基于不同共溶剂体系对于高电压正极材料LiCoPO_4的形貌控制
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摘要
水分别与乙醇、乙二醇、二乙二醇混合为共溶剂,通过溶剂热法制备高电压锂离子电池正极材料LiCoPO_4,研究不同醇类溶剂对于样品的微观形貌和颗粒尺寸的影响。借助X射线衍射、扫描电子显微镜和比表面积测试对样品的成分、晶型、微观形貌和颗粒尺寸进行分析。研究表明,制备得到的LiCoPO_4颗粒平均尺寸大小与醇类溶剂对于前驱体的溶解度差异相一致,而与溶剂粘度没有明显联系。通过乙二醇/水制备得到的LiCoPO_4颗粒呈六边形片状,平均尺寸最小,而通过乙醇/水和二乙二醇/水制备得到的LiCoPO_4颗粒呈菱形片状形态。此外,前者结晶度较高且循环性能较好,0.05C下首圈放电容量为130 mAh/g,20圈后容量保留率为88%。
Cathode material LiCoPO_4 was synthesized by solvothermal method with a variety of water/alcohol solvent mixtures,including ethanol(ET),ethylene glycol(EG),and diethylene glycol(DEG).Focus of this work was set on the effect of the different alcohol solvent on morphology and particle size of material.Composition,crystal structure,morphology and particle size of the as-prepared samples were characterized by X-ray-diffraction,scanning electron microscopy and specific surface area test.The results show that relationship of the average particle size of the LiCoPO_4 samples synthesized with different alcohols solvents is in agreement with solubility of solvent for the precursor,but is inconsistent with the viscosity of solvent.Furthermore,LiCoPO_4 sample synthesized with EG/H_2O possesses the smallest particle size,great crystallinity and excellent cycle performance.Its initial discharge specific capacities reaches to 130 mAh/g at 0.05C,and it shows a capacity retention of the initial value of 88%in 20th cycle.A variety of shapes are obtained from various co-solvents:hexagonal platelets for LiCoPO_4 obtained from EG,whereas,square platelets for LiCoPO_4 from ET/H_2O and DEG/H_2O.
Cathode material LiCoPO_4 was synthesized by solvothermal method with a variety of water/alcohol solvent mixtures,including ethanol(ET),ethylene glycol(EG),and diethylene glycol(DEG).Focus of this work was set on the effect of the different alcohol solvent on morphology and particle size of material.Composition,crystal structure,morphology and particle size of the as-prepared samples were characterized by X-ray-diffraction,scanning electron microscopy and specific surface area test.The results show that relationship of the average particle size of the LiCoPO_4 samples synthesized with different alcohols solvents is in agreement with solubility of solvent for the precursor,but is inconsistent with the viscosity of solvent.Furthermore,LiCoPO_4 sample synthesized with EG/H_2O possesses the smallest particle size,great crystallinity and excellent cycle performance.Its initial discharge specific capacities reaches to 130 mAh/g at 0.05C,and it shows a capacity retention of the initial value of 88%in 20th cycle.A variety of shapes are obtained from various co-solvents:hexagonal platelets for LiCoPO_4 obtained from EG,whereas,square platelets for LiCoPO_4 from ET/H_2O and DEG/H_2O.
引文
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[22]YOSHIDA J,NAKANISHI S,IBA H,et al.Effect of carbon composite on manganese phosphate particles for lithium ion battery properties.J.Soc.Powder Technol.,2011,48:389-395.
[23]WANG F,YANG J.Synthesis and electrochemical performance of nano LiCoPO4 by polyol method.Journal of Electrochemistry,2013,19(6):585-588.
[24]DOKKO K,KOIZUMI S,NAKANO H,et al.Particle morphology,crystal orientation,and electrochemical reactivity of LiFePO4 synthesized by the hydrothermal method at 443 K.Journal of Materials Chemistry,2007,17:4803-4810.
[25]BRAMNIK N N,NIKOLOWSKI K,BAEHTZ C,et al.Phase transitions occurring upon lithium insertion-extraction of LiCoPO4.Chem.Mater.,2007,19(4):908-915.
[26]WU B R,XU H L,MU D B,et al.Controlled solvothermal synthesis and electrochemical performance of LiCoPO4 submicron single crystals as a cathode material for lithium ion batteries.J.Power Sources,2016,304:181-188.
[27]仲维卓.人工水晶,2版.北京:科学出版社,1994:515.
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[29]THACKERAY M.Lithium ion batteries:an unexpected conductor.Nature Materials,2002,1(2):81-82.
[30]MANZI J,BRUTTI S.Surface chemistry on LiCoPO4 electrodes in lithium cells:SEI formation and self-discharge.Electrochimica Acta,2016,222:1839-1846.
[31]AURBACH D,MARKOVSKY B,SALITRA G,et al.Review on electrode-electrolyte solution interactions,related to cathode materials for Li-ion batteries.J.Power Sources,2007,165(2):491-499.
[32]JOHNSON L,LI C,LIU Z,et al.The role of LiO2 solubility in O2reduction in aprotic solvents and its consequences for Li-O2 batteries.Nat.Chem.,2014,6(12):1091-1099.
[33]FREUNBERGER S A,CHEN Y,DREWETT N E,et al.The lithiumoxygen battery with ether-based electrolytes.Angew.Chem.Int.Ed.,2011,50(37):8609-8613.
[34]BRUTTI S,PANERO S.Recent advances in the development of LiCoPO4 as high voltage cathode material for Li-ion batteries.ACSSymposium Series,2013,1140:67-99.
[35]NAKAYAMA M,GOTO S,UCHIMOTO Y,et al.X-ray absorption spectroscopic study on the electronic structure of Li1-xCoPO4electrodes as 4.8 V positive electrodes for rechargeable lithium ion batteries.J.Phys.Chem.B,2005,109:11197-11203.
[36]EHRENBERG H,BRAMNIK N N,SENYSHYN A,et al.Crystal and magnetic structures of electrochemically delithiated Li1-xCo PO4phases.Solid State Sciences,2009,11(1):18-23.
[37]BRAMNIK N N,BRAMNIK K G,BUHRMESTER T,et al.Electrochemical and structural study of LiCoPO4-based electrodes.J.Solid State Eletrochem.,2004,8:558-564.
[38]BRAMNIK N N,BRAMNIK K G,BAEHTZ C,et al.Study of the effect of different synthesis routes on Li extraction-insertion from LiCoPO4.J.Power Sources,2005,145:74-81.
[2]PADHI A K,NANJUNDASWAMY K S,GOODENOUGH J B.Phospho-olivines as positive-electrode materials for rechargeable lithium batteries.J.Electrochem.Soc.,1997,144(4):1188-1194.
[3]WOLFENSTINE J,ALLEN J.LiNiPO4-Li CoPO4 solid solutions as cathodes.J.Power Sources,2004,136(1):150-153.
[4]WOLFENSTINE J,ALLEN J.Ni3+/Ni2+redox potential in LiNiPO4.J.Power Sources,2005,142(1/2):389-390.
[5]MAEYOSHI Y,MIYAMOTO S,MUNAKATA H,et al.Enhanced cycle stability of LiCoPO4 by using three-dimensionally ordered macroporous polyimide separator.J.Power Sources,2017,350:103-108.
[6]DU CHENQIANG,TANG ZHIYUAN,XU QIANG.Research progress in preparing cathode material lithium cobalt phosphate.Battery,2013,43(5):293-295.
[7]STROBRIDGE F C,CLEMENT R J,LESKES M,et al.Identifying the structure of the intermediate,Li2/3CoPO4,formed during electrochemical cycling of LiCoPO4.Chem.Mater.,2014,26(21):6193-6205.
[8]BRUTTI S,PANERO S.Recent advances in the development of LiCoPO4 as high voltage cathode material for Li-ion batteries.J.Am.Chem.Soc.,2013,1140:67-99.
[9]HOWARD W F,SPOTNITZ R M.Theoretical evaluation of highenergy lithium metal phosphate cathode materials in Li-ion batteries.J.Power Sources,2007,165(2):887-891.
[10]WOLFENSTINE J.Electrical conductivity of doped LiCoPO4.J.Power Sources,2006,158(2):1431-1435.
[11]栗欢欢.新型5V锂离子二次电池正极材料LiCoPO4的制备与改性研究.天津:南开大学硕士学位论文,2009.
[12]KISHORE M V V M S,VARADARAJU U V.Influence of isovalent ion substitution on the electrochemical performance of LiCoPO4.Mater.Res.Bull.,2005,40(10):1705-1712.
[13]LI HUANHUAN,YANG XIAOLIANG,WEI JINPING.Effect of Mn2+doping on electrochemical performance of LiCoPO4.Electrochemistry,2008,14:210-212.
[14]KREDER K J,MANTHIRAM A.Vanadium-substituted LiCoPO4core with a monolithic LiFePO4 shell for high-voltage lithium-ion batteries.ACS Energy Letters,2017,2(1):64-69.
[15]JANG I C,SON C G,YANG S M G,et al.LiFePO4 modified Li1.02(Co0.9Fe0.1)0.98PO4 cathodes with improved lithium storage properties.J.Materials Chemistry,2011,21(18):6510-6514.
[16]LUDWIG J,MARINO C,HAERING D,et al.Morphologycontrolled microwave-assisted solvothermal synthesis of high-performance LiCoPO4 as a high-voltage cathode material for Li-ion batteries.J.Power Sources,2017,342:214-223.
[17]WANG F,YANG J,NULI Y N,et al.Novel hedgehog-like 5 VLiCoPO4 positive electrode material for rechargeable lithium battery.J.Power Sources,2011,196(10):4806-4810.
[18]PENG L,ZHANG X,FANG Z,et al.General facet-controlled synthesis of single-crystalline{010}-oriented LiMPO4(M=Mn,Fe,Co)nanosheets.Chemistry of Materials,2017,29(24):10526-10533.
[19]NI J P,WANG H B,GAO L J,et al.A high-performance LiCoPO4/C core/shell composite for Li-ion batteries.Electrochimica Acta,2012,70:349-354.
[20]JAYAPRAKASH N,KALAISELVI N,PERIASAMY P.A preliminary investigation into the new class of lithium intercalating LiNiSiO4cathode material.Nanotechnology,2008,19(2):025603-1-5.
[21]JIN B,GU H B,KIM K W.Effect of different conductive additives on charge/discharge properties of LiCoPO4/Li batteries.J.Solid State Electr.,2007,12(2):105-111.
[22]YOSHIDA J,NAKANISHI S,IBA H,et al.Effect of carbon composite on manganese phosphate particles for lithium ion battery properties.J.Soc.Powder Technol.,2011,48:389-395.
[23]WANG F,YANG J.Synthesis and electrochemical performance of nano LiCoPO4 by polyol method.Journal of Electrochemistry,2013,19(6):585-588.
[24]DOKKO K,KOIZUMI S,NAKANO H,et al.Particle morphology,crystal orientation,and electrochemical reactivity of LiFePO4 synthesized by the hydrothermal method at 443 K.Journal of Materials Chemistry,2007,17:4803-4810.
[25]BRAMNIK N N,NIKOLOWSKI K,BAEHTZ C,et al.Phase transitions occurring upon lithium insertion-extraction of LiCoPO4.Chem.Mater.,2007,19(4):908-915.
[26]WU B R,XU H L,MU D B,et al.Controlled solvothermal synthesis and electrochemical performance of LiCoPO4 submicron single crystals as a cathode material for lithium ion batteries.J.Power Sources,2016,304:181-188.
[27]仲维卓.人工水晶,2版.北京:科学出版社,1994:515.
[28]OSTWALD W Z.über die vermeintliche isomerie des roten und gelben quecksilberoxyds und die oberfl?chenspannung fester k?rper.Zeitschrift für Physikalische Chemie,1900,34:495-503.
[29]THACKERAY M.Lithium ion batteries:an unexpected conductor.Nature Materials,2002,1(2):81-82.
[30]MANZI J,BRUTTI S.Surface chemistry on LiCoPO4 electrodes in lithium cells:SEI formation and self-discharge.Electrochimica Acta,2016,222:1839-1846.
[31]AURBACH D,MARKOVSKY B,SALITRA G,et al.Review on electrode-electrolyte solution interactions,related to cathode materials for Li-ion batteries.J.Power Sources,2007,165(2):491-499.
[32]JOHNSON L,LI C,LIU Z,et al.The role of LiO2 solubility in O2reduction in aprotic solvents and its consequences for Li-O2 batteries.Nat.Chem.,2014,6(12):1091-1099.
[33]FREUNBERGER S A,CHEN Y,DREWETT N E,et al.The lithiumoxygen battery with ether-based electrolytes.Angew.Chem.Int.Ed.,2011,50(37):8609-8613.
[34]BRUTTI S,PANERO S.Recent advances in the development of LiCoPO4 as high voltage cathode material for Li-ion batteries.ACSSymposium Series,2013,1140:67-99.
[35]NAKAYAMA M,GOTO S,UCHIMOTO Y,et al.X-ray absorption spectroscopic study on the electronic structure of Li1-xCoPO4electrodes as 4.8 V positive electrodes for rechargeable lithium ion batteries.J.Phys.Chem.B,2005,109:11197-11203.
[36]EHRENBERG H,BRAMNIK N N,SENYSHYN A,et al.Crystal and magnetic structures of electrochemically delithiated Li1-xCo PO4phases.Solid State Sciences,2009,11(1):18-23.
[37]BRAMNIK N N,BRAMNIK K G,BUHRMESTER T,et al.Electrochemical and structural study of LiCoPO4-based electrodes.J.Solid State Eletrochem.,2004,8:558-564.
[38]BRAMNIK N N,BRAMNIK K G,BAEHTZ C,et al.Study of the effect of different synthesis routes on Li extraction-insertion from LiCoPO4.J.Power Sources,2005,145:74-81.