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Research Article Cite This: ACS Appl. Mater. Interfaces 2019, 11, 802−810

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Triboelectric Nanogenerator-Enabled Dendrite-Free Lithium Metal Batteries Nian-Wu Li,†,‡,∥ Yingying Yin,†,‡,∥ Xinyu Du,†,‡,∥ Xiuling Zhang,†,‡ Zuqing Yuan,†,‡ Huidan Niu,†,‡ Ran Cao,†,‡ Wei Fan,†,‡ Yang Zhang,†,‡ Weihua Xu,†,‡,§ and Congju Li*,†,‡,§ †

Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 100083, P. R. China School of Nanoscience and Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. China § School of Energy and Environmental Engineering, Beijing Key Laboratory of Resource-Oriented Treatment of Industrial Pollutants, University of Science and Technology Beijing, Beijing 100083, P. R. China ACS Appl. Mater. Interfaces 2019.11:802-810. Downloaded from pubs.acs.org by UNIV OF FLORIDA on 01/10/19. For personal use only.

‡

S Supporting Information *

ABSTRACT: Lithium metal batteries (LMBs) are prominent among next-generation energy-storage systems because of their high energy density. Unfortunately, the commercial application of LMBs is hindered by the dendrite growth issue during the charging process. Herein, we report that the triboelectric nanogenerator (TENG)-based pulse output with a novel waveform and frequency has restrained the formation of dendrites in LMBs. The waveform and operation frequency of TENG can be regulated by TENG-designed and smart power management circuits. By regulating the waveform and frequency of the TENG-based pulse output, the pulse duration becomes shorter than the lithium dendrite formation time at any current of pulse waveform, and lithium ions can replenish in the entire electrode surface during rest periods, eliminating concentration polarization. Therefore, the optimized TENG-based charging strategy can improve the Coulombic efficiency of lithium plating/stripping and realize homogeneous lithium plating in LMBs. This TENG-based charging technology provides an innovative strategy to address the Li dendrite growth issues in LMBs, and accelerates the application of TENG-based energy collection systems. KEYWORDS: triboelectric nanogenerator, lithium metal anode, lithium dendrites, pulse output, batteries

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simulation and experiments and at various scales.27,28 Based on these researches, the dendrite growth is driven by cation diffusion and electromigration at the anode/SEI interface under an electric driving force.29−31 Thus, uncontrolled dendrite growth can be reduced by pulse charging strategies, which have been successfully used for electroplating of metals (such as Cu and Ni).32,33 The concentration of Li ions is replenished in the entire electrode by diffusion during the rest periods, leading to a more homogeneous Li deposition.34,35 Notably, all these pulse charging strategies are based on square waves and complicated compact power, limiting the development of pulse charging technology. Triboelectric nanogenerator (TENG) is a newly developed portable device for microscale energy harvesting.36 TENGs have shown great potential in scavenging various forms of lowfrequency mechanical energy such as human motion, wind, and water wave.37−39 Pulse output is the characteristic of TENG, and the pulse waveforms can be regulated by structure design, power management circuits, and outside mechanical frequency. This regulated pulse waveform is beyond the reach of conventional

INTRODUCTION Energy storage systems with a high energy density are urgently needed to satisfy the ever-increasing demand in electric vehicles, consumer electronics, and grid-scale storage. However, the energy density of existing lithium (Li)-ion batteries remains insufficient for many of these applications.1−3 Li metal is the ultimate anode for rechargeable batteries because it has the most negative reduction potential (−3.04 V versus standard hydrogen electrode) and an ultrahigh theoretical specific capacity (3860 mAh g−1).4,5 Furthermore, the Li metal anode is indispensable for next-generation energy-storage systems, including Li−S, Li− air, and other Li batteries using intercalation compounds or conversion compounds as cathode materials.6−9 Unfortunately, the practical application of lithium metal batteries (LMBs) is hindered by dendritic deposition during the charging process, an unstable solid electrolyte interphase (SEI), and an almost infinite volume change during cycling. The dendrite growth can also accelerate side reactions, leading to serious safety issues and a low Coulombic efficiency.10−12 Many efforts have been made to address the dendritic deposition issues including three-dimensional (3D) current collectors,13−15 interfacial protective layers,16−21 and electrolyte optimization.22−26 In addition, the formation mechanism of lithium dendrites has been studied through theoretical © 2018 American Chemical Society

Received: October 5, 2018 Accepted: December 11, 2018 Published: December 11, 2018 802

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

Research Article

ACS Applied Materials & Interfaces

Figure 1. Charging of LMBs using a constant current power source (a) and UR-TENG (b).

of the AC output was consistent with the theoretical calculation using the equation f = nv, where n is the number of flexible layers and v is the rotation rate (rps). A smart power management circuit constituted of various transformers and bridge rectifiers was designed to regulate the pulse output of UR-TENG (Figure 1). Li|Cu cells were used to evaluate the Coulombic efficiency of Li plating/stripping under the TENG-based pulse output with various waveforms and frequencies. By regulating the size of the triboelectric layer, the coil ratio of the transformer, the bridge rectifier, and the rotational frequency, the UR-TENG-based pulse output with various waveforms and frequencies could be evaluated at the same equivalent current. The UR-TENG pulse outputs with an equivalent current of 0.405 mA and rotational frequencies of 1.9, 2.5, 2.8, and 4 Hz were used to plate Li in the Li|Cu cell (Figures 2 and S1), which were labeled as TENG1, TENG2, TENG3, and TENG4, respectively. The output currents in Figure S1 are stable within the acceptable range. The output currents show a slight instability because of the small change of battery impedance during Li plating, and the sampling rate we used in Figure S1 is 50 s−1. It is worth noting that the effective current value shows negligible difference under sampling rates of 50 and 1000 s−1 (Figure S2). The Li|Cu cell charging by TENG2 showed the highest Coulombic efficiency of Li plating/stripping (Figures S3 and S4). The Toff/Ton (Ton is the time for pulse duration, Toff is the intermittent time for pulse) plays an important role in restraining the Li dendrite growth, which is highlighted in previous reports.29,31 For the TENG-based pulse charging protocols (TPCPs), the Coulombic efficiency of Li plating/stripping did not increase with the increase of Toff/Ton (Figures 2e and S3). It is worth noting that TENG3 showed the highest Toff/Ton, whereas the corresponding Coulombic efficiency of Li plating/stripping was less than the Li|Cu cell charging by TENG2 and TENG4. Therefore, the

power sources, thereby expanding the understanding of the electric-driven dendrite growth mechanism and providing a promising charging technology for LMBs. Herein, we report that the ultrarobust TENG (UR-TENG) with a novel pulse waveform has restrained the formation of dendrites in LMBs (Figure 1). The waveform and operation frequency of UR-TENG can be regulated by TENG-designed and smart power management circuits. At the same effective current density, the Coulombic efficiency of Li plating/stripping can be improved by regulating the pulse waveform and frequency of the TENG output. Furthermore, the Li metal anode cannot reach the dendrite formation time during the pulse duration, and the Li ion can replenish in the entire electrode surface during rest periods, eliminating the concentration polarization. Therefore, the optimized TENG-based pulse output can achieve stable and homogeneous Li plating during cycling in lithium iron phosphate (LFP)|Li batteries.

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RESULTS AND DISCUSSION The self-powered system is mainly composed of UR-TENG, a smart power management circuit, and LMB (Figure 1). The URTENG consists of a three-dimensional printed polylactic acid (PLA) circular cylinder stator and a PLA rotor, which has been improved on the basis of our previous works.40,41 The fluorinated ethylene propylene (FEP) film coated with a Cu electrode (back electrode) is one triboelectric layer, and the Cu electrode (top electrode) with a kapton film coating is another triboelectric layer (Figure 1). Aiming to increase the output frequency of the pulse wave, eight electrodes were assembled on the stator and the rotor had four rollers. With the rotor rotating, the top Cu electrode will contact and separate with the FEP film, and thereby, the electron will flow through the external circuit because of the electrostatic induction effect.40 This process will produce an alternating current (AC) output, and the frequency 803

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

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ACS Applied Materials & Interfaces

Figure 2. Waveforms of TENG1 (a), TENG2 (b), TENG3 (c), and TENG4 (d) with the same equivalent current of 0.405 mA. The relationship between the Coulombic efficiency of Li plating/stripping and Toff/Ton of the TENG-based output (e). Schematic of the pulse duration and dendrite formation time of TENG2 (f). The ratios of Tpulse duration/Tdendrite formation (g) and their relationship with the Coulombic efficiency of Li plating/stripping (h).

ij eC yz τ = πDjjj 0 zzz j 2Jta z k { μa ≈ 1 − t Li+ ta = μa + μLi+ 2

shape of the pulse waveform may play a crucial role in the Coulombic efficiency of Li plating/stripping. The “Sand time” model is widely accepted to describe the dendrite formation time of a Li metal anode.10,27 The Sand time is the time for the ionic concentration at the lithium anode surface dropping to zero and dendritic lithium formation. Therefore, the Sand time is introduced to evaluate the waveform of TPCPs. The Sand time τ can be calculated by the following equations27

(1)

(2)

where D is the diffusion coefficient, e is the electronic charge, C0 is the initial cation (Li salt) concentration, J is current density, ta is the anionic transport number, and μa and μLi+ represent the anionic and Li+ transference numbers, respectively. The Sand 804

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

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ACS Applied Materials & Interfaces

Figure 3. Typical waveform of TENG5 (a) and TENG6 (b). Ratios of Tpulse duration/Tdendrite formation (c) and their relationship with the Coulombic efficiency of Li plating/stripping (d).

(ω−1/2), as shown in Figure S6. The Li+ diffusion coefficient obtained was 1.11 × 10−12 cm2 s−1. Based on the calculated Sand time, the dendrite formation curve at the corresponding current is shown at the typical peak of TENG2 (Figure 2f). The pulse duration was shorter than the dendrite formation time at any current of pulse waveform for TENG2. The pulse durations of TENG1 and TENG3 were longer than the dendrite formation time at a certain current, whereas the pulse durations of TENG2 and TENG4 were shorter than the dendrite formation time (Figures 2g and S7). Therefore, Li dendrite can generate during the pulse duration using TENG1- and TENG3-based charging technologies, thereby reducing the Coulombic efficiency of Li plating/ stripping (Figure 2h). By contrast, Li dendrite cannot generate during the pulse duration when using TENG2 and TENG4, thereby improving the Coulombic efficiency of Li plating/ stripping (Figures 2h and S3). Figure 2h shows that there is a negative correlation between the ratio of Tpulse duration/ Tdendrite formation and the Coulombic efficiency of Li plating/ stripping, except for TENG4. This is because TENG4 possesses a low Toff/Ton value, which is disadvantageous for the Li ion replenishing in the entire electrode surface by diffusion. For further optimization of TPCP, the UR-TENGs with different waveforms at a fixed rotational frequency (2.5 Hz) have been applied to Li|Cu cells, which are labeled as TENG5 and TENG6 (Figure S8), respectively. The typical waveforms of TENG5 and TENG6 are shown in Figure 3a,b. By integral calculation, the effective currents of TENG5, TENG3, and TENG6 were 0.33, 0.52, and 0.58 mA cm−2, respectively. Notably, the Coulombic efficiency of Li plating/stripping was 95.3% using TENG5-based charging strategy, which is higher than that of the direct current (DC) charging strategy. The ratio of Tpulse duration/Tdendrite formation increases with increasing effective current (Figures 3c and S9). The ratio of Tpulse duration/ Tdendrite formation has a negative correlation with the Coulombic

time model predicts that the dendrite formation time is proportional to J−1/2 and D. The Li ion transference number was calculated by the Bruce−Vincent method,42 as shown in Figure S5. The diffusion coefficient of the electrolyte (De) can be calculated by the Nernst−Einstein equation.43 De =

λkT ne 2

(3)

where λ is the ionic conductivity (7.6 × 10−3 S cm−1), k is the Boltzmann constant, T is the temperature (K), n is the ion concentration, and e is the charge of the diffusion species. The calculated diffusion coefficient is 2.03 × 10−6 cm2 s−1. Based on these results, the calculated τ is 2.5 × 104 s at a current density of 1 mA cm−2. However, the size of the Li dendrite could reach several micrometers within 120 s at a current density of 1 mA cm−2 or less in the previous experimental results.16,44 This is because the Li+ diffusion coefficient in the SEI is much lower than the Li+ diffusion coefficient in the liquid electrolyte, which is different from the solid polymer batteries. In the LMBs using a liquid electrolyte, the SEI will reach the Sand time quickly, at which time the ionic concentration will reach zero at the Li metal anode and the potential will eventually diverge at the interphase, leading to the formation of the Li dendrite. The diffusion coefficient of Li+ in the SEI can be obtained from the follow equation45 ij RT yz zz D = 0.5jjj 2 2 j An F σ C zz w { k

2

(4)

where R is the gas constant, T is the temperature (K), A is the area of electrode surface, n is the number of electrons per molecule during reduction, F is Faraday’s constant, and σw is the Warburg factor, respectively. σw is the slope for the plot of Z′ vs the reciprocal root square of the lower angular frequencies 805

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Figure 4. (a) Typical waveform of optimized TPCP for the LFP|Li battery. The charging curves of LFP|Li batteries using DC (b) and optimized TPCP (c). Scanning electron microscopy (SEM) images of the Li metal anode charging by DC for 1 h (d), 2 h (e), and 4 h (f), respectively. SEM images of the Li metal anode charging by optimized TPCP for 1 h (g), 2 h (h), and 4 h (i), respectively.

technology, the Li metal anode shows a porous dendrite structure at the micrometer scale after 1 h, exhibits a moss-like dendrite structure after 2 h, and ultimately demonstrates a bushlike dendrite structure after 4 h (Figure 4d−f). These moss-like and bush-like structures possess sharp edges at the nanoscale, thereby promoting the side reactions between Li metal and electrolytes. By using optimized TPCP, the Li metal anode shows a stone-like structure at dozens of microns after 1 h, and exhibits a smooth Li plating structure after 2 and 4 h (Figure 4g− i). These stone-like structures possess round-shaped edges at the micrometer scale, restricting their ability to penetrate the porous separators. The interphase polarization and dendrite formation cannot occur during the pulse duration because it is much shorter than the dendrite formation time. In other words, the diffusion of Li ion can match the electromigration during the pulse duration, thereby reducing the concentration polarization and the Li dendrite formation. Furthermore, the Li ion is periodically replenished on the entire electrode surface during the relaxation period, eliminating the concentration polarization at the sharp surface and resulting in a more homogeneous Li plating. Consequently, by using the optimized TPCP, the formation of Li dendrite has been restrained. The typical charge/discharge curves of LFP|Li batteries using optimized TPCP and DC charging strategies at the same effective current are shown in Figure 5a. The polarization

efficiency of Li plating/stripping (Figures 3d and S10). Thus, the ratio of Tpulse duration/Tdendrite formation can be used as an important evaluation criterion for TPCPs. TENG is a promising device to harvest low-frequency (typically 0.1−3 Hz) mechanical energy (such as human motions and ocean waves).46 Therefore, the self-power systems constituted by TENG and Li metal batteries have wide applications in low-frequency mechanical energy collection. Furthermore, to restrain the dendrite growth issues at higher current (>1 mA cm−2), the optimization of existing DC charging technology using TPCP and the integration of existing dendrite-suppressing strategies with TPCP will be carried out in our lab for further investigations. LMBs using lithium iron phosphate (LFP) as the cathode were used to evaluate the TPCP. Figure 4a shows the typical waveform of optimized TPCP, and the charging current for 4 h is shown in Figure S11. The pulse duration of the optimized TPCP is lower than the dendrite formation time (Figure S12) and the value of Toff/Ton was 3.29. To investigate the morphology of Li plating using different charging technologies, the LFP|Li batteries were charged at the same effective current. Furthermore, these LFP|Li were disassembled at 1, 2, and 4 h for morphology detection (Figure 4b,c). The LFP|Li battery charging by TPCP demonstrated a lower charging voltage than the LFP|Li charging by DC at the initial stage (Figure 4b,c), indicating a lower charging resistance. By using DC charging 806

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

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Figure 5. Charge/discharge curves (a) and Nyquist plots (b) of LFP|Li batteries. SEM images of the Li metal anode charging by DC (c) and TPCP (d) after 20 cycles. X-ray photoelectron spectroscopy (XPS) spectra of C 1s for Li metal anode charging by DC (e) and TPCP (f) after 20 cycles.

stone-like Li are connected together and constituted to one mainland, thereby restraining the formation of the electrochemical dead Li and reducing the interface resistance. By using TPCP, the LMBs can realize stable Li plating. The interface composition and valence on the surface of Li metal anodes were detected by X-ray photoelectron spectroscopy (XPS). As observed from the C 1s and F 1s spectra (Figures 5e,f and S15), reduction products of the electrolyte including COR, CO, Li2CO3, ROCO2Li, and LiF are found on the surface of Li metal anodes, which are the main components of SEI layers.7,19,24 Notably, the content of these side reaction products is clearly decreased on the surface of the Li metal anode by using TPCP (Figures 5f and S16). Combining with the SEM results, the bush-like Li dendrite with a high surface area possesses a lot of reduction products using the DC charging strategy. However, by using the TPCP, the stone-like Li with a smooth surface can markedly reduce the side reactions between the Li metal and electrolytes. Thus, stable and homogeneous Li deposition can be achieved during cycling. These results will exert a far-reaching influence on the development of TENG and LMBs. The TENG-based output can be efficiently stored in LMBs by using the optimization design and smart power management circuit, promoting the application of TENG in blue

between the charge and discharge plateaus for the LFP|Li battery using optimized TPCP is lower than that using DC charging strategy, showing that the resistance of the LFP|Li battery is reduced by using TPCP. To further investigate the kinetics and charge transfer behavior of LFP using different charging strategies, electrochemical impedance spectroscopy was applied to the LFP|Li batteries. As observed from the Nyquist plots (Figures 5b and S13), the LFP|Li battery charging by optimized TPCP shows a lower charge transfer and interface impedance than the LFP|Li battery charging by DC, thereby enhancing the battery performance, especially after 100 cycles (Figure S14). Furthermore, the LFP|Li battery shows a high charging stability for more than 120 cycles (Figure S14). The morphologies of Li metal anodes using different charging strategies for 20 cycles are shown in Figure 5c,d. The Li metal anode using the DC charging strategy shows a bush-like dendrite structure at the micrometer scale, thereby increasing the side reactions between the Li metal and electrolytes. In addition, a part of these bush-like dendrite structures detaches from the current collector forming electrochemically inactive “dead Li”, increasing the interface resistance and consuming a lot of Li metal. In contrast, the Li metal anode using TPCP shows a stone-like Li plating structure with a smooth surface at hundreds of micrometers. Besides, all these 807

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

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transferred to specially designed devices for ex situ characterization without exposing the samples to air including scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The microstructure of the samples was determined on a Hitachi SU8020 field-emission scanning electron microscope (FE-SEM). XPS was carried out on a Thermo Scientific ESCALab 250Xi using 200 W monochromated Al Kα radiation.

energy, wind energy, and wearable electronics. In addition, with the waveform and frequency regulation technology, the TENGbased charging technology can expand the understanding of electric-driven dendrite growth mechanism and provide an innovative strategy to address the Li dendrite growth issue in LMBs.

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CONCLUSIONS In summary, the TENG-based pulse current charging technology is demonstrated to be a promising strategy for achieving stable and homogeneous Li plating in LMBs. The waveform and operation frequency of the TENG output can be regulated by TENG design and smart power management circuit. By regulating the waveform and frequency, the pulse duration becomes shorter than the formation time of Li dendrite at any current of pulse waveform, and the high Toff/Ton enables Li ion to replenish in the entire electrode, eliminating concentration polarization, thereby improving the Coulombic efficiency of Li plating/stripping. Besides, homogeneous Li plating has been realized in the LFP|Li batteries during cycling. This TENG-based charging technology provides an innovative strategy to address the Li dendrite growth issue in LMBs, and accelerates the application of TENG-based energy collection systems.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b17364. Current of Li−Cu cells charging by different TENG, Li stripping curves of various Li−Cu cells, calculation method of lithium-ion transference number and Warburg factor, the comparison of TENG pulse duration time and dendrite formation time for various TENG, the cycling performance of LFP|Li batteries, and the XPS results of Li metal anode (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Nian-Wu Li: 0000-0001-9679-7699 Xinyu Du: 0000-0003-1101-7409 Zuqing Yuan: 0000-0003-3988-0618 Yang Zhang: 0000-0002-3002-4367 Congju Li: 0000-0001-6030-7002

METHODS

Fabrication of UR-TENG. The UR-TENG was prepared by 3D printing and surface modification, which has been reported in our previous work.40 UR-TENGs with various sizes were prepared. The coil ratios of the transformer used in the power management circuits were 36, 50, and 75 to obtain the same effective current in the Li|Cu cell. By regulating the size of the rectangular triboelectric layer (from 5 × 2.5 to 10 × 2.5 cm2), the coil ratio of the transformer, and the rational frequency, four UR-TENG-based outputs at the same effective current (0.405 mA) were obtained. These UR-TENG-based outputs at rotational frequencies of 1.9, 2.5, 2.8, and 4 Hz were labeled as TENG1, TENG2, TENG3, and TENG4, respectively. We chose the low rotational frequency because TENG has a better performance than the electromagnetic generators at low frequency. The coil ratio of the transformer, the size of the triboelectric layer, and the rotational frequency of the motor are positively related to the output of TENG. When the TENG triboelectric layer and the coil ratio of the transformer are selected, the frequency of TENG is also fixed for the same current output (0.405 mA). The frequency of TENG is regulated by the rotational speed of the motor. Thus, the regulation process shows stability and reliability. Preparation of Batteries. The Li|Cu cell was fabricated using the Cu foil, a separator, Li metal anode, and electrolyte. For the LFP|Li battery, the cathode slurry was prepared by mixing 80 wt % LFP, 10 wt % Super P, and 10 wt % poly(vinylidene difluoride) dissolved in Nmethyl-2-pyrrolidone. The cathodes were produced by coating the slurry onto an aluminum foil and drying at 80 °C for 12 h. The 2032 coin cells were fabricated in an argon-filled glove box using Li metal as the counter electrode and celgard 2325 as the separator. The electrolyte was 1 M LiPF6 dissolved in a mixture of ethylene carbonate/dimethyl carbonate (DMC)/diethyl carbonate (1:1:1 by volume). Characterization. For the Li|Cu cell, UR-TENGs with various waveforms and frequencies were used as the power source for Li plating, and the Li stripping processes were carried out by the LAND testing system. For the LFP|Li batteries, the charge processes were conducted by optimized TPCP and the discharge processes were performed on a LAND testing system. All the pulse currents were recorded by an electrometer (Keithley 6514), and corresponding voltages were recorded by multimeter (UT61E) with the help of a computer. The coin cells of LFP|Li batteries were disassembled in a glove box, and thus the Li metal anodes were washed three times using DMC to remove the residual electrolyte. Then, the Li metal anodes were

Author Contributions ∥

N.-W.L., Y.Y., and X.D. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is supported by the National Postdoctoral Program for Innovative Talents and the General Financial Grant from the China Postdoctoral Science Foundation (Grant nos. BX201700061 and 2017M620710), the National Natural Science Foundation of China (NSFC nos. 21703010, 51503005, and 21274006), National Key R&D Project from Minister of Science and Technology (2016YFA0202703, 2016YFA0202702, and 2016YFA0202704), and the Programs for Beijing Science and Technology Leading Talent (Grant no. Z161100004916168), and the Fundamental Research Funds for the Central Universities (Grant no. 06501000), and the “Ten thousand plan”-National High-level personnel of special support program, and the “Thousands Talents” Program for Pioneer Researcher and His Innovation Team, China.

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REFERENCES

(1) Lin, D.; Liu, Y. Y.; Cui, Y. Reviving the Lithium Metal Anode for High-Energy Batteries. Nat. Nanotechnol. 2017, 12, 194−206. (2) Tikekar, M. D.; Choudhury, S.; Tu, Z. Y.; Archer, L. A. Design Principles for Electrolytes and Interfaces for Stable Lithium-Metal Batteries. Nat. Energy 2016, 1, No. 16114. (3) Guo, L.; Deng, J.; Wang, G.; Hao, Y.; Bi, K.; Wang, X.; Yang, Y. N, P-doped CoS2 Embedded in TiO2 Nanoporous Films for Zn−Air Batteries. Adv. Funct. Mater. 2018, 28, No. 1804540. (4) Ye, H.; Xin, S.; Yin, Y.-X.; Guo, Y.-G. Advanced Porous Carbon Materials for High-Efficient Lithium Metal Anodes. Adv. Energy Mater. 2017, 7, No. 1700530. 808

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

Research Article

ACS Applied Materials & Interfaces (5) Li, B.; Wang, Y.; Yang, S. B. A Material Perspective of Rechargeable Metallic Lithium Anodes. Adv. Energy Mater. 2018, 8, No. 1702296. (6) Pang, Q.; Liang, X.; Kwok, C. Y.; Nazar, L. F. Advances in Lithium−Sulfur Batteries Based on Multifunctional Cathodes and Electrolytes. Nat. Energy 2016, 1, No. 16132. (7) Aurbach, D.; Zinigrad, E.; Cohen, Y.; Teller, H. A Short Review of Failure Mechanisms of Lithium Metal and Lithiated Graphite Anodes in Liquid Electrolyte Solutions. Solid State Ionics 2002, 148, 405−416. (8) Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Li-O2 and Li-S Batteries with High Energy Storage. Nat. Mater. 2012, 11, 19−29. (9) Yi, J.; Guo, S. H.; He, P.; Zhou, H. S. Status and Prospects of Polymer Electrolytes for Solid-State Li-O2 (Air) Batteries. Energy Environ. Sci. 2017, 10, 860−884. (10) Xu, W.; Wang, J. L.; Ding, F.; Chen, X. L.; Nasybutin, E.; Zhang, Y. H.; Zhang, J. G. Lithium Metal Anodes for Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 513−537. (11) Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev. 2017, 117, 10403−10473. (12) Li, N.-W.; Yin, Y.-X.; Xin, S.; Li, J.-Y.; Guo, Y.-G. Methods for the Stabilization of Nanostructured Electrode Materials for Advanced Rechargeable Batteries. Small Methods 2017, 1, No. 1700094. (13) Yun, Q.; He, Y. B.; Lv, W.; Zhao, Y.; Li, B. H.; Kang, F. Y.; Yang, Q. H. Chemical Dealloying Derived 3D Porous Current Collector for Li Metal Anodes. Adv. Mater. 2016, 28, 6932. (14) Yang, C.-P.; Yin, Y.-X.; Zhang, S.-F.; Li, N.-W.; Guo, Y.-G. Accommodating Lithium into 3D Current Collectors with A Submicron Skeleton towards Long-Life Lithium Metal Anodes. Nat. Commun. 2015, 6, No. 8058. (15) Li, Q.; Zhu, S.; Lu, Y. 3D Porous Cu Current Collector/Li Metal Composite Anode for Stable Lithium Metal Batteries. Adv. Funct. Mater. 2017, 27, No. 1606422. (16) Li, N.-W.; Shi, Y.; Yin, Y.-X.; Zeng, X.-X.; Li, J.-Y.; Li, C.-J.; Wan, L.-J.; Wen, R.; Guo, Y.-G. A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes. Angew. Chem., Int. Ed. 2018, 57, 1505−1509. (17) Liu, K.; Pei, A.; Lee, H. R.; Kong, B.; Liu, N.; Lin, D. C.; Liu, Y. Y.; Liu, C.; Hsu, P. C.; Bao, Z. A.; Cui, Y. Lithium Metal Anodes with an Adaptive “Solid-Liquid” Interfacial Protective Layer. J. Am. Chem. Soc. 2017, 139, 4815−4820. (18) Liu, Y.; Lin, D. C.; Yuen, P. Y.; Liu, K.; Xie, J.; Dauskardt, R. H.; Cui, Y. An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes. Adv. Mater. 2017, 29, No. 1605531. (19) Li, N. W.; Yin, Y. X.; Yang, C. P.; Guo, Y. G. An Artificial Solid Electrolyte Interphase Layer for Stable Lithium Metal Anodes. Adv. Mater. 2016, 28, 1853−1858. (20) Lu, Y.; Gu, S.; Hong, X.; Rui, K.; Huang, X.; Jin, J.; Chen, C.; Yang, J.; Wen, Z. Pre-modified Li3PS4 based interphase for lithium anode towards high-performance Li-S battery. Energy Storage Mater. 2018, 11, 16−23. (21) Pang, Q.; Liang, X.; Shyamsunder, A.; Nazar, L. F. An In Vivo Formed Solid Electrolyte Surface Layer Enables Stable Plating of Li Metal. Joule 2017, 1, 871−886. (22) Lu, Y.; Tu, Z. Y.; Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 2014, 13, 961− 969. (23) Qian, J.; Henderson, W. A.; Xu, W.; Bhattacharya, P.; Engelhard, M.; Borodin, O.; Zhang, J. G. High Rate and Stable Cycling of Lithium Metal Anode. Nat. Commun. 2015, 6, No. 6362. (24) Li, N. W.; Yin, Y. X.; Li, J. Y.; Zhang, C. H.; Guo, Y. G. Passivation of Lithium Metal Anode via Hybrid Ionic Liquid Electrolyte toward Stable Li Plating/Stripping. Adv. Sci. 2017, 4, No. 1600400. (25) Zeng, X.-X.; Yin, Y.-X.; Li, N.-W.; Du, W.-C.; Guo, Y.-G.; Wan, L.-J. Reshaping Lithium Plating/Stripping Behavior via Bifunctional Polymer Electrolyte for Room-Temperature Solid Li Metal Batteries. J. Am. Chem. Soc. 2016, 138, 15825−15828.

(26) Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114, 11503−11618. (27) Brissot, C.; Rosso, M.; Chazalviel, J. N.; Lascaud, S. Dendritic Growth Mechanisms in Lithium/Polymer Cells. J. Power Sources 1999, 81−82, 925−929. (28) Monroe, C.; Newman, J. Dendrite Growth in Lithium/Polymer Systems: A Propagation Model for Liquid Electrolytes under Galvanostatic Conditions. J. Electrochem. Soc. 2003, 150, A1377− A1384. (29) Aryanfar, A.; Brooks, D.; Merinov, B. V.; Goddard, W. A.; Colussi, A. J.; Hoffmann, M. R. Dynamics of Lithium Dendrite Growth and Inhibition: Pulse Charging Experiments and Monte Carlo Calculations. J. Phys. Chem. Lett. 2014, 5, 1721−1726. (30) Mayers, M. Z.; Kaminski, J. W.; Miller, T. F. Suppression of Dendrite Formation via Pulse Charging in Rechargeable Lithium Metal Batteries. J. Phys. Chem. C 2012, 116, 26214−26221. (31) Li, Q.; Tan, S.; Li, L.; Lu, Y.; He, Y. Understanding the Molecular Mechanism of Pulse Current Charging for Stable lithium-Metal Batteries. Sci. Adv. 2017, 3, No. e1701246. (32) Chandrasekar, M. S.; Pushpavanam, M. Pulse and Pulse Reverse PlatingConceptual, Advantages and Applications. Electrochim. Acta 2008, 53, 3313−3322. (33) Kirchev, A.; Perrin, M.; Lemaire, E.; Karoui, F.; Mattera, F. Studies of the Pulse Charge of Lead-Acid Batteries for PV Applications: Part I. Factors Influencing the Mechanism of the Pulse Charge of the Positive Plate. J. Power Sources 2008, 177, 217−225. (34) Yang, H.; Fey, E. O.; Trimm, B. D.; Dimitrov, N.; Whittingham, M. S. Effects of Pulse Plating on Lithium Electrodeposition, Morphology and Cycling Efficiency. J. Power Sources 2014, 272, 900−908. (35) García, G.; Dieckhofer, S.; Schuhmann, W.; Ventosa, E. Exceeding 6500 Cycles for LiFePO4/Li Metal Batteries Through Understanding Pulsed Charging Protocols. J. Mater. Chem. A 2018, 4746−4751. (36) Fan, F.-R.; Tian, Z. Q.; Wang, Z. L. Flexible Triboelectric Generator! Nano Energy 2012, 1, 328−334. (37) Cao, X.; Jie, Y.; Wang, N.; Wang, Z. L. Triboelectric Nanogenerators Driven Self-Powered Electrochemical Processes for Energy and Environmental Science. Adv. Energy Mater. 2016, 6, No. 1600665. (38) Pu, X.; Hu, W.; Wang, Z. L. Toward Wearable Self-Charging Power Systems: The Integration of Energy-Harvesting and Storage Devices. Small 2018, 14, No. 1702817. (39) Wang, Z. L. Catch Wave Power in Floating Nets. Nature 2017, 542, 159−160. (40) Du, X.; Li, N.; Liu, Y.; Wang, J.; Yuan, Z.; Yin, Y.; Cao, R.; Zhao, S.; Wang, B.; Wang, Z. L.; Li, C. Ultra-Robust Triboelectric Nanogenerator for Harvesting Rotary Mechanical Energy. Nano Res. 2018, 2862−2871. (41) Zhang, X.; Du, X.; Yin, Y.; Li, N.-W.; Fan, W.; Cao, R.; Xu, W.; Zhang, C.; Li, C. Lithium-Ion Batteries: Charged by Triboelectric Nanogenerators with Pulsed Output Based on the Enhanced Cycling Stability. ACS Appl. Mater. Interfaces 2018, 10, 8676−8684. (42) Evans, J.; Vincent, C. A.; Bruce, P. G. Electrochemical Measurement of Transference Numbers in Polymer Electrolytes. Polymer 1987, 28, 2324−2328. (43) Khurana, R.; Schaefer, J. L.; Archer, L. A.; Coates, G. W. Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries. J. Am. Chem. Soc. 2014, 136, 7395−7402. (44) Zhang, X. Q.; Chen, X.; Cheng, X. B.; Li, B. Q.; Shen, X.; Yan, C.; Huang, J. Q.; Zhang, Q. Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes. Angew. Chem., Int. Ed. 2018, 57, 5301−5305. (45) Chen, H.; Wang, C. H.; Dai, Y. F.; Qiu, S. Q.; Yang, J. L.; Lu, W.; Chen, L. W. Rational Design of Cathode Structure for High Rate Performance Lithium-Sulfur Batteries. Nano Lett. 2015, 15, 5443− 5448. 809

DOI: 10.1021/acsami.8b17364 ACS Appl. Mater. Interfaces 2019, 11, 802−810

Research Article

ACS Applied Materials & Interfaces (46) Zi, Y.; Guo, H.; Wen, Z.; Yeh, M.-H.; Hu, C.; Wang, Z. L. Harvesting Low-Frequency (