Response Surface Optimization for Process Parameters of LiFePO4/C Preparation by Carbothermal Reduction Technology

摘要/Abstract

摘要： A statistically based optimization strategy is used to optimize the carbothermal reduction technology for the synthesis of LiFePO₄/C using LiOH,FePO₄ and sucrose as raw materials.The experimental data for fitting the response are collected by the central composite rotatable design(CCD).A second order model for the discharge capacity of LiFePO₄/C is expressed as a function of sintering temperature,sintering time and carbon content.The effects of individual variables and their interactions are studied by a statistical analysis(ANOVA).The results show that the linear effects and the quadratic effects of sintering temperature,carbon content and the interactions among these variables are statistically significant,while those effects of sintering time are insignificant.Response surface plots for spatial representation of the model illustrate that the discharge capacity depends on sintering temperature and carbon content more than sintering time.The model obtained gives the optimized reaction parameters of sinter-ing temperature at 652.0℃,carbon content of 34.33 g·mol^-1 and 8.48 h sintering time,corresponding to a dis-charge capacity of 150.8 mA·h·g^-1.The confirmatory test with these optimum parameters gives the discharge capacity of 147.2 and 105.1 mA·h·g^-1 at 0.5 and 5 C,respectively.

关键词: lithium ion battery, cathode material, lithium iron phosphate, carbothermal reduction technology, response surface methodology

Abstract: A statistically based optimization strategy is used to optimize the carbothermal reduction technology for the synthesis of LiFePO₄/C using LiOH,FePO₄ and sucrose as raw materials.The experimental data for fitting the response are collected by the central composite rotatable design(CCD).A second order model for the discharge capacity of LiFePO₄/C is expressed as a function of sintering temperature,sintering time and carbon content.The effects of individual variables and their interactions are studied by a statistical analysis(ANOVA).The results show that the linear effects and the quadratic effects of sintering temperature,carbon content and the interactions among these variables are statistically significant,while those effects of sintering time are insignificant.Response surface plots for spatial representation of the model illustrate that the discharge capacity depends on sintering temperature and carbon content more than sintering time.The model obtained gives the optimized reaction parameters of sinter-ing temperature at 652.0℃,carbon content of 34.33 g·mol^-1 and 8.48 h sintering time,corresponding to a dis-charge capacity of 150.8 mA·h·g^-1.The confirmatory test with these optimum parameters gives the discharge capacity of 147.2 and 105.1 mA·h·g^-1 at 0.5 and 5 C,respectively.

Key words: lithium ion battery, cathode material, lithium iron phosphate, carbothermal reduction technology, response surface methodology

杨克迪, 谭芳香, 王凡, 龙云飞, 文衍宣. Response Surface Optimization for Process Parameters of LiFePO₄/C Preparation by Carbothermal Reduction Technology[J]. Chinese Journal of Chemical Engineering, 2012, 20(4): 793-802.

YANG Kedi, TAN Fangxiang, WANG Fan, LONG Yunfei, WEN Yanxuan. Response Surface Optimization for Process Parameters of LiFePO₄/C Preparation by Carbothermal Reduction Technology[J]. Chin.J.Chem.Eng., 2012, 20(4): 793-802.

参考文献

1 Padhi,A.K.,Nanjundaswamy,K.S.,Goodenough,J.B.,"Phospho-olivines as positive-electrode materials for rechargeable lithium batteries",J.Electrochem.Soc.,144(4),1188-1194(1997).
2 Padhi,A.K.,Nanjundaswamy,K.S.,Masquelier,C.,Okada,S., Goodenough,J.B.,"Effect of structure on the redox Fe³⁺/Fe²⁺ in iron phosphate",J.Electrochem.Soc.,144(10),1609-1613(1997).
3 Li,Z.H.,Zhang,D.M.,Yang,F.X.,"Developments of lithium-ion batteries and challenges of LiFePO₄ as one promising cathode material",J.Mater.Sci.,44(10),2435-2443(2009).
4 Jugović,D.,Uskoković,D.,"A review of recent developments in the synthesis procedures of lithium iron phosphate powders",J.Power Sources.,190(2),538-544(2009).
5 Chen,Z.H.,Dahn,J.R.,"Reducing carbon in LiFePO₄/C composite electrodes to maxing specific energy,volumetric energy,and tap density",J.Electrochem.Soc.,149(9),A1184-A1189(2002).
6 Huang,Y.,Park,K.,Goodenough,J.B.,"Improving lithium batteries by tethering carbon-coated LiFePO₄ to polypyrrole",J.Electrochem. Soc.,153(12),A2282-A2286(2006).
7 Doeff,M.M.,Wilcox,J.D.,Kostecki,R.,Lau,G.,"Optimization of carbon coatings on LiFePO₄",J.Power Sources,163(1),180-184 (2006).
8 Kim,J.K.,Cheruvally,G.,Ahn,J.H.,"Electrochemical properties of LiFePO₄/C synthesized by mechanical activation using sucrose as carbon source",J.Solid State Electrochem.,12(7-8),799-805 (2008).
9 Bodoardo,S.,Gerbaldi,C.,Meligrana,G.,Tuel,A.,Enzo,S., Penazzi,N.,"Optimisation of some parameters for the preparation of nanostructured LiFePO₄/C cathode",Ionics,15(1),19-26(2009).
10 Chung,S.Y.,Bloking,J.T.M.,Chiang,Y.,"Electronically conductive phospho-olivines as lithium storage electrodes",Nat.Mater.,1(2),123-128(2002).
11 Wagemaker,M.,Ellis,B.L.,Hecht,D.L.,Mulder,F.M.,Nazar,L.F., "Proof of supervalent doping in olivine LiFePO₄",Chem.Mater.,20 (20),6313-6315(2008).
12 Bauer,E.M.,Bellitto,C.,Righini,G.,Pasquali,M.,"A versatile method of preparation of carbon-rich LiFePO₄:A promising cathode material for Li-ion batteries",J.Power Sources,146(1-2),544-549 (2005).
13 Xia,Y.,Yoshio,M.,Noguchi,H.,"Improved electrochemical performance of LiFePO₄ by increasing its specific surface area",Electrochimica Acta,52(1),240-245(2006).
14 Zhang,D.,Cai,R.,Zhou,Y.K.,Shao,Z.P.,Liao,X.Z.,Ma,Z.F., "Effect of milling method and time on the properties and electrochemical performance of LiFePO₄/C composites prepared by ball milling and thermal treatment",Electrochim.Acta,55(8),2653-2661(2010).
15 Wang,K.,Cai,R.,Yuan,T.,Yu,X.,Ran,R.,Shao,Z.P.,"Process investigation,electrochemical characterization and optimization of LiFePO₄/C composite from mechanical activation using sucrose as carbon source",Electrochim.Acta,54(10),2861-2868(2009).
16 Barker,J.,Saidi,M.Y.,Swoyer,J.L.,"Lithium iron(Ⅱ)phosphoolivines prepared by a novel carbothermal reduction method",Electrochem.Solid-State Lett.,6(3),A53-A55(2003).
17 Mi,C.H.,Cao,G.S.,Zhao,X.B.,"Low-cost,one-step process for synthesis of carbon-coated LiFePO₄ cathode",Mater.Lett.,59(1),127-130(2005).
18 Zhu,B.Q.,Li.,X.H.,Wang,Z.X.,Guo,H.J.,"Novel synthesis of LiFePO₄ by aqueous precipitation and carbothermal reduction",Mater.Chem.Phys.,98(2-3),373-376(2006).
19 Wang,L.N.,Zhang,Z.G.,Zhang,K.L.,"A simple,cheap soft synthesis routine for LiFePO₄ using iron(Ⅲ)raw material",J.Power Sources,167(1),200-205(2007).
20 Zheng,J.C.,Li,X.H.,Wang,Z.X.,Guo,H.J.,Zhou,S.Y.,"LiFePO₄ with enhanced performance synthesized by a novel synthetic route", J.Power Sources,184(2),574-577(2008).
21 Liu,H.P.,Wang,Z.X.,Li,X.H.,Guo,H.J.,Peng,W.J.,Zhang,Y.H., Hu,Q.Y.,"Synthesis and electrochemical properties of olivine LiFePO₄ prepared by a carbothermal reduction method",J.Power Sources,184(2),469-472(2008).
22 Chang,Z.R.,Lv,H.J.,Tang,H.W.,Li,H.J.,Yuan,X.Z.,Wang,H.J., "Synthesis and characterization of high-density LiFePO₄/C composites as cathode materials for lithium-ion batteries",Electrochim.Acta,54(1),4595-4599(2009).
23 Liu,Z.L.,Zhang,X.H.,Hong,L.,"Preparation and electrochemical properties of spherical LiFePO₄ and LiFe_0.9Mg_0.1PO₄ cathode materials for lithium rechargeable batteries",J.Appl.Electrochem.,39 (12),2433-2438(2009).
24 Liu,J.,Wang,J.W.,Yan,X.D.,Zhang,X.F.,Yang,G.L.,Abraham,F., Wang,R.S.,"Long-term cyclability of LiFePO₄/carbon composite cathode material for lithium-ion battery applications",Electrochim. Acta,54(24),5656-5659(2009).
25 Wang,L.,Liang,G.C.,Ou,X.Q.,Zh,X.K.,Zhang,J.P.,Cui,J.Y., "Effect of synthesis temperature on the properties of LiFePO₄/C composites prepared by carbothermal reduction",J.Power Sources,189(1),423-428(2009).
26 Aimable,A.,Aymes,D.,Bernard,F.,Le Cras,F.,"Characteristics of LiFePO₄ obtained through a one step continuous hydrothermal synthesis process working in supercritical water",Solid State Ionics,180(11-13),861-866(2009).
27 Liu,Y.Y.,Cao,C.B.,Li,J.,"Enhanced electrochemical performance of carbon nanospheres-LiFePO₄ composite by PEG based sol-gel synthesis",Electrochim.Acta,55(12),3921-3926(2010).
28 Arnold,G.,Garche,J.,Hemmer,R.,Strobele,S.,Vogler,C.,Wohlfahrt-Mehrens,M.,"Fine-particle lithium iron phosphate LiFePO₄ synthesized by a new low-cost aqueous precipitation technique",J. Power Sources,119-121(1),247-251(2003).
29 Myers,R.H.,Montgomery,D.C.,Adweson-cook,C.M.,Response Surface Methodology:Process and product optimization using designed experiments,John Wiley and Sons,Inc.,New York,(2008).
30 Guven,G.,Perendeci,A.,Tanyolac,A.,"Electrochemical treatment of deproteinated whey wastewater and optimization of treatment conditions with response surface methodology",J.Hazard.Mater.,157(1),69-78(2008).
31 Bashir,M.J.K.,Aziz,H.A.,Yusoff,M.S.,Adlan,M.N.,"Application of response surface methodology(RSM)for optimization of ammoniacal nitrogen removal from semi-aerobic landfill leachate using ion exchange resin",Desalination,254(1-3),154-161(2010).
32 Guo,J.Q.,Luo,Y.E.,Fan,D.D.,Gao,P.F.,Ma,X.X.,Zhu,C.H., "Analysis of metabolic products by response surface methodology for production of human-like collagen Ⅱ",Chin.J.Chem.Eng.,18 (5),830-836(2010).
33 Zhang,C.,Fan,D.D.,Shang,L.A.,Ma,X.X.,Luo,Y.E.,Xue,W.J., Gao,P.F.,"Optimization of fermentation process for human-like collagen production of recombinant Escherichia coli using response surface methodology",Chin.J.Chem.Eng.,18(1),137-142(2010).
34 Lola,K.,Cai,S.H.,Chen,K.C.,"Optical resolution of DL-tartaric acid mediated by diastereomeric salts crystallization:A useful method for exploring and optimizing experimental conditions",Chin. J.Chem.Eng.,10(2),244-248(2010).
35 Joglekar,A.M.,May,A.T.,"Product excellence through design of experiments",Cereal Foods World,32(12),857-868(1987).
36 Takahashi,M.,Tobishima,S.,Takei,K.,Sakurai,Y.,"Characterization of LiFePO₄ as the cathode material for rechargeable lithium batteries",J.Power Sources,97/98(1),508-511(2001).
37 Yamada,A.,Chung,S.C.,Hinokuma,K.,"Optimized LiFePO₄ for lithium battery cathodes",J.Electrochem.Soc.,148(2),A224-A229 (2001).
38 Huang,H.,Yin,S.C.,Nazar,L.F.,"Approaching theoretical capacity of LiFePO₄ at room temperature at high rates",Electrochem. Solid-state Lett.,10(4),A170-A172(2001).
39 Andersson,A.S.,Thomas,J.O.,"The source of first-cycle capacity loss in LiFePO₄",J.Power Sources,97/98(1),498-502(2001).
40 Prosini,P.P.,Carewska,M.,Scaccia,S.,Wisniewski,P.,Passweini, S.,Pasquali,M.,"A new synthetic route for preparing LiFePO₄ with enhanced electrochemical performance",J.Electrochem.Soc.,149 (7),886-890(2002).

[1]	Kamel Hendaoui, Malika Trabelsi-Ayadi, Fadhila Ayari. Optimization of continuous electrocoagulation-adsorption combined process for the treatment of a textile effluent[J]. 中国化学工程学报, 2022, 44(4): 310-320.
[2]	Zenan Wang, Xin Zheng, Yan Wang, Heng Lin, Hui Zhang. Evaluation of phenanthrene removal from soil washing effluent by activated carbon adsorption using response surface methodology[J]. 中国化学工程学报, 2022, 42(2): 399-405.
[3]	Qingjun Zhang, Youguang Ma, Xigang Yuan, Aiwu Zeng. Box-Behnken experimental design for optimizing process parameters in carbonate-promoted direct thiophene carboxylation reaction with carbon dioxide[J]. 中国化学工程学报, 2022, 50(10): 222-234.
[4]	Yunke Wang, Yongjia Li, Yenan Zhang, Guozheng Zha, Feng Liang, Yongnian Dai, Yaochun Yao. Influence of synergistic effect of LiNi_0.8Co_0.15Al_0.05O₂@Cr₂O₅ composite on the electrochemical properties[J]. 中国化学工程学报, 2021, 33(5): 327-336.
[5]	Xiaodong Tang, Qiankun Guo, Miaomiao Zhou, Shengwen Zhong. Direct regeneration of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material from spent lithium-ion batteries[J]. 中国化学工程学报, 2021, 40(12): 278-286.
[6]	Chengyi Ai, Tingting Li, Rongzheng Ren, Zhenhua Wang, Wang Sun, Jinsheng Feng, Kening Sun, Jinshuo Qiao. Barium-doped Pr₂Ni_0.6Cu_0.4O_4+δ with triple conducting characteristics as cathode for intermediate temperature proton conducting solid oxide fuel cell[J]. 中国化学工程学报, 2021, 39(11): 269-276.
[7]	Kamel Hendaoui, Malika Trabelsi-Ayadi, Fadhila Ayari. Optimization and mechanisms analysis of indigo dye removal using continuous electrocoagulation[J]. 中国化学工程学报, 2021, 29(1): 242-252.
[8]	Xin Yuan, Lujun Wang, Panliang Zhang, Weifeng Xu, Kewen Tang. Enantioselective esterification of (R,S)-2-(4-methylphenyl) propionic acid via Novozym 435: Optimization and application[J]. 中国化学工程学报, 2020, 28(7): 1816-1823.
[9]	Haifeng Yu, Zhaofeng Yang, Huawei Zhu, Hao Jiang, Chunzhong Li. Nitrogen-doped carbon stabilized LiFe_0.5Mn_0.5PO₄/rGO cathode materials for high-power Li-ion batteries[J]. 中国化学工程学报, 2020, 28(7): 1935-1940.
[10]	Mohammad Dana, Mohammad Amin Sobati, Shahrokh Shahhosseini, Aminreza Ansari. Optimization of a continuous ultrasound assisted oxidative desulfurization (UAOD) process of diesel using response surface methodology (RSM) considering operating cost[J]. 中国化学工程学报, 2020, 28(5): 1384-1396.
[11]	Mohammed Abdullah Issa, Zurina Zainal Abidin, Shafreeza Sobri, Suraya Abdul-Rashid, Mohd Adzir Mahdi, Nor Azowa Ibrahim, Musa Y. Pudza. Fabrication, characterization and response surface method optimization for quantum efficiency of fluorescent nitrogen-doped carbon dots obtained from carboxymethylcellulose of oil palms empty fruit bunch[J]. 中国化学工程学报, 2020, 28(2): 584-592.
[12]	Huisheng Lü, Jinyi Zhou, Jiatao Liu, Chunliu Lü, Feng Lian, Yonghui Li. Optimization of hydrothermal pretreatment for co-utilization of xylose and glucose of cassava anaerobic residue for producing ethanol[J]. 中国化学工程学报, 2019, 27(4): 920-927.
[13]	Mohammad Bagher Sabeti, Mohammad Amin Hejazi, Afzal Karimi. Enhanced removal of nitrate and phosphate from wastewater by Chlorella vulgaris: Multi-objective optimization and CFD simulation[J]. 中国化学工程学报, 2019, 27(3): 639-648.
[14]	Zhijuan Niu, Sitao Zhang, Yanhe Han, Mengmeng Qi. Optimization of the N₂ generation selectivity in aqueous nitrate reduction using internal circulation micro-electrolysis[J]. 中国化学工程学报, 2019, 27(12): 3010-3016.
[15]	Kangning Xiong, Yun Chen, Shuai Shen. Experimental optimization and mathematical modeling of supercritical carbon dioxide extraction of essential oil from Pogostemon cablin[J]. 中国化学工程学报, 2019, 27(10): 2407-2417.

Response Surface Optimization for Process Parameters of LiFePO₄/C Preparation by Carbothermal Reduction Technology

Response Surface Optimization for Process Parameters of LiFePO₄/C Preparation by Carbothermal Reduction Technology

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价