正极材料Li_3V_2（PO_4）_3溶胶—凝胶法的制备及性能研究
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摘要
采用溶胶-凝胶法合成了Li_3V_2(PO_4)_3材料,利用XRD和SEM对产物的微观结构和形貌进行了分析;并采用恒流充放电、循环伏安(CV)和电化学阻抗谱(EIS)技术研究了其电化学性能。重点考察了不同合成温度、不同锂源、不同pH值和不同预烧气氛对Li_3V_2(PO_4)_3材料的结构和电化学性能的影响。
以水合氢氧化锂为锂源,柠檬酸为配位体,采用溶胶-凝胶法制备Li_3V_2(PO_4)_3,研究了不同温度、不同气氛和溶胶pH值对样品Li_3V_2(PO_4)_3的组织结构和电化学性能的影响。结果表明,当以水合氢氧化锂为锂源时,干凝胶在氢氩混合气氛中300℃预烧4 h之后,再600℃氢氩混合气烧结8 h制备的Li_3V_2(PO_4)_3样品结晶较好,颗粒均匀,具有较好的电化学性能。当放电电流为0.1C时,在3.0 V-4.2 V充放电范围内下,首次放电容量可以达到130 mAh·g-1。当放电电流为1C时,在2.5 V-4.2 V充放电范围内下,首次放电容量可以达到128 mAh·g-1,经40次循环后仍为126 mAh·g-1,容量保持率达98 %,表现出较好的循环性能。溶胶pH值对样品的放电容量有较大的影响,与pH=8时制备的Li_3V_2(PO_4)_3相比,溶胶pH=3时所得的样品具有更高的放电容量。
以氟化锂为锂源,柠檬酸为配位剂,采用溶胶-凝胶法制备Li_3V_2(PO_4)_3,研究了不同温度和pH值对样品Li_3V_2(PO_4)_3的组织结构和电化学性能的影响。结果表明,当烧结温度在600℃-800℃范围内,均可得到结晶较好,晶相较纯的Li_3V_2(PO_4)_3颗粒。在1C倍率放电电流,充放电范围为2.5 V-4.2 V条件下,800℃烧结所得样品首次放电容量最高,为111 mAh·g-1,经过36次循环后容量仅有82 mAh·g-1,容量保持率为74 %。600℃烧结所得样品首次放电容量为91 mAh·g-1,经过30次1C循环后容量剩余84 mAh·g-1,容量保持率为92 %。而在700℃烧结时所得样品具有较好的循环性能,首次放电容量为108 mAh·g-1,经过70次1 C放电后容量仍为106 mAh·g-1,容量保持率为98 %,容量衰减很小。相比较而言,700℃烧结时所得样品具有较好的电化学性能。pH值对样品的组织结构影响并不明显,但对电化学性能影响较大。
从CV扫描的结果可知,在两次扫描过程中氧化峰和还原峰重合的较好,说明样品循环稳定性较好,第二次氧化峰和还原峰之间的相位差变小,说明材料的可逆性变好; EIS的测试结果可知,合成温度升高电化学反应电阻变小。
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method, and The surface morphologies and structures was observed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical performances were characterized by charge-discharge test, cycle voltammogram(CV) and electrochemical impedance spectroscopy (EIS). The effects of different synthesis temperatures, lithium sources, pH values and reaction ambiences on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material.
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method using citric acid and LiOH·H2O as a chelating agent and lithium source, respectively, and the effect of different synthesis temperatures, pH values and reaction ambiences on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material. The results show that the dry gel was pre-baked at 300℃for 4 h, then baked at 600℃for 8 h in H2/Ar ambience, yielding Li_3V_2(PO_4)_3 material which has better crystallinity, uniform particle sizes and electrochemical performance. The initial discharge capacity reaches 130 mAh·g-1 between 3.0 V-4.2 V at 0.1 C discharge rate.The initial discharge capacity reaches 128 mAh·g-1 between 2.5 V-4.2 V at 1 C discharge rate, and the discharge capacity after 40 cycles is 126 mAh·g-1, and the capacity retention is 98 %, which exhibits better cycle performance. The pH values of solution obviously affect the discharge capacity, and Li_3V_2(PO_4)_3 material synthesized at pH=3 has higher discharge capacity than that of material synthesized at pH=8.
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method using citric acid and LiF as a chelating agent and lithium source, respectively, and the effect of different synthesis temperatures and pH values on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material. The results indicate that all samples have high phase purity and are well crystallized when the synthesis temperature is between 600℃-800℃. The samples synthsized 800℃have the best initial discharge capacity which reaches 111 mAh·g-1 between 2.5 V-4.2 V at 1 C discharge rate ,and the discharge capacity after 36 cycles is 82 mAh·g-1, and the capacity retention is 74 %. The initial discharge capacity of samples synthsized 600℃is 91 mAh·g-1, and the discharge capacity after 30 cycles at 1 C discharge rate is 84 mAh·g-1, and the capacity retention is 92 %. The samples synthsized 700℃has better cycle performance, and the initial discharge capacity is 108 mAh·g-1, and the discharge capacity after 70 cycles is 106 mAh·g-1 at 1 C discharge rate, and the capacity retention is 98%. As a result, the samples synthsized 700℃has better electrochemical performance, and the pH value has almost no effects on the structure, but it has significant effects on the electrochemical performance.
CV results reveal that the oxidation peak and reduction peak lapped well from the two scanning process,meaning that the samples has good cycle performance, and the separation of peak potentials between the oxidation peak and reduction peak decreases at the twice scanning process, indicating that the reversibility of the samples becomes better. EIS results exhibit that electrochemical reaction resistance decreases with increasing of synthesis temperatures of samples
以水合氢氧化锂为锂源,柠檬酸为配位体,采用溶胶-凝胶法制备Li_3V_2(PO_4)_3,研究了不同温度、不同气氛和溶胶pH值对样品Li_3V_2(PO_4)_3的组织结构和电化学性能的影响。结果表明,当以水合氢氧化锂为锂源时,干凝胶在氢氩混合气氛中300℃预烧4 h之后,再600℃氢氩混合气烧结8 h制备的Li_3V_2(PO_4)_3样品结晶较好,颗粒均匀,具有较好的电化学性能。当放电电流为0.1C时,在3.0 V-4.2 V充放电范围内下,首次放电容量可以达到130 mAh·g-1。当放电电流为1C时,在2.5 V-4.2 V充放电范围内下,首次放电容量可以达到128 mAh·g-1,经40次循环后仍为126 mAh·g-1,容量保持率达98 %,表现出较好的循环性能。溶胶pH值对样品的放电容量有较大的影响,与pH=8时制备的Li_3V_2(PO_4)_3相比,溶胶pH=3时所得的样品具有更高的放电容量。
以氟化锂为锂源,柠檬酸为配位剂,采用溶胶-凝胶法制备Li_3V_2(PO_4)_3,研究了不同温度和pH值对样品Li_3V_2(PO_4)_3的组织结构和电化学性能的影响。结果表明,当烧结温度在600℃-800℃范围内,均可得到结晶较好,晶相较纯的Li_3V_2(PO_4)_3颗粒。在1C倍率放电电流,充放电范围为2.5 V-4.2 V条件下,800℃烧结所得样品首次放电容量最高,为111 mAh·g-1,经过36次循环后容量仅有82 mAh·g-1,容量保持率为74 %。600℃烧结所得样品首次放电容量为91 mAh·g-1,经过30次1C循环后容量剩余84 mAh·g-1,容量保持率为92 %。而在700℃烧结时所得样品具有较好的循环性能,首次放电容量为108 mAh·g-1,经过70次1 C放电后容量仍为106 mAh·g-1,容量保持率为98 %,容量衰减很小。相比较而言,700℃烧结时所得样品具有较好的电化学性能。pH值对样品的组织结构影响并不明显,但对电化学性能影响较大。
从CV扫描的结果可知,在两次扫描过程中氧化峰和还原峰重合的较好,说明样品循环稳定性较好,第二次氧化峰和还原峰之间的相位差变小,说明材料的可逆性变好; EIS的测试结果可知,合成温度升高电化学反应电阻变小。
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method, and The surface morphologies and structures was observed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical performances were characterized by charge-discharge test, cycle voltammogram(CV) and electrochemical impedance spectroscopy (EIS). The effects of different synthesis temperatures, lithium sources, pH values and reaction ambiences on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material.
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method using citric acid and LiOH·H2O as a chelating agent and lithium source, respectively, and the effect of different synthesis temperatures, pH values and reaction ambiences on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material. The results show that the dry gel was pre-baked at 300℃for 4 h, then baked at 600℃for 8 h in H2/Ar ambience, yielding Li_3V_2(PO_4)_3 material which has better crystallinity, uniform particle sizes and electrochemical performance. The initial discharge capacity reaches 130 mAh·g-1 between 3.0 V-4.2 V at 0.1 C discharge rate.The initial discharge capacity reaches 128 mAh·g-1 between 2.5 V-4.2 V at 1 C discharge rate, and the discharge capacity after 40 cycles is 126 mAh·g-1, and the capacity retention is 98 %, which exhibits better cycle performance. The pH values of solution obviously affect the discharge capacity, and Li_3V_2(PO_4)_3 material synthesized at pH=3 has higher discharge capacity than that of material synthesized at pH=8.
Li_3V_2(PO_4)_3 material was synthesized by sol-gel method using citric acid and LiF as a chelating agent and lithium source, respectively, and the effect of different synthesis temperatures and pH values on the structures and electrochemical performance of Li_3V_2(PO_4)_3 material. The results indicate that all samples have high phase purity and are well crystallized when the synthesis temperature is between 600℃-800℃. The samples synthsized 800℃have the best initial discharge capacity which reaches 111 mAh·g-1 between 2.5 V-4.2 V at 1 C discharge rate ,and the discharge capacity after 36 cycles is 82 mAh·g-1, and the capacity retention is 74 %. The initial discharge capacity of samples synthsized 600℃is 91 mAh·g-1, and the discharge capacity after 30 cycles at 1 C discharge rate is 84 mAh·g-1, and the capacity retention is 92 %. The samples synthsized 700℃has better cycle performance, and the initial discharge capacity is 108 mAh·g-1, and the discharge capacity after 70 cycles is 106 mAh·g-1 at 1 C discharge rate, and the capacity retention is 98%. As a result, the samples synthsized 700℃has better electrochemical performance, and the pH value has almost no effects on the structure, but it has significant effects on the electrochemical performance.
CV results reveal that the oxidation peak and reduction peak lapped well from the two scanning process,meaning that the samples has good cycle performance, and the separation of peak potentials between the oxidation peak and reduction peak decreases at the twice scanning process, indicating that the reversibility of the samples becomes better. EIS results exhibit that electrochemical reaction resistance decreases with increasing of synthesis temperatures of samples
引文
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