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Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array Wei Dong, Xian-Xiang Zeng, Xu-Dong Zhang, Jin-Yi Li, Ji-Lei Shi, Yao Xiao, Yang Shi, Rui Wen, Ya-Xia Yin, Tai-shan Wang, Chun-Ru Wang, and Yu-Guo Guo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05288 • Publication Date (Web): 02 May 2018 Downloaded from http://pubs.acs.org on May 2, 2018

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ACS Applied Materials & Interfaces

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array Wei Dong, †, ‡ Xian-Xiang Zeng, ⊥, Xu-Dong Zhang, †, ‡, Jin-Yi Li, †, ‡ Ji-Lie Shi, †, ‡ Yao Xiao, † Yang Shi, †, ‡ Rui Wen, †, ‡ Ya-Xia Yin, †, ‡ Tai-shan Wang, †, ‡ Chun-Ru Wang, *, †, ‡ and Yu-Guo Guo *, †, ‡ †

CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS

Research/Education, Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P. R. China ‡

School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R.

China ⊥

College of Science, Hunan Agricultural University, Changsha 410128, P. R. China

KEYWORDS: allied micro-array • cathode design • gradient polymerization • interface modification • solid state electrolyte

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ABSTRACT:

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.


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1. Introduction The pressing demand for high-energy-density storage devices has revived the metallic lithium as anode, 1-4 due to its highest theoretical specific capacity (3860 mA h g-1 or 2061 mA h cm–3). 5-7 However, the issues of lithium dendrite growth in the Li metal batteries have provoked the researches for solid-state electrolyte (SSE) to solve the hidden danger. 8-9 Many of the advances in the protection of Li metal anodes from dendrites have been achieved using SSEs.

10-12

These

advancements in SSE technology have revolutionized the safety and stability in solid Li metal batteries. 13-17 However, the high interfacial resistance between cathode materials and the SSE has seriously hindered the exertion of cycle performance and charge-discharge rates.

18-19

Structural

homogeneous SSE satisfies the demand for inhibition of Li dendrites with high mechanical strength,

20-21

yet causing restricted figurability and poor contacts with cathode materials. 22 The

improvement of cycling safety by using SSE is at the expense of sacrificing the advantages of conventional organic liquid electrolytes including high ionic conductivity and good wettability. Lots of approaches have been proposed to optimize interfacial contact and ion transportation, including minimizing the cathode material particle size of to the nanoscale to increase the contact areas with SSE,

23-24

artificially modifying the layer between cathode and SSE to convert the

point contact into surface contact, coating ionic liquids on the cathode surface to achieve a solidliquid-solid interface structure.

25-28

However, when the cathode area loading is higher,

situation of the electrolyte with poor wettability,

30-31

29

or a

the function of layer modifications would

become very limited, with only a small fraction of cathode contact being improved. The root 3 ACS Paragon Plus Environment


causes of these problems remain unresolved, and the structure manipulation and exploration for cathode materials and current collector as an integral,

32-34

which are of great significance, to

boost battery performance has been ignored. 35 Herein, an integrative design strategy of Li metal battery which reconciles the stability and ionic conductivity is introduced (Figure 1). For the Li metal side, because of dendrites formation, a high ionic conductivity solid electrolyte with high mechanical strength is required to prevent dendrite-induced short circuits.

36

For the cathode side, good surface contact with active

materials enable the reduction of high interfacial resistances and shorten the ion transport distance. To realize this purpose, a UV light triggered gradiently polymerized solid electrolyte (GPSE) with a solid stiff surface on the anode side and ductile inclusions on the cathode side is in situ formed. The uniform layer with high degree of polymerization (DP) provides mechanical stability to inhibit Li dendrites, the inclusions with gradiently descending DP on the cathode side improve the interface contact, which reconciles the demand of mechanical properties and interface modification for high-rate solid Li metal batteries. 2. Experimental Section 2.1 Materials synthesis. The hollow V2O5 nanospheres were obtained from a previous report. 37 The V2O5-H nanospheres was obtained by H2 thermal treatment at 200℃ for 2 hours. The aluminous current collector with allied micro-channel (Al-AMC) was obtained by Laser micro-processing system from Shanghai Fermi Laser Technology with a pore diameter of 15 µm, a pore depth of 80 µm and a space of 10 µm, the diameter of AL-AMC was 1cm and the thickness was about 100 µm. The GPSE was prepared in dry room with dew temperature below -70°C. The V2O5-H nanospheres, Super P, 4 ACS Paragon Plus Environment

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poly (vinyl difluoride) (PVDF, Aldrich) were mixed to obtain a slurry in N-methylpyrrolidone with the weight ratio of 8: 1: 1. The slurry was uniformly poured on the Al-AMC and then transferred to a high-pressure reactor. After applying 5 M Pa N2 atmosphere and kept for 30 minutes, the slurry was compressed into the Al-AMC. Then, the Al-AMC loaded with V2O5-H was dried in vacuum chamber at 80 °C for 12 h. The electrolyte we used in this work was reported from one of our group’s previous report

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which integrates high mechanical strength

(ca. 12 GPa) to suppress dendrite growth, a high room temperature ionic conductance (0.22 mS cm−1) that can operate effectively within 4.5V vs Li+/Li. To achieve a gradient polymerization degree, the precursor was dropwise added onto the surface of the Al-AMC loaded with V2O5-H nanospheres. The cathode can only be perfused in the channels when it mixed with NMP to become a slurry state to maintain the mobility. After drying, the NMP was volatilized and the space it took transform into the gaps between the channel wall and the particles. These gaps are very important because in the next step, the precursor of electrolyte took the gaps’ space and contact directly with each particle. After curing for 5 minutes, the liquid precursor transformed into solid state and were in-situ formed with gradient DP. Batteries based on LiNi0.5Mn0.3Co0.2O2 and LiFePO4 commercial cathode and GPSE were assembled by using the same method. The conventional curing solid electrolyte (CCSE) was acquired by evenly spreading the same amount liquid precursor on the surface of Li foil and then directly curing the precursor with same experiment condition as GPSE. The explosion time, the UV light intensity, irradiation height and all the other experimental elements were the same with the synthesis of GPSE. After polymerization, a uniform layer was formed on the surface of Li foil and the solid Li metal battery with CCSE was assembled without polymerization gradient as a contrast. 5 ACS Paragon Plus Environment


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2.2 Characterization The XRD profiles of the as-obtained samples were obtained using a D/max 2500 X-ray diffractometer (Rigaku) with Cu Kα radiation (λ = 1.5418 Å) operated at 40 kV and 200 mA using a continuous scanning mode at 2° min-1 over 2θ range of 10-70°. Raman spectra were collected with a laser wavelength of 532 nm. The SEM images and corresponding EPMA image were obtained with a field emission SEM (JEOL 6701F) and EPMA (1720). The HRTEM images and the linear scanning curves were obtained on the TEM (JEM 2100F) with an accelerating voltage of 200 kV. The X-ray photoelectron spectra (XPS) of the samples were conducted on the ESCALab 250Xi (Thermo Scientific) spectrometer equipped with an Al Kα achromatic X-ray source. The binding energies of all elements were calibrated with respect to carbon (284.6 eV) and the XPS peaks were deconvoluted by the Avantage software. An AFM system (Bruker Multimode 8 with a Nanoscope V controller) in the Ar-filled glove box was employed to measure the morphology and adhesion force for GPSE surface. 2.3 Electrochemistry The CR2032-type coin cells were assembled in the Ar-filled glove box (H2O, O2 ˂ 0.1 ppm). The loading of active materials was about 1.5 mg cm−2. All the coin cells were assembled using a hollow Celgard separator as spacer (Ф 10 mm) for the sake of avoiding short circuit. Cyclic voltammetry was carried out on a ParSTAT MC electrochemical work station (Princeton) at 60 °C. Galvanostatic tests were carried out using LAND cycler (Wuhan Kingnuo Electronic Co., China) at 60 °C. 3. Results and Discussion


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To implement the proposed strategy, an aluminous cathode current collector with allied microchannel (Al-AMC) (Figure S1) is synthesized through laser drilling technology. Al-AMC not only provides space for the storage of the positive electrode material, but also regulates the polymerization degree by controlling UV light distribution. The cathode nanoparticles are in advanced embedded into the micro-channels by adding 5 M Pa N2 (see details in method). The GPSE precursor was dropwise added on the cathode to fulfill the gaps between the cathode materials and the micro-channel. After the polymerization, ductile inclusions and the cathode nanoparticles with high specific surface area are steadily enclosed inside the channel which largely increased the overall safety and stability sharply reduced interfacial resistance. In the meanwhile, the stiff surface layer of GPSE on the array is formed to inhibit dendrite growth. This integrative battery architecture (Figure 2) exploits the advantage of cathode nanoparticles with the cooperation of GPSE and AL-AMC, which are three indispensable elements in achieving enhanced rate capacities and reduced interfacial resistance. The COMSOL Multiphysics numerical analysis has been carried out to simulate the UV light intensity distribution in the GPSE precursor loaded Al-AMC system when the polymerization happens (Figure 3a). The color map represents energy density of UV light, which can be seen that the light density is concentrated on the surface layer of the liquid GPSE precursor and the conical part inside of the channels because of structure regulation. With equal reaction time, more photoinitiator cracks into free radicals in the high light density areas. The simulation results are in good agreement with the experimental design. Fluorescence imaging experiments are carried out to testify the distribution of GPSE. The precursor of GPSE (labeled by fluorescein isothiocyanate) presents good liquidity that can easily penetrate the micro-channels (Figure 3b). After photopolymerization, the cross section of 7 ACS Paragon Plus Environment


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fluorescence image shows that the GPSE with high DP forms a uniform layer above the Al-AMC and a conical structure inside the channel. As the intensity of UV light decreases sharply with the depth incensement inside the channel, low DP GPSE is formed which can be washed away by ethanol with no fluorescence existed (Figure 3c). The in-situ formed GPSE has a distinct variation of polymerization degree which agrees with the COMSOL simulation results. Furthermore, the atomic force microscopy (AFM) images of 3D adhesion force mapping (Figure 3d, e) and the optical photograph (Figure S2) shows that the adhesion force of GPSE dramatically decreases within the channel. However, when the probe moves to the uniform layer above the Al-AMC, the adhesion force tends to be constant. The variation tendency of adhesion force is consistent with the simulation results and the fluorescence phenomenon. All the results confirm that we have successfully synthesized multifunctional GPSE with construction regulated UV light triggered polymerization. The hollow hydrogenated vanadium pentoxide (V2O5-H) nanospheres were synthesized through a solvothermal method as model cathode material. The TEM image and the line scanning (Figure 4a and Figure S3) test shows the void space in hollow particles, which improves the particles’ ability to withstand cyclic changes in volume and increases the long-term stability.

39

After H2

thermal treatment, 40 the oxygen vacancies at O (II) sites have been produced in hollow V2O5-H nanospheres to increase Li+ diffusion rate.

41

The X-ray photoelectron spectroscopy (XPS)

reveals that a weak peak at 515.59 eV ascribed to V4+ is observed in addition to the strong peak at 516.96 eV attributed to V 2p3/2 from V5+ (Figure 4b and Figure S4),

42

X-Ray diffraction

(XRD) pattern (Supplementary Figure. S5a, b) and Raman spectra (Figure S6a, b) are also carried out to testify the existence of oxygen vacancies. 43


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The SEM (Figure 4c-e) and the electron probe microanalysis (EPMA) (Figure S7a, b) images show that the V2O5-H nanospheres are successfully perfused into the micro-channels. Other nanosized cathode particles include LiNi0.5Mn0.3Co0.2O2 (NCM523) and LiFePO4 (LFP) (Figure S8) are also utilized with the same method in this system to show that the developed strategy is widely-applied. It should be noted that the cathode materials with nanosized structure is significant and favorable for perfusion into the channels of Al-AMC. The low DP inclusions and cathode materials are firmly sealed inside each micro-channel to form a stable interfacial structure after polymerization. The thickness of the high DP layer above the Al-AMC is about 20 µm (Figure 4f). A smooth surface of GPSE is shown by SEM and AFM morphology (Figure 4g, h) with a high mechanical strength of 9.8 G Pa (Figure S9). Such an in-situ formed GPSE is conductive to lower the interface impedance and release the rate capacity and cycling stability. To further ascertain the superiority of GPSE and micro/nano-structured cathode array in liberating discharging capability of nanosized cathode materials, the Li metal batteries with conventional cured solid electrolyte (CCSE) without Al-AMC array have been fabricated as contrasts, the discharging specific capacity shows only 129 and 107.5 mA h g-1 at 1 and 5 C for V2O5-H, 128.7 and 27.9 mA h g-1 at 1 and 5 C for LFP, 149.7 and 47.4 mA h g-1 at 0.2 and 2 C for NCM523 (Figure 5a-f). Whereas the Li metal batteries based on GPSE and micro/nanostructured cathode array show almost constant overpotential in the first two cycles (Figure S10), and exhibit an outstanding rate performance with the speed-up Li+ transportation, the specific capacities are 139.2 and 125.9 mA h g-1 at 1 C and 5 C for V2O5-H (1 C = 150 mA h g-1), 142.9 and 90.8 mA h g-1 at 1 C and 5 C for LiFePO4 (1 C = 170 mA h g-1), 155.9 and 97 mA h g-1 at 0.2 C and 2 C for LiNi0.5Mn0.3Co0.2O2 (1 C = 200 mA h g-1), respectively.



For the long-term cycling performance of the solid Li metal battery with GPSE and V2O5-H cathode, the capacity retention remains at 78% even after 300 cycling tests at 5 C with an ultralow long-term capacity fade rate of 0.07% per cycle (Figure 5g). Also, a specific capacity of 112.5 mA h g-1 is maintained at 1 C after 200 cycles for the full cells based on GPSE and V2O5H, while the contrast battery with CCSE shows obvious capacity degradation, with a specific capacity of only 102.6 mA h g-1 (Figure S11). The interfacial resistances of V2O5-H cathode solid Li metal battery with CCSE dramatically increases on the cathode side after 200 cycles at 1 C comparing with the solid Li metal battery with GPSE (Figure S12a-c). Obviously, the GPSE facilitates the migration of lithium ions as the in-situ photopolymerization eliminates the gaps between the cathode particles and the solid electrolyte with a high Li+ transporting speed, leading to significantly reduced interfacial resistances on the cathode side (Table S1). After 300 cycling tests, a smooth surface of Li metal is observed after the battery are disassembled (Figure S13). Also, the pouch cells work normally even after being cut (Figure 5h). Before and after bending tests, the pouch cell can still light the LED devices. The above results manifests that such a battery design own remarkable safety and flexibility. 4. Conclusion In this work, the design strategy that combines a high mechanical strength layer to suppress Li dendrites and ductile inclusions on the micro/nano-structured cathode side to realize interface modification, is put forward via structure-regulated photo-polymerization. The micro-channel cathode array provides improved safety and stability with encapsulated nanoparticles and low DP solid electrolyte. The GPSE-based Li metal battery exhibits an excellent rate capability and a long-term cycling stability at high rate. This interfacial engineering endows good contact between cathode materials and GPSE, superior ion transportation compared with conventional 10 ACS Paragon Plus Environment

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coating configuration in solid Li metal batteries. This design strategy will inspire a deep comprehension of interface regulation and integral structure design for other electrochemical energy storage systems at micro and nano level.



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ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI:10.1021/XXXXXXXX. SEM image of Al-AMC/ Optical photograph of the AFM probe position/ Photographs and morphology evolution V2O5/ XPS spectrum of hollow V2O5 microspheres/ XRD patterns/ Raman peaks/ Cross section view of EPMA images/ SEM images of two Li-contained cathodes/ CV curves of GPSE Li metal batteries/ Cycling performance/ Electrochemical impedance profiles/ SEM image of the Li metal anode/ Table of interfacial resistances AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. *E-mail: [email protected]. Tel/Fax: (+86)-10-82617069 (Y.-G. G.). ORCID: Yu-Guo Guo: 0000-0003-0322-8476 Chun-Ru Wang: 0000-0001-7984-6639

Notes The authors declare no competing ﬁnancial interest.


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ACKNOWLEDGMENT This work was supported by the National Key R&D Program of China (Grant 2016YFA0202500), the National Natural Science Foundation of China (21773264 and 51672281) and the “Strategic Priority Research Program” of the Chinese Academy of Sciences (Grant No. XDA09010300).



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Figure 1. Comparison of different electrolytes-based Li metal batteries and schematic design of GPSE formation in the Al-AMC architecture. a, Li dendrites growth in a Li metal battery using liquid electrolyte may cause short circuit and safety issues. b, The poor contacts between SSE and cathode materials leads to high interfacial impedance in a solid Li metal battery. c, GPSE constrains the Li dendrite and improves contacts with electrodes via stiff surface on the anode side and ductile inclusions on the cathode side. d, The formation principle of GPSE. After UV curing, the GPSE reveals high DP on the surface of Al-AMC (anode side) and low DP inside the channels (cathode side) due to uneven light distribution.



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Figure 2. Schematic illustration of preparing GPSE-based Li metal battery. Aluminous current collector with allied micro-channel is manufactured by laser drilling technology. The slurry containing cathode nanoparticles were poured on the Al-AMC and high-pressure infusion was carried out by adding 5 M Pa N2. GPSE was in situ formed by UV curing and a scheme of the Li+ transportation for GPSE encapsulated cathode materials in the Al-AMC is presented.


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Figure 3. Structure simulation and characterization of GPSE. a, The COMSOL simulation analysis for light distribution above and inside the Al-AMC, the color mapping represents energy density of UV light. b-c, The fluorescence images of FITC molecules in the GPSE before and after UV curing. d, Schematic illustration for the scanning direction of AFM probe. e, 3D adhesion force mapping of the GPSE formed in the Al-AMC.



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Figure 4. Characterization for the cathode and GPSE encapsulated Al-AMC. a, TEM image and line scanning curves of V2O5-H nanospheres. b, The XPS spectrum of V element in the hollow V2O5-H nanospheres. c, Top view SEM image of the Al-AMC. d, e, Top and cross section view SEM image of the Al-AMC after loading with V2O5-H. f, Cross section view of the Al-AMC and V2O5-H encapsulated by GPSE. g, h SEM and AFM topography images of the GPSE surface.


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Figure 5. Electrochemical performances of solid Li metal batteries with GPSE. a, b Rate capabilities of NCM523 cathode and corresponding galvanostatic discharging/charging profiles. c, d Rate capabilities of LFePO4 cathode and corresponding galvanostatic discharging/charging profiles. e, f Rate capabilities of V2O5-H cathode and corresponding galvanostatic discharging/charging profiles. g, Cycling performances of V2O5-H at 5 C rate. h, The pouch cell with V2O5-H cathode and GPSE can still lighten the LED devices before and after bending tests, and even after being cut.



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