-able graphite. 1925 Recently, FGS-metal oxide composites suchas FGS-SnO 2, FGS-TiO 2, FGS-Co 3O 4 , GO-mesoporous SiO 2, etc. have been prepared either by direct deposition or surfactant-mediated synthesis. 6 , 7 , 1012 , 15 , 26 G raphene not only serves as a key component of nano-composite

6、 materials, it also is an ideal template to control the structures and properties of nanocomposite materials because of their good electronic and mechanical properties, two-dimen-sional nature of the structure and tunable surface chemistry. There are quite a few reports on the interaction between me

7、taloxides and graphene. 2730 Recently, it was reported that defectsor functional groups on graphene could be the binding/reac-tive sites for Pt, sulfur, Li 2O 2, and indium tin oxide (ITO/Pt in lithium batteries and fuel cell applications. 8 , 9 , 13 , 31 However,considering the wide interests in me

8、tal oxides (e.g., SnO 2, TiO 2, ZrO 2, etc. and their composites for a broad range of applica-tions, 6 , 7 , 10 , 11 a more systematic study on how the metal oxides interact with the graphene surface, and what kind of crystalline phases and new structures can be produced by controlling the surface c

9、hemistry, is desired.I n this paper, we combined theoretical and experimental study of the nucleation and self-assembly process in FGS-metal oxide systems (FGS-SnO 2, FGS-TiO 2 , and FGS-ZrO 2. The aim of the paper is two-fold: i to provide a general understandingof how graphene surface controls nuc

10、leation of metal oxides;and ii to explore novel synthesis methods to control nucleation during self-assembly processes. For the rst objective, we syn-thesized FGS-SnO 2 and FGS-TiO 2 and demonstrated that the functional groups on FGS surface determine the nucleation energy, and thus control the nucl

11、eation sites and nucleation density. We also demonstrated that FGS can tune the nucleation energies for different crystalline structures and thereby control the crystalline phases. For the second objective, we use FGS as a molecular template to direct the self-assembly of surfactant micellar structu

12、res and produce ordered, mesoporous arrays of crystalline metal oxide composites (FGS-mesoporous TiO 2and FGS-mesoporous ZrO 2 .T o reveal the role of functional groups on graphene sheets, templated nucleation and growth of metal oxides (e.g. SnO 2 is studied on FGS with different amounts of defects

13、/functional groups. The relative content of functional groups associatedwith the defects is indicated by the C/O ratio. 4 A smaller C/Oratio re ects a higher number of functional groups on FGS. Therefore, the number of functional groups increases for FGS with a C/O ratio of 100 (FGS-100, to, 14 (FGS

14、-14, to graphene oxides (GO, with a C/O ratio of 3. 4 , 22 As a result, the nuclea-tion density of SnO 2 increases in the same order (F igure 1 . The transmission electron microscopy (TEM image in Figure 1 a reveals a low SnO 2 density on FGS-100 with only parts of the surface covered. As the number

15、 of defect sites increase, more SnO 2 particles nucleate as shown for FGS-14 in Figure 1 b . The GO-SnO 2 composite further corroborated this trend with the GO surface almost fully covered with a uniform layer of SnO 2 (Figure 1 c . High-resolution TEM images (Figure 1 d & 1 e also clearly showe

16、d a higher SnO 2 density on GO than on FGS-14. T heoretical simulation con rms that the functional groupson FGS play a role of nucleation sites for metal oxides. 3234 Weshow the result of the interaction between a carboxylic group on the graphene surface and the metal oxide to demonstrate that the n

17、ucleation energy of metal oxides can be changed sig-ni cantly even with an individual functional group on the sur-face. Preliminary studies show that different oxygen-containing groups and different functionalization degree (or amounts of functional groups have similar effects, although the exact na

18、ture of different functional groups and how it affects the nucleation need to be carefully studied in the future. Figure 1 f shows the density functional theory (DFT calculation of the nucleation energy for (SnO 2 n clusters on FGS with a carboxyl group linking to an embedded 5-8-5 defect (other fun

19、ctional groups like hydroxyl groups show similar trends, data not shown and on pristine graphene (perfect graphene without defects/functional groups. The nucleation of SnO 2 on FGS isAdv. Mater. 2012, 24, 51365141 5137 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim energetically favorabl

20、e with the nucleation energy decreasing by approximately 1.5 eV as the cluster size, n, increases from 1 to 6 (Figure 1 f and Supporting information, Figure S1. On the other hand, on pristine graphene, there is a + 2.0 eV energy penalty for (SnO 2 nclusters to grow from 1 to 6 (Figure 1 f and Figure

21、 S2. The metal oxides prefer to nucleate and grow on the FGS surface because of the low nucleation energy at the functional groups sites. It explains why the nucleation density increases with the increase of the density of functional groups.O ther factors such as the edge and side of graphene also p

22、lay important role for the nucleation of metal oxides, but our studies use FGS with a lateral dimension of several microm-eters. What happens on the edge or the side of FGS is not studied.T he effect of FGS on nucleation is also observed on TiO 2 ( F igure 2 a ,b. For both anatase and rutile phases,

23、 the nuclea-tion processes on pristine graphene (Figure 2 a & Figure S3 are energetically unfavorable ( + 0.47 eV energy increase for rutile-like TiO 2 and + 2.79 eV energy increase for anatase-like TiO 2 as the cluster size increases from 3 to 24, but the formation of TiO 2 on FGS with a carbox

24、yl group linking to an embedded 5-8-5 defect (Figures 2 b & Figure S4 is thermodynamically favorable (4 eV energy drop. As reference calculation, precipi-tation of bulk anatase and rutile TiO 2 is energetically favored in solution (Figure 2 c .I n addition to controlling the nucleation sites, FG

25、S can also alter the stability of a speci c crystalline phase. TiO 2 obtained in solution without FGS has an anatase structure with small nano-particles aggregated into secondary spherical particles of 50 to 200 nm in size (Figure 2 d . Surprisingly, rutile-structured TiO 2 was formed with the addit

26、ion of FGS under the same experi-mental conditions. Figure 2 e shows that the composite with rutile TiO 2 forms large, elongated, rod-shaped aggregates onFGS. The change of crystalline phase with and without FGS is also con rmed by X-ray diffraction patterns (Figure 2 f .D FT simulation corroborated

27、 the FGS-induced polymorph selection. 3234 The interfacial interaction between FGS andmetal oxide nanoparticles is believed to control the nucleation energy for different phases of TiO 2 leading to different crys-tallines.The change in nucleation energies for anatase- and rutile-phase TiO 2 without

28、graphene support and on FGS is quite different. In bulk phase, anatase TiO 2 is more stable than rutile-structured TiO 2 by 0.43 eV without graphene support (Figure 2 c & Figure S5. On FGS (e.g., a carboxyl group linking to an embedded 5-8-5 defect, the formation of rutile TiO 2is energetically

29、more favorable by 0.3 eV than forming ana-tase TiO 2 (Figure2 b & Figure S4, which is consistent with our experimental observations.R esults discussed above demonstrate that the nucleation on FGS and thereby the crystalline structure obtained, are deter-mined by the functional groups on FGS surf

30、ace, but the ability to increase the number of functional groups on native FGS is limited without signi cantly oxidizing the FGS. Another way to functionalize the graphene surface is to use bifunctional sur-factants. 10 , 11 , 26 The use of surfactants can signi cantly lower thenucleation energy and

31、 facilitate the nucleation of metal oxides on FGS. F igure 3 a shows the calculation of the nucleation of TiO 2 on FGS with a hydroxyl terminated ligand (CCH 2C H 2C H 2O H linking to the 5-8-5 defect. Most likely due to the exibility and the spatial freedom provided by the ligand, the nucleation of

32、 anatase is favorable (Figure S6 and is similar to the solution precipitation without FGS (Figures 2 c and Figure S5.T he above calculation shows that ligands and surfactants thus can be used to induce dense nucleation on FGS. 10 , 11 More F igure 1. E xperimental observation and theoretical simulat

33、ion of the defect-directed nucleation of SnO 2 on FGS. a SnO 2 nanoparticles on FGS (C/O= 100. b SnO 2 nanoparticles on FGS (C/O = 14. c SnO 2 nanoparticles on GO. d,e High-resolution TEM images of SnO 2nanoparticles on FGS (C/O = 14 and GO. f DFT calculation of SnO 2 nucleation (free energy as a fu

34、nction of cluster size on pristine graphene (black curve and on FGS with a carboxylic group linking to the defect site (red curve.Adv. Mater. 2012, 24, 51365141 5138 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim via hydrothermal reactions. 38, 39 However, there are two limi-tations for

35、using these templates. Firstly, the hard substrate (graphite and silicon etc template approach only produces sup-ported lms and structures, but not bulk, functional composite materials. Secondly, it is dif cult to obtain ordered crystallineinterestingly, previous studies showed that surfactants can

36、form ordered hemi-micelle structures on graphite template andother surfaces along speci c crystallographic directions 3537 (Figure 3 b . Graphite and other substrates thus have been used as templates for growing ordered mesophase silicate materials F igure 3. S ynthesis of ordered crystalline mesopo

37、rous TiO 2 on FGS. a DFT calculation of TiO 2 nucleation on FGS with an OH-terminated ligand.b Graphene template with the formation of ordered surfactant micelle structures. c Schematic illustration showing the structural evolution of the micelle-metal oxide-FGS composites upon drying. d TEM image o

38、f ordered, amorphous mesoporous TiO 2 on FGS after self-assembly. e TEM image showing possible hemi-micelles at the FGS interfaces. f High-resolution TEM image of the crystalline mesoporous TiO 2 on FGS.F igure 2. E xperimental observation and theoretical simulation of the controlled nucleation and

39、crystal growth of TiO 2 on pristine graphene, on FGS, and in vacuum. a DFT calculation of TiO 2 nucleation on pristine graphene (free energy as a function of cluster size. b DFT calculation of TiO 2 nucleation on FGS with a carboxylic group linking to the defect site. c DFT calculation of the free e

40、nergy of TiO 2 clusters as a function of sizes without graphene. d TEM image of anatase TiO 2 produced in a solution. e TEM image of rutile TiO 2 particles on FGS. f XRD patterns of anatase TiO 2pro-duced in solution and rutile TiO 2on FGS. Adv. Mater. 2012, 24, 51365141 5139 © 2012 WILEY-VCH V

41、erlag GmbH & Co. KGaA, Weinheim are maintained after annealing at 400 ° C in argon. High-resolu-tion TEM analysis reveals that the mesopores, 610 nm in diam-eter, are surrounded by 4 nm walls made of small TiO 2crystals of 4 nm × 7 nm in size (Figure 3 f & Figure S8. The selection

42、area electron diffraction (image not shown shows a typical ana-tase polycrystalline pattern. According to the results of thermal gravimetric analysis (TGA, more than 97 wt% of the surfactant is removed after annealing (Figure S9. BrunauerEmmett - T eller (BET and Barrett -J oyner - H alenda (BJH mea

43、surements (Figure S10 show a surface area of 150 m 2 /g and a pore size of 6.5 nm, which is consistent with the result of our TEM analysis.T o further demonstrate the surfactant effect on the synthesis of FGS-mesoporous TiO 2 nanocomposites, we performed con-trol experiments and synthesized FGS-TiO

44、2nanocomposites under the same conditions without using surfactants. As shown in Figure S11, TiO 2 nanoparticles are obtained on FGS surfaces instead of the ordered mesoporous structure.I t must be noted that since ordered micellar structures are only formed on crystalline hydrophobic/hydrophilic su

45、r-faces, 35 , 36 GO, which has extremely disordered graphitic plane, 4 , 22 leads to disordered micellar structures and the depo-sition of TiO 2 nanocrystallites instead of ordered mesoporous metal oxides (Figure S12. In contrast, FGS retains the ordered crystalline structure in its graphitic plane

46、and hence supports the formation of ordered mesoporous materials. These results con rm the templating effect of the graphene surfaces for the ordered micellar structures.T he presented self-assembly approach is a general method and can be applicable to other metal oxides, such as, for example, FGS-m

47、esoporous ZrO 2 composites. The composite obtained after drying is amorphous. Then, after annealing at 400 ° C in argon, the surfactants were removed, and crystalline mes-oporous composites formed, as indicated by the TEM analysis ( F igure 4 a & 4 b , XRD (Figure S13, and TGA (Figure S14.

48、Themesoporous metal oxides because the ordered surfactant struc-tures are hard to maintain during crystal growth. Our study also suggested that only nanocrystalline lms and layered structures can be obtained from the traditional hydrothermal reaction that is widely used in the literature.I n order t

49、o stablize the ordered micellar structure and control the crystal growth, we developed a graphene templated rapid evaporation and self-assembly method (GTES to prepare ordered crystalline metal oxides on FGS. The GTES process, inspired bythe rapid evaporation-induced self-assembly method, 40 is illu

50、s-trated in Figure 3 c . Firstly, FGS is dispersed in a pre-preparedsolution of surfactants, acid, and metal oxide precursor. The surfactant molecules dispersed in the solution are likely to beabsorbed on FGS surface as hemi-micelles (stage I. 35 , 36 Duringthe drying process (stage II, the micelle

51、and ceramic precursor concentration around FGS increase. The ceramic precursors gradually hydrolyze to form amorphous metal oxides. Upon fur-ther drying (stage III, the amorphous metal oxides and the sur-factant micelles condense on FGS and self-assemble into ordered nanostructures. After the self-a

52、ssembled structures are formed, the materials can be annealed to achieve desired nanocrystallites. Because of the physical con nement provided by the condensed, amorphous metal oxide matrix, the ordered structures are stable and resistant to deformation during crystallization. T he validity of this

53、approach was con rmed experimentally. TEM and X-ray diffraction (XRD characterizations show that after drying FGS-TiO 2 mesoporous composite is completely amorphous with pores of 6 to 10 nm (Figure 3 d & Figure S7. Figure 3 e shows a high-resolution TEM image of the interface between FGS and the

54、 mesophase TiO 2. Despite the poor contrast because of the amorphous nature of TiO 2, the possible hemi-micelle structures are visible close to FGS surface. It is dif cult to image mesoporous metal oxide on single-layer FGS, therefore only few-layer FGS are shown here. The ordered mesostructures F i

55、gure 4. O rdered mesostructured ZrO 2 on FGS. a FGS-mesoporous ZrO 2 composite after self-assembly. b Crystalline mesoporous ZrO 2 on FGSafter annealing at 400 ° C in argon atmosphere. c High-resolution TEM image of Figure 4b.Adv. Mater. 2012, 24, 51365141 5140 © 2012 WILEY-VCH Verlag GmbH

56、 & Co. KGaA, Weinheim 16 h. The product was collected by centrifugation, washed with water,and dried in vacuum. For the synthesis of the GO-SnO 2, GO ( 71.3 mg was used, replacing the FGS. The other conditions were the same as the synthesis of FGS-SnO 2. T he FGS-TiO 2 nanocomposite was synthesi

57、zed using hydrothermal methods with titanium isopropoxide (Ti(Oipr 4 as the precursor. FGS-14 ( 17 mg was dispersed in H 2S O 4 (1 M , 40 mL by 2 h sonication. After Ti(Oipr 4( 0.71 g was added to the suspension, the mixture then was transferred to a polytetra uoroethylene (Te on-lined autoclave and

58、 heated to 100 ° C . After cooling to room temperature, the product was collected by centrifugation, washed with water, and dried at 80 °C . A control experiment of TiO 2 synthesis was conducted at similar conditions without adding FGS.T he mesoporous metal oxides on FGS were synthesized using an evaporation-induced self-assembly approach. For FGS-mesoporous TiO 2, Ti(Oipr 4( 1.082 g was added into an ethanol solution (3 g of P123 ( 0.2 g. Then, while stirring, concentrated HCl (0.592 mL was added to the solution. FGS-14 ( 10 mg was added to the solution while stirring