Graphene-Based Composite Anodes for Lithium-Ion Batteries

  • Nathalie Lavoie
  • Fabrice M. Courtel
  • Patrick R. L. Malenfant
  • Yaser Abu-Lebdeh
Chapter
Part of the Nanostructure Science and Technology book series (NST)

Abstract

Graphene has emerged as a novel, highly promising material with exceptional properties and potential application in a wide range of technologies. As an anode material for lithium-ion batteries, it was shown that it cannot be used in the pure form due to its large irreversible capacity but as part of a composite with other active materials. Transition metal oxides, silicon, and tin have been explored as active anode materials to replace graphite because of their high theoretical capacities. However, these materials have large volume changes during cycling that leads to the failure of the batteries. To resolve this problem, additives have been added to these materials to mitigate this volume change. In recent years, graphene has been employed as an encapsulating agent for these materials. In this chapter, an overview of the work exploring composites made of graphene as a novel support for nanoscale materials that react with lithium and provide high capacities will be presented.

6.1 Introduction

The world is moving toward low-carbon “clean energy,” driven by increasing concern over climate change and energy security. New technologies are required to address clean energy generation, distribution, storage, and system management. Implementation of the smart grid, renewable integration, and sustainable transportation will require innovation across many scientific disciplines. Energy storage, and specifically electrochemical energy storage, will play an integral role in the introduction of electric vehicles and the stabilization of the electrical power grid that will increasingly include intermittent renewable energy sources. Many technical challenges remain with regard to lithium-ion battery technology such as energy density, cost, reliability, and cycle life. One approach to address energy density is the use of composite anodes capable of reacting with lithium and thus providing two- to threefold enhancements in capacity compared to graphite. This chapter will focus on recent work exploring the use of graphene as a novel support for nanoscale materials that react with lithium and provide high capacities.

In 2010, the Noble prize in physics was awarded to Andre Geim and Konstantin Novoselov for their groundbreaking work on graphene [1]. Graphene is the name used to describe a single 2D sheet of sp2-hybridized carbon [2]. Stacks of graphene in 3D will provide graphite, whereas the 2D rolled form provides nanotubes; it can also be wrapped up into buckyballs (0D) (see Fig. 6.1).
Fig. 6.1

Forms of carbon [3]

Graphite has very impressive electrical (~104 S cm−1) and thermal (~3,000 W mK−1) conductivity values [4, 5, 6, 7, 8, 9] and a good lithium-ion diffusion coefficient (10−7 to 10−10 cm2 s−1 [10, 11, 12]), which makes it a potentially excellent material for negative electrodes in lithium-ion batteries. Graphene is equally impressive in terms of mechanical integrity. Furthermore, stacked sheets of graphene derived from exfoliated graphite provide a modular approach to exploring lithium storage in layered carbon as well as layered carbon/metal nanocomposites (see Fig. 6.2). For example, composite graphene electrodes can be made with nanometals or nanometal oxides (0D, 1D, 2D) capable of reacting with lithium while dispersed between the graphene sheets, thus providing a novel route to significantly enhance gravimetric and volumetric capacities.
Fig. 6.2

Graphene-metal/oxide nanocomposite electrodes

Thin stacks of graphene sheets, often referred to as graphene platelets, can be prepared using scalable processes starting from abundantly available graphite. Alternatively, many avenues can be pursued in order to oxidize and exfoliate graphite to provide graphene oxide (GO) [4, 5, 6, 7, 8, 9]. From there, the material can be processed in different ways to obtain graphene paper, or graphene sheets (see Fig. 6.3), that can be used to prepare graphene/metal nanocomposites. With high electrical conductivity (~10x S cm−1 [15]) and good mechanical properties, graphene paper will provide a layered carbon electrode material that may not require the need for binders or other additives. This will maximize the content of active material, eliminate components from the formulation, simplify the fabrication process, and reduce the cost of the final product. With a more open structure, the lithium-ion mobility may also be enhanced versus graphite, yet higher surface areas are prone to high irreversible capacities, and this issue must be addressed for practical devices to emerge [16]. While multi-walled nanotubes/single-walled nanotubes (MWNTs/SWNTs) have provided encouraging results as an alternative to graphite in lithium-ion batteries, there are many challenges that limit their use in commercial processes that need to be addressed [17, 18]. In particular, a consistent supply of adequate scale and purity of SWNTs (metal content, tube diameter, tube chirality) must be provided, thus making their implementation, at this juncture, prohibitively expensive. In contrast, the established large-scale supply of graphite coupled with scalable processing methods toward graphene makes the graphene paper approach conceivable, yet the economics still need to be demonstrated. To date, a limited number of results have been published using graphene as the active anode material, and several reports have been published on graphene/metal or graphene/metal oxide nanocomposites. This chapter will review progress in both areas.
Fig. 6.3

Graphene paper (a) (Reprinted with permission from [13]. Copyright (2009) American Chemical Society) and graphene single sheet (b) (Reprinted from [14]. Copyright (2011), with permission from Elsevier)

6.2 Graphene Anodes

Carbon-based anodes have been studied extensively, and great progress has been made in understanding lithium intercalation mechanisms since the pioneering work of Dahn [19]. Several reviews have examined work on ordered and disordered carbon-based anodes in lithium batteries; hence, this area will not be discussed here [20, 21]. The following discussion will focus on graphene-based anodes in which graphene is used as the active material. In the following examples, graphene is either isolated from exfoliated graphite, from reduced GO (RGO) or via unzipping carbon nanotubes to provide graphene nanoribbons (GNRs).

Guo et al. prepared graphene from artificial graphite by oxidation, rapid expansion, and ultrasonic treatment. They tested the graphene sample in half-cells and obtained an irreversible capacity of approximately 1,250 mAh g−1 for the first cycle and 672 mAh g−1 of reversible capacity up to 30 cycles [22].

Figure 6.4 shows the charge-discharge curves for the three first cycles. In the first cycle, the graphene materials have a plateau at 0.7 V that is due to the formation of the solid electrolyte interface (SEI) which is a layer that forms on the surface of the electrode due to the electrolyte decomposition. The formation of the SEI contributes to the large irreversible capacity.
Fig. 6.4

Three first charge–discharge curves for graphene nanosheets (Reprinted from [22]. Copyright (2011), with permission from Elsevier)

With an inherently high surface area, graphene paper has been shown to be prone to high irreversible lithium insertion upon the first cycle. As shown by Wang et al., graphene paper made from reduced GO dispersions can yield a discharge capacity of 680 mAh g−1, yet upon the second cycle, the capacity drops significantly to 84 mAh g−1 [23]. While annealing the graphene paper at 800°C under N2 for 1 h further removes oxygen functional groups and provides 301 mAh g−1 of reversible discharge capacities after 10 cycles. This performance is still significantly lower than that of commercial graphite.

Similar observations have been made by Abouimrane et al. in which non-annealed graphene paper, prepared by preparing GO using a modified Hummers method followed by hydrazine reduction, was used to evaluate its performance in a half-cell [24]. As shown in Fig. 6.5, it exhibited an initial reversible capacity of 84 mAh g−1 (at 50 mA g−1), whereas an anode made of graphene powder using polyvinylidene fluoride (PVDF) as a binder had a reversible capacity of 288 mAh g−1. Various current rates were explored with the binder-free graphene paper devices, in which case initial reversible capacities of 214, 151, and 84 mAh g−1 were obtained at 10, 20, and 50 mA g−1, respectively. After 70 cycles, the capacities were approximately 190, 150, and 55 mA g−1. A large part of the capacity loss is due to the formation of the SEI that is more prominent in graphene than in graphite due to the higher surface area.
Fig. 6.5

Cycle performance of a Li/graphene paper half-cell at three different current densities. Charge and discharge capacities under each current density are represented by open and solid shapes, respectively (Reprinted from [24]. Copyright (2011) with permission from American Chemical Society)

Recent work by Bhardwaj et al. explored the use of GNRs derived from MWNTs in which the tubes are unzipped to yield narrow strips of GNRs [25]. The GNRs exhibit higher first charge and discharge capacities compared to MWNTs. However, high irreversible charge capacity is reported (1,400 mAh g−1) with a discharge capacity of 820 mAh g−1 for the oxidized graphene nanoribbons (ox-GNRs). Only 14 cycles were shown, and a capacity loss of 3% per cycle indicates that these cells degrade rapidly and are not likely to provide extended cycling capability. The ox-GNR can be annealed (900°C; H2/Ar; 15 min) to give GNRs. These ribbons yielded cells with an irreversible capacity of approximately 775 mAh g−1 and a reversible capacity of approximately 200 mAh g−1 after 14 cycles, still much lower than graphite.

Yoo et al. took an interesting approach at investigating graphene as an anode active material for lithium storage in that fullerenes and carbon nanotubes (CNTs) were used as spacers to increase the distance between sheets to enhance lithium-ion storage capacity [26]. Graphene nanosheets used in these experiments were made of 10–20 layers (3–7 nm thick). Voltage curves clearly indicate that lithium insertion into the graphene/CNT or graphene/fullerene devices is different. Furthermore, reversible capacities of 540, 730, and 784 mAh g−1 are obtained for graphene, graphene/CNTs, and graphene/fullerene, respectively. These are high values, but as observed previously, the rate at which these devices degrade is significant, and data is only shown for 20 cycles. It is unclear at this juncture, if the increased d-spacing obtained with CNTs and fullerenes can yield enhanced lithium accommodation as observed with polyacenic semiconductors (PAS) since Yoo’s results are very similar to what was observed with GNRs [27].

High capacities were also observed for graphene sheets prepared by oxidation of graphite, followed by rapid thermal expansion [28]. After 40 cycles, at current densities from 100 to 1,000 mA g−1, the reversible capacity was maintained at 848 mAh g−1 as shown in Fig. 6.6. In addition, this graphene also provided good rate capability with a reversible specific capacity that remained at 718 mAh g−1 at high current density of 500 mA g−1. The influence of the graphene oxide reduction temperature was studied by Wan et al. [29]. The irreversible capacities of the graphene nanosheet in the first cycle decrease with increasing annealing temperatures (2,137 mAh g−1 for 300°C, 1,523 mAh g−1 for 600°C, and 1,167 mAh g−1 for 800°C). This is potentially due to the larger number of lithium insertion active sites in larger surface area graphene obtained with lower annealing temperature. After 100 cycles, the capacity of the three cells is much closer, varying from 478 mAh g−1 for the graphene prepared at 300°C to approximately 350 mAh g−1 for the sample prepared at 800°C.
Fig. 6.6

Cycle performance of graphene sheets at current densities from 100 to 1,000 mAg−1 (Reprinted from [28]. Copyright (2010), with permission from Elsevier)

It is important to note that these high capacities are at odds with several reports that suggest that the capacity of anodes where graphene is the active material is typically <200 mAh g−1. Graphene characteristics are highly dependent on the processing method, resulting defect density and surface area, among other critical properties such as electrical conductivity that will strongly impact the capacity for lithium-ion storage. At this juncture, there is much to be learned about the mechanism of lithium-ion storage in graphene, and this should be a fruitful area for further research (Table 6.1).
Table 6.1

Graphene employed as anode materials in lithium-ion batteries

Graphene source

Irr. cap. (mAh g−1)

Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/ Li+)

Ref.

Hydrazine reduction of GO

680

84

50

50

3.0–0

[23]

Hydrazine reduction of GO

310

50

70

50

3.0–0

[24]

Unzipping of MWCNTs for ?ox-GNR? followed by H2 reduction for GNR

ox-GNR 1400

ox-GNR 500

14

0.1 mA cm−2 (~C/10)

3.5–0

[25]

GNR

GNR

[14]

775

200

Reduction of OGS with hydrazine

 

290

20

50

3.5–0.01

[26]

GO exfoliated at 1,050°C for several minutes

2,035

848

40

100

3.5–0.01

[28]

GO rapid heat at 1,050°C and ultrasonic agitation at 400 W for 4 h

1,233

502

30

0.2 mA cm−2

3.5–0

[22]

Thermal reduction of GO under argon atmosphere

2,137

478

100

200

3.0–0.01

[29]

Sonication of natural graphite, ammonium peroxydisulfate, and hydrogen peroxide, followed by microwave irradiation

580

420

50

0.1 C

3.0–0.01

[30]

6.3 Graphene Composite Anodes

Carbon/metal composites made of metals that are able to alloy with lithium hold great promise at enhancing the capacity of lithium-ion batteries, yet reports in the literature are mixed [20, 31, 32, 33, 34]. In fact, next-generation products are already hitting the market in portable electronics applications whereby manufacturers are claiming 30% improvements in battery capacities where alloying is used, yet these batteries do not fully exploit the potential of alloys [Miyaki, Y. US Patent, Patent No: US 6,908,709 B2 (2005).]. While it may be impractical to attain the maximum theoretical capacities that can be potentially achieved with alloy-based anodes (e.g., due to capacity limitations of cathode materials), there is great utility in having new anode materials that can reliably yield 600–1,000 mAh g−1 of reversible capacity for long cycle use. Hence, improved materials that can withstand the enormous volume expansion (up to 400% [35]) and mechanical stresses that come with the alloying/de-alloying process must still be developed. The literature points to binders [36], nanostructured materials [37, 38, 39, 40, 41], and graphite/metal composites [42] as a possible solution to the mechanical instability caused by the repeated alloying/de-alloying process.

Graphene, as a support material for active nanostructured metal or metal oxide species distributed onto the surface of graphene or between the graphene layers, is a very compelling approach given graphene’s large surface area (2,600 m2 g−1) [43] and both its mechanical [44] and electrical [45] conductivity. This section will discuss graphene/metal or graphene/metal oxide nanocomposites made either by mechanical mixing or fabricated by stacking graphene sheets in the presence of the corresponding organometallic precursor. The rationale is that this material nano-architecture will provide the necessary means of limiting the aggregation of the nanoparticles and accommodating large volume expansions that occur upon cycling while maintaining the mechanical integrity and electrical conductivity needed to provide long-term cyclability.

6.3.1 Graphene/Silicon-Based Materials

Silicon has been explored as anode material for lithium-ion batteries because of its high theoretical capacity (4,200 mAh g−1 or 9,805 mAh mL−1) and its natural abundance [46, 47, 48]. Silicon reacts with lithium via the following alloying/de-alloying reactions:
$$ {\text{Si}} + {\text{xL}}{{\text{i}}^{ + }} + {\text{x}}{{\text{e}}^{ - }} \leftrightarrow {\text{SiL}}{{\text{i}}_{\rm{x}}}\;{\text{with}}\;0 \leq {\text{x}} \leq 4.4(4,200\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}}) $$
(6.1)
Up to 4.4, lithium can alloy with silicon leading to a maximum capacity of 4,200 mAh g−1. However, this large capacity is associated with a large volume change of 300–400% upon cycling [35, 49, 50]. The latter gives rise to mechanical stresses that lead to cracks, eventual disintegration of the electrode, and a failure of the battery [51]. All strategies to fix this problem have shown their limitations: use of nanoparticles, cellulose-based binder, composites, and nanostructures [37, 38, 39, 40, 41]. Graphene/silicon nanocomposite materials, where silicon nanoparticles are trapped between graphene sheets, might be a way to better mitigate the effect of the large volume change. Several research groups worked on making these nanocomposites using mixing procedures of either graphene or GO with commercial silicon nanoparticles. Table 6.2 summarizes the preparation procedure, ratio, and different capacity values of the composites prepared by different research groups around the world.
Table 6.2

Graphene/silicon nanocomposites preparation methods and capacity values

Graphene/GO

Preparation of composite material

C/Si ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

Graphene Kovtyukhova’s method

–GO and nano-Si suspension (sonication)

~40/60

20–25

1,750 800

300

1,000–80

1.5–0.005

[52]

–Annealing at 700°C, Ar/H2

 

GO modified Hummers’ method

–GO and nano-Si suspension (stirring)

~40/60

50

~2,500

30

300

1.2–0.005

[14]

~750

– Annealing at 500°C in Ar

  

Graphene heat treatment of graphite

–Graphene sheets and nano Si mechanically mixed

~33/67

50

3,500

30

300

1.2–0.005

[14]

2,300

Graphene solvothermal method

–Graphene and nano Si mechanically mixed

50/50

~40

2,158

30

100

1.2–0.02

[53]

1,168

Graphene prepared by liquid-phase exfoliation technique

–Preparation of Si nanowires via an electroless etching process

50/50

Length: 10 μm

3,646 2,470

20

105

0.8–0.005

[54]

–Graphene and Si nanowires mechanically are mixed

Diameter: 100

 

GO modified Hummers method Exfoliated by ultrasonication

–Silicon nanoparticles and GO suspended in water (sonication)

33/67

100–200 nm

1,650 1,040

30

50

1.5–0.05

[55]

–Suspension filtered to produce a self-supporting film

 

–Film is thermally reduced under Ar at 700°C

Two groups worked on making composites of GO and silicon nanoparticles by mechanical mixing [14, 52]. As shown by the TEM micrograph in Fig. 6.7, Lee et al. obtained graphene/silicon nanocomposite paper [52]. The latter was prepared by annealing (700°C, Ar/H2, 1 h) a nanocomposite paper of GO and silicon nanocomposite (20–25 nm) [52]. An initial discharge capacity of about 1,750 mAh g−1 was obtained when cycled at 50 mA g−1 with almost no first irreversible capacity. With only 0.5% capacity decrease per cycle, this nanocomposite provided good capacity retention with a discharge capacity of 1,000 mAh g−1 after 200 cycles [52].
Fig. 6.7

TEM micrograph of a graphene/Si nanocomposite paper [52] (Reproduced by permission of the Royal Society of Chemistry)

Xiang et al. also used a composite made of GO and silicon nanoparticles (50 nm) in order to prepare their graphene/silicon nanocomposite, obtained after annealing at 500°C in argon for 1 h [14]. Three different graphene to silicon ratios were experimented, 1:1, 1:2, and 1:3 and named SG1, SG2, and SG3, respectively. The TEM micrographs showed in Fig. 6.8 confirm that the silicon nanoparticles bonded to graphene are well dispersed between the graphene sheets.
Fig. 6.8

TEM micrographs of graphene/silicon nanocomposites SG1, SG2, SG3, and SGE and SEM micrographs of SGE (see text for details) (Reprinted from [14]. Copyright (2011) with permission from Elsevier)

Figure 6.9 shows the cycling performance of pristine silicon nanoparticles and the three different nanocomposites (SG1, SG2, and SG3). The nanocomposites show better performance than the pristine silicon nanoparticles. Having the silicon nanoparticles trapped between graphene sheets helps to mitigate the effect of the volume change by keeping an electrical contact between the silicon particles and the electrical path. In addition, upon inspection the pure silicon anode was brittle, whereas the nanocomposite anodes were not. Nonetheless, large irreversible capacities ranging from 600 to 750 mAh g−1 are observed with these samples. After 30 cycles, samples SG2 and SG3 showed capacities of 700–800 mAh g−1 at a rate of 300 mA g−1 which represents about 70–80% of the initial capacity.
Fig. 6.9

Cycling performance of pristine silicon nanoparticles and graphene/silicon nanocomposites having graphene to silicon ratios of 1:1 (SG1), 1:2 (SG2), and 1:3 (SG3). Capacities are calculated using the weight of composite (Reprinted from [14], Copyright (2011), with permission from Elsevier)

Using expandable graphite, a last graphene/silicon nanocomposite was prepared by Xiang et al. [14] Expandable graphite was rapidly heated to 1,050°C and then blended with silicon nanoparticles using mechanical blending in a 1:2 ration (SGE sample). TEM and SEM micrographs of an SGE sample (see Fig. 6.8) show that the silicon nanoparticles occupy the pores of the expanded graphene [14]. It is worth mentioning that sonication of SGE led to separation of some of the silicon nanoparticles from the graphene sheets [14]. As shown in Fig. 6.10, this modified method led to a material with higher capacity values (1,800 mAh g−1) than the ones observed with SG2 and SG3.
Fig. 6.10

Cycling performance of pristine silicon nanoparticles and graphene/silicon nanocomposites having a graphene to silicon ratio of 1:2 (SG2 and SGE) (see text for details). Capacities are calculated using the weight of composite (Reprinted from [14], Copyright (2011), with permission from Elsevier)

Another useful study was performed by Chou et al. where they studied the performance of a graphene/silicon nanocomposite versus neat graphene and neat silicon nanoparticles [53]. The graphene used was synthesized via a solvothermal method [56], and the nanocomposite was prepared via mechanical mixing of the as-prepared graphene with silicon nanoparticles (~40 nm). The comparative study performed is shown in Fig. 6.11. The cycling data obtained clearly show that due to the large volume change that occurs upon cycling, silicon nanoparticles cannot sustain a stable capacity; after 20 cycles the capacity is already below 500 mAh g−1. When the nanoparticles are dispersed within a graphene matrix, much better capacity retention is observed; the nanocomposite yields a lithium cell with a capacity of about 1,400 mAh g−1 after 20 cycles at 100 mA g−1 [53].
Fig. 6.11

Cycling performance of pristine graphene (squares), silicon nanoparticles (triangles), graphene/silicon nanocomposite (circles) electrodes, and the calculated pure silicon contribution from the graphene/silicon composite (stars) (Reprinted from [53], Copyright (2011), with permission from Elsevier)

Nanostructured silicon arrays, such as silicon nanowires, have recently been investigated by Cui et al. [57]. Due to their better tolerance to strain and also the empty space between the wires, nanowires can better accommodate the volume change that occurs upon cycling. Wang et al. recently prepared single-crystalline silicon nanowires, and they showed that adding graphene significantly enhances the reversible capacity of the silicon nanowires [54]. As shown in Fig. 6.12a, the graphene/silicon-nanowire nanocomposite showed a charge capacity of 2,470 mAh g−1 after 20 cycles, which is higher than the carbon-black/silicon-nanowire nanocomposite (1,256 mAh g−1). The rate capability of the graphene nanocomposite is also enhanced; for instance, at 2C, a discharge capacity representing 75% of the capacity obtained at C/10 was observed (see Fig. 6.12b). This is due to the favorable charge-transportation properties of the graphene additive. Before making any conclusions, longer cycling data would be required since it is often the case that these silicon-based types of anodes tend to catastrophically fail between 30 and 50 cycles.
Fig. 6.12

(a) Charge capacities and Coulomb efficiency of cells for 20 cycles. NW silicon nanowires, G graphene, CB carbon black, NP silicon nanoparticles. (b) Rate capacities from 0.1 C to 2 C, with the rate for discharge fixed to 0.1 C (Reprinted with permission from [54]. Copyright (2011) American Chemical Society)

6.3.2 Graphene/Tin-Based Materials

Like silicon, tin is a metalloid that reacts reversibly with lithium via an alloying/de-alloying reaction depicted by the following equation:
$$ {\text{Sn}} + {\text{xL}}{{\text{i}}^{ + }} + {\text{x}}{{\text{e}}^{ - }} \leftrightarrow {\text{SnL}}{{\text{i}}_{\rm{x}}}\;{\text{with}}\;0 \leq {\text{x}} \leq 4.4(993\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}}) $$
(6.2)

With a maximum of 4.4 lithium per tin, a capacity up to 993 mAh g−1 (7,313 mAh mL−1) can be reached. However, like silicon, tin suffers from large volume changes upon cycling, about 260% [35]. Mechanical stresses usually lead to cracks and disintegration of the electrode. To prevent pulverization during the battery cycling, it has been suggested that minimizing the particle size along with the use of binders that can better accommodate volume changes, such as sodium carboxymethylcellulose (NaCMC) [42] or styrene butadiene rubber [58]. Other approaches would be to use an inert matrix such as a transition metal that alloys with tin (Fe, Cu, Co, Mn, etc.) [59], Li2O as in the case of SnO2 [60], or even a carboneous matrix such as nanotubes or graphene [61].

Tin oxide (SnO2) reacts with lithium via a two-step reaction: First it is irreversibly reduced to tin embedded in a Li2O matrix, and then tin reversibly alloys with lithium [62], as shown by the following equations:
$$ 4{\text{L}}{{\text{i}}^{ + }} + {\text{Sn}}{{\text{O}}_2} + 4{{\text{e}}^{ - }} \to {\text{Sn}} + 2{\text{L}}{{\text{i}}_2}{\text{O}}(707\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}}) $$
(6.3)
$$ {\text{Sn}} + {\text{xL}}{{\text{i}}^{ + }} + {\text{x}}{{\text{e}}^{ - }} \leftrightarrow {\text{SnL}}{{\text{i}}_{\rm{x}}}\;{\text{with}}\;0 \leq {\text{x}} \leq 4.4(783\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}}\;{\text{of}}\;{\text{Sn}}{{\text{O}}_2}) $$
(6.4)
As a result, the Li2O matrix prevents severe volume change and keeps tin metal in nano-sized form. Even though building up the Li2O helps to mitigate the volume expansion associated to the alloying reaction of Sn with lithium, it is usually not enough to prevent the degradation of the electrode. In addition, the reduction of SnO2 to tin metal leads to an irreversible capacity of 707 mAh g−1, which represents about half of the electrode capacity. Preparations of graphene/SnO2 and graphene/tin nanocomposite materials have been explored to reduce the negative effects of the volume change that occurs during cycling (Table 6.3).
Table 6.3

Graphene/SnO2 and graphene-/Sn-based nanocomposites preparation methods and capacity values

Active material Graphene/GO source

Preparation of composite material

C/SnO2 C/Sn ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

SnO2

GO prepared by modified Hummers method

–GO and SnCl2 in ethylene glycol and H2O.

–Reflux 500°C, Ar

22/78

2–4

̃1,800

665

50

50

2.0–0.005

[63]

SnO2

GO prepared by modified Hummers method

–SnCl2 and GO – addition of citric acid and NaBH4

–Heated at 120°C

60/40

4–6

1,420

520

100

55

3.0–0.1

[64]

SnO2

–NaOH solution is added to an aqueous solution of SnCl4

 

̃4

̃675

403

60

130, 450, 1,400, 6,000, 8,000, 450

3.0–0.05

[61]

Graphene produce by arc-discharge evaporation of graphite in a NH3-He mixed atmosphere[65]

–The solution is then mixed with a graphene dispersion in ethylene glycol

       
 

–Addition of H2SO4

       
 

–Precipitate is to 400°C under argon

       

SnO2

–Hydrolysis of SnCl4 with NaOH

40/60

̃5.4

̃1,850

30

50

2.0–0.05

[13]

GO prepared by modified Hummers method

–Mixing of graphene and SnO2 in ethylene glycol

       
    

570

    
 

–Heat treatment at 400°C in Ar

       

SnO2

–GO and HCl in H2O

2.4/97.6

3–5

̃875

50

400

2.0–0.01

[66]

Chemical exfoliation of graphite

–Addition of SnCl2

  

̃590

    
 

–Heat treatment at 400°C in Ar

       

Sn@C

–Graphene in ethylene glycol

46.9/53.1

50–200

846

660

100

100

3.0–0.01

[67]

Thermal exfoliation of graphite oxide

–SnCl4 and NaOH in H2O

       
 

–Two solutions mixed

       
 

– Hydrothermal carbon coating (glucose), 180°C

       
 

–Annealing 800°C in N2/H2

       

SnO2

–GO and SnCl2 in isopropanol

25/75

20

1,700

775

50

100

3.0–0.005

[68]

GO prepared by modified Hummers method

–Ultrasonification for 30 min

       
 

– Annealing at 500°C in N2

       

SnO2

– SnCl4, urea and GO in H2O

20/80

100–200

2,140

650

30

50

2.0–0.005

[69]

GO prepared by modified Hummers method

–Ultrasonication for 30 min

       
 

–Microwaved 60 s

       
 

–Addition of hydrazine

       
 

–Microwaved 60 s

       
 

–Annealing 500°C in N2

       

SnS2

l-cysteine and SnCl4·5H2O dissolved in water

 

Curved nanosheets

1,664

920

50

100

1.5–0.01

[70]

GO prepared using modified Hummers method

–Addition of GO

       
 

–Heated in autoclave 180°C

 

̃2 μm diameter

     
 

–Product filtered and washed

       
It is mostly tin oxide that has been studied in a composite with graphene [13, 61, 63, 64, 66]; up to now, only one publication reports the use of elemental tin and graphene nanocomposite. In the case of SnO2, usually large first irreversible capacities are observed due to the irreversible reduction of SnO2 to Sn and also the irreversible capacity associated with graphene. This is illustrated by Fig. 6.13b where an initial discharge capacity of 1,800 mAh g−1 and reversible discharge capacity of 665 mAh g−1 (at 50 mA g−1) after 50 cycles were observed for the graphene/SnO2 nanocomposite [63]. The as-prepared graphene gave a capacity of 380 mAh g−1 after 100 cycles. Figure 6.13a shows a TEM micrograph of the nanocomposite made of SnO2 nanoparticles of 2–4 nm evenly distributed on the graphene sheets [63]. The nanocomposite was prepared via reflux of SnCl2 and GO at 190°C in ethylene glycol which was then annealed (500°C, Ar, 2 h).
Fig. 6.13

(a) TEM micrograph of the graphene/SnO2 nanocomposite [63]. (b) Discharge (solid) and charge (hollow) capacity versus cycle number for a graphene/SnO2 nanocomposite and pure graphene nanosheets (Reprinted from [63], Copyright (2011), with permission from Elsevier)

An interesting study was performed by Yao et al. where they demonstrated the advantage of a graphene/SnO2 nanocomposite over pristine SnO2 nanoparticles and pristine graphene. Figure 6.14a–d shows four TEM micrographs of the graphene/SnO2 nanocomposite prepared using SnCl2 as the precursor and NaBH4 as a reducing agent [64]. The nanocomposite is made of SnO2 nanoparticles of 4–6 nm uniformly distributed on the graphene sheets. Figure 6.14c–d shows HRTEM micrograph of graphene/SnO2 nanocomposite and lattice-resolved HRTEM image of graphene/SnO2 nanocomposite, in which the lattices of SnO2 nanoparticles and graphene nanosheets are clearly visible. The inset is an atomically resolved lattice image of a SnO2 nanoparticle, from which two perpendicular crystal planes, (110) and (200), can be distinguished. As previously mentioned, for all SnO2 containing electrodes, a large first irreversible capacity ranging from 500 to 900 mAh g−1 is observed. After 100 cycles, the nanocomposite shows a capacity of 520 mAh g−1, whereas the capacity of the pristine SnO2 nanoparticles declines very rapidly with a capacity of less than 50 mAh g−1 after 20 cycles. The controlled experiment showed that the graphene alone provides a capacity less than 300 mAh g−1 after 100 cycles.
Fig. 6.14

(a) Low-magnification TEM micrograph of the graphene/SnO2 nanocomposite. (b) High-magnification TEM micrograph of graphene/SnO2 nanocomposite (c) HRTEM micrograph of graphene/SnO2 nanocomposite showing. (d) Lattice-resolved HRTEM image of graphene/SnO2 nanocomposite. (e) Cycling performance of SnO2/graphene nanocomposite electrode, bare SnO2 nanoparticle electrode, and bare graphene electrode (Reprinted from [64], Copyright (2011), with permission from Elsevier)

Graphene is known for its high electronic conductivity which is a good add-on for obtaining high rate capability with active materials that are poor electronic conductors. Wang et al. performed these rate capability measurements on a graphene/SnO2 nanocomposite [61]. They prepared the GNS via arc-discharge evaporation of graphite in a NH3/He atmosphere. The SnO2 nanoparticles were prepared by the hydrolysis of SnCl4, and the resulting hydrosol was combined with an ethylene glycol dispersion of GNS. The isolated powder was then annealed (400°C, Ar, 2 h) [61].

Figure 6.15a–b shows TEM micrographs of the nanocomposite which are quite similar to the previous examples with well-distributed 4 nm SnO2 nanoparticles on GNS.
Fig. 6.15

(a) Low-magnification (top left) and (b) high-magnification TEM micrographs of laterally confined graphene/SnO2 composites (top right). (c) Cycle performance of the graphene/SnO2 composites at various charge–discharge current densities (bottom) (Reprinted from [61]. Copyright (2010), with permission from Springer)

Figure 6.15c shows the rate capability performance of the nanocomposite for various current densities. The performance is pretty impressive: At 130 mA g−1, a stable capacity of about 515 mAh g−1 was observed, whereas at current density as high as 8,000 mA g−1, a capacity value of about 100 mAh g−1 was measured.

Two other papers reported the synthesis and the use of a graphene/SnO2 nanocomposite as anode materials [13, 66]. One was prepared from GO and SnCl2, and upon cycling, it was found that an optimal graphene to SnO2 ratio of 1:3.2 provided the best performance with a charge capacity of about 590 mAh g−1 after 50 cycles at 400 mA g−1 [66]. Surprisingly enough, a relatively low irreversible capacity is obtained. Figure 6.16 shows SEM and TEM micrographs of this composite. The other one was reported by Paek et al. who combined chemically reduced GO and in situ synthesized SnO2 nanoparticles (ca. 5 nm) made from SnCl4, in ethylene glycol, and then annealed (400°C, Ar, 2 h) [13]. TEM images of this material show SnO2 nanoparticles well dispersed between graphene sheets (see Fig. 6.17). A comparative study on the performance of bare SnO2 nanoparticle, graphite, and graphene was also performed by Paek et al. [13] The graphite and graphene exhibit capacities slightly above 250 mAh g−1 after 30 cycles, while the bare SnO2 nanoparticles have a capacity of almost zero after only 15 cycles. The composite made of a 1:1.5 ratio of graphene to SnO2 yields a first irreversible capacity of ca. 1,900 mAh g−1, whereas a reversible capacity of 810 mAh g−1 on the second cycle and 570 mAh g−1 after 30 cycles is observed at a cycling rate of 50 mA g−1 (see Fig. 6.18).
Fig. 6.16

SEM and TEM micrographs of the spray-dried graphene/SnO2 nanocomposite, (a) low-magnification SEM, (b) high-magnification SEM, and (c) high-magnification TEM (Reprinted from [66], Copyright (2011), with permission from Elsevier)

Fig. 6.17

SEM and TEM micrographs of graphene and graphene/SnO2 nanocomposite, SEM micrographs for (a) graphene and (b) graphene/SnO2 nanocomposite cross-sectional TEM micrographs for (c) graphene, (d) graphene (high magnification), (e) as-prepared graphene/SnO2 nanocomposite, and (f) heat-treated graphene/SnO2 nanocomposite. The white arrows denote the graphene nanosheets (Reprinted with permission from [13], Copyright (2009) American Chemical Society)

Fig 6.18

Cyclic performances for (a) bare SnO2 nanoparticle, (b) graphite, (c) graphene, and (d) graphene/SnO2 nanocomposite (Reprinted with permission from [13], Copyright (2009) American Chemical Society)

The major issue that prevents the use of SnO2 for commercial lithium-ion batteries is its unavoidable irreversible capacity associated with the first lithiation reaction that represents about half of SnO2 theoretical capacity. In this sense, elemental tin is more interesting in this regard with a theoretical capacity of 993 mAh g−1 or 7,313 mAh mL−1. A graphene/Sn nanocomposite material was prepared from a dispersion of graphene and carbon-coated SnO2 which was then reduced (800°C, N2/10% H2, 12 h). As shown in Fig. 6.19a, a graphene and carbon-coated Sn nanocomposite was obtained. It was tested in half-cells and showed a capacity of 660 mAh g−1 (100 mA g−1) after 100 cycles and very good rate capability (see Fig. 6.19b) [67]. A similar nanocomposite made of GNS and Sn nanoparticles chemically reduced with NaBH4 was prepared by Wang et al. [71]. The observed well-dispersed Sn nanoparticles between GNS showed a capacity of 508 mAh g−1 (55 mA g−1) after 100 cycles. The performance of the nanocomposite was better than the bare graphene and pristine Sn powder. However, a large first irreversible capacity of 450 mAh g−1 was also observed. Finally a composite made of GNS (10–20 layers) and carbon-coated Sn-Sb nanoparticles (50–150 nm) provided a very impressive capacity retention with a capacity of about 700 mAh g−1 at 2C (1,600 mA g−1) [72].
Fig. 6.19

TEM micrograph of the Sn-coated nanoparticle anchored on the graphene (left). Rate capability of the nanocomposite of graphene/Sn carbon-coated nanoparticles (right) (Reprinted from [67], Copyright (2011), with permission from Elsevier)

SnS2 /graphene hybrid materials were prepared and tested in lithium-ion batteries by Chant et al. [70]. SnS2 reacts with Li+ in the same way SnO2 does, (Eqs. 6.3 and 6.4) producing Li2S and SnLix. The authors believe that since SnS2 is structurally and morphologically analogous to graphene, it would be more compatible for the preparation of nanocomposite than SnO2 particles, leading to high capacities with good cycle stability. SEM images of the SnS2/graphene are presented in Fig. 6.20. The images show a three-dimensional architecture made of curved nanosheets. The performance of the composite in lithium-ion batteries was evaluated. The first discharge capacity for the SnS2/graphene composite was 1,664 mAh g−1 and dropped down to 920 mAh g−1 after 50 cycles and appears to be stable (Fig. 6.20).
Fig. 6.20

(a) and (b) SEM images of SnS2/graphene composite and (c) cycling performance of SnS2/graphene composite at 100 mA g−1 (Reprinted with permission from Journal of Power Sources, doi:10.1016/j.jpowsour.2011.10 Copyright (2011) Springer)

6.4 Graphene/Transition Metal Oxide (TMO) Materials (Mn, Fe, Co, and Cu)

In 2000, Poizot et al. were the first to introduce the concept of using TMOs as anode materials for lithium-ion batteries [73]. TMOs have the advantage of delivering large theoretical capacities, usually ranging from 600 to 1,000 mAh g−1 [35] which translates to volumetric capacities ranging from 3,000 to 5,000 mAh mL−1 (assuming an average density of ~5 g mL−1 [74]). They react with lithium via an unusual way. They undergo a conversion reaction in which the TMO is converted into metallic nanoparticles embedded in a matrix of Li2O as in the following example:
$$ {\text{NiO}} + 2{\text{L}}{{\text{i}}^{ + }} + 2{{\text{e}}^{ - }} \leftrightarrow {\text{Ni}} + {\text{L}}{{\text{i}}_2}{\text{O}}\left( {718\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}}} \right) $$
(6.5)

However, unlike in the case of the SnO2, the Li2O matrix formed during the first lithiation is in this case decomposable upon delithiation, and the metallic nanoparticles are oxidized back into TMO nanoparticles. This solid-state oxidation occurs only at nanometric scale. It is believed that the size confinement of the metallic nanoparticles enhances their electrochemical activity toward the decomposition of the Li2O matrix [73]; a similar phenomenon has also been observed with LiF for transition metal fluorides (TMFs) [75].

However, the use of TMOs lithium-ion batteries is limited by their low intrinsic electrical conductivity (i.e., Mn3O4: 2 × 10−7 S cm−1 [76], Cr2O3: 1.8 × 10−7 S cm−1 [77]). This observation generally applies for all TMOs which exhibit typical insulator or semiconductor behavior; indeed they exhibit band gaps ranging from 3 to 4 eV [78]. Graphene can potentially serve as an excellent matrix due to its tunable surface area, mechanical flexibility, and high electrical conductivity that can compensate for the low conductivity of TMOs and lead to improved capacity retention [79, 80, 81, 82]. Several TMOs ranging from manganese oxides to copper oxides have been investigated in nanocomposites with graphene, and the following section focuses on their batteries performance.

6.4.1 Graphene/Manganese Oxide

Manganese oxides are attractive materials for lithium-ion batteries due to the high abundance of manganese [48] and its low cost but more importantly because of its very low oxidation potential (1.2–1.3 V vs. Li/Li+) compared to other TMOs [83]. The anode oxidation potential (or delithiation potential) is very important for a battery since it will dictate the battery output voltage; the lower the potential, the larger the output voltage. Table 6.4 summarizes the preparation method and the performance of graphene/manganese oxide nanocomposites prepared by several research groups around the world.
Table 6.4

Graphene-/manganese oxide-based nanocomposites preparation methods and capacity values

TMO and graphene/GO source

Preparation of composite material

C/TMO wt. ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

Mn3O4

–GO and MnAc. in MF/H2O (10:1) at 80°C

10/90

10–20

1,300 810

5

40

3.0–0.1

[79]

GO prepared by modified Hummers method

–Hydrothermal 180°C

       

Mn3O4

–Graphene, MnOOH, and sodium dodecyl sulfate are suspended in water

35/65

200–450

(A) ̃ 1,180

̃680 (B)̃ 1,370 ̃720

100

75

3.0–0.01

[80]

(A) GO prepared by modified Hummers method and reduced under H2 atmosphere or (B) commercial graphene platelets

–Mixture is sonicated for 20 min, filtered, and washed with water

       
 

–Annealed at 450°C for 1 h under argon atmosphere

       

MnO2

–Graphene and sodium dodecyl sulfate in H2O

N/A

N/A

1,400

635.5

30

C/10

3.0–0.005

[81]

Graphene prepared via solvothermal reaction with Na and EtOH

–Addition of Na2SO4 and KMnO4

       
 

–Precipitate washed and dried

       

MnO2

–MnO2 NT prepared via hydrothermal reaction using KMnO4

50/50

Length: 1,000

1,250

495

40

100

3.0–0.01

[82]

GO prepared by modified Hummers method

–Assembly of the electrode layer-by-layer

 

Diameter: 70–80

     
   

Wall thickness: 30

     
Two different reversible processes with lithium have been reported in the literature for Mn3O4 [84, 85]. According to Fang et al., first insertion of lithium occurs to form LiMn3O4 as shown by Eq. 6.6. A second reaction with lithium then takes place to obtain MnO, as shown by Eq. 6.7. It has been shown that once MnO is obtained, reactions (6.6) and (6.7) are not reversible anymore. From MnO, the reversible conversion reaction occurs, as shown by Eq. 6.8; the latter observation has been demonstrated by high-resolution TEM and selected area electron diffraction (SAED) measurements [84]. A second path has also been proposed by Gao et al. where they state that the reaction shown by Eq. 6.9 is totally reversible [85].
$$ {\text{M}}{{\text{n}}_3}{{\text{O}}_4} + {\text{L}}{{\text{i}}^{ + }} + {{\text{e}}^{ - }} \to {\text{LiM}}{{\text{n}}_3}{{\text{O}}_4} $$
(6.6)
$$ {\text{LiM}}{{\text{n}}_3}{{\text{O}}_4} + {\text{L}}{{\text{i}}^{ + }} + {{\text{e}}^{ - }} \to 3{\text{MnO}} + {\text{L}}{{\text{i}}_2}{\text{O}} $$
(6.7)
$$ {\text{MnO}} + 2{\text{L}}{{\text{i}}^{ + }} + 2\;{{\text{e}}^{ - }} \leftrightarrow {\text{Mn}} + {\text{L}}{{\text{i}}_2}{\text{O}} $$
(6.8)
$$ {\text{M}}{{\text{n}}_3}{{\text{O}}_4} + 8{\text{L}}{{\text{i}}^{ + }} + 8{{\text{e}}^{ - }} \leftrightarrow 3{\text{Mn}} + 4{\text{L}}{{\text{i}}_2}{\text{O}} $$
(6.9)

The use of manganese oxides in lithium-ion batteries has been limited by the low intrinsic electrical conductivity (2 × 10−7 S cm−1) [76]. Wang et al. [79] and Lavoie et al. [80] improved this issue by preparing graphene/Mn3O4 nanocomposites whereas Xing et al. [81] and Yu et al. [82] investigated graphene/MnO2 nanocomposites.

Wang et al. prepared a nanocomposite made of Mn3O4 nanoparticles (ca. 10–15 nm) grown directly on RGO. This nanocomposite showed a reversible capacity of 810 mAh g−1 when cycled at 40 mA g−1, and at a higher cycling rate, a capacity of 730 mAh g−1 was retained after 40 cycles at 400 mA g−1 (see Fig. 6.21a). An initial irreversible capacity of ca. 400 mAh g−1 was observed, which represents about 30% capacity loss. It is interesting to note that the electrical conductivity of Mn3O4 is much lower than that of cobalt or iron oxides [76], yet the graphene nanocomposite architecture seems to address this limitation, as shown by Fig. 6.21b, which may in part be due to the nanoscale size of the Mn3O4 particles and the high electrical conductivity of graphene [86]. We prepared similar composites made of graphene platelets or RGO and Mn3O4 needles [80]. We demonstrated the advantage of using a composite with graphene over pristine Mn3O4 needles. A capacity of 720 mAh g−1 was obtained when using graphene platelets (XGM-5) and 675 mAh g−1 when using RGO; half-cells were cycled at 75 mA g−1 for 100 cycles (see Fig. 6.22).
Fig. 6.21

Electrochemical characterizations of a half-cell composed of graphene/Mn3O4 and Li. The specific capacities are based on the mass of Mn3O4 in the graphene/Mn3O4 nanocomposite. (a) Capacity retention of the graphene/Mn3O4 nanocomposite at various current densities. (b) Capacity retention of free Mn3O4 nanoparticles without graphene at a current density of 40 mA g−1 (Reprinted with permission from [79]. Copyright (2010) American Chemical Society)

Fig. 6.22

Cycling performance of Mn3O4/graphene composites (0.01–3.0 V), XGM-5 (0.005–2 V), and Mn3O4 (0.01–3 V) cycled at 75 mAh g−1 with LiCMC binder [80] (Reprinted with permission from Elsevier)

As depicted by Ref. [84], MnO2 is known for having a large irreversible capacity due to the thick SEI that forms on manganese and also due to the fact that the starting oxidation state of manganese is +4. Xing et al. reported a capacity of 718 mAh g−1 at C/20 after 30 cycles [81]. An irreversible capacity of about 50% is observed. Yu et al. made a comparative study on the performance of freestanding MnO2 nanotubes and a free-standing porous nanocomposite made of an intimate mixture of MnO2 nanotubes and graphene [82]. They clearly showed the advantage of having graphene as a conductive matrix. The nanocomposite had a capacity of 500 mAh g−1 after 40 cycles when cycled at 100 mA g−1, while pristine MnO2 nanotubes showed a capacity of about 150 mAh g−1.

6.4.2 Graphene/Iron Oxide

Iron oxide is one of the most interesting TMOs. Iron oxides have an oxidation potential of about 1.8 V versus Li/Li+; the latter is a bit higher than manganese oxide but lower than cobalt oxide. Iron is naturally very abundant [48] and is quite inexpensive. In addition, it shows high theoretical capacities, about 1,000 mAh g−1, and lower irreversible capacity than other TMOs [87], but like many other materials, one of the problems with iron oxide is the pulverization due to volume change upon cycling. No graphene/FeO nanocomposite has been prepared up to now; however, several graphene/Fe2O3 [88, 89] and graphene/Fe3O4 [90, 91, 92, 93, 94, 95] have been reported in the literature. Table 6.5 summarizes the preparation method and the performance of these graphene/iron oxide nanocomposites. The electrochemical reaction of iron oxides with lithium is presented by Eqs. 6.10 and 6.11:
Table 6.5

Graphene-/iron oxide-based nanocomposites preparation methods and capacity values

TMO and graphene/GO source

Preparation of composite material

C/TMO wt. ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

Fe2O3

–FeCl3 and urea in H2O

20/80

60

1,693

50

100

3.0–0.005

[88]

GO prepared by modified Hummers method

–Addition of GO and ultrasonication

1,027

–Addition of hydrazine

–Microwaved for 2 min.

Fe2O3

Graphene prepared via thermal reduction of GO under H2

–FeCl3,ascorbic acid, PEG-6000, and urea in H2O

30/70

2,000–5,000

1,800

660

100

160

3.0–0.005

[89]

–Addition of graphene and ultrasonication

–Hydrothermal 120°C

Fe3O4

GO prepared by modified Hummers method

–Graphene, (NH4)2Fe(SO4) •6H2O, and NH4Fe(SO4)2• 12H2O in H2O

5.5/94.5

15–30

1,237

857

20

46.3

2.8–0.002

[90]

–Addition of NH4OH

–Annealing 600°C in Ar

Fe3O4

–FeCl2 and GO in H2O

38/62

3–15

1,100

100

100

3.0–0.0

[91]

GO prepared by modified Hummers method

–Addition of NaOH, pyrenebutyric acid, and hydrazine

650

–Hydrothermal 150°C

Fe3O4

Graphene prepared via by rapid thermal expansion in N2

–Fe(NO3)3, ethylene glycol, and graphene

22.7/77.3

12.5

1,400

1,048

90

100

3.0–0.01

[92]

–Ultrasonication for 6 h

–Addition of NH4OH

–Hydrothermal 180°C

Fe3O4

GO prepared by modified Hummers method

–GO, Fe(NO3)3, urea, and ascorbic acid in H2O

N/A

20–70

1,350

650

50

C/10

3.0–0.0

[93]

–Refluxed for 1 h with a microwave heater

–Annealing 600°C in Ar

Fe3O4

–Graphene and FeCl3 in H2O

13.3/86.7

100–500

~1,400

30

35

3.0–0

[94]

Graphene prepared via thermal reduction of GO under Ar and then H2

–Sonication for 1 h

1,026

–Annealing 600°C in Ar

Fe3O4

Graphene prepared via thermal reduction of GO under H2

–Fe(NO3)3, NaAc, PEG-20000 in ethylene glycol

30/70

100–200

2,315

771

50

200

3.0–0.005

[95]

–Addition of graphene

–Hydrothermal 180°C

$$ {\text{F}}{{\text{e}}_3}{{\text{O}}_4} + 8{{\text{e}}^{ - }} + 8{\text{L}}{{\text{i}}^{ + }} \leftrightarrow 3{\text{F}}{{\text{e}}^0} + 4{\text{L}}{{\text{i}}_2}{\text{O}}\quad \quad 926\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}} $$
(6.10)
$$ {\text{F}}{{\text{e}}_2}{{\text{O}}_3} + 6{{\text{e}}^{ - }} + 6{\text{L}}{{\text{i}}^{ + }} \leftrightarrow 2{\text{F}}{{\text{e}}^0} + 3{\text{L}}{{\text{i}}_2}{\text{O}}\quad \quad 1,007\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}} $$
(6.11)
Two graphene/Fe2O3 nanocomposites have been reported. The first one used GO reduced by hydrazine and Fe2O3 nanoparticles (60 nm) made via a microwave-assisted method [88]. As shown in Fig. 6.23, Zhu et al. demonstrated the advantage of using an in situ–prepared graphene/Fe2O3 nanocomposite over pristine Fe2O3 particles or mechanical mixing of graphene and Fe2O3 particles. They reported a first discharge capacity of 1,693 mAh g−1 with an irreversible capacity of about 30%. After 50 cycles the nanocomposite showed a discharge capacity of 1,027 mAh g−1, whereas the mechanically mixed composite showed a capacity below 150 mAh g−1. The second composite prepared by Wang et al. [89] was made using GO reduced via H2 and Fe2O3 agglomerates (2–5 μm) prepared via a hydrothermal method and gave similar behavior to the first composite. The specific capacities are based on the mass of Fe2O3 in the RGO/Fe2O3 composite.
Fig. 6.23

Electrochemical performance of the RGO/Fe2O3 composite. (a) Voltage profile (discharge/charge) of RGO/Fe2O3 composite for the first cycle at the current density of 100 mA g−1. (b) Cycling performance of RGO/Fe2O3 composite at the current density of 100 mA g−1. (c) Rate capacity of RGO/Fe2O3 composite between 0.005 and 3.0 V with increasing current density. (d) Capacity retention of free Fe2O3 nanoparticles physically mixed with RGO platelets at a current density of 100 mA g−1 (Reprinted with permission from [88]. Copyright 2011 American Chemical Society)

An interesting study on graphene/Fe3O4 nanocomposites was performed by Zhou et al., and a very high reversible capacities were obtained [94]. In this example, FeOOH spindles (ca. 200 nm) were used to prepare a graphene/FeOOH precursor composite. The latter was annealed at 600°C in Argon and gave graphene/Fe3O4 nanocomposite (see Fig. 6.24a–d). The composite has a reversible capacity of 1,026 mAh g−1 after 30 cycles (at 35 mAh g−1) and 580 mAh g−1 after 100 cycles at 700 mA g−1 with an irreversible capacity of ca. 30% in the first cycle. Analysis of the iron oxide particle size after cycling reveals that in the graphene composite, the size of the particles is almost unchanged, whereas in the case graphene-free iron oxide particles, pulverization is obvious based on the fact that the particle size decreased by 50%.
Fig. 6.24

(a) SEM micrograph of the cross-section of graphene/Fe3O4 nanocomposite, (b) TEM and (c) high-resolution TEM micrographs of graphene/Fe3O4 nanocomposite, and (d) detailed interface structure of the square area in (c) (Reprinted with permission from [94]. Copyright 2010 American Chemical Society)

Other groups observed similar behavior [90, 91, 92, 93, 95]; for example, Wang et al. reported a nanocomposite having a reversible capacity of 771 mAh g−1 after 50 cycles at a current density of 200 mA g−1 [95]. Li et al. went further than just making half-cells; they actually made a full cell with the graphene/Fe3O4 nanocomposite as anode and a cathode of LiNi1/3Mn1/3Co1/3O2 [90]. The full cell was cycled between 1.2 and 3.2 V. As shown in Fig. 6.25a and b, the cell shows a working potential ranging from 2.8 to 1.6 V. Based on the cathode weight, after 10 cycles at C/10 and C/5 a capacity of 80 mAh g−1 was measured for this battery (see Fig. 6.25c and d).
Fig. 6.25

Voltage profiles of graphene/Fe3O4 – LiNi1/3Mn1/3Co1/3O2/full cells at cycling rate of (a) 0.1 C and (b) 0.2 C. The specific capacity is calculated according to the mass of graphene/Fe3O4 nanocomposites. The corresponding cycling performance curves in cycling rate of (c) 0.1 C and (d) 0.2 C, according to the LiNi1/3Mn1/3Co1/3O2 cathode weight (Reprinted from [90]. Copyright 2011, reproduced by permission of the PCCP Owner Societies)

6.4.3 Graphene/Co3O4

Co3O4 has been one of the most studied TMOs due to its high lithium-storage capacities and impressive performance [73]. Its electrochemical conversion reaction with lithium is Co3O4 + 8Li+ ↔ 4Li2O + 3Co. However, the large volume changes and aggregation of particles upon lithiation lead to limited cycling [96, 97]. Encapsulating or trapping the Co3O4 in a carbon material such as graphene was explored as a method of reducing the degradation of the electrodes [98, 99, 100, 101, 102, 103, 104, 105]. Table 6.6 summarizes the preparation method and the performance of these graphene/Co3O4 nanocomposites as reported by several research groups around the world.
Table 6.6

Graphene-/Co3O4-based nanocomposites preparation methods and capacity values

Graphene/GO source

Preparation of composite material

C/TMO wt. ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Number of cycles

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

Graphene prepared by H2 reduction

–Graphene, Co(NO3)2, NH4OH

24.6/75.4

10–30

1,097

30

50

3.0–0.01

[98]

–Stirring in Ar

935

–Annealing at 450°C in air

GO prepared by modified Hummers method

–Dispersion of GO and CoPc in H2O by ultrasonication

34/66

20–30

1,200 754

30

74

3.0–0.01

[99]

–Reduction GO by hydrazine

 

–Annealing 800°C in Ar

–Oxidation at 400°C in Air

GO

–GO and CoCl2 in H2O ultrasonicated

10/90

10–50

941 740

60

200

3.0–0.001

[100]

–Addition of NaOH and H2O2

–Hydrothermal at 100°C

 

–Addition of NaBH4

–Hydrothermal at 120°C

GO prepared by modified Hummers method

–In EtOH: Co(NO3)2 and hexamethylenetetramine

46.2/53.8

Sheets 100 × 1,000

~2,250 ~1,065

30

89

3.0–0.005

[101]

–Dispersion of GO

 

–Microwaved at 180°C for 5 min in a sealed in glass tube

GO prepared by modified Hummers method

–Preparation of aminopropyltrimethoxysilane (APS)-modified Co3O4 nanoparticles

8.5/91.5

>500

1,700 1,000

130

74

3.0–0.01

[102]

–Addition of GO in the suspension

 

–Reduction of with hydrazine

GO prepared by modified Hummers method

–GO and CoAc in H2O

30/70

5

1,550

42

200

3.0–0.001

[103]

–Addition of NH4OH and hydrazine

800

–Annealing 200°C in Ar

GO prepared by modified Hummers method

–GO and Co(NO3)2 in H2O

10.7/89.3

Thickness 3–5

1,250

100

180

3.0–0.1

[104]

–Hydrothermal at 170°C

700

–Annealing 350°C in air

GO prepared by modified Hummers method

–GO and CoCl2 in H2O

45.4/54.6

15–25

1433 650

50

55

3.0–0.1

[105]

–Addition of NaBH4

–Refluxed at 100°C

 

–Annealing 200°C in air

GO prepared by modified Hummers method

–GNS obtained via ultrasonication/ exfoliation

20/80

Rod shape

1,303

40

100

3.0–0.01

[106]

30 nm diameter

~1,310

–CoSO4·7H2O, urea dissolved in alcohol-water

1–2 μm length

–GNS and 25% NH3·H2O solution are added

–Heated at 120°C for 12 h

–Filtered and dried

–Composite calcinated at 450°C under N2 for 3 h

One example of a graphene/Co3O4 nanocomposite was reported by Wu et al. By annealing of a graphene/Co(OH)2 precursor at 450°C in air, they made a nanocomposite of well-dispersed Co3O4 nanoparticles (10–30 nm) between graphene sheets made of three layers or less [98]. As shown by the TEM micrograph in Fig. 6.26a, Co3O4 nanoparticles are homogeneously attached to the graphene sheets. Figure 6.26b shows a comparison of the performance of the nanocomposite versus bare graphene and bare Co3O4 nanoparticles. It is undeniable that graphene improves the performances of Co3O4 by reducing the agglomeration of particles upon cycling, by better accommodation of the volume changes, and also by improving the electrical and mechanical properties of the electrode. Here a reversible capacity of 935 mAh g−1 was obtained after 30 cycles for a battery cycled at 50 mA g−1. A columbic efficiency of 98% was calculated. The performance of the graphene-free Co3O4 electrode showed a capacity of 184 mAh g−1 after 30 cycles. It is interesting to note that a graphene electrode provides a capacity of 638 mAh g−1 but with a large irreversible capacity. High-rate studies were also undertaken in which a capacity >500 mAh g−1 was obtained at 500 mA g−1 (see Fig. 6.26c). Because Co3O4 nanoparticles were not as well dispersed as those of Wu et al. [98], Yang et al. obtained slightly lower performance [99]; similar results were obtained by four other research groups [100, 103, 104, 105].
Fig. 6.26

(a) TEM micrograph of the graphene/Co3O4 nanocomposite; (b) cycling performance of graphene, Co3O4 nanoparticle, and the graphene/Co3O4 nanocomposite; (c) rate capability of the graphene/Co3O4 nanocomposite at various current densities between 50 and 500 mA g−1 (Reprinted with permission from [98]. Copyright (2011) American Chemical Society)

As shown in Table 6.6, better results were obtained by Chen and Wang when using a composite made of Co3O4 (0.1 × 1 μm) sheets. However this good performance has been associated with a large irreversible capacity of about 1,200 mAh g−1 [101]. Astonishing performance was reported by Yang et al. when using graphene-encapsulated Co3O4 particles [102]. A stable capacity of about 1,000 mAh g−1 was observed after 130 cycles at 74 mAg−1. Even though a first irreversible capacity of about 500 mAh g−1 has been measured, the performance is impressive. It is believed that confining the Co3O4 particles in a graphene shell restrains the aggregation of nanoparticles and better accommodates the volume change that occurs upon cycling. In addition, it reduces the carbon content (increased capacity) and maintains a high electrical conductivity of the overall electrode [102].

6.4.4 Graphene/NiO and Graphene/CuO

Graphene/NiO and graphene/CuO are the two last graphene/TMO nanocomposites investigated. NiO reacts with lithium via the conventional reversible conversion reaction, as shown by Eq. 6.12. CuO interacts a bit differently with lithium, as shown by Eqs. 6.13 and 6.14. An insertion reaction followed by the reversible conversion reaction occurs during cycling (see Chap. 5 for more details). Table 6.7 summarizes the preparation method and the performance of these composites.
Table 6.7

Graphene/NiO and graphene-/CuO-based nanocomposites preparation methods and capacity values

TMO and graphene/GO source

Preparation of composite material

C/TMO wt. ratio

Particle size (nm)

Irr. cap. Rev. cap. (mAh g−1)

Cycles #

Current density (mA g−1)

Voltage range (V vs. Li/Li+)

Ref.

NiO

Graphene prepared by modified Hummers method

–In H2O: NiAc., hexamethylenetetramine, and cetyltrimethylammonium bromide

77.2/22.8

Thickness (500–2,000) × (30–50)

1,750 1,050

40

71.8

3.0–0.005

[107]

–Addition of graphene

–Hydrothermal 120°C

–Annealing 360°C in Air

CuO

Graphene prepared by arc discharge method

–Graphene and CuAc. dispersed in H2O/EtOH

26/74

1,500

850

650

100

65

3.0–0.01

[108]

–Addition of NH4OH

–Reflux for 2 h

Nanoplates 25 thick

 

CuO

Graphene prepared by using modified Staudenmaier’s method [9]

–GNS prepared by rapid heat treatment and ultrasonication

35/65

50

1,248

743

50

50

3.0–0.01

[109]

–GNS and Cu(NO3)2·3H2O dispersed in EtOH and ultrasonicated for 1 h

Wall thickness 10

–Reduction to Cu/graphene in NaBH4 solution

–Oxidation to CuO-HNPs/ graphene in air at 300°C

CuO

GO prepared by modified Hummers method

–GO in H2O and DMF

12/88

30

817

50

67

3.0–0.02

[110]

–Heating at 90°C

–Addition of CuAc.

–Heating at 90°C

423

–Hydrothermal 180°C

–GO reduction by hydrazine vapors at 50°C

CuO

–GNS dispersed in H2O

46/54

20–30

~2,150

40

70

3.0–0.01

[111]

GO modified Hummers method

–CuCl2 is and solution heated to 60°C

~750

–Addition of NaOH

–Filtration

$$ {\text{NiO}} + 2{\text{L}}{{\text{i}}^{ + }} + 2{{\text{e}}^{ - }} \to {\text{N}}{{\text{i}}^0} + {\text{L}}{{\text{i}}_2}{\text{O}}\quad \quad \quad \quad 718\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}} $$
(6.12)
$$ {\text{C}}{{\text{u}}^{\rm{II}}}{\text{O}} + {\text{xL}}{{\text{i}}^{ + }} + {\text{x}}{{\text{e}}^{ - }} \to \left[ {{\text{C}}{{\text{u}}^{\rm{II}}}_{{1 - {\rm{x}}}}{\text{C}}{{\text{u}}^{\rm{I}}}_{\rm{x}}} \right]{{\text{O}}_{{1 - {\rm{x/}}2}}} + {\text{x/}}2\;{\text{L}}{{\text{i}}_2}{{\text{O}}_{{(0 \leq {\rm{x}} \leq 1)}}}\ \ \ \ \ \ \ \ \ \ \ 674\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}} $$
(6.13)
$$ {\text{C}}{{\text{u}}^{\rm{I}}}_2{\text{O}} + 2{\text{L}}{{\text{i}}^{ + }} + 2{{\text{e}}^{ - }} \to 2{\text{C}}{{\text{u}}^0} + {\text{L}}{{\text{i}}_2}{\text{O}}\quad \quad \quad \quad \quad 674\;{\text{mAh}}\;{{\text{g}}^{{ - 1}}} $$
(6.14)
Only one graphene/NiO nanocomposite has been reported in the literature. It is made of graphene nanosheets (GNS) and NiO nanosheets [107]. Zou et al. made a sandwich of GNS and NiO nanosheets, as shown in Fig. 6.27b and c. They showed improved capacity retention when using this composite compared to bare NiO nanosheet or bare NiO nanoparticles, mostly due to the improved electrical conductivity and also the shorted path length for Li+ transport. Conductivity values of 2.14 × 10−5 S cm−1 for the NiO nanosheets versus 1.36 × 10−3 S cm−1 for the nanocomposite were reported. The capacity performance is impressive; however, one should be careful with these values since the C to NiO ratio is quite high: 77.2:22.8. As shown by Fig. 6.27g, the reported capacity is about 1,050 mAh g−1 at 71.8 mA g−1 (C/10) after 40 cycles. This nanocomposite also showed good rate capability with capacities of 870, 660, and 500 at C, 2C, and 5C, respectively (see Fig. 6.27h).
Fig. 6.27

SEM micrographs of (a) GNS; (b) NiO nanosheets; (c) GNS-/NiO-nanosheet nanocomposite; (d) the EDS spectrum of GNS-/NiO-nanosheet nanocomposite; (e) SEM image of GNS-/NiO-nanoparticle nanocomposite; (f) GNS-/NiO-nanoparticle nanocomposite. Electrochemical performances of GNS, NiO nanosheets, and GNS-/NiO-nanosheets and GNS-/NiO-nanoparticle nanocomposites; (g) cycling performances at 0.1 C; (h) cycling performances at stepwise increased current rates (Reprinted from [107]. Reproduced by permission of The Royal Society of Chemistry)

CuO is a bit less interesting than other TMOs because of its lower capacity, 674 mAh g−1, and like NiO it has a higher delithiation potential (over 2 V vs. Li/Li+). However, it has a low cost and is environmentally benign and safe. Up to now, the four following references reported battery performance of graphene/CuO nanocomposites [108, 109, 110, 111]. One of them has been reported by Wang et al. who prepared their graphene via an arc discharge method [65, 112] prior to the preparation of the graphene/CuO nanocomposite materials [108]. Figure 6.28 shows the SEM micrograph of the composite material made of graphene sheets and 1.5 μm urchin-like clusters themselves made of 25 nm nanoplates. Figure 6.28 shows cycling data for the CuO/graphene composite, bare CuO, and graphene. The results clearly show the advantage of the nanocomposite over bare CuO urchin-like clusters. A stable capacity of 650 mAh g−1 after 100 cycles at 65 mA g−1 was measured. Lu et al. also show the superiority of the bare CuO with capacities ~750 mAh g−1 of after 40 cycles at 70 mA g−1 [111]. Similar performance and observation were obtained by Mai et al. by using a composite of 30 nm CuO nanoparticles [110] and Zhou et al. who prepared a composite with 50 nm CuO hollow nanoparticles [109].
Fig. 6.28

(a) SEM micrograph of graphene/CuO nanocomposite. (b) Specific capacity of graphene/CuO nanocomposite, graphene, and CuO under different current density. (c) Discharge-charge capacity of the CuO/graphene up to 100 cycles under 65 mA g−1 and the corresponding 2nd, 50th, and 100th discharge-charge voltage profiles (Reprinted from [108]. Reproduced by permission of The Royal Society of Chemistry)

6.5 Summary and Outlook

Transition metal oxide, silicon, tin, and tin oxide have been studied as a replacement for graphite as anode materials in lithium-ion batteries because of their high theoretical capacities. Cycling of these materials however is often associated with large volume changes, giving rise to mechanical stresses that lead to cracks, eventual disintegration of the electrode, and a failure of the battery. Graphene can be utilized to encapsulate nanoparticles of these materials to mitigate the effect of the large volume expansion. Low intrinsic electrical conductivity has also limited the usefulness of some of these materials. The mechanical flexibility and high electrical conductivity of graphene makes it a good matrix to help compensate for the low conductivity of some TMOs, leading to improved capacity retention.

This chapter gives an overview of the work exploring graphene as a novel support for nanoscale materials that react with lithium and provide high capacities. In general, anodes made of graphene only do not look to be promising materials to replace graphite due to their high irreversible capacity and low capacities. When graphene is employed as a support for materials such as silicon, tin, or transition metal oxide, it does help improve the capacity retention, but long-term stability still needs improvement for these materials to be applicable for commercial applications. The graphene preparation method and the source of particles greatly influence the capacity of the composites. Further research will be needed to find the best combination that will give satisfactory capacity and capacity retention.

References

  1. 1.
    Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306:666–669Google Scholar
  2. 2.
    Allen MJ, Tung VC, Kaner RB (2010) Honeycomb Carbon: A Review of Graphene. Chem Rev 110:132–145Google Scholar
  3. 3.
  4. 4.
    Brodie BC (1859) On the atomic weight of graphite. Philos Trans Roy Soc Lond 149:249–259Google Scholar
  5. 5.
    Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240Google Scholar
  6. 6.
    Park S, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4:217–224Google Scholar
  7. 7.
    Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339Google Scholar
  8. 8.
    Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814Google Scholar
  9. 9.
    Staudenmaier L (1898) Verfahren zur Darstellung der Graphitsäure. Berichte der deutschen chemischen Gesellschaft 31:1481–1487Google Scholar
  10. 10.
    Takami N, Satoh A, Hara M, Ohsaki T (1995) Structural and kinetic characterization of lithium intercalation into carbon anodes for secondary lithium batteries. J Electrochem Soc 142:371–379Google Scholar
  11. 11.
    Funabiki A, Inaba M, Ogumi Z, Yuasa S-i, Otsuji J, Tasaka A (1998) Impedance study on the electrochemical lithium intercalation into natural graphite powder. J Electrochem Soc 145:172–178Google Scholar
  12. 12.
    Guo H-j, Li X-h, Zhang X-m, Wang H-q, Wang Z-x, Peng W-j (2007) Diffusion coefficient of lithium in artificial graphite, mesocarbon microbeads, and disordered carbon. New Carbon Mater 22:7–10Google Scholar
  13. 13.
    Paek S-M, Yoo E, Honma I (2009) Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. Nano Lett 9:72–75Google Scholar
  14. 14.
    Xiang H, Zhang K, Ji G, Lee JY, Zou C, Chen X, Wu J (2011) Graphene/nanosized silicon composites for lithium battery anodes with improved cycling stability. Carbon 49:1787–1796Google Scholar
  15. 15.
    Fuhrer MS, Lau CN, MacDonald AH (2010) Graphene: materially better carbon. MRS Bull 35:289–295Google Scholar
  16. 16.
    Hu Y-S, Adelhelm P, Smarsly BM, Hore S, Antonietti M, Maier J (2007) Synthesis of hierarchically porous carbon monoliths with highly ordered microstructure and their application in rechargeable lithium batteries with high-rate capability. Adv Funct Mater 17:1873–1878Google Scholar
  17. 17.
    Wallace GG, Chen J, Li D, Moulton SE, Razal JM (2010) Nanostructured carbon electrodes. J Mater Chem 20:3553–3562Google Scholar
  18. 18.
    Landi BJ, Ganter MJ, Cress CD, DiLeo RA, Raffaelle RP (2009) Carbon nanotubes for lithium ion batteries. Energy Environ Sci 2:638–654Google Scholar
  19. 19.
    Dahn JR, Zheng T, Liu Y, Xue JS (1995) Mechanisms for lithium insertion in carbonaceous materials. Science 270:590–593Google Scholar
  20. 20.
    Liang M, Zhi L (2009) Graphene-based electrode materials for rechargeable lithium batteries. J Mater Chem 19:5871–5878Google Scholar
  21. 21.
    Kaskhedikar NA, Maier J (2009) Lithium storage in carbon nanostructures. Adv Mater 21:2664–2680Google Scholar
  22. 22.
    Guo P, Song H, Chen X (2009) Electrochemical performance of graphene nanosheets as anode material for lithium-ion batteries. Electrochem Commun 11:1320–1324Google Scholar
  23. 23.
    Wang C, Li D, Too CO, Wallace GG (2009) Electrochemical properties of graphene paper electrodes used in lithium batteries. Chem Mater 21:2604–2606Google Scholar
  24. 24.
    Abouimrane A, Compton OC, Amine K, Nguyen ST (2010) Non-annealed graphene paper as a binder-free anode for lithium-ion batteries. J Phys Chem C 114:12800–12804Google Scholar
  25. 25.
    Bhardwaj T, Antic A, Pavan B, Barone V, Fahlman BD (2010) Enhanced electrochemical lithium storage by graphene nanoribbons. J Am Chem Soc 132:12556–12558Google Scholar
  26. 26.
    Yoo E, Kim J, Hosono E, Zhou H-s, Kudo T, Honma I (2008) Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. Nano Lett 8:2277–2282Google Scholar
  27. 27.
    Yata S, Kinoshita H, Komori M, Ando N, Kashiwamura T, Harada T, Tanaka K, Yamabe T (1994) Structure and properties of deeply Li-doped polyacenic semiconductor materials beyond C6Li stage. Synth Met 62:153–158Google Scholar
  28. 28.
    Lian P, Zhu X, Liang S, Li Z, Yang W, Wang H (2010) Large reversible capacity of high quality graphene sheets as an anode material for lithium-ion batteries. Electrochim Acta 55:3909–3914Google Scholar
  29. 29.
    Wan L, Ren Z, Wang H, Wang G, Tong X, Gao S, Bai J (2011) Graphene nanosheets based on controlled exfoliation process for enhanced lithium storage in lithium-ion battery. Diamond Relat Mater 20:756–761Google Scholar
  30. 30.
    Shanmugharaj AM, Choi WS, Lee CW, Ryu SH (2011) Electrochemical performances of graphene nanosheets prepared through microwave radiation. J Power Sources 196:10249–10253Google Scholar
  31. 31.
    Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, Yushin G (2010) High-performance lithium-ion anodes using a hierarchical bottom-up approach. Nat Mater 9:353–358Google Scholar
  32. 32.
    Derrien G, Hassoun J, Panero S, Scrosati B (2007) Nanostructured Sn-C Composite as an advanced anode material in high-performance lithium-ion batteries. Adv Mater 19:2336–2340Google Scholar
  33. 33.
    Kim H, Han B, Choo J, Cho J (2008) Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew Chem Int Ed 47:10151–10154Google Scholar
  34. 34.
    Zhang T, Fu L, Gao J, Yang L, Wu Y, Wu H (2006) Core-shell Si/C nanocomposite as anode material for lithium ion batteries. Pure Appl Chem 78:1889–1896Google Scholar
  35. 35.
    Nazri G-A, Pistoia G (2004) Lithium batteries: science and technology. Kluwer, Boston/Dordrecht/New York/London, p 708Google Scholar
  36. 36.
    Inoue H (2006) High capacity negative-electrode materials next to carbon; Nexelion. In: International meeting on lithium batteries, BiarritzGoogle Scholar
  37. 37.
    Kim H, Cho J (2008) Superior lithium electroactive mesoporous Si@Carbon core-shell nanowires for lithium battery anode material. Nano Lett 8:3688–3691Google Scholar
  38. 38.
    Park M-H, Kim MG, Joo J, Kim K, Kim J, Ahn S, Cui Y, Cho J (2009) Silicon nanotube battery anodes. Nano Lett 9:3844–3847Google Scholar
  39. 39.
    Cui L-F, Yang Y, Hsu C-M, Cui Y (2009) Carbon − silicon core − shell nanowires as high capacity electrode for lithium ion batteries. Nano Lett 9:3370–3374Google Scholar
  40. 40.
    Chan CK, Patel RN, O’Connell MJ, Korgel BA, Cui Y (2010) Solution-grown silicon nanowires for lithium-ion battery anodes. ACS Nano 4:1443–1450Google Scholar
  41. 41.
    Cui L-F, Ruffo R, Chan CK, Peng H, Cui Y (2009) Crystalline-amorphous core − shell silicon nanowires for high capacity and high current battery electrodes. Nano Lett 9:491–495Google Scholar
  42. 42.
    Beattie SD, Larcher D, Morcrette M, Simon B, Tarascon JM (2008) Si electrodes for Li-ion batteries–-a new way to look at an old problem. J Electrochem Soc 155:A158–A163Google Scholar
  43. 43.
    Stoller MD, Park S, Zhu Y, An J, Ruoff RS (2008) Graphene-based ultracapacitors. Nano Lett 8:3498–3502Google Scholar
  44. 44.
    Fasolino A, Los JH, Katsnelson MI (2007) Intrinsic ripples in graphene. Nat Mater 6:858–861Google Scholar
  45. 45.
    Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grigorieva IV, Dubonos SV, Firsov AA (2005) Two-dimensional gas of massless Dirac fermions in graphene. Nature 438:197–200Google Scholar
  46. 46.
    Larcher D, Beattie S, Morcrette M, Edstrom K, Jumas J-C, Tarascon J-M (2007) Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries. J Mater Chem 17:3759–3772Google Scholar
  47. 47.
    Obrovac MN, Christensen L (2004) Structural changes in silicon anodes during lithium insertion/extraction. Electrochem Solid State Lett 7:A93–A96Google Scholar
  48. 48.
    CRC Handbook of Chemistry and Physics, 91st ed. CRC Press (2011–2012) http://www.hbcpnetbase.com. Accessed December 2011
  49. 49.
    Li J, Christensen L, Obrovac MN, Hewitt KC, Dahn JR (2008) Effect of Heat Treatment on Si Electrodes Using Polyvinylidene Fluoride Binder. J Electrochem Soc 155:A234–A238Google Scholar
  50. 50.
    Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sources 163:1003–1039Google Scholar
  51. 51.
    Balbuena PB, Wang Y (2004) Lithium-Ion Batteries: Solid-Electrolyte Interphase. Imperial College Press, LondonGoogle Scholar
  52. 52.
    Lee JK, Smith KB, Hayner CM, Kung HH (2010) Silicon nanoparticles-graphene paper composites for Li ion battery anodes. Chem Commun 46:2025–2027Google Scholar
  53. 53.
    Chou S-L, Wang J-Z, Choucair M, Liu H-K, Stride JA, Dou S-X (2010) Enhanced reversible lithium storage in a nanosize silicon/graphene composite. Electrochem Commun 12:303–306Google Scholar
  54. 54.
    Wang X-L, Han W-Q (2011) Graphene Enhances Li Storage Capacity of Porous Single-Crystalline Silicon Nanowires. ACS Appl Mater Interfaces 2:3709–3713Google Scholar
  55. 55.
    Tao H-C, Fan L-Z, Mei Y, Qu X (2011) Self-supporting Si/reduced graphene oxide nanocomposite films as anode for lithium ion batteries. Electrochem Commun 13(12):1332–1335Google Scholar
  56. 56.
    Choucair M, Thordarson P, Stride JA (2009) Gram-scale production of graphene based on solvothermal synthesis and sonication. Nat Nano 4:30–33Google Scholar
  57. 57.
    Chan CK, Peng H, Liu G, McIlwrath K, Zhang XF, Huggins RA, Cui Y (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nano 3:31–35Google Scholar
  58. 58.
    Buqa H, Holzapfel M, Krumeich F, Veit C, Novák P (2006) Study of styrene butadiene rubber and sodium methyl cellulose as binder for negative electrodes in lithium-ion batteries. J Power Sources 161:617–622Google Scholar
  59. 59.
    Besenhard JO, Yang J, Winter M (1997) Will advanced lithium-alloy anodes have a chance in lithium-ion batteries? J Power Sources 68:87–90Google Scholar
  60. 60.
    Brousse T, Crosnier O, Santos-Peña J, Sandu I, Fragnaud P, Schleich DM (2002) Recent progress in the development of tin-based negative electrodes for Li-ion batteries. In: Kumagai N, Komaba S (eds) Materials chemistry in lithium batteries. Research Signpost, KeralaGoogle Scholar
  61. 61.
    Wang Z, Zhang H, Li N, Shi Z, Gu Z, Cao G (2010) Laterally confined graphene nanosheets and graphene/SnO2 composites as high-rate anode materials for lithium-ion batteries. Nano Res 3:748–756Google Scholar
  62. 62.
    Courtney IA, Dahn JR (1997) Electrochemical and in situ x-ray diffraction studies of the reaction of lithium with tin oxide composites. J Electrochem Soc 144:2045–2052Google Scholar
  63. 63.
    Du Z, Yin X, Zhang M, Hao Q, Wang Y, Wang T (2010) In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery. Mater Lett 64:2076–2079Google Scholar
  64. 64.
    Yao J, Shen X, Wang B, Liu H, Wang G (2009) In situ chemical synthesis of SnO2-graphene nanocomposite as anode materials for lithium-ion batteries. Electrochem Commun 11:1849–1852Google Scholar
  65. 65.
    Li N, Wang Z, Zhao K, Shi Z, Gu Z, Xu S (2010) Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method. Carbon 48:255–259Google Scholar
  66. 66.
    Wang X, Zhou X, Yao K, Zhang J, Liu Z (2011) A SnO2/graphene composite as a high stability electrode for lithium ion batteries. Carbon 49:133–139Google Scholar
  67. 67.
    Liang S, Zhu X, Lian P, Yang W, Wang H (2011) Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries. J Solid State Chem 184:1400–1404Google Scholar
  68. 68.
    Zhao B, Zhang G, Song J, Jiang Y, Zhuang H, Liu P, Fang T (2011) Bivalent tin ion assisted reduction for preparing graphene/SnO2 composite with good cyclic performance and lithium storage capacity. Electrochim Acta 56:7340–7346Google Scholar
  69. 69.
    Zhu X, Zhu Y, Murali S, Stoller MD, Ruoff RS (2011) Reduced graphene oxide/tin oxide composite as an enhanced anode material for lithium ion batteries prepared by homogenous coprecipitation. J Power Sources 196:6473–6477Google Scholar
  70. 70.
    Chang K, Wang Z, Huang G, Li H, Chen W, Lee JY (2012) Few-layer SnS2/graphene hybrid with exceptional electrochemical performance as lithium-ion battery anode. J Power Sources 201:259–266Google Scholar
  71. 71.
    Wang G, Wang B, Wang X, Park J, Dou S, Ahn H, Kim K (2009) Sn/graphene nanocomposite with 3D architecture for enhanced reversible lithium storage in lithium ion batteries. J Mater Chem 19:8378–8384Google Scholar
  72. 72.
    Chen S, Chen P, Wu M, Pan D, Wang Y (2010) Graphene supported Sn-Sb@carbon core-shell particles as a superior anode for lithium ion batteries. Electrochem Commun 12:1302–1306Google Scholar
  73. 73.
    Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM (2000) Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 407:496–499Google Scholar
  74. 74.
    Banerjee B, Lahiry S (1983) Superparamagnetism in γ-Mn2O3–α-Fe2O3–α-Mn2O3 system. Phys Status Solidi 76:683–694Google Scholar
  75. 75.
    Li H, Richter G, Maier J (2003) Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries. Adv Mater 15:736–739Google Scholar
  76. 76.
    Dhaouadi H, Madani A, Touati F (2010) Synthesis and spectroscopic investigations of Mn3O4 nanoparticles. Mater Lett 64:2395–2398Google Scholar
  77. 77.
    Hu J, Li H, Huang X, Chen L (2006) Improve the electrochemical performances of Cr2O3 anode for lithium ion batteries. Solid State Ion 177:2791–2799Google Scholar
  78. 78.
    Anisimov VI, Korotin MA, Kurmaev EZ (1990) Band-structure description of Mott insulators (NiO, MnO, FeO, CoO). J Phys Condens Matter 2:3973–3987Google Scholar
  79. 79.
    Wang H, Cui L-F, Yang Y, Sanchez Casalongue H, Robinson JT, Liang Y, Cui Y, Dai H (2010) Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries. J Am Chem Soc 132:13978–13980Google Scholar
  80. 80.
    Lavoie N, Malenfant PRL, Courtel FM, Abu-Lebdeh Y, Davidson IJ (2012) High gravimetric capacity and long cycle life in Mn3O4/graphene platelet/LiCMC composite lithium ion batteries anodes. J Power Sources 213:249–254Google Scholar
  81. 81.
    Xing L, Cui C, Ma C, Xue X (2011) Facile synthesis of α-MnO2/graphene nanocomposites and their high performance as lithium-ion battery anode. Mater Lett 65:2104–2106Google Scholar
  82. 82.
    Yu A, Park HW, Davies A, Higgins DC, Chen Z, Xiao X (2011) Free-standing layer-by-layer hybrid thin film of graphene-MnO2 nanotube as anode for lithium ion batteries. J Phys Chem Lett 2(15):1855–1860Google Scholar
  83. 83.
    Courtel FM, Duncan H, Abu-Lebdeh Y, Davidson IJ (2011) High capacity anode materials for Li-ion batteries based on spinel metal oxides AMn2O4 (A = Co, Ni, and Zn). J Mater Chem 21:10206–10218Google Scholar
  84. 84.
    Fang X, Lu X, Guo X, Mao Y, Hu Y-S, Wang J, Wang Z, Wu F, Liu H, Chen L (2010) Electrode reactions of manganese oxides for secondary lithium batteries. Electrochem Commun 12:1520–1523Google Scholar
  85. 85.
    Gao J, Lowe MA, Abruna HD (2011) Spongelike nanosized Mn3O4 as a high-capacity anode material for rechargeable lithium batteries. Chem Mater 23:3223–3227Google Scholar
  86. 86.
    Zhu Y, Stoller MD, Cai W, Velamakanni A, Piner RD, Chen D, Ruoff RS (2010) Exfoliation of graphite oxide in propylene carbonate and thermal reduction of the resulting graphene oxide platelets. ACS Nano 4:1227–1233Google Scholar
  87. 87.
    Ban C, Wu Z, Gillaspie DT, Chen L, Yan Y, Blackburn JL, Dillon AC (2010) Nanostructured Fe3O4/SWNT electrode: binder-free and high-rate Li-ion anode. Adv Mater 22:E145–E149Google Scholar
  88. 88.
    Zhu X, Zhu Y, Murali S, Stoller MD, Ruoff RS (2011) Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries. ACS Nano 5:3333–3338Google Scholar
  89. 89.
    Wang G, Liu T, Luo Y, Zhao Y, Ren Z, Bai J, Wang H (2011) Preparation of Fe2O3/graphene composite and its electrochemical performance as an anode material for lithium ion batteries. J Alloys Compd 509:L216–L220Google Scholar
  90. 90.
    Ji L, Tan Z, Kuykendall TR, Aloni S, Xun S, Lin E, Battaglia V, Zhang Y (2011) Fe3O4 nanoparticle-integrated graphene sheets for high-performance half and full lithium ion cells. Phys Chem Chem Phys 13:7170–7177Google Scholar
  91. 91.
    Wang J-Z, Zhong C, Wexler D, Idris NH, Wang Z-X, Chen L-Q, Liu H-K (2011) Graphene-encapsulated Fe3O4 nanoparticles with 3D laminated structure as superior anode in lithium ion batteries. Chem Eur J 17:661–667Google Scholar
  92. 92.
    Lian P, Zhu X, Xiang H, Li Z, Yang W, Wang H (2010) Enhanced cycling performance of Fe3O4-graphene nanocomposite as an anode material for lithium-ion batteries. Electrochim Acta 56:834–840Google Scholar
  93. 93.
    Zhang M, Lei D, Yin X, Chen L, Li Q, Wang Y, Wang T (2010) Magnetite/graphene composites: microwave irradiation synthesis and enhanced cycling and rate performances for lithium ion batteries. J Mater Chem 20:5538–5543Google Scholar
  94. 94.
    Zhou G, Wang D-W, Li F, Zhang L, Li N, Wu Z-S, Wen L, Lu GQ, Cheng H-M (2010) Graphene-wrapped Fe3O4 anode material with improved reversible capacity and cyclic stability for lithium ion batteries. Chem Mater 22:5306–5313Google Scholar
  95. 95.
    Wang G, Liu T, Xie X, Ren Z, Bai J, Wang H (2011) Structure and electrochemical performance of Fe3O4/graphene nanocomposite as anode material for lithium-ion batteries. Mater Chem Phys 128:336–340Google Scholar
  96. 96.
    Li Y, Tan B, Wu Y (2008) Mesoporous Co3O4 nanowire arrays for lithium ion batteries with high capacity and rate capability. Nano Lett 8:265–270Google Scholar
  97. 97.
    Yao W-L, Wang J-L, Yang J, Du G-D (2008) Novel carbon nanofiber-cobalt oxide composites for lithium storage with large capacity and high reversibility. J Power Sources 176:369–372Google Scholar
  98. 98.
    Wu Z-S, Ren W, Wen L, Gao L, Zhao J, Chen Z, Zhou G, Li F, Cheng H-M (2010) Graphene anchored with Co3O4 nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and cyclic performance. ACS Nano 4:3187–3194Google Scholar
  99. 99.
    Yang S, Cui G, Pang S, Cao Q, Kolb U, Feng X, Maier J, Müllen K (2010) Fabrication of cobalt and cobalt oxide/graphene composites: towards high-performance anode materials for lithium ion batteries. ChemSusChem 3:236–239Google Scholar
  100. 100.
    Li B, Cao H, Shao J, Li G, Qu M, Yin G (2011) Co3O4@graphene composites as anode materials for high-performance lithium ion batteries. Inorg Chem 50:1628–1632Google Scholar
  101. 101.
    Chen SQ, Wang Y (2010) Microwave-assisted synthesis of a Co3O4-graphene sheet-on-sheet nanocomposite as a superior anode material for Li-ion batteries. J Mater Chem 20:9735–9739Google Scholar
  102. 102.
    Yang S, Feng X, Ivanovici S, Müllen K (2010) Fabrication of graphene-encapsulated oxide nanoparticles: towards high-performance anode materials for lithium storage. Angew Chem Int Ed 49:8408–8411Google Scholar
  103. 103.
    Kim H, Seo D-H, Kim S-W, Kim J, Kang K (2010) Highly reversible Co3O4/graphene hybrid anode for lithium rechargeable batteries. Carbon 49:326–332Google Scholar
  104. 104.
    Zhu J, Sharma YK, Zeng Z, Zhang X, Srinivasan M, Mhaisalkar S, Zhang H, Hng HH, Yan Q (2011) Cobalt oxide nanowall arrays on reduced graphene oxide sheets with controlled phase, grain size, and porosity for Li-ion battery electrodes. J Phys Chem C 115:8400–8406Google Scholar
  105. 105.
    Wang B, Wang Y, Park J, Ahn H, Wang G (2011) In situ synthesis of Co3O4/graphene nanocomposite material for lithium-ion batteries and supercapacitors with high capacity and supercapacitance. J Alloys Compd 509:7778–7783Google Scholar
  106. 106.
    Tao L, Zai J, Wang K, Zhang H, Xu M, Shen J, Su Y, Qian X (2012) Co3O4 nanorods/graphene nanosheets nanocomposites for lithium ion batteries with improved reversible capacity and cycle stability. J Power Sources 202:230–235Google Scholar
  107. 107.
    Zou Y, Wang Y (2011) NiO nanosheets grown on graphene nanosheets as superior anode materials for Li-ion batteries. Nanoscale 3:2615–2620Google Scholar
  108. 108.
    Wang B, Wu X-L, Shu C-Y, Guo Y-G, Wang C-R (2010) Synthesis of CuO/graphene nanocomposite as a high-performance anode material for lithium-ion batteries. J Mater Chem 20:10661–10664Google Scholar
  109. 109.
    Zhou J, Ma L, Song H, Wu B, Chen X (2011) Durable high-rate performance of CuO hollow nanoparticles/graphene-nanosheet composite anode material for lithium-ion batteries. Electrochem Commun 13(12):1357–1360Google Scholar
  110. 110.
    Mai YJ, Wang XL, Xiang JY, Qiao YQ, Zhang D, Gu CD, Tu JP (2011) CuO/graphene composite as anode materials for lithium-ion batteries. Electrochim Acta 56:2306–2311Google Scholar
  111. 111.
    Lu LQ, Wang Y (2012) Facile synthesis of graphene supported shuttle- and urchin-like CuO for high and fast Li-ion storage. Electrochem Commun 14(1):82–85Google Scholar
  112. 112.
    Hashimoto A, Suenaga K, Urita K, Shimada T, Sugai T, Bandow S, Shinohara H, Iijima S (2005) Atomic correlation between adjacent graphene layers in double-wall carbon nanotubes. Phys Rev Lett 94:045504Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Nathalie Lavoie
    • 1
  • Fabrice M. Courtel
    • 2
  • Patrick R. L. Malenfant
    • 1
  • Yaser Abu-Lebdeh
    • 1
  1. 1.National Research Council of CanadaOttawaCanada
  2. 2.Atomic Energy of Canada LimitedChalk RiverCanada

Personalised recommendations