Article www.acsaem.org
Cite This: ACS Appl. Energy Mater. 2019, 2, 4513−4520
UV-Initiated Soft−Tough Multifunctional Gel Polymer Electrolyte Achieves Stable-Cycling Li-Metal Battery Wei Fan,†,‡,§,∥,∇ Xiuling Zhang,†,‡,§,∥,∇ Congju Li,*,†,‡ Shuyu Zhao,†,‡ and Jing Wang⊥,# †
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China Beijing Key Laboratory of Resource-Oriented Treatment of Industrial Pollutants, Beijing 100083, P. R. China § 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 ⊥ Institute of Environmental Engineering, ETH Zurich, 8093 Zurich, Switzerland # Advanced Analytical Technologies Laboratory, EMPA, Ü berlandstrase 129, 8600 Dübendorf, Switzerland
Downloaded via UNIV OF SOUTHERN INDIANA on July 19, 2019 at 01:08:50 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
‡
S Supporting Information *
ABSTRACT: A semi-interpenetrating gel polymer electrolyte (S-GPE) membrane is successfully designed through combining high-molecular polyacrylonitrile (PAN), polyethylene glycol (PEG) oligomers, ethoxylated trimethylolpropane triacrylate (ETPTA) monomers, and silica (SiO2) nanoparticles as a whole through an ultraviolet (UV) initiating process. The highly polymerized PAN ensures the thermal stability and toughness, while the oligomer of PEG acts as a soft component and facilitates an improved contact between different interfaces. SiO2 nanoparticles are added with the aim to restrain the crystallinity and improve ionic conductivity. Here, the obtained SGPE achieves a high ionic conductivity of 8.9 × 10−4 S cm−1 at room temperature and effective dendrites inhibition. Hence, the S-GPE shows an eminent stability that enables the Li|S-GPE|Li cell to stably cycle at 6 mA cm−2 under 3 mA h cm−2 for over 1000 h without a polarization voltage increase. The Li|S-GPE|LiFePO4 battery shows a 131.4 mA h g−1 initial discharge capacity at the first cycle and keeps 93.23% capacity retention after 500 cycles at 0.5 C under room temperature, which is far beyond liquid electrolyte with a conventional PE/PP separator. Prospectively, this work enlightens a promising and optional way in electrolyte design for long-life energy storage devices. KEYWORDS: polymer electrolyte, interpenetrating, long life, lithium-metal battery, stable
■
INTRODUCTION Electric vehicles and energy saving storage devices are everincreasingly needed toward the convenient and advanced rechargeable power sources.1−5 Lithium metal shows its great potential due to a high theoretical capacity of 3860 mA h g−1 simultaneously with low density (0.534 g cm−3), which make the lithium-metal battery an appropriate candidate for an exceptional anode material applied in electronic devices.6−11 Unfortunately, conventional liquid electrolyte could hardly inhibit the formation of lithium dendrites, because lithium is thermodynamically unstable in liquid electrolyte. Thus, lithium dendrites growth in conventional liquid electrolyte sets severe limitations to cycling efficiency and safety concerns in lithiummetal battery practical applications.12−18 Thus, researchers are reviving their thinking about polymers and solid electrolytes, aiming to effectively settle the aforementioned issues.19−22 The flexible polymer electrolyte guarantees the good contact of electrolyte with the electrode compared with traditional inorganic electrolytes.23,24 Moreover, it restrains dendrites nucleation blocking, simultaneously ensuring the design of various styles of batteries, showing a great potential in the settling of the aforementioned issues.25−27 On the contrary, © 2019 American Chemical Society
low ionic conductivity and undesirable battery performances at room temperature severely hinder polymer electrolyte applications in the long run.28 Many corresponding works have been working to solve the above-mentioned issues.29−32 Polyacrylonitrile (PAN) is extensively applied in polymer electrolyte construction and design due to its thermal stability and electrochemical oxidation resistance. Additionally, PAN ensures the mechanical strength of semi-interpenetrating gel polymer electrolyte (S-GPE) and could restrain the growth of lithium dendrites. Moreover, nitrile groups interacting with Li+ enhanced the ionic conductivity greatly.33 Polyethylene glycol (PEG) oligomers, which seems to be viscous liquid or soft, waxy solids, are known for dissolving and conducting small cations and are also beneficial for the improvement of the contact issues. The trivalent vinyl groups in trimethylolpropane triacrylate (ETPTA) furnish the possibility of UV-curing participation, constructing an interpenetrating network, and further serving as a mechanical framework in the system.34 Received: April 16, 2019 Accepted: May 24, 2019 Published: May 24, 2019 4513
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
Figure 1. (a) Step of producing a semi-interpenetrating polymer electrolyte (S-GPE) through UV irritation. (b) Photo image of prepared S-GPE. (c) XRD pattern of PEG and polymer membranes. (d) FT-IR spectra of ETPTA and polymer membranes. (e) Surface morphology, (f) Young’s modulus mapping, and (g) adhesion of the polymer membrane after UV-initiating. Finally, 2-hydroxy-2-methylpropiophenone (HMPP) is added into the mixture acting as a polymerization initiator. The ultraviolet (UV) photoinitiating method is applied for polymerization of ETPTA to form a semi-interpenetrating polymer network structure; finally, the LiTFSI is introduced into this system. This synthesis method not only simplifies the procedure of polymer electrolyte construction in a short time but also obtains the membrane in a relatively large scale. Characterizations. The morphologies of S-GPE, lithium-metal foil, and Al current were observed by SEM (SU8020) at 5 kV 10 μA. The crystal structure was characterized by XRD with Cu Kα radiation. A Fourier-transform infrared (FT-IR) test was conducted on a spectrometer (Vertex 80, Bruker) in the frequency range 400−4000 cm−1 with a resolution of 4 cm−1 and 32 scans at room temperature. Thermogravimetric analysis (TGA) was tested under a flow of nitrogen at the rate of 10 °C min−1, from room temperature to 500 °C. An AFM system (Bruker Dimension ico) was employed to measure the Young’s modulus, surface morphology, and adhesion of the membrane. Energy-dispersive X-ray spectroscopy (EDS) was applied to analyze different elements of S-GPE by SU 8020. Preparation of the Flexible Battery. The assembly processes of the flexible polymer-state cell are as follows. The area size of the flexible cell is 2 cm × 3 cm. First, the LiFePO4 (LFP) on the Al current collector and graphite (GT) on the Cu current collector and S-GPE are cut into the same size (2 cm × 3 cm). Then, the Al cathode tab and Ni anode tab are connected with corresponding electrodes. Later, they are set in Al plastic foil and packaged through thermal melting and bonding. Electrochemical Measurement. The galvanostatic charging− discharging of battery cells were carried out by the commercial battery
Here, we have successfully designed a semi-interpenetrating network structured gel polymer electrolyte (S-GPE) through UV-initiating ETPTA monomers with PEG and PAN polymer matrix. Bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) is introduced into this system as a lithium salt, making S-GPE achieve an eminent elevation of ionic conductivity up to 8.9 × 10−4 S cm−1 at room temperature. Additionally, Li dendrites are successfully inhibited by adopting such an S-GPE, which enables the symmetric Li|S-GPE|Li cell to stably cycle for over 2500 h at 0.5 mA cm−2 without short-circuiting occurring. Thus, the high ionic conductivity and dendrite-free surface of Li metal greatly contribute to LiFePO4|S-GPE|Li full cell performance, which shows 93.23% and 83.25% capacity retention after cycling for 500 cycles under room temperature at 0.5 and 1 C, respectively. The cycling performance and dendrites restraint of S-GPE reveal tremendous advantages over liquid electrolyte, and all of these superiorities make this S-GPE an optional reference for further polymer electrolyte design.
■
EXPERIMENTAL SECTION
Preparation of S-GPE. The synthesis process of S-GPE is completely illustrated in Figure 1a. PAN polymer (Mw = 150 000), PEG oligomer (Mw ≈ 800), and SiO2 nanoparticles (≈15 nm) are mixed together to form a homogeneous precursor. Then, the ethoxylated ETPTA is added with magnetic stirring homogeneously. 4514
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
Figure 2. (a) CV of the S-GPE. The inset is the enlarged figure at the high-voltage region. (b) Temperature-dependent ionic conductivity of SGPE. (c) Open-circuit voltage of S-GPE and liquid electrolyte with time. (d) Impedance response with time evolution of the Li|S-GPE|Li. testing system (LAND CT2001A). The voltage range of charge− discharge was 2.0−4.0 V. AC impedances (from 100 kHz to 0.01 Hz) of the batteries were performed by an electrochemical workstation (CHI660E). The electrochemical stability of S-GPE was tested by linear sweep voltammetry (LSV) performed with a stainless steel (SS)|S-GPE|Li coin cell at a scan rate of 1 mV s−1 from 0 to 5 V. The ionic conductivity of the S-GPE was calculated by the following equation: σ = d/RS. Here, d is the thickness of S-GPE, R the interfacial resistance, and S the area of electrolyte. Activation energy Ea was used to illustrate the difficulty of Li-ion transference; the relationship of σ and Ea obeys the Arrhenius equation: σ = σ0 exp(−Ea/RT). For the LFP|Li test, LiFePO4, super-P, and poly(vinylidene fluoride) (PVDF) are dissolved in N-methly-2-pyrrolidone at the weight ratio of 80:10:10. Then, the slurry was cast onto an aluminum foil. The cast film was dried in a vacuum oven at 120 °C for 720 min. The active material weight of LFP applied in this experiment is ≈1.5 mg cm−2. The coin cells are assembled in an Ar-filled glovebox with the concentrations of moisture and oxygen below 0.01 ppm.
An obtained homogeneous S-GPE is directly shown in Figure 1b, the easy-rolling property and flexibility of S-GPE achieves a compact contact with electrodes, necessary adaptation to volume changes, and potential applications in conformable and flexible devices. The scanning electronic microscopy (SEM) morphology and cross-section of S-GPE are revealed in Figure S1, and the thickness is about 100 μm. PEG could easily convert into the crystal state at room temperature, which severely inhibits chains movement and ion transference. It could be vividly seen from Figure 1c that crystallization is effectively avoided by adding SiO2, while compared with pure PEG polymer. To investigate the consequence of the polymerization reaction, ETPTA monomer together with different GPEs are compared together by using the Fourier-transform infrared (FT-IR) method (Figure 1d), showing the disappearance of acrylate groups and polymerization of monomers (peaks in the range 1610−1680 cm−1 contributed from the CC stretching vibration are illustrated in the inset image). The peaks between 1300 and 1000 cm−1 are mainly attributed to the vibration of CO in OC O groups; the characteristic peaks at 1710 cm−1 are ascribed to the CO vibration. It has been confirmed that CO and CO groups enable the faster migration of Li+; numerous CO and CO groups enable faster transference of Li+. The thermogravimetric analysis (TGA) image (Figure S2) reveals the excellent thermal resistance property of the membrane over 200 °C, which could endure large temperature changes. Such excellent thermal stability is mainly ascribed to the heat resistance of PAN chains. Energy-dispersive spectrometry (EDS) is used to measure the elements dispersed in the polymer membrane, just as shown in Figure S3; the elements of O, S, and Si are all uniformly dispersed, proving that the polymer matrix and particles are all forming a uniform system.
■
RESULTS AND DISCUSSION The synthesis process of S-GPE is completely illustrated in Figure 1a. PEG oligomer, PAN polymer, and SiO2 nanoparticles are mixed together to form a homogeneous precursor. Then, the ethoxylated ETPTA is added with magnetic stirring homogeneously. Finally, 2-hydroxy-2-methylpropiophenone (HMPP) is added into the mixture acting as a polymerization initiator. The ultraviolet (UV) photoinitiating method is applied for polymerization of ETPTA to form a semiinterpenetrating polymer network structure; finally, the LiTFSI is introduced into this system. This synthesis method not only simplifies the procedure of polymer electrolyte construction in a short time but also obtains the membrane in a relatively large scale. 4515
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
Figure 3. (a) Polarization test by using Li|S-GPE|Li symmetric cells and liquid electrolyte at a current density of 0.5 mA cm−2, 1 mA h cm−2. (b) Polarization test by using Li|S-GPE|Li symmetric cells under different current densities. (c) Polarization test by using Li|S-GPE|Li symmetric cells under 6 mA cm−2, 3 mA h cm−2.
Figure 2a is conducted ranging from −0.5 to 4.5 V with the scanning rate of 1 mV s−1. The repetitive peaks from −0.5 to 0.5 V are attributed to the lithium stripping and plating process, demonstrating that the stripping/plating process is a reversible process. The image inset indicates that, upon oxidation of S-GPE, it exhibits as flat and stable up to 4.5 V. On the contrary, liquid electrolyte (1 M LiTFSI in TEGDME) shows an evident current polarization increment in oxidation and reduction peaks. From Figure 2b, it could be seen that the S-GPE delivers a temperature-dependent behavior. The S-GPE delivers ionic conductivity of 8.9 × 10−4 S cm−1 at room temperature and 4.0 × 10−3 S cm−1 at 100 °C, the increment of ionic conductivity with temperature mainly due to the higher chains mobility and elevated activity under higher temperature (Figure 2b, Figure S4). It could be noted that
The surface morphology and Young’s modulus together with adhesion images of the polymer membrane (Figure 1e−g) are analyzed by atomic force microscopy (AFM). The consequences verify that the obtained S-GPE combines the softness of PEG and toughness of PAN together. This structure not only ensures the adhesive property to eliminate the contacting issues with electrodes but also possesses considerable mechanical strength to restrain lithium dendrites growth. Sufficient electrochemical stability is absolutely essential to avoid side reactions arising between electrolyte and electrodes. To ensure the success of the charging/discharging procedure, cyclic voltammetry (CV) is carried out to evaluate the electrochemical stability of S-GPE with Li|StSt electrode cells. The CV evaluation on the oxidation and reduction in 4516
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
Figure 4. (a, b) Surface of lithium metal after being cycled by liquid electrolyte for 10 and 50 cycles. (c, d) Surface of lithium metal after being cycled by S-GPE for 10 and 50 cycles.
Figure 5. (a) Surface of Al current after being cycled by liquid electrolyte for 50 cycles. (b) Surface of Al current after being cycled by S-GPE for 50 cycles. (c) EDS spectra and percentages of elements identified of the lithium-metal anode cycled by liquid electrolyte after 300 cycles. (d) EDS spectra and percentages of elements identified of the lithium-metal anode cycled by S-GPE after 300 cycles.
that no appreciable decline of voltage could be observed in both cells; S-GPE even shows a better performance than conventional liquid electrolyte with PE. Moreover, the interfacial resistance change with time in Figure 2d also certify that the S-GPE designed by us forms a stable structure and electrolyte stability in cells with the increment of time.
activation energy (Ea) calculated by the Arrhenius equation is 7.21 × 10−3 eV; the low activation energy reveals a low energy requirement. The open-circuit voltage (OCV) changes with time are tested to certify the electrolyte stability in cells. Liquid electrolyte with the PE separator and polymer electrolyte are tested together for a comparison. It is revealed from Figure 2c 4517
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
Figure 6. (a) Cycling performance of LiFePO4|S-GPE|Li and LiFePO4|liquid electrolyte|Li at a current density of 0.5 C. (b) Cycling performance of LiFePO4|S-GPE|Li at a current density of 1 C. (c) Photograph showing the voltage of a GT|S-GPE|LFP pouch cell. The LED device can be lighted before deformation (d) after recovery and (e) after the cutting test.
meet diverse current density requirements for Li-metal batteries under the long cycling test. Lithium dendrites growth sets severe concerns in battery performance decline and safety issues. Traditional liquid electrolyte could hardly inhibit lithium dendrites growth because Li metal is thermodynamically unstable in liquid electrolyte. As depicted in Figure 4a,b, tiny dendrites are formed after cycling under liquid electrolyte for 10 cycles, and they grow apparently after cycling for 50 cycles. In contrast, there is little dendrite emerged upon cycling by S-GPE assembled cells under the same circumstance, which successfully avoids the separator impaling and short-circuit risks (Figure 4c,d). LiTFSI shows advantages over traditional lithium salts for possessing not only substantially enhanced ionic conductivity and thermal, chemical, and electrochemical stability but also hydrolysis insensitivity and lower cost.35 However, long-term cycling causes soluble corrosion product Al(TFSI)3 to diffuse and deposit onto the lithium surface, further inducing Al current collector corrosion, cathode separation, and battery performance decline.36−38 Just as shown in Figure 5a, apparent cracks are generated by cycling with liquid electrolyte after 50 cycles on the Al current collector (without carbon coating), and the cathode has partially fallen off. To our great surprise, the cell assembled with S-GPE shows negligible cracks after cycling for 50 cycles on the surface of the Al current collector
The dynamical stability of electrolyte with the anode is tested by Li|Li symmetric cells (Figure 3a). With a constant current density of 0.5 mA cm−2 and 1 mA h cm−2, the overpotential for the plating and stripping of lithium metal in Li|liquid electrolyte|Li shows as beginning at 20 mV while with a quick increment with the elevation of the cycle number. A large and irregular voltage drop could be easily observed at less than 400 h; this phenomenon mainly is ascribed to the lithium dendrite growth and increment of impedance. Fortunately, stable-cycle performance could be observed in S-GPE cells. The overpotential for plating and stripping of lithium metal in Li|S-GPE|Li delivers a stable voltage maintained around 50 mV except for the high-voltage polarization in the first few cycles, which is attributed to electrode activation and stable SEI formation. Furthermore, no apparent dendrites and defects could be observed until 2500 h of the plating and stripping process. The specific stripping/plating of Li|S-GPE|Li at 350− 600, 1000−1250, and 2200−2450 h is revealed under Figure 3a. Moreover, the symmetric Li|S-GPE|Li cells are evaluated under different current densities from 1 to 4 mA cm−2 under 1 mA h cm−2 (Figure 3b) and cycled under 4 mA cm−2 (Figure S5). Apparently, this reveals steady lithium stripping/plating at various current densities. Moreover, the symmetric Li|S-GPE| Li cell is evaluated under 6 mA cm−2 and 3 mA h cm−2 for 1000 h, demonstrating its stable properties under larger current density (Figure 3c). Therefore, the S-GPE we designed could 4518
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials
and wearable electronics possibilities compared with liquid electrolytes.
(Figure 5b). Figure S6 shows that cracks also appeared on the carbon-coated Al current collector with liquid electrolyte after cycling for 100 cycles, compared with no apparent changes with S-GPE (Figure S7). Thus, the Al current collector is effectively preserved by applying S-GPE. To further verify the experimental consequences, a further testing method is adopted. The specific corresponding elements of the Li-metal surface are measured by energy-dispersive X-ray spectroscopy (EDS). After cycling for 300 cycles, a considerable content of 3.8% Al element is detected on the Li surface cycled by liquid electrolyte (Figure 5c, Figure S8). The reasons are as follows: the Al current collector will react with LiTFSI and obtain the soluble Al(TFSI)3, and it will transfer to the anode during repeated charging/discharging processes. In contrast, only 0.38% Al element (Figure 5d) is detected on Li metal cycled by S-GPE, further verifying the aforementioned consequences. A full cell is assembled to evaluate the electrochemical performance by using a Li-metal anode and LiFePO4 cathode. As is demonstrated in Figure 6a, the Li|S-GPE|LiFePO4 cell has an initial discharge capacity of 131.4 mA h g−1 at 0.5 C and possesses 99.73% Coulombic efficiency in the first cycle at room temperature (25 °C). Furthermore, Li|S-GPE|LiFePO4 shows an excellent cycling performance, and it delivers a discharge capacity of 122.5 mA h g−1 after 500 cycles and keeps 93.23% capacity retention. However, Li|liquid electrolyte|LiFePO4 only keeps a discharge capacity of 90 mA h g−1 after 300 cycles and maintains 74.19% capacity retention. Thus, the polymer electrolyte assembled cell shows an excellent cycling performance beyond liquid electrolyte. The excellent cycling performance of S-GPE over liquid electrolyte is mainly ascribed to successful dendrites inhibition and Al current corrosion avoidance by S-GPE. Additionally, to investigate the cycling performance of S-GPE under higher current densities, the Li|S-GPE|LiFePO4 cell is also tested at 1 C to verify whether it keeps an excellent cycling performance. It shows a 114.6 mA h g−1 discharge capacity in the first cycle, and it delivers 95.4 mA h g−1 after 500 cycles, retaining 83.25% capacity retention at 1 C under room temperature (Figure 6b). Moreover, the Li|S-GPE|LiFePO4 cell shows a discharge capacity of 133.4, 130.6, and 113.1 mA h g−1 at 0.2. 0.5, and 1 C, respectively, under room temperature over the voltage range 2.0−4.0 V; the charge−discharge capacity changes with different current densities and profiles are demonstrated in Figures S10 and S11. In comparison, normal polymer electrolyte (C-GPE), which is produced by simple polymer mixing without the ETPTA UV reaction, obtains a discharge capacity of 121.9, 108.5, and 91.4 mA h g−1 at 0.2. 0.5, and 1 C under the same circumstances. This result verifies that the semi-interpenetrating structure of ETPTA polymerized electrolyte makes it more uniform and integral. The S-GPE reveals a promising application potential in long-time cycling cells in the future. Since potential safety concerns of liquid electrolyte in lithium batteries have undermined the confidence of consumers and impeded limitations in further applications, polymer electrolyte reveals advantages in these fields. As demonstrated in Figure 6c, the flexible polymer-state cell could easily light up a green LED lamp under normal conditions. After being bent and folded, it almost exhibits no voltage loss (Figure 6d). Notably, the obtained lithium-ion cell (LiFePO4| S-GPE|graphite (GT)) is also capable of lighting up the same LED lamp even after having been cut by scissors (Figure 6e). It is self-evident that S-GPE exhibits improved safety properties
■
CONCLUSIONS In summary, we have successfully designed a semi-interpenetrating polymer electrolyte (S-GPE) by adopting multifunctional polymers and applying a UV-initiating method. The obtained S-GPE shows an excellent ionic conductivity of 8.9 × 10−4 S cm−1 at room temperature. Additionally, the combination of softness and toughness in a system ensures the overcoming of contacting issues and availability to portable electronic devices. Additionally, lithium dendrites inhibition and Al current collector corrosion avoidance are basically achieved by S-GPE, which further promote battery performances as practical experiments. Thus, the battery assembled by Li|S-GPE|LiFePO4 shows an excellent cycle performance, with 131.4 mA h g−1 initial discharge capacity at the first cycle and keeping 93.23% capacity retention after 500 cycles at 0.5 C under room temperature. All of these excellent properties prevail over liquid electrolyte, which shows the superiority of S-GPE beyond liquid electrolyte.
■
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.9b00766. Additional figures including TGA results, EDS maps, EIS results, voltage profiles, SEM morphologies, surface morphologies, charge−discharge profiles, and charge− discharge rate capacity (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Congju Li: 0000-0001-6030-7002 Jing Wang: 0000-0003-2078-137X Author Contributions ∇
W.F. and X.Z. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (NSFC 51503005 and 21274006), the Programs for Beijing Science and Technology Leading Talent (Grant Z161100004916168), the Fundamental Research Funds for the Central Universities (06500100), and the “Ten thousand plan” National High-level personnel of special support program, China.
■
REFERENCES
(1) Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294−303. (2) Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652−657. (3) Tarascon, J. M.; Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414, 359−367. (4) 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. 4519
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
Article
ACS Applied Energy Materials (5) Zhang, Z.; Liao, M.; Lou, H.; Hu, Y.; Sun, X.; Peng, H. Conjugated Polymers for Flexible Energy Harvesting and Storage. Adv. Mater. 2018, 30, 1704261. (6) Fan, W.; Li, N.-W.; Zhang, X.; Zhao, S.; Cao, R.; Yin, Y.; Xing, Y.; Wang, J.; Guo, Y.-G.; Li, C. A Dual-Salt Gel Polymer Electrolyte with 3D Cross-Linked Polymer Network for Dendrite-Free Lithium Metal Batteries. Adv. Sci. 2018, 5, 1800559. (7) Mao, L.; Meng, Q.; Ahmad, A.; Wei, Z. Mechanical Analyses and Structural Design Requirements for Flexible Energy Storage Devices. Adv. Energy Mater. 2017, 7, 1700535. (8) Xie, H.; Yang, C.; Fu, K. K.; Yao, Y.; Jiang, F.; Hitz, E.; Liu, B.; Wang, S.; Hu, L. Flexible, Scalable, and Highly Conductive GarnetPolymer Solid Electrolyte Templated by Bacterial Cellulose. Adv. Energy Mater. 2018, 8, 1703474. (9) Blake, A. J.; Kohlmeyer, R. R.; Hardin, J. O.; Carmona, E. A.; Maruyama, B.; Berrigan, J. D.; Huang, H.; Durstock, M. F. 3D Printable Ceramic-Polymer Electrolytes for Flexible High-Performance Li-Ion Batteries with Enhanced Thermal Stability. Adv. Energy Mater. 2017, 7, 1602920. (10) Lee, H.; Lee, D. J.; Kim, Y.-J.; Park, J.-K.; Kim, H.-T. A simple composite protective layer coating that enhances the cycling stability of lithium metal batteries. J. Power Sources 2015, 284, 103−108. (11) Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J.-G. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 2014, 7, 513−537. (12) Wang, D.; Zhang, W.; Zheng, W.; Cui, X.; Rojo, T.; Zhang, Q. Towards High-Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy. Adv. Sci. 2017, 4, 1600168. (13) 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. (14) Yang, H.; Guo, C.; Naveed, A.; Lei, J.; Yang, J.; Nuli, Y.; Wang, J. Recent Progress and Perspective on Lithium Metal Anode Protection. Energy Storage Materials 2018, 14, 199−221. (15) Zhang, H.; Eshetu, G. G.; Judez, X.; Li, C.; Rodriguez-Martínez, L. M.; Armand, M. Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progresses and perspectives. Angew. Chem., Int. Ed. 2018, 57, 15002−15027. (16) Li, X.; Zheng, J.; Ren, X.; Engelhard, M. H.; Zhao, W.; Li, Q.; Zhang, J.-G.; Xu, W. Dendrite-Free and Performance-Enhanced Lithium Metal Batteries through Optimizing Solvent Compositions and Adding Combinational Additives. Adv. Energy Mater. 2018, 8, 1703022. (17) Yan, C.; Cheng, X.-B.; Tian, Y.; Chen, X.; Zhang, X.-Q.; Li, W.J.; Huang, J.-Q.; Zhang, Q. Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition. Adv. Mater. 2018, 30, 1707629. (18) 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. (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, 1853−8. (20) Chen, L.; Fan, L. Z. Dendrite-free Li metal deposition in allsolid-state lithium sulfur batteries with polymer-in-salt polysiloxane electrolyte. Energy Storage Materials 2018, 15, 37−45. (21) Yan, K.; Lu, Z.; Lee, H.-W.; Xiong, F.; Hsu, P.-C.; Li, Y.; Zhao, J.; Chu, S.; Cui, Y. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nature Energy 2016, 1, 16010. (22) Duan, H.; Yin, Y. X.; Shi, Y.; Wang, P. F.; Zhang, X. D.; Yang, C. P.; Shi, J. L.; Wen, R.; Guo, Y. G.; Wan, L. J. Dendrite-Free LiMetal Battery Enabled by a Thin Asymmetric Solid Electrolyte with Engineered Layers. J. Am. Chem. Soc. 2018, 140, 82−85. (23) Fan, L.; Wei, S.; Li, S.; Li, Q.; Lu, Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries. Adv. Energy Mater. 2018, 8, 1702657.
(24) Guo, Q.; Han, Y.; Wang, H.; Xiong, S.; Li, Y.; Liu, S.; Xie, K. New Class of LAGP-Based Solid Polymer Composite Electrolyte for Efficient and Safe Solid-State Lithium Batteries. ACS Appl. Mater. Interfaces 2017, 9, 41837−41844. (25) Zhou, W.; Wang, S.; Li, Y.; Xin, S.; Manthiram, A.; Goodenough, J. B. Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte. J. Am. Chem. Soc. 2016, 138, 9385−9388. (26) Duan, H.; Yin, Y.-X.; Zeng, X.-X.; Li, J.-Y.; Shi, J.-L.; Shi, Y.; Wen, R.; Guo, Y.-G.; Wan, L.-J. In-situ plasticized polymer electrolyte with double-network for flexible solid-state lithium-metal batteries. Energy Storage Materials 2018, 10, 85−91. (27) Zhang, S.; Wang, M.; Zhou, Z.; Tang, Y. Multifunctional Electrode Design Consisting of 3D Porous Separator Modulated with Patterned Anode for High-Performance Dual-Ion Batteries. Adv. Funct. Mater. 2017, 27, 1703035. (28) Wu, H.; Cao, Y.; Su, H.; Wang, C. Tough Gel Electrolyte Using Double Polymer Network Design for the Safe, Stable Cycling of Lithium Metal Anode. Angew. Chem., Int. Ed. 2018, 57, 1361. (29) Ha, H.-J.; Kil, E.-H.; Kwon, Y. H.; Kim, J. Y.; Lee, C. K.; Lee, S.-Y. UV-curable semi-interpenetrating polymer network-integrated, highly bendable plastic crystal composite electrolytes for shapeconformable all-solid-state lithium ion batteries. Energy Environ. Sci. 2012, 5, 6491. (30) Liu, Y.; Tzeng, Y.-K.; Lin, D.; Pei, A.; Lu, H.; Melosh, N. A.; Shen, Z.-X.; Chu, S.; Cui, Y. An Ultrastrong Double-Layer Nanodiamond Interface for Stable Lithium Metal Anodes. Joule 2018, 2, 1595−1609. (31) Oh, Y.-S.; Jung, G. Y.; Kim, J.-H.; Kim, J.-H.; Kim, S. H.; Kwak, S. K.; Lee, S.-Y. Janus-Faced, Dual-Conductive/Chemically Active Battery Separator Membranes. Adv. Funct. Mater. 2016, 26, 7074− 7083. (32) Choudhury, S.; Mangal, R.; Agrawal, A.; Archer, L. A. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 2015, 6, 10101. (33) Kim, S.-H.; Choi, K.-H.; Cho, S.-J.; Yoo, J.; Lee, S.-S.; Lee, S.-Y. Flexible/shape-versatile, bipolar all-solid-state lithium-ion batteries prepared by multistage printing. Energy Environ. Sci. 2018, 11, 321− 330. (34) Zhou, D.; He, Y.-B.; Liu, R.; Liu, M.; Du, H.; Li, B.; Cai, Q.; Yang, Q.-H.; Kang, F. In Situ Synthesis of a Hierarchical All-SolidState Electrolyte Based on Nitrile Materials for High-Performance Lithium-Ion Batteries. Adv. Energy Mater. 2015, 5, 1500353. (35) Kil, E. H.; Choi, K. H.; Ha, H. J.; Xu, S.; Rogers, J. A.; Kim, M. R.; Lee, Y. G.; Kim, K. M.; Cho, K. Y.; Lee, S. Y. Imprintable, bendable, and shape-conformable polymer electrolytes for versatileshaped lithium-ion batteries. Adv. Mater. 2013, 25, 1395−400. (36) Seo, D. M.; Boyle, P. D.; Sommer, R. D.; Daubert, J. S.; Borodin, O.; Henderson, W. A. Solvate structures and spectroscopic characterization of LiTFSI electrolytes. J. Phys. Chem. B 2014, 118, 13601−13608. (37) Bolloli, M.; Kalhoff, J.; Alloin, F.; Bresser, D.; Phung Le, M. L.; Langlois, B.; Passerini, S.; Sanchez, J.-Y. Fluorinated Carbamates as Suitable Solvents for LiTFSI-Based Lithium-Ion Electrolytes: Physicochemical Properties and Electrochemical Characterization. J. Phys. Chem. C 2015, 119, 22404−22414. (38) Zheng, J.; Engelhard, M. H.; Mei, D.; Jiao, S.; Polzin, B. J.; Zhang, J.-G.; Xu, W. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2017, 2, 17012.
4520
DOI: 10.1021/acsaem.9b00766 ACS Appl. Energy Mater. 2019, 2, 4513−4520
