Stable and Reversible Lithium Storage with High Pseudocapacitance

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Stable and Reversible Lithium Storage with High Pseudocapacitance in GaN Nanowires Changlong Sun, Mingzhi Yang, Tailin Wang, Yongliang Shao, Yongzhong Wu, and Xiaopeng Hao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b16416 • Publication Date (Web): 22 Dec 2017 Downloaded from http://pubs.acs.org on December 22, 2017

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ACS Applied Materials & Interfaces

Stable

and

Reversible

Lithium

Storage

with

High

Pseudocapacitance in GaN Nanowires Changlong Sun,† Mingzhi Yang,† Tailin Wang, Yongliang Shao, Yongzhong Wu, and Xiaopeng Hao* State Key Lab of Crystal Materials, Shandong University, Jinan 250100, Shandong, P. R. China *E-mail: [email protected] [†] These authors contributed equally to this work.

1

ACS Paragon Plus Environment

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Abstract In this work, gallium nitride (GaN) nanowires (NWs) were synthesized by chemical vapor deposition (CVD) process. The hybrid electrode showed the capacity up to 486 mAh g−1 after 400 cycles at 0.1 A g−1. Even at 10 A g−1, the reversible capacity can stabilize at 75 mAh g−1 (after 1000 cycles). Pseudocapacitive capacity was defined by kinetics analysis. The dynamics analysis and electrochemical reaction mechanism of GaN with Li+ was also analyzed by ex situ XRD, HRTEM and XPS results. These results not only cast new light on pseudocapacitance enhanced high-rate energy storage devices by self-assembled nanoengineering but also extend the application range of traditional binary III/V semiconductors.

Keywords: Gallium nitride; Nanowires; Graphite layer; CVD; Pseudocapacitive; Lithium-ion batteries 2


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1. INTRODUCTION Lithium ion batteries (LIBs) with higher energy capacity and longer cycle life have received much attention.1,2 In fact, the performance of the LIBs relies intimately on the electrode materials.3 Because of the low capability (372 mA h g−1) and relative poor cycling performance,4 commercialized graphite will be unable to meet the increasing needs of energy.5 To resolve these questions, metal nitrides (MNs) have been received much attention.6 Because of the low conversion reaction potentials with Li,7 MNs have always been considered as promising electrode candidates for LIBs,8 such as Fe3N,9 SnN,10 Co3N,9 Mn3N2,11 TiN,12−14 Zn3N215 etc. In fact, group III nitride in energy storage devices and photocatalysis fields have attracted considerable attention.16−24 Compared to oxygen 2p orbital, the more negative potential of the nitrogen 2p orbital guarantee MNs possess higher carrier mobility and electrical/ionic conductivity.21 In addition, the intrinsic chemical physical stability of MNs favors the utilization in harsh electrochemical reaction. To enhance the rate capability, direct synthesis of GaN on conductive substrate in nanowire (NW) arrays form is very necessary. The bridging/connecting of GaN NWs through the conductive substrate guarantees that each NW has the tight contact with conductive substrate.25 In consequence, not only the unique functions of both GaN NWs and conductive substrate are fully utilized, but also the strong synergistic effect will be achieved.25 In this work, GaN NWs/graphite layer are designed by facile and scalable CVD method. This self-supported GaN NWs growth on the conductive substrate are highly 3



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desirable electrode architecture with large specific surface area, which significantly shortens transport distance for Li+ and ensures fast electron transport. The unique structural features and synergistic effect manifest high rate capability and enhanced cycling performance, as revealed by the dynamics analysis and electrochemical reaction mechanism study. This work also creates an opportunity to design novel self-supported metal nitride NWs for intercalation pseudocapacitive enhanced high-rate energy storage devices.

2. RESULTS AND DISCUSSION 2.1 Phase and morphology characterization

Figure 1. (a, b) Schematic illustration and synthesis protocol of the CVD method. (c) SEM image of the GaN NWs; the top right inset images show the color variation of the graphite layer before and after GaN NWs growth, the below left inset is the SEM image of the graphite layer. (d) SEM image and EDS elemental mapping of Ga, N for 4


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the GaN NWs arrays, the middle inset is the EDS microanalysis. (e) XRD of GaN NWs, the inset peaks located at 54.8° is from graphite layer. (f) TEM, HRTEM and SAED images of single GaN NW. The GaN NW arrays with high density were synthesized on graphite layer in a CVD tube furnace using Ga2O3 and NH3 as source materials (Figure 1a). Figure 1b shows the typical growth process (S1.1). Because of the large-scale presence GaN NWs, the smooth graphite layer became rough (Figure 1c). In contrast, the unmodified graphite layer without GaN NWs had smooth surface (below left inset of Figure 1c). The color variation of the graphite layer before and after GaN NWs growing also shows the presence of GaN NWs (top right inset of Figure 1c). The elemental mapping analysis (Figure 1d) reveals the symmetrical distribution of Ga and N. The entire nanostructures were found to consist of only C, Ga, and N elements in the EDS microanalysis (middle inset of Figure 1d). The X-ray diffraction peaks can be indexed as wurtzite GaN (JCPDS: No. 50-0792), Figure 1e. The peak located at 54.8° is from the graphite (inset of Figure 1e). Figure 1f shows the low-magnification TEM image with the diameter of ~50 nm. The corresponding HRTEM image reveals -

-

the interplanar spacing of 2.76 Å, corresponding to the (1010) and (1100) lattice plane of wurtzite GaN. A selected area electron diffraction (SAED) pattern manifest GaN NWs grow in the [1000] direction and proves the single crystal structure. The tight integration interface significantly shortens transport distance for Li+ and ensures fast electron transport. Thus, the unique structural features and synergistic effect manifest enhanced electrochemical performance. 5



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Figure 2. (a, b) Photoluminescence and Raman characterization of GaN NWs. The peak marked with an asterisk in Raman spectrum is from graphite layer. (c) Current-voltage response of single GaN NW at room temperature. The top left inset is schematic diagram of the GaN NW device, below right inset depicts an optical microscope image of the GaN NW device. (d) N2 adsorption-desorption isotherms. Inset is the corresponding pore distribution. As shown in Figure 2a, the strong band-edge emission (~365 nm) and defect related band emission (~600 nm) are observed. The defect related yellow luminescence (YL) band emission may be related to Ga or N vacancies.26,27 As shown in the Raman spectrum (Figure 2b), the broad band from 500 to 600 cm−1 can be matched by two sub-band located at 534 and 569 cm‒1, corresponding to A1 (TO) and E2 (high) modes of wurtzite GaN, respectively. The E2 (high) mode at 569 cm‒1 can be attributed to non-polar optical phonon mode.28 The peak located at 144 cm‒1 is associated with the 6


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E2 (low) mode of hexagonal GaN.29 The broad band from 620 to 750 cm−1 also can be indexed by two sub-band located at 657 and 736 cm‒1. The sub-band located at 736 cm‒1 can be attributed to A1 (LO) mode of hexagonal GaN.30 The broad and asymmetric sub-band located at 657 cm‒1 can be indexed to the defect band under the conduction band of GaN.31 The additional band located at 420 cm‒1 can be attributed to nitrogen vacancies and/or interstitials.32 The corresponding conductivity was determined to be ~1.54 × 103 S·m‒1 (Figure 2c), which is comparable with graphite layer (~7.5 × 104 S·m‒1). The good conductivity of the hierarchical architectures ensure efficient electron and Li+ transport.33 As shown in Figure 2d, the surface area is about 146 m2 g−1. The inset of Figure 2d shows the pore size distribution is centered at 17 nm, which evidences the existence of mesopores (2-50 nm).

2.2 Electrochemical performance

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Figure 3. (a) CVs of the hybrid electrode at 0.1 mV s−1. (b) Charge/discharge curves and (c) Cycle property at 0.1 A g−1. (d) Rate capabilities from 0.1 to 10 A g−1. (e) Nyquist plots of the hybrid electrode and bare graphite layer. (f) Schematic diagram of operation principle of Li+/electron transport. (g) Cycling property at 10 A g−1 and corresponding Coulombic efficiency. The cyclic voltammetry (CV) analysis was employed at 0.1 mV s−1, Figure 3a. The irreversible peaks (~0.5 V and 0.75 V) can be ascribed to the formation of solid electrolyte interphase (SEI),34 in accordance with that of GaN powder electrode (Figure S3a). In the subsequent second discharge process, the peaks of 0.5 V and 0.75 V disappear, but a pronounced peak at 1.0 V appears. The oxidation peak located at around 1.0 V is discernable in the corresponding charge process, which is related to the electrochemical reaction of MNs.9,35 In the following cycle, the oxidation peak located at 0.48 V shifts to 0.41 V, but charge profile remains almost unchanged. The oxidation and reduction peaks in the second to fifth CV cycle become very stable, indicating that the lithiation/delithiation reaction is highly reversible. The reduction/oxidation profiles are almost the same for GaN NWs and GaN powder (Figure S3). The hybrid electrode delivered the initial discharge/charge capacities of 943.4 and 519.7 mAh g−1 at 0.1 A g−1, respectively (Figure 3b). As shown in Figure 3c, the capacity is still as high as 486 mAh g−1 after 400 cycles at 0.1 A g−1. Note that the capacity contribution of the graphite layer is estimated to be about 10.4 % (Figure S2 and S4). For comparison, the capacities of GaN powder are shown in Figure S3b. Obviously,

lower

specific

capacity

can

be

attributed

to

the

inferior 8


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lithiation/delithiation reactions (Figure S5).4 As shown in Figure 3e, the Nyquist plots for the hybrid electrode consist of a single depressed semicircle (charge-transfer resistance, Rct) in the high-to-medium frequency region and an inclined line at low frequencies (mass-transfer process).36 The relatively smaller Rct increase demonstrates the good conductivity both of GaN NWs and graphite layer (Figure 3e and Figure S6). These results demonstrate that the obtained nitrogen doped graphite ensures the fast electron transport (Figure S7).37,38 The rate property was evaluated at current densities ranging from 0.1 to 10 A g−1 (Figure 3d). On increasing the current density, the hybrid electrode delivered the reversible capacities of 520, 475, 415, 370, 320, 115, and 90 mAh g−1 at 0.1, 0.2, 0.5, 1, 2, 5, and 10 A g−1, respectively. In addition, a capacity over 520 mAh g−1 could be recovered when the current density was switched back to 0.1 A g−1, indicating excellent Li+ storage reversibility. This result also suggests that the stable hybrid electrode facilitates both transports of electrons and Li+ (Figure 3f). The long time cycling property was tested at 10 A g−1 (Figure 3g). After 1000 cycles, this hybrid electrode still maintained reversible discharge capacity of 75 mAh g−1, retaining 74 % of the initial discharge capacity, revealing highly reversible Li+ intercalation kinetics.25 Table S1 shows the comparison of GaN NWs/graphite layer electrode and other previously reported metal nitrides. For all we know, the GaN NWs/graphite layer electrodes deliver the favorable capacities and long-term cycling performance among these results at 0.1 and 10 A g−1, respectively.

2.3 Kinetics characterization 9



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Figure 4. Kinetics analysis of Li+ storage behavior. (a) CV curves from 0.1 to 1.0 mV s−1. (b) Determination of the b value. (c) CV with the separation of the capacitive (purple region) and diffusion contribution at 1.0 mV s−1. (d) Bar chart showing the contribution ratio of the capacitive and diffusion-controlled charge versus scan rate. To gain further insight into the electrochemical kinetics, CV measurements were performed. The negligible lithiation/delithiation peak shift implies the low polarization and good reversibility of the hybrid GaN NWs electrode.39 The degree of capacitive effect (graphite and GaN NWs) can be qualitatively analyzed according to the relation between current (i) and scan rate (v): i = avb, where a and b both are constants. For a diffusion controlled process b approaches 0.5, while the surface capacitance dominated process b is close to 1.0. The value of b is calculated from the slope of the log i versus log v plot.40 As shown in Figure 4b, a linear relationship (b=0.89 and 0.94) between log(i) and log(v) is observed (v < 1 mV s–1), indicating that 10


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the capacity consists of both capacitive and diffusion-controlled contributions. The value of b decreases at a higher scan rate (> 1 mV s–1), Figure S8, reflecting the restrictive to the rate capability at high scan rates.41 The capacitive contribution (graphite and GaN NWs) at a fixed voltage is quantitatively determined on the base of the capacitive effect (k1v) and diffusion controlled insertion (k2v1/2), where the k1 and k2 are fixed for the same electrochemical reaction. The linear relationship between i/v1/2 and v1/2 is observed in Figure S9, which allows for a quantification of the pseudocapacitive current according to i/v1/2 = k1 v1/2 + k2 based on peak currents. The diffusion controlled capacitance is mainly generated at peak region, indicating that the diffusion process occurs in those peaks region (Figure 4c).42 More specifically, contribution ratios between the two different processes at specific scan rates are also quantitatively separated. As the scan rate increases, the quantified results (Figure 4d) show that the capacitive capacity (graphite and GaN NWs) is improved, and the diffusion contribution is depressed.

2.4 Electrochemical reaction mechanism

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Figure 5. (a) The different charge states for ex situ XRD at 1st CV curve. (b) Ex situ XRD. The shallow region represents the (c) enlarged ex situ XRD profiles between 31° and 40°. The peak marked with asterisks in the XRD profiles are from graphite layer. (d) Ex situ XRD after 400 cycles at 0.1 A g−1. (e) Ex situ HRTEM image after 400 cycles. The top right inset is the low-magnification TEM of single GaN NW, the below right inset is the SAED pattern, scale bars: 5 1/nm. (f) Ex-situ N 1s XPS spectra after 400 cycles. Figure 5a is the first discharge/charge profile at 0.1 mV s−1 with labeled points for ex situ XRD. The diffraction peaks (Figure 5b) can be ascribed to wurtzite GaN and graphite layer (marked by red asterisks). To identify of the crystal structure evolution explicit, ex situ XRD profiles are enlarged between 31° and 40° (Figure 5c). The main (100), (002), and (101) peaks show progressively broadening and evidently shifting toward low-angle region along with a gradual decrease in diffraction intensity during the discharge process. This obviously indicates that the insertion reaction of GaN with Li with the formation of LixGaN. For the following charging process, the ex situ XRD profiles show opposite changes. Those result indicates the gradually reformation process of crystalline GaN. The ex situ XRD analysis manifest Li+ could reversibly insertion/desertion from wurtzite GaN during the cycling. Moreover, we performed the ex situ XRD profiles after 400 cycles at 0.1 A g−1. The crystallinity of the wurtzite GaN NWs tends to become weaker (Figure 5d), which is caused by the cyclic lithiation/delithiation process. The typical peaks at 32.6° (100), 34.7° (002), and 37.1° (101) of wurtzite GaN still can be detected. This means that the wurtzite GaN phase 12


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can be maintained after long cycling. Reduced semicircle of the impedance spectrum (Figure S10) suggested that the charge transport was improved during cycling. Ex situ SEM (Figure S11) indicates GaN NWs distributed uniformly throughout the entire electrode after extended cycling and remained intact. As shown in the ex situ TEM image after 400 cycles (top right inset in Figure 5e), the structure of the GaN NW was preserved. The HRTEM image still confirmed the wurtzite GaN structure (Figure 5e). The corresponding SAED pattern (below right inset of Figure 5e) showed poor crystallization of GaN NWs after 400 cycles, corresponding to the ex situ XRD results (Figure 5d). As shown in Figure 5f, the N 1s XPS spectrum after 400 cycles is obviously different from that of the as-prepared electrode (Figure S12). The broad peak ranging from 390 to 408 eV can be well fitted by two sub-peaks located at 397.2 and 400.2 eV, corresponding to the N-Ga17,24 and N-Li43,44 bonds, respectively. This scenario unambiguously reveals insertion reaction of GaN with Li with the formation of LixGaN.

3. CONCLUSIONS In summary, GaN NWs/graphite layer structure has been introduced into LIBs as high-performance electrode. The hybrid electrode deliver enhanced electrochemical performance with a discharge capacity of 486 mAh g−1 for the 400 cycles at 0.1 A g−1 and 75 mAh g−1 after 1000 cycles at 10 A g−1 with the insertion/desertion mechanism. Kinetics analysis reveals interesting Li+ pseudocapacitive behavior in the hybrid electrode and a high contribution of capacitive charge. As revealed by ex situ results,

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the stable cycle performance is also related to the reversible intercalation reaction with the formation of LixGaN. This study extends the application range of group-III nitrides based semiconductors in the field of energy storage.

4. EXPERIMENTS Preparation GaN nanowires (NWs). Single-crystalline GaN NWs were synthesized using aurum (Au) catalyst deposited graphite layer by Chemical Vapor Deposition (CVD) method. The CVD steps in more detail are shown in supporting information (S1.1). The contribution from graphite layer (S1.3).43 The total mass of the electrode is around ~8.2 mg (~2.7 mg GaN NWs and ~5.5 mg graphite layer). The hybrid electrode delivers the capacity of ~2.01 mA h cm−2, so the capacity for the total electrode is 352.9 mA h g−1. As graphite layer has capacity of ~ 55 mA h g−1, the total contribution of the graphite layer is therefore roughly 55 mA h g−1 × 3.82 mg cm−2 = 0.21 mA h cm−2. Therefore, the capacity percentage of the graphite layer is roughly 0.21/2.01 = 10.4 %. If we subtract the contribution of the graphite layer, the capacity for the GaN NWs along can be estimated to be (2.01-0.21) mA h cm−2/1.9 mg cm−2 = 943.4 mA h g−1 during the first discharge. Electrochemical measurements. Graphite layer with GaN NWs were directly used as anodes for battery assembly as the work electrode. Electrolyte was LiPF6 (1 M) in ethylene

carbonate/dimethyl

carbonate/diethyl

carbonate

(1:1:1

vol

%).

Electrochemical performances were recorded by NEWARE measurement system, and

14


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CV was performed using CHI660D electrochemical workstation (Shanghai CH Instruments Co., China). Characterization. The structural characterization was performed by SEM (Hitachi S-4800) and TEM (Philips Tecnai 20U-Twin microscope). XRD results were collected by Bruker diffractometer (D8 Advance). Raman results were collected with Ar+ laser (532 nm). PL results were collected by He-Cd laser (325 nm). The semiconductor characterization system (Agilent B2902A) linked to a probe station was used for measuring the conductivity characterization (S 1.2). The surface area results were obtained by BET measurements (ASAP 2020 sorptometer). XPS results were obtained by Thermo ESCALAB 250 with Al Kα radiation excitation source (1486.8 eV).

ASSOCIATED CONTENT Supporting Information

Raman spectrum of the graphite layer; Electrochemical performances of the blank graphite layer and GaN powder; Nitrogen adsorption/desorption measurements; the change of the impedance spectra; Ex situ SEM image and N 1s XPS spectra after cycling; Comparisons of the capacity between GaN NWs anode and other previously reported metal nitrides. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author 15



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*E-mail: [email protected].

ORCID

Changlong Sun: 0000-0003-0208-0262

Author Contributions †

C.S. and M.Y. contributed equally to this work.

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by NSFC (Contract 51572153, 51602177) and the Major Basic Program of the Natural Science Foundation of Shandong Province (Contract ZR2017ZB0317).

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Appl. Mater. Interfaces 2017, 9, 26631−26636. (25) Ding, Y. L.; Kopold, P.; Hahn, K.; van Aken, P. A.; Maier, J.; Yu, Y. A Lamellar Hybrid Assembled from Metal Disulfide Nanowall Arrays Anchored on a Carbon Layer: In Situ Hybridization and Improved Sodium Storage. Adv. Mater. 2016, 28, 7774−7782. (26) Glaser, E. R.; Kennedy, T. A.; Doverspike, K.; Rowland, L. B.; Gaskill, D. K.; Freitas, J. A.; Asif Khan, M.; Olson, D. T.; Kuznia, J. N.; Wickenden, D. K. Optically Detected

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Organometallic

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Figure 1. (a, b) Schematic illustration and synthesis protocol of the CVD method. (c) SEM image of the GaN NWs; the top right inset images show the color variation of the graphite layer before and after GaN NWs growth, the below left inset is the SEM image of the graphite layer. (d) SEM image and EDS elemental mapping of Ga, N for the GaN NWs arrays, the middle inset is the EDS microanalysis. (e) XRD of GaN NWs, the inset peaks located at 54.8° is from graphite layer. (f) TEM, HRTEM and SAED images of single GaN NW. 91x52mm (300 x 300 DPI)


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Figure 2. (a, b) Photoluminescence and Raman characterization of GaN NWs. (c) Current-voltage response of single GaN NW measured at room-temperature. The top left inset is the schematic diagram of the GaN NW device, the below right inset depicts an optical microscope image of the GaN NW device. (d) N2 adsorption-desorption isotherms. Inset is the corresponding pore distribution. 103x77mm (300 x 300 DPI)



Figure 3. (a) CVs of the hybrid electrode at 0.1 mV s−1. (b) Charge/discharge curves and (c) Cycle performance at 0.1 A g−1. (d) Rate capabilities from 0.1 to 10 A g−1. (e) Nyquist plots of the hybrid electrode and bare graphite layer. (f) Schematic diagram of operation principle of Li+/electron transport. (g) Cycling performance and the corresponding Coulombic efficiency at 10 A g−1. 113x80mm (300 x 300 DPI)


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Figure 4. Kinetics analysis of Li+ storage behavior. (a) CV curves at various scan rates, from 0.1 to 1.0 mV s−1. (b) Determination of the b value. (c) CV with the separation of the capacitive (purple region) and diffusion contribution at 1.0 mV s−1. (d) Bar chart showing the contribution ratio of the capacitive and diffusion-controlled charge versus scan rate. 105x74mm (300 x 300 DPI)



Figure 5. (a) The different charge states for ex situ XRD at 1st CV curve. (b) Ex situ XRD. The shallow region represents the (c) enlarged ex situ XRD profiles between 31° and 40°. (d) Ex situ XRD after 400 cycles at 0.1 A g−1. (e) Ex situ HRTEM image after 400 cycles. The top right inset is the low-magnification TEM of single GaN NW, the below right inset is the SAED pattern, scale bars: 5 1/nm. (f) Ex-situ N 1s XPS spectra after 400 cycles. 82x39mm (300 x 300 DPI)


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Stable and Reversible Lithium Storage with High Pseudocapacitance

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