Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

Son, In Hyuk; Park, Jong Hwan; Kwon, Soonchul; Park, Seongyong; Rümmeli, Mark H.; Bachmatiuk, Alicja; Song, Hyun Jung; Ku, Jun-Hwan; Choi, Jang Wook; Choi, Jae‐Man; Doo, Seok‐Gwang; Chang, Hyuk

doi:10.1038/ncomms8393

Cited by 492 publications

(266 citation statements)

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“…The SNC‐G electrode contained carbon along with Si, and a very small amount of O 2 (0.79%). Similarly, Son et al113 demonstrated the direct growth of high quality MLG on Si nanoparticles at 900–1100 °C via APCVD using a gas mixture of CH 4 , CO 2 , and H 2 . CO 2 was used as a mild oxidant which helped in achieving robust and uniform growth of MLG around each Si nanoparticle by generating catalytic sites.…”

Section: Catalyst‐free Direct Cvd Growth Of Graphene On Technologicalmentioning

confidence: 95%

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

et al. 2018

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To fabricate graphene based electronic and optoelectronic devices, it is highly desirable to develop a variety of metal‐catalyst free chemical vapor deposition (CVD) techniques for direct synthesis of graphene on dielectric and semiconducting substrates. This will help to avoid metallic impurities, high costs, time consuming processes, and defect‐inducing graphene transfer processes. Direct CVD growth of graphene on dielectric substrates is usually difficult to accomplish due to their low surface energy. However, a low‐temperature plasma enhanced CVD technique could help to solve this problem. Here, the recent progress of metal‐catalyst free direct CVD growth of graphene on technologically important dielectric (SiO2, ZrO2, HfO2, h‐BN, Al2O3, Si3N4, quartz, MgO, SrTiO3, TiO2, etc.) and semiconducting (Si, Ge, GaN, and SiC) substrates is reviewed. High and low temperature direct CVD growth of graphene on these substrates including growth mechanism and morphology is discussed. Detailed discussions are also presented for Si and Ge substrates, which are necessary for next generation graphene/Si/Ge based hybrid electronic devices. Finally, the technology development of the metal‐catalyst free direct CVD growth of graphene on these substrates is concluded, with future outlooks.

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Section: Catalyst‐free Direct Cvd Growth Of Graphene On Technologicalmentioning

confidence: 95%

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

et al. 2018

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“…[ 419 ] Here, only 33 cycles were reported, all showing unsatisfactory electrochemical behavior in terms Coulombic effi ciency (always lower than 90%) ( Table 3 ). H. Chang et al, [ 420 ] by means of CVD, anchored multilayer graphene onto the surface of Si nanoparticles (the graphene content was 5 wt%), with the aim of accommodating the volume expansion of silicon via a sliding process between adjacent graphene layers. When such anode material was paired (without any prior pre-lithiation step) with a commercial LiCoO 2 cathode, energy densities of 972 and 700 Wh L −1 at the 1 st and 200 th cycle were achieved, respectively (i.e., 1.8 and 1.5 times higher than those of current commercial lithium-ion batteries calculated based on the same metric).…”

Section: Full-cells Employing Graphene and Graphene-containing Anodesmentioning

confidence: 99%

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

et al. 2016

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that its extraordinary properties would enable revolutionary new technologies, which gave birth to the "graphene era". [ 3,4 ] Relying on this scenario, in 2013, the European Union launched the ¤1 billion "Graphene Flagship" project aimed to investigate the properties of this new form of carbon for various applications (e.g., electronics, sensors and energy storage devices), with the ambitious goal of guiding graphene from laboratories to commercial applications within a decade. [ 5,6 ] In the same period, the Chinese Government set up a similar investment to mass-produce graphene as thin fi lms (e.g., for touchscreen electrodes) and platelets (e.g., for use in batteries). [ 6 ] In the following years, hundreds of patents, mainly focused on manufacturing and application in energy storage, were fi led and the worldwide production of graphene and graphene-containing materials rapidly increased. Although a few Chinese industries claimed to already use graphene-containing materials for smartphone production, no revolutionary practical application relying on graphene has been yet developed. [ 6 ] Specifi cally with respect to the battery fi eld, a close analysis of the scientifi c literature reveals a struggle to meet the ambitious initial targets. A potential loss of focus from the fi nal application caused by hype and ease of publication on such a novel matter, together with the delivery of very misleading information [ 7,8 ] and erroneous statements [ 7 ] concerning the use of graphene in batteries are emerging as possible reasons of the ineffective graphene-era outburst. In this progress report, we do not focus on production and classifi cation of graphene and graphene-containing materials, which were already well reported in the past years. [ 3,[9][10][11] In contrast, due to the lack of an exhaustive analysis of the progression of the use of such materials in lithium-ion battery (LIB) anodes, we report here a critical evaluation of the most prominent research papers published from 2008 until the end of 2015. As shown in Figure 1 , three different stages of the graphene research in LIB anodes can be distinguished: a fi rst stationary phase between 2008 and 2010 where the lithium-ion storage properties of different graphene and graphene-containing materials were preliminarily explored, a second exponential stage, spanning from 2010 to 2014, where graphene and graphene-containing anode materials were broadly developed and investigated, and fi nally, a third phase, (i.e., starting from 2015), where the research seems to have approached a plateau. After Used as a bare active material or component in hybrids, graphene has been the subject of numerous studies in recent years. Indeed, from the fi rst report that appeared in late July 2008, almost 1600 papers were published as of the end 2015 that investigated the properties of graphene as an anode material for lithium-ion batteries. Although an impressive amount of data has been collected, a real advance in the fi eld still seems to be missing. In this framework, atten...

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“…For this reason, most of the full cells using nanosized silicon or micron sized silicon negative electrodes show poor capacity retention. 17,25,[34][35][36][37][38][39] …”

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confidence: 99%

“…For this reason, most of the full cells using nanosized silicon or micron sized silicon negative electrodes show poor capacity retention. 17,25,[34][35][36][37][38][39] Studies of the failure mechanisms of full cells with Si-containing negative electrodes need to be performed. Studying full cells can identify further challenges faced by Si-based negative electrodes and quite possibly guide researchers toward electrode and electrolyte designs that are more commercially relevant.…”

mentioning

confidence: 99%

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Petibon

Chevrier

Aiken

et al. 2016

J. Electrochem. Soc.

132

137

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The capacity fade mechanisms of LiCoO 2 /Si-alloy:graphite pouch cells filled with a 1M LiPF 6 EC:EMC:FEC (27:63:10) electrolyte were studied using galvanostatic cycling, electrochemical impedance spectroscopy on symmetric cells, gas-chromatography and differential voltage analysis. Analysis of the gas generated during the first cycle indicated that FEC reacts at the negative electrode following a 1-electron reduction pathway and other pathways that do not lead to the formation of gaseous products. An analysis of the electrolyte showed that FEC is continuously consumed during the first 80% of the first charge (formation cycle). Typical cells charged and discharged at 40 • C showed a gradual capacity loss for the first 250 cycles followed by a sudden capacity drop associated with a large polarization growth. Analysis of the electrolyte showed that this sudden failure is associated with the depletion of FEC. The capacity loss as well as the consumption of FEC prior to the sudden failure was fitted using a model that includes a time dependence and a cycle number dependence. The time dependence was associated with the thickening solid electrolyte interface at the surface of the negative electrode particles (Si-alloy and graphite) and the cycle number dependence was associated with the solid electrolyte interface repair at the surface of Si-alloy particles during repeated expansion and contraction. Cost reduction and an increase in the volumetric energy density of Li-ion cells can possibly be attained using silicon-based negative electrodes.1-3 While these benefits have been known for many years, commercial implementation remains limited due to silicon's inherent challenges.Si-based electrodes can suffer from particle pulverization upon cycling (e.g. micron sized silicon), 1,4-7 can have loss of electronic contact between particles after repeated expansion and contraction during cycling, 2,8-10 can have high irreversible first cycle coulombic efficiency 11,[12][13][14][15] and can have low coulombic efficiency (compared to graphite electrodes) during cycling. 1,16,17 The root cause of these challenges is the large volume expansion 1,18 of the material during lithiation and subsequent contraction during delithiation. Several issues have been solved through the use of either nanosized Si or nanostructured Si. For instance the use of nanosized Si particles solves some of the pulverization problems encountered by micron sized Si particles. 1,4,11,[19][20][21] However, nanosized Si still suffers from inter-particle contact loss during cycling as well as low coulombic efficiency due to large specific surface area. 1,16In a recent publication, Chevrier et al. 16 presented a rational way to design commercially relevant Si-based negative electrodes. They showed that confining nano-domains of silicon in an alloy matrix suppresses particle pulverization and greatly reduces the surface area of Si exposed to the electrolyte. This approach yields materials with lower first cycle irreversible capacity (IRC) loss, better coulombic e...

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Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

Cited by 492 publications

References 50 publications

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

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Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density

Cited by 492 publications

References 50 publications

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates

Critical Insight into the Relentless Progression Toward Graphene and Graphene‐Containing Materials for Lithium‐Ion Battery Anodes

Studies of the Capacity Fade Mechanisms of LiCoO2/Si-Alloy: Graphite Cells

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Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells