CN107492635B - 一种复合钠离子电池正极材料Na3V2(PO4)3/C及其制备方法 - Google Patents
一种复合钠离子电池正极材料Na3V2(PO4)3/C及其制备方法 Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
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- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000007774 positive electrode material Substances 0.000 title abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 claims abstract description 23
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
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- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
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- 239000003054 catalyst Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 239000012071 phase Substances 0.000 abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
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- 229930006000 Sucrose Natural products 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明提供一种中间液相引碳的方法来制备Na3V2(PO4)3/C正极材料，具体步骤是称取钠源、钒源、C6H12N4于小烧杯中，添加去离子水，搅拌20min至其完全溶解，将溶解后的液体转移至水热内胆中，添加去离子水至内胆体积的80%，在120~160℃的鼓风烘箱中水热24~36h。称取磷源及碳源于烧杯中，加入去离子水，搅拌20min至其完全溶解；之后将自然冷却后的中间相液体缓慢滴加到溶有磷源和碳源的烧杯中，搅拌20min至溶液变成橙黄色；之后将烧杯放置在65℃的鼓风烘箱中烘24~36h至其完全干燥成粉末。将所得的抹绿色前驱体粉末放置在氮气气氛下350℃预烧4~6h，在700~800℃下煅烧6~10h，自然冷却后得到Na3V2(PO4)3/C复合材料，以其作为钠离子电池正极材料显示出较好的电化学性能。
Description
技术领域
本发明涉及一类高性能的钠离子电池正极材料，特别涉及一种Na3V2(PO4)3/C复合材料的制备方法，属于电化学电源领域。
技术背景
锂离子电池由于高能量密度、低自放电、无记忆效应、长循环寿命等特点被广泛地用作便携式电子产品、混合动力汽车及纯动力汽车的电源。随着市场对锂离子电池的需求量越来越大，锂资源短缺逐渐成为限制锂离子电池发展的致命因素，因此寻找新的储能电池成为目前的研究热点。钠与锂处于同一主族，有着相似的物理化学性质，且钠资源与锂资源相比，储量更为丰富，分布广泛，提取简单，钠离子电池也有着与锂离子电池相似的工作原理。基于此，近年来钠离子电池也发展得如火如荼，成为了锂离子电池的最佳替代物。然而，钠离子的直径较锂离子要大，这导致了钠离子电池电极材料在钠离子嵌入/脱出过程中要经受更为严重的破坏。因此，与锂离子电池相比，钠离子电池性能优越的电极材料更为难求。
Na3V2(PO4)3作为钠离子电池的一种正极材料，其充/放电平台在3.4 V左右，与其他钠离子电池正极材料相比有着较高的平均电压。Na3V2(PO4)3作为一种NASICON (钠超离子导体) 型框架结构的材料，具有供钠离子快速迁移扩散的三维通道，钠离子扩散率较大，大电流充放电循环性能明显优于其他的钠离子电池正极材料。但是Na3V2(PO4)3导电性差的特点，使其倍率性能很差，在充放电过程中很难达到其理论容量 (117 mAh g-1)，因此有必要对Na3V2(PO4)3进行改性提高其导电性，以改善其电化学性能。
基于以上背景，本专利发明一种新型的碳复合方法来提高Na3V2(PO4)3的导电性，以中间液相引碳的方法来制备Na3V2(PO4)3/C材料。通过水热法制备了中间液相，在中间相液体中引入碳源，利用烘干过程中中间相液体结晶诱导有机碳源分子在其表面吸附，在随后固相反应中，Na3V2(PO4)3形成的同时，有机碳源分子沿Na3V2(PO4)3表面原位炭化。这能显著提升Na3V2(PO4)3与C在微观尺度复合均匀性，增强材料导电性；同时，C能够有效抑制Na3V2(PO4)3晶粒长大，保证高锂离子扩散效率。所制备的Na3V2(PO4)3/C复合材料作为钠离子电池正极材料显示出了优异的电化学性能。
发明内容
本发明涉及一种钠离子电池正极材料的制备方法，所述的正极材料为Na3V2(PO4)3/C复合材料，该材料的形貌为复合形貌，由尺寸约300nm的Na3V2(PO4)3颗粒和尺寸约1μm的片状构成。具体制备方法如下：称取一定量的钠源、钒源、C6H12N4于小烧杯中，添加适量的去离子水，搅拌20min至其完全溶解，将溶解后的液体转移至水热内胆中，添加去离子水至内胆体积的80%，在120~160℃的鼓风烘箱中水热24~36h。称取一定量的磷源及碳源于烧杯中，加入适量的去离子水，搅拌20min至其完全溶解；之后将自然冷却后的中间相液体缓慢滴加到溶有磷源和碳源的烧杯中，搅拌20min至溶液变成橙黄色；之后将烧杯放置在65℃的鼓风烘箱中烘24~36h至其完全干燥成粉末。将所得的抹绿色前驱体粉末放置在氮气气氛下350℃预烧4~6h，在700~800℃下煅烧6~10h，自然冷却后得到Na3V2(PO4)3/C复合材料。
所述的钠、钒、磷与六次甲基四胺的摩尔比为3：2：3：2~10。所述的碳源占总质量的0~15%。
所述的钠源为碳酸钠、氢氧化钠、醋酸钠或草酸钠，钒源为五氧化二钒或偏矾酸铵，磷源为磷酸二氢铵、磷酸氢二铵或磷酸铵，碳源为柠檬酸、葡萄糖、蔗糖或坏血酸。
本发明所涉及的Na3V2(PO4)3/C复合材料的制备方法、材料及性能具有以下几个显著的特点：
（1）合成工艺简单，易于操作，重复性好，成本低；
（2）合成过程中间相为液相，有利于提升最终材料微观结构均匀性；
（3）所制备的Na3V2(PO4)3/C复合材料呈复合形貌，由尺寸约300nm的Na3V2(PO4)3颗粒和尺寸约1μm的片状构成；
（4）本发明所制得的Na3V2(PO4)3/C复合材料用作钠离子电池正极材料显示出较好的循环性能及较高的充放电容量。
附图说明
图1实施例1所制备样品的XRD图谱。
图2实施例1所制备样品的SEM图。
图3实施例1所制备样品的前三次充放电曲线图（a）和循环性能图（b）。
图4实施例2所制备样品的循环性能图。
图5实施例3所制备样品的循环性能图。
具体实施方式
实施例 1
称取3mmol碳酸钠、2mmol五氧化二钒、5mmol六次甲基四胺溶于装有20mL去离子水的小烧杯中，搅拌30min至其充分溶解；将得到的混合溶液转移至水热内胆中，添加去离子水至内胆体积的80%，之后在120℃的鼓风烘箱中水热24h，自然冷却得到中间相液体。称取0.05g柠檬酸和6mmol磷酸二氢铵溶于装有20mL去离子水的烧杯中，搅拌20min至其充分溶解，之后缓慢向烧杯中滴加冷却后的中间相液体，滴加完毕后搅拌30min至颜色呈橙黄色。之后将烧杯放在65℃的鼓风烘箱中烘36h至其完全干燥。将干燥后所得的前驱体粉末放置在氮气气氛下350℃预烧4h，750℃煅烧8h。冷却后得到Na3V2(PO4)3/C复合材料。所制备的样品经XRD图谱分析，如图1所示，所有的衍射峰和Na3V2(PO4)3（XRD卡片JCPDS，No. 62-0345）对应，表明成功地制备了Na3V2(PO4)3/C样品。对样品进行了SEM表征，由图2可以看出，Na3V2(PO4)3/C复合材料呈复合形貌，由尺寸约300nm的Na3V2(PO4)3颗粒和尺寸约1μm的片状构成。将上述步骤得到的Na3V2(PO4)3/C复合材料（7.5:1.5:1，Na3V2(PO4)3/C：乙炔黑：PVDF）涂覆在铝箔上，裁剪成14mm的圆片，在120℃下真空干燥12h。以金属钠片为对电极，Grade GF/D为隔膜，溶解有NaPF6 (1mol/L) 的EC +DEC(体积比为1:1)的溶液为电解液，在氩气保护的手套箱中组装成CR2025型电池。电池组装完后静置8h，再用CT2001A电池测试系统进行恒流充、放电测试，测试电压为2.3-3.9V。图3 表明，实施例 1 所制备的Na3V2(PO4)3/C电极首次充、放电容量分别为111.6和108.7mAh/g，100次循环之后充、放电容量分别为107.2和106.9mAh/g，显示了较好的电化学性能。
实施例 2
称取3mmol醋酸钠、2mmol五氧化二钒、5mmol六次甲基四胺溶于装有20mL去离子水的小烧杯中，搅拌30min至其充分溶解；将得到的混合溶液转移至水热内胆中，添加去离子水至内胆体积的80%，之后在120℃的鼓风烘箱中水热24h，自然冷却得到中间相液体。称取0.05g葡萄糖和6mmol磷酸二氢铵溶于装有20mL去离子水的烧杯中，搅拌20min至其充分溶解，之后缓慢向烧杯中滴加冷却后的中间相液体，滴加完毕后搅拌30min至颜色呈橙黄色。之后将烧杯放在65℃的鼓风烘箱中烘36h至其完全干燥。将干燥后所得的前驱体粉末放置在氮气气氛下350℃预烧4h，750℃煅烧8h。冷却后得到Na3V2(PO4)3/C复合材料。按照实施例1的方式组装电池。图 4 表明，实施例2所制备的Na3V2(PO4)3/C电极首次充、放电容量分别为103.6和101.3mAh/g，100次循环之后充、放电容量分别为97.7和97.6mAh/g，显示了较好的电化学性能。
实施例 3
称取3mmol氢氧化钠、2mmol偏钒酸铵、5mmol六次甲基四胺溶于装有20mL去离子水的小烧杯中，搅拌30min至其充分溶解；将得到的混合溶液转移至水热内胆中，添加去离子水至内胆体积的80%，之后在120℃的鼓风烘箱中水热24h，自然冷却得到中间相液体。称取0.05g蔗糖和6mmol磷酸二氢铵溶于装有20mL去离子水的烧杯中，搅拌20min至其充分溶解，之后缓慢向烧杯中滴加冷却后的中间相液体，滴加完毕后搅拌30min至颜色呈橙黄色。之后将烧杯放在65℃的鼓风烘箱中烘36h至其完全干燥。将干燥后所得的前驱体粉末放置在氮气气氛下350℃预烧4h，750℃煅烧8h。冷却后得到Na3V2(PO4)3/C复合材料。按照实施例1的方式组装电池。图 5 表明，实施例 3 所制备的Na3V2(PO4)3/C电极首次充、放电容量分别为103.5和101.2mAh/g，100次循环之后充、放电容量分别为99.5和99.2mAh/g，显示了较好的电化学性能。
Claims (1)
1.一种Na3V2(PO4)3/C复合材料作为钠离子电池正极，其形貌为复合形貌，由尺寸约300nm的Na3V2(PO4)3颗粒和尺寸约1μm的片状构成，其特征在于，所述组分为Na3V2(PO4)3/C，该Na3V2(PO4)3/C的制备工艺如下：称取3mmol碳酸钠、2mmol五氧化二钒、5mmol六次甲基四胺溶于装有20mL去离子水的小烧杯中，搅拌30min至其充分溶解；将得到的混合溶液转移至水热内胆中，添加去离子水至内胆体积的80%，之后在120℃的鼓风烘箱中水热24h，自然冷却得到中间相液体；称取0.05g柠檬酸和6mmol磷酸二氢铵溶于装有20mL去离子水的烧杯中，搅拌20min至其充分溶解，之后缓慢向烧杯中滴加冷却后的中间相液体，滴加完毕后搅拌30min至颜色呈橙黄色；之后将烧杯放在65℃的鼓风烘箱中烘36h至其完全干燥；将干燥后所得的前驱体粉末放置在氮气气氛下350℃预烧4h，750℃煅烧8h；冷却后得到Na3V2(PO4)3/C复合材料。
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