金属—水固态电池研究
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摘要
本论文共分四个部分:
第一部分为背景材料与综述。概述粘土矿物快离子导体及其在固态电池中的应用的研究成果,同时介绍聚合物凝胶电解质的最新研究成果,锂水电池、锂离子电池及锂离子电池正极材料研究概况。
第二部分为含水的固体电解质研究。主要介绍两类含水固体电解质的研究,第一类为以聚甲基丙烯酸为基的含水凝胶电解质,按自由基聚合方法制备聚甲基丙烯酸,用溶液浇注法制备电解质膜。新制的聚甲基丙烯酸室温电导率为1.63×10~(-7)S.cm~(-1),含水量为19.2%,电导率会随着水分含量增加而增加,说明水分的存在会降低聚合物分子链之间的相互作用。聚甲基丙烯酸膜露置空气中会逐渐失去水分,使电导率降低。往聚甲基丙烯酸膜中加入用自由基法合成的聚甲基丙烯酸锂,随重量比的增加,电导率先增大后减小,在重量比为Li-PMAA:PMAA=1:1时电导率达到最大。往聚甲基丙烯酸、聚甲基丙烯酸锂混合物中加入甘油,电导率先略微下降,后迅速上升,电解质膜呈现最大电导率时其组分为聚甲基丙烯酸、聚甲基丙烯酸锂和甘油,重量比为3:2:3,最大室温电导率为2.3×10~(-4)S.cm~(-1)。膜呈现固态。在凝胶膜中加入氧化铝,可增强凝胶膜的硬度,加入极少量氧化铝时,电导率上升,但重量百分数超过0.2%时,电导率下降。交流阻抗谱测试表明,凝胶膜中含有硬段微区和软段微区,硬段微区电阻和软段微区的电阻都随水分的增多而减小。以石墨为电极的稳态极化曲线测试表明,凝胶膜中的H+能在石墨表面放电,生成氢气,该过程相当于电解水。凝胶膜电导率随温度变化的曲线表明,凝胶膜的电导率在62℃时呈现最大值,说明水分子在凝胶膜的导电过程中起重要作用;甘油对氢离子导电也起帮助作用,因为它能减弱聚合物分子链间的相互作用。凝胶膜的平衡电位是-90mV,交换电流密度0.7μA/cm~2,凝胶膜与石墨组成的电极是一个不可逆电极。凝胶膜的直流电导是2.25×10~(-7)S.cm~(-1),凝胶膜的直流电导:交流电导<0.1%,说明凝胶膜是一种以离子导电为主的固体电解质膜。
第二类含水固体电解质是聚甲基丙烯锂复合的蒙脱石固体电解质。聚甲基丙烯酸锂重量分数在50%以内,采用两种方法复合,一种是水溶液复合方法,另一
This dissertation involves the following four parts:
The first part describes some background materials which include mineral fast ion conductors and their application in full solid state cell; gel polymer electrolytes; lithium-water primary batteries; lithium ion battery and corresponding cathode materials.
The second part describes the solid electrolytes containing water. Two kinds of electrolytes are introduced, one is poly(methyl methacrylic acid)(PMAA) based gel polymer electrolyte membrane. PMAA was prepared by free radical polymerization, and the solvent casting method was used to manufacture gel electrolyte membrane. The ionic conductivity at room temperature is 1.63×10~(-7)S.cm-1 for the newly produced PMAA with 19.2% water amount. Interaction between polymer chains can be lowered by the presentation of water. PMAA membrane lost water when exposed in air, so its ionic conductivity decreases. When Poly(methyl methacrylic lithiumate)(Li-PMAA) was added in PMAA whose ionic conductivity increases first and then decreases with increasing the weigh ratio(Li-PMAA:PMAA). The ionic conductivity reaches maximum at the weigh ratio of Li-PMAA:PMAA=1:1. When glycerol was added to PMAA membrane, its ionic conductivity lowers down slightly first then increases fast, the maximum conductivity occurs at the weigh ratio of ( PMAA: Li-PMAA: glycerol=3:2:3), the maximum conductivity is 2.3×10~(-4)S.cm-1. When aluminum oxide is added into membrane, it gets stiff, when weigh percent of Al_2O_3 exceeds 0.2%, the ionic conductivity of membrane decreases.
AC Impedance Spectra show that there are stiff micro-area and soft micro-area in the gel membrane, the resistance of both stiff section and soft section decreases with increasing water amount of membrane. It proved that water molecule can disperse in the gel membrane. Steady Polarization Curve of GPW when use graphite as electrode show that hydrogen ion can be reduced to hydrogen at the surface of graphite, this procedure is just like water electrolysis. The plot of ionic conductivity vs. temperature showed that water molecule plays a major role in the course of GPW’s conduction,
glycerol is also helpful for the hydrogen ion migration because it can lower the interaction between polymer chains. The equilibrium potential of GPW is –90mV, exchange current is 1.182μA. The electrode consists of GPW and graphite is irreverse electrode. The direct Current conductivity of GPW is 2.25 ×10-7S.cm-1 ,DC conductivity : AC conductivity <0.1%. The other kind of solid electrolyte containing water is Li-PMAA composited Montmorillonite(Mont.), Weigh percent of Li-PMAA is smaller than 50%. Two methods are employed to prepare composite Mont.. One is by solution, the other is by heat. X Ray Powder Diffraction Patterns indicated that when Li-PMAA is mixed with Mont., the pure phase can’t be obtained even weigh ratio of Li-PMAA:Mont. smaller than 1:10. Composite Mont. by solution method gives a new diffraction peak at 2θ=0-10o, it means that a new phase of composite Mont. occurs at the presence of water molecule. The analysis program of X’Pert Plus show that although composite Mont. isn’t pure phase, some Li-PMAA molecule embeds into Mont. which were prepared by solution method and heat method. It makes spacing of Mont. crystal change at c axis. Both IR Spetra and DTA analysis showed that Li-PMAA molecule embeds into Mont. AC Impedance Spetra showed that ionic conductivity of composite Mont. is smaller than pure Mont., composite Mont. by heat method smaller than that by solution method. Also, the ionic conductivity of composite Mont. containing higher weigh percent of Li-PMAA are smaller than that of lower weigh percent. The third part is solid-state cell by using water as oxidation agent. The cell assembly is Re| SE| GPW| graphite, Me stands for negative electrode which is lithium or magnesium, SE is solid electrolyte; GPW is gel polymer containing water. Principle of cell reaction is (a) reaction at negative electrode: Me+nOH-=Me(OH)n+ne-…(1)or Me=Men++ne-…(2),n=1 for lithium, n=2 for magnesium. Both of reaction (1) and (2) are occurred in the process of cell reaction, the ratio of (1) : (2) depends on the solid electrolyte. (b) Reaction at positive electrode: RH+H2O+e=RH+OH-+1/2H2,RH stands for PMAA ,and R stands for PMAA anion. Hydrogen ion of PMAA in GPW embeds into the graphite, it combines with one electron to produce hydrogen atom, PMAA anion seizes one hydrogen ion, it makes
water molecule disaggregate to produce hydroxide anion. Hydroxide anion migrate through GPW layer, solid electrolyte layer and reach the surface of metal, combines with metal ion to produce metal hydroxide. The results of cell reaction is to make surface of metal covered with metal hydroxide, so the internal resistance of cell increases. When magnesium was used as negative electrode, the cell is called magnesium water cell. The cell using Mont as solid electrolyte, the open circuit voltage (OCV) is 1.45V, the discharging time is 30 hours when constant load (51KΩ) discharging at voltage plateau above 1.0V, the discharge capacity is 2mAh/g. The cell using reformed Mont as solid electrolyte, the discharging time is 90 hours when constant load(51KΩ) discharging at voltage plateau above 1.0V, the discharge capacity is 6mAh/g. Discharging time of cell using sintering gaolinite disc, sintering magnesium oxide disc, gel polymer electrolyte (LiClO4-PMMA), cross-linking GPW as solid electrolyte is 6 days, 40 hours, 48 hours and 14 hours respectively at the same discharging condition. Store property of cell is poor; the utilization rate of magnesium is 2.8%. When the negative electrode is lithium, the cell is lithium water cell. The solid electrolyte employed is gel polymer electrolyte (GPE) LiClO4-PMMA of weigh ratio(LiClO4:PMMA= 3:2), OCV of cell is 3.2V, discharge capacity is 1.4mAh/g when constant current 0.05mA discharge. Negative electrode can be eroded by electrolyte, the OCV decreases when cell was storaged. When solid electrolyte is LiClO4-PEG20,000, negative electrode can also be eroded by the electrolyte with even a little amount water, the short current is 12.5mA, average short current 7mA can maintain one hour, discharge capacity 7mAh. Discharging time is 7 hours when constant load 51KΩat voltage plateau above 2.8V with discharge capacity 2.1mAh/g. The fourth part is primary study on cerium dioxide base embedded compound, lithium ion doped cerium dioxide was synthesized by high temperature solid phase reaction, lithium oxide and cerium dioxide can be molted together to get molten solid solution at about 950℃.DTA analysis at the synthetic process and XRD patterns showed that lithium oxide and cerium dioxide can turn into fluorite type solid solution
at mole ratio 0.4-1.0(Li+:Ce4+), a new phase is occurred at mole ratio below 0.3. Intensity of new phase peak decreases with increasing the mole ratio of Li+:Ce4+. When lithium ion doped into cerium dioxide, unit-cell shrinks slightly, unit-cell parameters decrease from 5.4124? to 5.4034?,d-spacing for(1,1,1)shrinks from 3.1248? to 3.12268?.Charge discharge examination indicated that the OCV of lithium ion cell assembly by using lithium ion doped cerium dioxide as cathode material is 3.26V, discharge capacity at 2.5V plateau is 10.5mAh when 0.2mA constant current discharge. It proved that lithium doped cerium dioxide can be embedded and unimpeded by lithium ion, and it is a potential cathode material for the lithium ion battery.
第一部分为背景材料与综述。概述粘土矿物快离子导体及其在固态电池中的应用的研究成果,同时介绍聚合物凝胶电解质的最新研究成果,锂水电池、锂离子电池及锂离子电池正极材料研究概况。
第二部分为含水的固体电解质研究。主要介绍两类含水固体电解质的研究,第一类为以聚甲基丙烯酸为基的含水凝胶电解质,按自由基聚合方法制备聚甲基丙烯酸,用溶液浇注法制备电解质膜。新制的聚甲基丙烯酸室温电导率为1.63×10~(-7)S.cm~(-1),含水量为19.2%,电导率会随着水分含量增加而增加,说明水分的存在会降低聚合物分子链之间的相互作用。聚甲基丙烯酸膜露置空气中会逐渐失去水分,使电导率降低。往聚甲基丙烯酸膜中加入用自由基法合成的聚甲基丙烯酸锂,随重量比的增加,电导率先增大后减小,在重量比为Li-PMAA:PMAA=1:1时电导率达到最大。往聚甲基丙烯酸、聚甲基丙烯酸锂混合物中加入甘油,电导率先略微下降,后迅速上升,电解质膜呈现最大电导率时其组分为聚甲基丙烯酸、聚甲基丙烯酸锂和甘油,重量比为3:2:3,最大室温电导率为2.3×10~(-4)S.cm~(-1)。膜呈现固态。在凝胶膜中加入氧化铝,可增强凝胶膜的硬度,加入极少量氧化铝时,电导率上升,但重量百分数超过0.2%时,电导率下降。交流阻抗谱测试表明,凝胶膜中含有硬段微区和软段微区,硬段微区电阻和软段微区的电阻都随水分的增多而减小。以石墨为电极的稳态极化曲线测试表明,凝胶膜中的H+能在石墨表面放电,生成氢气,该过程相当于电解水。凝胶膜电导率随温度变化的曲线表明,凝胶膜的电导率在62℃时呈现最大值,说明水分子在凝胶膜的导电过程中起重要作用;甘油对氢离子导电也起帮助作用,因为它能减弱聚合物分子链间的相互作用。凝胶膜的平衡电位是-90mV,交换电流密度0.7μA/cm~2,凝胶膜与石墨组成的电极是一个不可逆电极。凝胶膜的直流电导是2.25×10~(-7)S.cm~(-1),凝胶膜的直流电导:交流电导<0.1%,说明凝胶膜是一种以离子导电为主的固体电解质膜。
第二类含水固体电解质是聚甲基丙烯锂复合的蒙脱石固体电解质。聚甲基丙烯酸锂重量分数在50%以内,采用两种方法复合,一种是水溶液复合方法,另一
This dissertation involves the following four parts:
The first part describes some background materials which include mineral fast ion conductors and their application in full solid state cell; gel polymer electrolytes; lithium-water primary batteries; lithium ion battery and corresponding cathode materials.
The second part describes the solid electrolytes containing water. Two kinds of electrolytes are introduced, one is poly(methyl methacrylic acid)(PMAA) based gel polymer electrolyte membrane. PMAA was prepared by free radical polymerization, and the solvent casting method was used to manufacture gel electrolyte membrane. The ionic conductivity at room temperature is 1.63×10~(-7)S.cm-1 for the newly produced PMAA with 19.2% water amount. Interaction between polymer chains can be lowered by the presentation of water. PMAA membrane lost water when exposed in air, so its ionic conductivity decreases. When Poly(methyl methacrylic lithiumate)(Li-PMAA) was added in PMAA whose ionic conductivity increases first and then decreases with increasing the weigh ratio(Li-PMAA:PMAA). The ionic conductivity reaches maximum at the weigh ratio of Li-PMAA:PMAA=1:1. When glycerol was added to PMAA membrane, its ionic conductivity lowers down slightly first then increases fast, the maximum conductivity occurs at the weigh ratio of ( PMAA: Li-PMAA: glycerol=3:2:3), the maximum conductivity is 2.3×10~(-4)S.cm-1. When aluminum oxide is added into membrane, it gets stiff, when weigh percent of Al_2O_3 exceeds 0.2%, the ionic conductivity of membrane decreases.
AC Impedance Spectra show that there are stiff micro-area and soft micro-area in the gel membrane, the resistance of both stiff section and soft section decreases with increasing water amount of membrane. It proved that water molecule can disperse in the gel membrane. Steady Polarization Curve of GPW when use graphite as electrode show that hydrogen ion can be reduced to hydrogen at the surface of graphite, this procedure is just like water electrolysis. The plot of ionic conductivity vs. temperature showed that water molecule plays a major role in the course of GPW’s conduction,
glycerol is also helpful for the hydrogen ion migration because it can lower the interaction between polymer chains. The equilibrium potential of GPW is –90mV, exchange current is 1.182μA. The electrode consists of GPW and graphite is irreverse electrode. The direct Current conductivity of GPW is 2.25 ×10-7S.cm-1 ,DC conductivity : AC conductivity <0.1%. The other kind of solid electrolyte containing water is Li-PMAA composited Montmorillonite(Mont.), Weigh percent of Li-PMAA is smaller than 50%. Two methods are employed to prepare composite Mont.. One is by solution, the other is by heat. X Ray Powder Diffraction Patterns indicated that when Li-PMAA is mixed with Mont., the pure phase can’t be obtained even weigh ratio of Li-PMAA:Mont. smaller than 1:10. Composite Mont. by solution method gives a new diffraction peak at 2θ=0-10o, it means that a new phase of composite Mont. occurs at the presence of water molecule. The analysis program of X’Pert Plus show that although composite Mont. isn’t pure phase, some Li-PMAA molecule embeds into Mont. which were prepared by solution method and heat method. It makes spacing of Mont. crystal change at c axis. Both IR Spetra and DTA analysis showed that Li-PMAA molecule embeds into Mont. AC Impedance Spetra showed that ionic conductivity of composite Mont. is smaller than pure Mont., composite Mont. by heat method smaller than that by solution method. Also, the ionic conductivity of composite Mont. containing higher weigh percent of Li-PMAA are smaller than that of lower weigh percent. The third part is solid-state cell by using water as oxidation agent. The cell assembly is Re| SE| GPW| graphite, Me stands for negative electrode which is lithium or magnesium, SE is solid electrolyte; GPW is gel polymer containing water. Principle of cell reaction is (a) reaction at negative electrode: Me+nOH-=Me(OH)n+ne-…(1)or Me=Men++ne-…(2),n=1 for lithium, n=2 for magnesium. Both of reaction (1) and (2) are occurred in the process of cell reaction, the ratio of (1) : (2) depends on the solid electrolyte. (b) Reaction at positive electrode: RH+H2O+e=RH+OH-+1/2H2,RH stands for PMAA ,and R stands for PMAA anion. Hydrogen ion of PMAA in GPW embeds into the graphite, it combines with one electron to produce hydrogen atom, PMAA anion seizes one hydrogen ion, it makes
water molecule disaggregate to produce hydroxide anion. Hydroxide anion migrate through GPW layer, solid electrolyte layer and reach the surface of metal, combines with metal ion to produce metal hydroxide. The results of cell reaction is to make surface of metal covered with metal hydroxide, so the internal resistance of cell increases. When magnesium was used as negative electrode, the cell is called magnesium water cell. The cell using Mont as solid electrolyte, the open circuit voltage (OCV) is 1.45V, the discharging time is 30 hours when constant load (51KΩ) discharging at voltage plateau above 1.0V, the discharge capacity is 2mAh/g. The cell using reformed Mont as solid electrolyte, the discharging time is 90 hours when constant load(51KΩ) discharging at voltage plateau above 1.0V, the discharge capacity is 6mAh/g. Discharging time of cell using sintering gaolinite disc, sintering magnesium oxide disc, gel polymer electrolyte (LiClO4-PMMA), cross-linking GPW as solid electrolyte is 6 days, 40 hours, 48 hours and 14 hours respectively at the same discharging condition. Store property of cell is poor; the utilization rate of magnesium is 2.8%. When the negative electrode is lithium, the cell is lithium water cell. The solid electrolyte employed is gel polymer electrolyte (GPE) LiClO4-PMMA of weigh ratio(LiClO4:PMMA= 3:2), OCV of cell is 3.2V, discharge capacity is 1.4mAh/g when constant current 0.05mA discharge. Negative electrode can be eroded by electrolyte, the OCV decreases when cell was storaged. When solid electrolyte is LiClO4-PEG20,000, negative electrode can also be eroded by the electrolyte with even a little amount water, the short current is 12.5mA, average short current 7mA can maintain one hour, discharge capacity 7mAh. Discharging time is 7 hours when constant load 51KΩat voltage plateau above 2.8V with discharge capacity 2.1mAh/g. The fourth part is primary study on cerium dioxide base embedded compound, lithium ion doped cerium dioxide was synthesized by high temperature solid phase reaction, lithium oxide and cerium dioxide can be molted together to get molten solid solution at about 950℃.DTA analysis at the synthetic process and XRD patterns showed that lithium oxide and cerium dioxide can turn into fluorite type solid solution
at mole ratio 0.4-1.0(Li+:Ce4+), a new phase is occurred at mole ratio below 0.3. Intensity of new phase peak decreases with increasing the mole ratio of Li+:Ce4+. When lithium ion doped into cerium dioxide, unit-cell shrinks slightly, unit-cell parameters decrease from 5.4124? to 5.4034?,d-spacing for(1,1,1)shrinks from 3.1248? to 3.12268?.Charge discharge examination indicated that the OCV of lithium ion cell assembly by using lithium ion doped cerium dioxide as cathode material is 3.26V, discharge capacity at 2.5V plateau is 10.5mAh when 0.2mA constant current discharge. It proved that lithium doped cerium dioxide can be embedded and unimpeded by lithium ion, and it is a potential cathode material for the lithium ion battery.
引文
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77. 玻璃的本质、结构和性质【联邦德国】H、舒尔兹黄照柏译北京:中国建筑工业出版社1984年
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58. Hyuk-Soo Moon, Jung-Ki Park Solid State Ionics, 1999,120 (1-4):1-12
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61. 贺可英硅酸盐物理化学武汉工业大学出版社武汉:1995
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63. 徐光年电池1990,20,(5): 19
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67. Mirna Urquidi-Macdonald, Digby D. Macdonald, Osvaldo Pensado, etal ,Electrochimica Acta,2001,47: 833
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70. 陈文徐庆郜定山等武汉工业大学学报1998,20(4):5
71. Yancheng Zhang, Mirna Urquidi-Macdonald, Journal of Power Source, 2004,129:312-318
72. 吴浩青李永舫电化学动力学[M] 北京:高等教育出版社,1998年,163-167
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76. 静电手册【日】营义夫主编,北京:科学出版社1981年:473-475
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78. M.Broussely , P.Biensan, B.Simon,Electrochimica Acta,1999, 45 :3-22
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89. A.A.M.Prince, S.Mylswamy, T.S.Chan, et al, Solid State Communication, 132(2004):455-458