Sustainable and Superior Heat-Resistant Alginate Nonwoven

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Sustainable and Superior Heat-resistant Alginate Nonwoven Separator of LiNi0.5Mn1.5O4/Li Batteries Operated at 55 oC Huijie Wen, Jianjun Zhang, Jingchao Chai, Jun Ma, Liping Yue, Tiantian Dong, Xiao Zang, Zhihong Liu, Botao Zhang, and Guanglei Cui ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b14352 • Publication Date (Web): 11 Jan 2017 Downloaded from http://pubs.acs.org on January 14, 2017

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ACS Applied Materials & Interfaces

Sustainable and Superior Heat-resistant Alginate Nonwoven Separator of LiNi0.5Mn1.5O4/Li Batteries Operated at 55 oC Huijie Wen,a,b Jianjun Zhang,b Jingchao Chai,b Jun Ma,b Liping Yue,b Tiantian Dong,b Xiao Zang,b Zhihong Liu,b Botao Zhang,a,* Guanglei Cuib,* a

College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, 266071,

Shandong Province, P. R. China b

Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences,

Qingdao, 266101, P. R. China

Abstract: Nowadays’ high-voltage lithium ion battery becomes the research focus. As a major part of lithium batteries, separator plays a critical role in the development of high-voltage lithium batteries. Herein, we demonstrated a sustainable and superior heat-resistant alginate nonwoven separator for high-voltage (5 V) lithium batteries. It was demonstrated that the resultant alginate nonwoven separator exhibited better mechanical property (37 MPa), superior thermal stability (up to 150 oC) and higher ionic conductivity (1.4×10-3 S/cm) as compared to commercially available polyolefin (PP) separator. More impressively, the 5 V-class LiNi0.5Mn1.5O4 (LNMO)/Li cell with this alginate nonwoven separator delivered much better cycling stability (maintaining 79.6 % of its initial discharge capacity) than that (69.3 %) of PP separator after 200 cycles at an elevated temperature of 55 oC. In addition, the LiFePO4/Li cell assembled with such alginate

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nonwoven separator could still charge and discharge normally even at an elevated temperature of 150 oC. The abovementioned fascinating characteristics of alginate separator provide great probability for its application for high-voltage (5 V) lithium batteries at elevated temperatures. Keywords: alginate nonwoven separator, sustainable, heat-resistant, high voltage, lithium batteries 1. Introduction With the rapid boosting of electric vehicles, the bottleneck of short range appear more increasingly prominent. As main power for electric vehicles, the key to improve the range is to increase the energy density of the power battery1-7. Current lithium ion batteries (LiCoO2, LiMn2O4 and LiFePO4) cannot meet the demand of high energy density. The most efficient method is to enhance the cathode materials operating voltage. Under the background, the LiNi0.5Mn1.5O4 (LNMO) cathode exhibit higher voltage platform (4.7 V) and can work at high voltage condition (5 V). Nevertheless, the practical realization still faces many challenges especially for separators8-10. Therefore, it is essential and urgent to fabricate high-performance separators with integrated performance due to high ionic conductivity, appropriate mechanical strength, excellent heat resistance and wide electrochemical window11-16. Polyolefin separators, which have been widely used in commercialized lithium ion batteries often suffered from poor compatibility with liquid electrolytes and severe dimensionally thermal stability17,18,19. In an effort to resolve these aggressive issues, there has been an ongoing research to develop high-performance separators, such as cellulose separator, PET separator and so on. Unfortunately, they cannot meet the demand of high-potential lithium battery. Hence, there is an urgent need to develop reliable and high-performance separator. Alginate, obtained from brown seaweeds, is a natural biomass material. In 1881, the British chemist E.C. Stanford firstly used


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alginate obtained by brown alga for scientific research. And then it was commercialized in 192720,21. Nowadays, it is widely applied in food and pharmaceutical industry due to its amazing biodegradability and biocompatibility. In the field of lithium batteries, alginate is usually used as binder to enhance the cycling stability, indicating its excellent electrochemical stability and considerable ionic conductivity. In addition, previous study showed the carboxyl would chelate with transition metals and fixed soluble transition metal ions22-24. There is no doubt that alginate is an ideal material of separator for high-voltage lithium batteries owing to its strong polymer binding, good electrochemical stability and special carboxyl structure25-30. Herein, in this research, alginate is firstly explored for the feasibility of high-voltage lithium battery separator. It was demonstrated that such alginate nonwoven separator (Hereafter, abbreviated as “CA separator”) possessed superior electrochemical stability, high ionic conductivity and improved electrochemical performance. Moreover, when used as the separator of high-voltage (5 V) lithium batteries at 55 oC, such CA exhibited much better cycle performance than PP separator after 200 cycles. The reason could be attributed to abundant carboxyl group in alginate structure and its capability to chelate with Mn2+, which subsequently stabilize the electrode/electrolyte interface. 2. Experiment section 2.1 Materials collection Commercialized polypropylene separator (Celgard 2500 separator) was received from Celgard Company (USA). Alginate nonwoven was purchased from Huaren Pharmaceutical and used without special treatment. 2.2 Characterization


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The morphology of the samples was tested by a Hitachi S-4800 field emission scanning electron microscope (SEM). The stress experiment was used an Inston-3300 universal testing machine (USA) to test the mechanical property at a stretching speed of 100 mm min-1 with the sample of 1 cm wide and 8 cm long, the ends of sample was clasped for 1cm long and stretched until the sample was broken, tensile speed was 100 mm/min. To evaluate the thermal shrinkage property, the dimensional changes of the separator was measured before and after storing in oven for 2 hrs. Linear sweep voltammetry of the samples were carried out on electrochemical workstation with a sweep rate of 1 mV/s between 2.5 V and 6.0 V. A stainlesssteel/separator/stainless-steel was assembled and AC impedance measurements was operated by Zahner Electrik IM6 impedance analyzer. The frequency is range from 1 MHz to 1Hz and the temperature range from 25 oC to 80 oC. The cycled batteries were dismantled and dried at 25 oC in a glove box filled with argon to obtain the dried separator and cathode. Then separator was examined by ex situ SEM and Energy Dispersive X-ray Detector (EDX) to test the element distribution on the surface of PP and CA separator. X-ray photoelectron spectroscopy (XPS) was used to test the different valence state of Mn on the surface of cathode. The cathode was prepared by mixing LiNi0.5Mn1.5O4 (LNMO), carbon black, and PVDF (8:1:1/w:w:w). The slurry was coated onto an aluminum current collector, dried at 120 oC for 24 hrs, and keep in glove box for the following evaluation. The LNMO/Li battery was charged and discharged between 3.5 V-5 V. The LiFePO4 cathode was composed of 80 wt% LiFePO4, 10 wt% PVDF and 10 wt% carbon black. The LiFePO4 cathode was made by a film preparation via mixing the LiFePO4, carbon black, PVDF (8:1:1/w:w:w). The PVDF was solved in N-Methyl pyrrolidone (NMP). The slurry was coated onto an aluminum current collector, dried at 120 oC


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for 24 hrs, rolled and stamped discs. The LiFePO4/Li battery was charged and discharged between 2.5 V-4 V at the elevated temperature of 150 oC31-32. 3. Results and discussion 3.1 Morphology and physical properties

Figure 1. Typical SEM images of a) PP separator (×8000) and b) CA separator (×400). The cross-section SEM images of c) PP and d) CA separator. Typical SEM images of PP separator and CA separator were vividly exhibited in Figure 1. As shown in Figure 1a, elliptic pores of PP separator which were generated by a uniaxial stretching technology were homogeneous and unidirectional. The pores were between 100 nm and 500 nm long and about 50 nm wide. The thickness of PP separator was 25 µm (Figure 1c). Figure 1b and Figure 1d showed that CA separator was randomly accumulated by amount of


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fibers with diameter 30±5 µm and the thickness of CA separator was 140 µm (Figure 1d). In addition, it possessed intact and well-connected porous structure which was hopeful to be as a critical part in terms of preventing avoiding self-discharge and internal short-circuits to improve the safety property33-35.

Figure 2. a) Thermal shrinkage rate of PP separator and CA separator ranging from 100 oC to 150 oC. b) Stress–strain curves of PP separator and CA separator. It was necessary for separator to possess excellent thermally dimentional stability.As shown in Figure 2a, thermal shrinkage of PP separator in 100 oC, 110 oC, 120 oC, 130 oC, 140 oC, 150 o

C were 5 %, 10 %, 12.5 %, 20 %, 28.75 %, 50 %, respectively. In contrast, the size of CA

separator was rarely changed. Superior thermal stability of CA separator would improve the safety characteristic of lithium batteries. Figure 2b exhibited the stress-strain curves of PP separator and CA separator. The tensile strength of CA separator was 37 MPa, which was 25MPa higher than that of PP separator (12 MPa). Splendid heat resistance and excellent mechanical property would enhance security of lithium batteries36,37. In view of practical consideration, CA separator could provide more reliable mechanical property and followingly


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reduce the probability of internal short circuit of the lithium batteries, thus the safety performance of lithium batteries was improved 12, 38. 3.2 Ionic conductivity and electrochemical stability. With an aim to measure the electrochemical performance of the separators, a stainlesssteel/separator/ lithium metal was prepared and measure by a linear sweep voltammetry test. The electrochemical window of PP separator and CA separator was exhibited in Figure 3a. As can be seen in Figure 3a that the cell with CA separator and PP separator had no typical decomposition peak of below 5.0 V vs. Li+/Li. Thus, the cell with CA separator and PP separator own considerable electrochemical stability performance. It was confirmed that CA separator had the capability to apply to high voltage lithium ion batteries.

Figure 3. a) Linear sweep voltammetry and b) Arrhenius plots of ionic conductivity of PP separator and CA separator. Figure 3b showed Arrhenius plots of ionic conductivity of PP separator and CA separator ranging from 30 oC to 80 oC. The obtained ionic conductivity of PP separator was 6.4×10-4 S/cm and that of CA separator was 1.4×10-3 S/cm at 30 oC, respectively. The ionic conductivity of


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liquid CA separator was superior to that of PP separator owing to its better intrinsic hydrophilic performance. Ionic conductivity of PP separator and CA separator can be well fitted with Arrhenius equation39-41. σ =A exp(-Ea /RT)

(1)

Where σ is an ionic conductivity, Ea is the activation energy related to the segmental mobility, A is the pre-exponential factor, and R is the ideal gas constant. It is worth noticing that the Ea value of CA separator (6.1 KJ/mol) is little lower than that for PP separator (7.6 KJ/mol). It was reported that lower Ea is favorable to the movement of ions through in CA separator42. 3.3 Rate capability and cycle performance of LNMO/Li cell at 55 oC


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Figure 4. Charge-discharge curves of LNMO/Li cells using a) PP separator and b) CA separator at various rates at 55 oC. c) Rate capability and d) cycle performance of the LNMO/Li cells using PP separator and CA separator at 55 oC. To investigate the reliability of CA-separator in high-voltage lithium battery at high temperature, rate capability and cycling performance of LNMO/Li cells using PP separator and CA separator at 55 oC were displayed in Figure 4a-4c. The discharge capacity of battery with PP separator was 137 mAh g-1 at 1 C, under equal conditions, the discharge capacity of cell used CA separator was 151 mAh g-1 at 1 C, much higher than that of PP separator. As the current increased, the discharge capacity of PP separator and CA separator decreased. As shown in Figure 4c, the discharge capacity of cell using CA separator at 2 C, 3 C, 4 C, 6 C, 8 C, 10 C was 147 mA hg-1, 144 mA hg-1, 143 mA hg-1, 142 mA hg-1, 139 mA hg-1, 133 mA hg-1, 126 mA hg-1, respectively. However, the discharge capacity of battery using PP separator at 2 C, 3 C, 4 C, 5 C, 6 C, 8 C, 10 C was 135 mA hg-1, 130 mA hg-1, 127 mA hg-1, 123 mA hg-1, 119 mA hg-1, 109 mA hg-1, 98 mA hg-1, respectively. This superior rate capacity of CA separator was attributed to the excellent ionic conductivity and favorable interfacial compatibility41. Cycle life at high temperature was also an important property for evaluating lithium ion battery. A comparison of the cycling performance of LNMO/Li cell using PP separator and CA separator was presented in Figure 4d. A notable finding was that the obtained discharge capacity of CA separator after 200 cycles was around 117 mAh g-1, capacity retention at 79.6 % better than 69.3 % of the PP separator. Favorable interface characteristic as well as strong affinity of CA separator and Mn2+ result in higher capacity retention 43,45.


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Figure 5. XPS spectra of LNMO electrodes of lithium-ion battery after 100 cycles with a) PP separator b) CA separator.

Figure 6. a) SEM image of PP separator after 200 cycles and corresponding elemental mapping images of b) C and c) O.


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Figure 7. a) SEM image of CA separator after 200 cycles and corresponding elemental mapping images of b) C, c) O and d) Mn. To further confirm the effects of CA-separator on the enhanced cycling stability of LNMO/Li battery at high temperature, XPS spectra of the LNMO electrodes after 200 cycles with PP and CA separator was displayed in Figure 5. The amount of Mn2+ and the ratio of Mn2+ to Mn4+ on the surface of LNMO electrode with CA separator (Figure 5a) was a little lower than that in the electrode with PP separator (Figure 5b). It’s well known that the disproportion reaction (2Mn3+(s) →Mn2+(aq) + Mn4+(s)) could generate Mn2+ which was soluble and destructive to the layer of anode or cathode-electrolyte interface42-47. Mn2+ ions was dissolved into the electrolyte after cycling, this loss of Mn lead to poor capacity retention31,43,46. To verify the chelate effect of CA separator with Mn2+, we conducted elemental mapping images of CA separator and PP separator after 200 cycles. It can be found in Figure 6 that Mn are not detected on PP separator. In a sharp contrast, the certain amount of Mn was detected on


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the surface of CA separator (Figure 7). The reason are as follows: the disembedded Mn2+ from LNMO dissolved in the electrolyte and chelated with the carboxyl group of alginate, then the Mn2+ was immobilized by CA separator, which further referred the dissolution of Mn2+28-30. Therefore, the alginate could restrain the Mn2+ crossing from cathode to anode and prevent the damage of lithium anode31,32,49,50. That’s why the cycle performance of LNMO/Li battery with CA separator was superior to that of PP separator at 55oC51,52. This result proves that the CA separator is a much effective material to improve cycling stability of Li/Li, LNMO/Li battery cells at elevated temperatures 3.4 Charge/discharge profiles and cycling stability of LiFePO4/Li cell at 150 oC.

Figure 8. a) Charge-discharge curves and b) cycling stability of LiFePO4/Li cells using PP separator and CA separator at an elevated temperature of 150 oC. Typical SEM images of c) PP separator and d) CA separator after stored in 150 oC for 0.5 h.


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But behind our public enthusiasm for high-voltage performance, cycling stability of the cell in the elevated temperature is also vital for actual application. As can be seen in Figure 8a-8b that the LiFePO4/Li cell with CA separator delivered normal charge/discharge curves at 1 C and the discharge capacity was 138 mAh g-1. Meanwhile, the cell assembled with PP separator can hardly charge and discharge at 150 oC owning to its poor dimensionally thermal stability. The surface microstructure of PP separator and CA separator after storing at 150 oC for 0.5 h was vividly displayed in Figure 8c-8d. It was obviously that the pores of PP separator by heating treatment were smaller than that of 25 oC (Figure 1a). The thermal shrinkage of PP separator was 50 % after heated at 150 oC for 0.5 h. Severely thermal shrinkage will lead to the direct contact of anode and cathode and result in the short circuit of battery5,6,12. However, the pores size and the nano-fiber shape of CA separator hardly changed even at 150 oC. Hence, CA separator is expected to play an important part in avoiding shortage and enhancing the safety performance of lithium-ion battery at higher temperature because of its heat resistance property. 4. Conclusion In summary, we have fabricated sustainable and heat-resistant alginate nonwoven separator for 5 V lithium batteries successfully. As compared to commercially available PP separator, our alginate nonwoven separator exhibited comprehensive performance in terms of relatively higher ionic conductivity, wider electrochemical window and more excellent thermal stability. When evaluated as separator of LNMO/Li cell, a wonderful capacity retention of 79.6 % over 200 cycles was achieved at an elevated temperature of 55 oC. To our knowledge, this is the best cycling performance of separator for 5 V lithium battery at high temperatures. More impressively, such alginate nonwoven separator-based LiFePO4/Li cell delivered relatively


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satisfactory battery performance at the elevated temperature of 150 oC. We believe these features promise alginate separator for high-voltage lithium batteries.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Tel.: +8653280662746. *E-mail: [email protected]. Author Contributions All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. Acknowledgments This work was financially supported by the Programs of the National Natural Science Foundation of China (Grant No. 21271180), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA09010105), the Qingdao Institute of Bioenergy and Bioprocess Technology Director Innovation Foundation for Young Scientists (Grant Number: QIBEBT-DIFYS-201508) and Shandong Provincial Natural Science Foundation, China (No. ZR2013FZ001).

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Table of Contents Graphic


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Sustainable and Superior Heat-Resistant Alginate Nonwoven

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