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Retrograded starches as potential anodes in lithium-ion rechargeable batteries
International Journal of Biological Macromolecules 51 (2012) 632–634
Contents lists available at SciVerse ScienceDirect
International Journal of Biological Macromolecules journal homepage: www.elsevier.com/locate/ijbiomac
Retrograded starches as potential anodes in lithium-ion rechargeable batteries Lian Xijun a,b,c,∗ , Wen Yan d , Zhu Wei d , Li Lin b,c,∗∗ , Zhang Kunsheng a,∗ ∗ ∗ , Wang Wanyu a a
The Tian Jin Key Laboratory of Food Biotechnology, School of Food Science and Biotechnology, Tian Jin University of Commerce, Tianjin 300134, PR China College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China c Guangdong Province Key Laboratory For Green Processing of Natural Products and Product Safety, Guangzhou 510640, PR China d School of Science, Tian Jin University of Commerce, Tianjin 300134, PR China b
a r t i c l e
i n f o
Article history: Received 17 May 2012 Received in revised form 11 June 2012 Accepted 12 June 2012 Available online 2 July 2012 Keywords: Retrograded potato amylose and amylopectin Crystal Rechargeable batteries
a b s t r a c t Retrograded starch is a crystal formed by starch molecules with hydrogen bonds. Many literatures have reported its physicochemical character, but its crystal structure is so far unclear. As we isolate amylose and amylopectin from retrograded maize, sweet potato and potato starches in 4.0 M KOH solutions and make them retrograde alone in neutral solution (adjusted by HCl) to form crystal, a new phenomenon appears, crystals of KCl do not appear in retrograded potato amylose, potato amylopectin, and maize amylose, indicating that those crystals may absorb K+ and (or) Cl− , and those ions probably act with aldehyde of starch or hydroxy of fatty acid attached in starch, such characteristic may make retrograded starches replace graphite as anode with high-capacity in lithium-ion rechargeable batteries. © 2012 Elsevier B.V. All rights reserved.
1. Introduction
2.2. Methods
Rechargeable Li-ion batteries are pushed recently for more and more demanding applications, their anodes are mainly made by graphite [1–4], graphene nanosheet hybrid with metal salts [5–9] and metal salts alloy [10–23], but the low storage capacities of Li-ion batteries limits their applications such as car and train. Materials of anode in Li-ion battery determine its storage capacity, retrograded starches, especially retrograded amylopectin, show the same spatial structure to that of graphite and may be a potential anode with high storage capacity for rechargeable Li-ion battery.
2.2.1. Preparation of retrograded starches and their purification The retrograded starches were prepared according to Ref. [15]. The samples were dried in oven at 80 ◦ C, until constant weight reached. To purify the retrograded starches, the dry samples (2 g) were resolved in water (pH 6.0) and treated with protease (2 mg) for 18 h at 37 ◦ C in a shaking water bath, then ␣-amylase was added and kept reaction for 6 h at 90 ◦ C. Purified retrograded starches were obtained by washing the remaining precipitate 3 times with deionized water and drying.
2. Experimental 2.1. Materials Starches were offered by Shan Dong Jin-Cheng Limited Company. Butanol and ethanol were purchased from Tianjin Fuyu Fine Chemical Co., Ltd.
∗ Corresponding author at: The Tian Jin Key Laboratory of Food Biotechnology, School of Food Science and Biotechnology, Tian Jin University of Commerce, Tianjin 300134, PR China. Tel.: +86 13602864341; fax: +86 20 87110249. ∗∗ Corresponding author at: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China. ∗ ∗ ∗ Corresponding author. E-mail addresses: [email protected] (X. Lian), [email protected] (L. Li), [email protected] (K. Zhang). 0141-8130/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ijbiomac.2012.06.015
2.2.2. Fractionation of retrograded starches and retrogradation of their parts alone The purified retrograded starches were resolved in 4 M potassium hydroxide and subsequently neutralized by HCl. Then n-butanol was added to solution to precipitate amylose. The supernatants, containing amylopectin, were collected, concentrated, and excess ethanol was added in to precipitate amylopectin. The separated amylose and amylopectin were used to retrograde again and purified according to Section 2.2.1.
2.2.3. Optical micrographs taken in retrograded starches The wet retrograded starch was moved to the slide, dried at room temperature and observed by Microscope (OLYMPUS IX71). All optical micrographs were taken in 400 total magnification.
X. Lian et al. / International Journal of Biological Macromolecules 51 (2012) 632–634
633
Fig. 1. Micrographs of KCl crystals in retrograded amylose and amylopectin. (a) Retrograded maize amylose; (b) retrograded maize amylopectin; (c) retrograded sweet potato amylose; (d) retrograded sweet potato amylopectin; (e) retrograded potato amylose; and (f) retrograded potato amylopectin.
2.2.4. Scanning electron microscopy (SEM) Starch granules were mounted directly onto aluminum stubs using double-sided carbon tape, and coated with 20 nm gold–palladium (60:40). Images of starch granules were obtained with a field emission SEM (Hitachi S-3700, Tokyo, Japan) at an accelerating voltage of 13 kV.
3. Results and discussion 3.1. Formation of KCl crystal in different retrograded starches Fig. 1 shows the micrographs of KCl crystals in retrograded amylose and amylopectin of maize, sweet potato and potato starch. The chlorination potassium crystals do not appear in samples of retrograded maize amylose, potato amylose, and potato amylopectin after drying, indicating that those crystals may absorb K+ and (or) Cl− , and those ions probably act with aldehyde of starch or hydroxy of fatty acid attached in starch, such characteristic may make retrograded starches replace graphite as anode with high-capacity in lithium-ion rechargeable batteries. The morphology of KCl crystal is obviously affected by retrogradation of
different retrograded starches, acicular, thin rectangular and coarse rectangular correspond to maize retrograded amylopectin, sweet potato retrograded amylose and sweet potato retrograded amylopectin, respectively. Retrograded maize amylopectin encourages KCl crystal to grow in the direction of C axis so as to form acicular shape, the reason for this should be further studied. Many studies involve the impact of metal ions on the polymer crystalline morphology [1–3], very few relate to the effect of polymer on metal salt crystal morphology. Gniadek et al. reported that metallic gold practically appeared only porous granules in the presence of polypyrrole [4]. Haber et al. found that para-sexiphenyl crystallitesis consisted of edge-on molecules aligned parallel to (0 1 1) KCl forming needles [5], and Tsai et al. published that morphology of a Bi deposit changed to nano-sized, sphere-like and porous with adding citric acid (CA), ethylene diamine tetra acetic acid (EDTA) and polyethylene glycol (PEG) [6]. 3.2. Scanning electron microscopy of retrograded amylose and amylopectin Fig. 2 shows the scanning electron microscopies of retrograded amylose and amylopectin.
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X. Lian et al. / International Journal of Biological Macromolecules 51 (2012) 632–634
Fig. 2. SEM of maize retrograded amylose and amylopectin. (a) Maize retrograded amylose and (b) maize retrograded amylopectin.
The obvious difference in Fig. 2a and b is that there exists layered structure in retrograded maize amylopectin, which is same to that of graphite and may be the channel for K+ and Cl− to go through. More closely layered structure may also exist in retrograded maize amylose and the distance between interlayer may control the out of K+ and Cl− , because K+ concentration of 4 M is comparable high, so preparation of retrograded starches with proper interlayer having ability of absorbing 4 M K+ may serves as graphite anode with highcapacity in lithium-ion rechargeable batteries. The difficulties for retrograded starch to be used as the negative electrode of lithium-ion battery are: first, compared to graphite, the physical and chemical properties of retrograded starch are unstable, which are mainly caused by the composition of the crystalline with starch molecular weight unevenly, containing a very small amount of protein and lipids. Starch with narrow molecular weight distribution may be prepared by repeatedly retrogradation, protein and lipids can be reduced by enzymatic hydrolysis; second, poor binding properties of retrograded starch with protective film; last, more experiments are needed to explore the deintercalation of Liions from the mosaic of retrograded starch layered structure in the discharge. 4. Conclusion Retrograded starches with proper interlayer may serve as anode with high-capacity in lithium-ion rechargeable batteries. Acknowledgements This work is supported by the State Key Program of National Natural Science of China (No. 31130042), the National Key Technology R&D Program (No. 2012BAD37B01), “12th Five-Year” National
Science and Technology Support Project (No. 2012BAD37B06). Authors would like to thank Zhao Shuang, Liu Xueyan, and Wang Chen for their kindly help in experiments. References [1] Z. Wanhong, Transactions of Nonferrous Metals Society of China 21 (2011) 2466–2475. [2] L. JinLong, W. Jie, X. YongYao, Electrochimica Acta 56 (2011) 7392–7396. [3] S. Mehdi, T.A. Ahmet, Journal of Power Sources 196 (2011) 7771–7778. [4] B. Chang-Keun, P. Jai, Thermochimica Acta 520 (2011) 93–98. [5] B. Fuchsbichler, C. Stangl, H. Kren, F. Uhlig, S. Koller, Journal of Power Sources 196 (2011) 2889–2892. [6] Z. Chaofeng, P. Xing, G. Zaiping, C. Chuanbin, C. Zhixin, W. David, L. Sean, L. Huakun, Carbon 50 (2012) 1897–1903. [7] C. Kun, W. Zhen, H. Guochuang, L. He, C. Weixiang, L. Jim Yang, Journal of Power Sources 201 (2012) 259–266. [8] L. Zhaolin, T. Siok Wei, Materials Letters 72 (2012) 74–77. [9] G. Wang, Z.Y. Liu, P. Liu, Electrochimica Acta 56 (2011) 9515–9519. [10] L. Haixia, C. Fangyi, Z. Zhiqiang, B. Hongmei, T. Zhanliang, C. Jun, Journal of Alloys and Compounds 509 (2011) 2919–2923. [11] J. Limin, Q. Yongcai, D. Hong, L. Weishan, L. Hong, Y. Shihe, Electrochimica Acta 56 (2011) 9127–9132. [12] K. Palanichamy, G.A. Suresh, K.P. Ajay, Journal of Power Sources 196 (2011) 7755–7759. [13] C. Lifeng, S. Jian, C. Fangyi, T. Zhanliang, C. Jun, Journal of Power Sources 196 (2011) 2195–2201. [14] H. Chang-Mook, P. Jong-Wan, Electrochimica Acta 56 (2011) 6737–6747. [15] L. Xijun, Z. Shuyi, L. Qinsheng, Z. Xu, International Journal of Biological Macromolecules 48 (2011) 125–128. [16] T. Yi-Da, L. Chein-Hung, H. Chi-Chang, Electrochimica Acta 56 (2011) 7615–7621. [17] H. Thomas, R. Roland, A. Andrey, O. Martin, S. Detlef-M, S. Helmut, Journal of Crystal Growth 312 (2010) 333–339. [18] G. Marianna, D. Mikolaj, S. Zbigniew, Electrochimica Acta 55 (2010) 7737–7744. [19] S.S. Jeon, C.S. Yoon, S.S. Im, Polymer 51 (2010) 5400–5406. [20] T. Okubo, S. Takahashib, A. Tsuchidaa, Colloids and Surfaces B: Biointerfaces 87 (2011) 11–17. [21] S. Peng, W. Changjun, Y. Xianyan, C. Xiaoyi, G. Changyou, F. Xin-Xing, C. JianYong, Y. Juan, G. Zhongru, Carbohydrate Polymers 84 (2011) 239–246.
Contents lists available at SciVerse ScienceDirect
International Journal of Biological Macromolecules journal homepage: www.elsevier.com/locate/ijbiomac
Retrograded starches as potential anodes in lithium-ion rechargeable batteries Lian Xijun a,b,c,∗ , Wen Yan d , Zhu Wei d , Li Lin b,c,∗∗ , Zhang Kunsheng a,∗ ∗ ∗ , Wang Wanyu a a
The Tian Jin Key Laboratory of Food Biotechnology, School of Food Science and Biotechnology, Tian Jin University of Commerce, Tianjin 300134, PR China College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China c Guangdong Province Key Laboratory For Green Processing of Natural Products and Product Safety, Guangzhou 510640, PR China d School of Science, Tian Jin University of Commerce, Tianjin 300134, PR China b
a r t i c l e
i n f o
Article history: Received 17 May 2012 Received in revised form 11 June 2012 Accepted 12 June 2012 Available online 2 July 2012 Keywords: Retrograded potato amylose and amylopectin Crystal Rechargeable batteries
a b s t r a c t Retrograded starch is a crystal formed by starch molecules with hydrogen bonds. Many literatures have reported its physicochemical character, but its crystal structure is so far unclear. As we isolate amylose and amylopectin from retrograded maize, sweet potato and potato starches in 4.0 M KOH solutions and make them retrograde alone in neutral solution (adjusted by HCl) to form crystal, a new phenomenon appears, crystals of KCl do not appear in retrograded potato amylose, potato amylopectin, and maize amylose, indicating that those crystals may absorb K+ and (or) Cl− , and those ions probably act with aldehyde of starch or hydroxy of fatty acid attached in starch, such characteristic may make retrograded starches replace graphite as anode with high-capacity in lithium-ion rechargeable batteries. © 2012 Elsevier B.V. All rights reserved.
1. Introduction
2.2. Methods
Rechargeable Li-ion batteries are pushed recently for more and more demanding applications, their anodes are mainly made by graphite [1–4], graphene nanosheet hybrid with metal salts [5–9] and metal salts alloy [10–23], but the low storage capacities of Li-ion batteries limits their applications such as car and train. Materials of anode in Li-ion battery determine its storage capacity, retrograded starches, especially retrograded amylopectin, show the same spatial structure to that of graphite and may be a potential anode with high storage capacity for rechargeable Li-ion battery.
2.2.1. Preparation of retrograded starches and their purification The retrograded starches were prepared according to Ref. [15]. The samples were dried in oven at 80 ◦ C, until constant weight reached. To purify the retrograded starches, the dry samples (2 g) were resolved in water (pH 6.0) and treated with protease (2 mg) for 18 h at 37 ◦ C in a shaking water bath, then ␣-amylase was added and kept reaction for 6 h at 90 ◦ C. Purified retrograded starches were obtained by washing the remaining precipitate 3 times with deionized water and drying.
2. Experimental 2.1. Materials Starches were offered by Shan Dong Jin-Cheng Limited Company. Butanol and ethanol were purchased from Tianjin Fuyu Fine Chemical Co., Ltd.
∗ Corresponding author at: The Tian Jin Key Laboratory of Food Biotechnology, School of Food Science and Biotechnology, Tian Jin University of Commerce, Tianjin 300134, PR China. Tel.: +86 13602864341; fax: +86 20 87110249. ∗∗ Corresponding author at: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China. ∗ ∗ ∗ Corresponding author. E-mail addresses: [email protected] (X. Lian), [email protected] (L. Li), [email protected] (K. Zhang). 0141-8130/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ijbiomac.2012.06.015
2.2.2. Fractionation of retrograded starches and retrogradation of their parts alone The purified retrograded starches were resolved in 4 M potassium hydroxide and subsequently neutralized by HCl. Then n-butanol was added to solution to precipitate amylose. The supernatants, containing amylopectin, were collected, concentrated, and excess ethanol was added in to precipitate amylopectin. The separated amylose and amylopectin were used to retrograde again and purified according to Section 2.2.1.
2.2.3. Optical micrographs taken in retrograded starches The wet retrograded starch was moved to the slide, dried at room temperature and observed by Microscope (OLYMPUS IX71). All optical micrographs were taken in 400 total magnification.
X. Lian et al. / International Journal of Biological Macromolecules 51 (2012) 632–634
633
Fig. 1. Micrographs of KCl crystals in retrograded amylose and amylopectin. (a) Retrograded maize amylose; (b) retrograded maize amylopectin; (c) retrograded sweet potato amylose; (d) retrograded sweet potato amylopectin; (e) retrograded potato amylose; and (f) retrograded potato amylopectin.
2.2.4. Scanning electron microscopy (SEM) Starch granules were mounted directly onto aluminum stubs using double-sided carbon tape, and coated with 20 nm gold–palladium (60:40). Images of starch granules were obtained with a field emission SEM (Hitachi S-3700, Tokyo, Japan) at an accelerating voltage of 13 kV.
3. Results and discussion 3.1. Formation of KCl crystal in different retrograded starches Fig. 1 shows the micrographs of KCl crystals in retrograded amylose and amylopectin of maize, sweet potato and potato starch. The chlorination potassium crystals do not appear in samples of retrograded maize amylose, potato amylose, and potato amylopectin after drying, indicating that those crystals may absorb K+ and (or) Cl− , and those ions probably act with aldehyde of starch or hydroxy of fatty acid attached in starch, such characteristic may make retrograded starches replace graphite as anode with high-capacity in lithium-ion rechargeable batteries. The morphology of KCl crystal is obviously affected by retrogradation of
different retrograded starches, acicular, thin rectangular and coarse rectangular correspond to maize retrograded amylopectin, sweet potato retrograded amylose and sweet potato retrograded amylopectin, respectively. Retrograded maize amylopectin encourages KCl crystal to grow in the direction of C axis so as to form acicular shape, the reason for this should be further studied. Many studies involve the impact of metal ions on the polymer crystalline morphology [1–3], very few relate to the effect of polymer on metal salt crystal morphology. Gniadek et al. reported that metallic gold practically appeared only porous granules in the presence of polypyrrole [4]. Haber et al. found that para-sexiphenyl crystallitesis consisted of edge-on molecules aligned parallel to (0 1 1) KCl forming needles [5], and Tsai et al. published that morphology of a Bi deposit changed to nano-sized, sphere-like and porous with adding citric acid (CA), ethylene diamine tetra acetic acid (EDTA) and polyethylene glycol (PEG) [6]. 3.2. Scanning electron microscopy of retrograded amylose and amylopectin Fig. 2 shows the scanning electron microscopies of retrograded amylose and amylopectin.
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X. Lian et al. / International Journal of Biological Macromolecules 51 (2012) 632–634
Fig. 2. SEM of maize retrograded amylose and amylopectin. (a) Maize retrograded amylose and (b) maize retrograded amylopectin.
The obvious difference in Fig. 2a and b is that there exists layered structure in retrograded maize amylopectin, which is same to that of graphite and may be the channel for K+ and Cl− to go through. More closely layered structure may also exist in retrograded maize amylose and the distance between interlayer may control the out of K+ and Cl− , because K+ concentration of 4 M is comparable high, so preparation of retrograded starches with proper interlayer having ability of absorbing 4 M K+ may serves as graphite anode with highcapacity in lithium-ion rechargeable batteries. The difficulties for retrograded starch to be used as the negative electrode of lithium-ion battery are: first, compared to graphite, the physical and chemical properties of retrograded starch are unstable, which are mainly caused by the composition of the crystalline with starch molecular weight unevenly, containing a very small amount of protein and lipids. Starch with narrow molecular weight distribution may be prepared by repeatedly retrogradation, protein and lipids can be reduced by enzymatic hydrolysis; second, poor binding properties of retrograded starch with protective film; last, more experiments are needed to explore the deintercalation of Liions from the mosaic of retrograded starch layered structure in the discharge. 4. Conclusion Retrograded starches with proper interlayer may serve as anode with high-capacity in lithium-ion rechargeable batteries. Acknowledgements This work is supported by the State Key Program of National Natural Science of China (No. 31130042), the National Key Technology R&D Program (No. 2012BAD37B01), “12th Five-Year” National
Science and Technology Support Project (No. 2012BAD37B06). Authors would like to thank Zhao Shuang, Liu Xueyan, and Wang Chen for their kindly help in experiments. References [1] Z. Wanhong, Transactions of Nonferrous Metals Society of China 21 (2011) 2466–2475. [2] L. JinLong, W. Jie, X. YongYao, Electrochimica Acta 56 (2011) 7392–7396. [3] S. Mehdi, T.A. Ahmet, Journal of Power Sources 196 (2011) 7771–7778. [4] B. Chang-Keun, P. Jai, Thermochimica Acta 520 (2011) 93–98. [5] B. Fuchsbichler, C. Stangl, H. Kren, F. Uhlig, S. Koller, Journal of Power Sources 196 (2011) 2889–2892. [6] Z. Chaofeng, P. Xing, G. Zaiping, C. Chuanbin, C. Zhixin, W. David, L. Sean, L. Huakun, Carbon 50 (2012) 1897–1903. [7] C. Kun, W. Zhen, H. Guochuang, L. He, C. Weixiang, L. Jim Yang, Journal of Power Sources 201 (2012) 259–266. [8] L. Zhaolin, T. Siok Wei, Materials Letters 72 (2012) 74–77. [9] G. Wang, Z.Y. Liu, P. Liu, Electrochimica Acta 56 (2011) 9515–9519. [10] L. Haixia, C. Fangyi, Z. Zhiqiang, B. Hongmei, T. Zhanliang, C. Jun, Journal of Alloys and Compounds 509 (2011) 2919–2923. [11] J. Limin, Q. Yongcai, D. Hong, L. Weishan, L. Hong, Y. Shihe, Electrochimica Acta 56 (2011) 9127–9132. [12] K. Palanichamy, G.A. Suresh, K.P. Ajay, Journal of Power Sources 196 (2011) 7755–7759. [13] C. Lifeng, S. Jian, C. Fangyi, T. Zhanliang, C. Jun, Journal of Power Sources 196 (2011) 2195–2201. [14] H. Chang-Mook, P. Jong-Wan, Electrochimica Acta 56 (2011) 6737–6747. [15] L. Xijun, Z. Shuyi, L. Qinsheng, Z. Xu, International Journal of Biological Macromolecules 48 (2011) 125–128. [16] T. Yi-Da, L. Chein-Hung, H. Chi-Chang, Electrochimica Acta 56 (2011) 7615–7621. [17] H. Thomas, R. Roland, A. Andrey, O. Martin, S. Detlef-M, S. Helmut, Journal of Crystal Growth 312 (2010) 333–339. [18] G. Marianna, D. Mikolaj, S. Zbigniew, Electrochimica Acta 55 (2010) 7737–7744. [19] S.S. Jeon, C.S. Yoon, S.S. Im, Polymer 51 (2010) 5400–5406. [20] T. Okubo, S. Takahashib, A. Tsuchidaa, Colloids and Surfaces B: Biointerfaces 87 (2011) 11–17. [21] S. Peng, W. Changjun, Y. Xianyan, C. Xiaoyi, G. Changyou, F. Xin-Xing, C. JianYong, Y. Juan, G. Zhongru, Carbohydrate Polymers 84 (2011) 239–246.