CN106531985B - 一种碳纳米带包覆磷酸铁锂材料的制备方法 - Google Patents
一种碳纳米带包覆磷酸铁锂材料的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000002127 nanobelt Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910010707 LiFePO 4 Inorganic materials 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005253 cladding Methods 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229960005191 ferric oxide Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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Abstract
本发明提供一种碳纳米带包覆磷酸铁锂材料的制备方法，包括如下步骤：步骤一：将碳纳米带通过搅拌和超声分散方式充分均匀分散于水溶液中；步骤二：在惰性气体保护下，向步骤一得到的混合物中按摩尔比为Li：Fe：P＝1：1：1的比加入锂源、铁源及磷源，并加入水搅拌成为浆料并进行回流；步骤三：洗涤并干燥得到初级的碳纳米带包覆的磷酸铁锂材料；步骤四：将步骤三得到的初级的碳纳米带包覆的磷酸铁锂材料在5‑10v/v％H2的氩气混合气氛中进行高温退火，获得最终的碳纳米带包覆的磷酸铁锂材料。
Description
【技术领域】
本发明涉及电池材料技术领域，尤其涉及一种碳纳米带包覆磷酸铁锂材料的制备方法。
【背景技术】
磷酸铁锂(LiFePO4)电池作为一种绿色环保能源，以其高安全性、良好的高温特性、长的循环寿命、对环境友好、来源广、价格低廉等优点引起人们的高度关注，逐渐成为动力电池的重要选择。然而，磷酸铁锂材料本身较差的电子导电性和低的锂离子扩散性，导致其电化学性能并不太理想，对磷酸铁锂材料的改进通常采用碳包覆技术，现有的碳包覆磷酸铁锂技术中使用常规的碳源进行包覆，包覆后的磷酸铁锂导电性能一般，且碳包覆质量分数通常达到5％甚至10％，大量碳材料的使用会促进电极活性材料的溶解以及电解液在其表面的氧化，从而使得电极的循环性能变差、不可逆容量增加。
近几年来迅速兴起的两种用于磷酸铁锂包覆的纳米材料为碳纳米管和石墨烯。然而，碳纳米管包覆为线接触包覆，包覆接触面积小；石墨烯为二维纳米结构，比表面积较大，但其柔韧性、结构灵活可调性比碳纳米管差，难以充分包覆磷酸铁锂纳米颗粒的表面。
【发明内容】
本发明的目的是提供一种锂离子导电率高且所应用的电池倍率性能优异的碳纳米带包覆磷酸铁锂材料的制备方法。
为了实现上述目的，本发明提供一种碳纳米带包覆磷酸铁锂材料的制备方法，包括如下步骤：
步骤一：将碳纳米带通过搅拌和超声分散方式充分均匀分散于水溶液中；
步骤二：在惰性气体保护下，向步骤一得到的混合物中按摩尔比为Li：Fe：P＝1：1：1的比加入取锂源、铁源及磷源，并加入水搅拌成为浆料并进行回流；
步骤三：洗涤并干燥得到初级的碳纳米带包覆的磷酸铁锂材料；
步骤四：将步骤三得到的初级的碳纳米带包覆的磷酸铁锂材料在5-10v/v％H2的氩气混合气氛中进行高温退火，获得最终的碳纳米带包覆的磷酸铁锂材料；所述步骤一中的碳纳米带的厚度为2-30nm，宽度与厚度的比例为(10-20)：1，宽度与长度的比例为1：(5-25)。
相比于现有技术，本发明提供的碳纳米带包覆磷酸铁锂材料的制备方法，使用的碳包覆材料为碳纳米带，碳纳米带的碳层是一种开放的结构，相对碳纳米管具有更大的比表面积及孔结构，提供了更多的锂离子反应界面；同时带与带之间由于大的比表面积及柔韧性的相互作用，形成了三维多孔结构，能很好的形成导电网络，更加有利于电极活性材料与电解液的接触，缩短了锂离子及电解液的传输扩散路径，能很好的提升其作为锂离子电池倍率性能。
【附图说明】
图1为本发明实施例1所使用的碳纳米带的SEM图；
图2为本发明实施例1所制备的碳纳米带包覆磷酸铁锂材料的SEM图；
图3为本发明实施例1所制备的碳纳米带包覆磷酸铁锂材料的的锂离子电池倍率充电性能图；
图4为本发明实施例3所制备的碳纳米带包覆磷酸铁锂材料的SEM图；
图5为本发明实施例1和实施例4所制备的碳纳米带包覆磷酸铁锂材料的锂离子电池循环性能图。
【具体实施方式】
为了使本发明的目的、技术方案和有益技术效果更加清晰明白，以下结合附图和具体实施方式，对本发明进行进一步详细说明。应当理解的是，本说明书中描述的具体实施方式仅仅是为了解释本发明，并不是为了限定本发明。
本发明提供一种碳纳米带包覆磷酸铁锂材料的制备方法，包括如下步骤：
步骤一：将碳纳米带通过搅拌和超声分散方式充分均匀分散于水溶液中；
步骤二：在惰性气体保护下，向步骤一得到的混合物中按摩尔比为Li：Fe：P＝1：1：1的比加入锂源、铁源及磷源，并加入水搅拌成为浆料并进行回流；
步骤三：洗涤并干燥得到初级的碳纳米带包覆的磷酸铁锂材料；
步骤四：将步骤三得到的初级的碳纳米带包覆的磷酸铁锂材料在5-10v/v％H2(即氢气在氩气中的体积比为5-10％)的氩气混合气氛中进行高温退火，获得最终的碳纳米带包覆的磷酸铁锂材料。
具体的，所述步骤一中的碳纳米带的厚度为2-30nm，宽度与厚度的比例为(10-20)：1，宽度与长度的比例为1：(5-25)；所述步骤一得到的混合物的固含量为2-10wt％；所述步骤一中的搅拌和超声分散方式为：先搅拌分散0.5-4h，后进行超声分散0.5-4h。
具体的，所述步骤二所得的浆料的含碳量为2-5wt％，固含量为35-65wt％；所述步骤二中的回流温度为90℃-110℃，回流时间为4-12h；所述步骤二中的锂源为：碳酸锂或氢氧化锂或磷酸二氢锂；所述步骤二中的铁源为：氧化铁或磷酸铁或草酸亚铁；所述步骤二中的磷源为：磷酸二氢铵或磷酸氢二铵或磷酸二氢锂或磷酸铁。
具体的，所述步骤四中的退火温度为400-1200℃，退火时间为4-16h。
本发明提供的碳纳米带包覆磷酸铁锂材料的制备方法，使用的碳包覆材料为碳纳米带，碳纳米带的碳层是一种开放的结构，相对碳纳米管具有更大的比表面积及孔结构，提供了更多的锂离子反应界面；同时带与带之间由于大的比表面积及柔韧性的相互作用，形成了三维多孔结构，能很好的形成导电网络，更加有利于电极活性材料与电解液的接触，缩短了锂离子及电解液的传输扩散路径，能很好的提升其作为锂离子电池倍率性能。
实施例1：
1、将碳纳米带分散于水溶液中，通过搅拌和超声分散方式事情充分均匀分散于水溶液中；其中，碳纳米带的厚度为5-15nm，宽度与厚度的比例为(10-15)：1，宽度与长度的比例为1：(10-20)；所得混合物的固含量为5wt％；所述搅拌和超声分散方式为：先搅拌分散2h，后进行超声分散2h；
2、在惰性气体保护下，向步骤一所得的混合物按摩尔比为Li：Fe：P＝1：1：1的比加入锂源、铁源和磷源，并加入水搅拌成为浆料并进行回流；其中，所得浆料的含碳量为3wt％，固含量为45wt％；所述锂源、铁源及磷源分别为：碳酸锂、氧化铁及磷酸二氢铵；所述回流温度为100℃，回流时间为8h；
3、洗涤并干燥得到初级的碳纳米带包覆的磷酸铁锂材料；
4、将步骤三得到的初级的碳纳米带包覆的磷酸铁锂材料在5v/v％H2的氩气混合气氛中进行高温退火获得最终的碳纳米带包覆的磷酸铁锂材料；其中，所述退火温度为600℃，退火时间为8h。
实施例2：
制备方法基本与实施例1相同，不同之处为步骤1的碳纳米带的厚度为5-10nm，宽度与厚度的比例为(15-20)：1，宽度与长度的比例为1：(10-15)。
实施例3：
制备方法基本与实施例1相同，不同之处为步骤1所得的混合物的固含量为8wt％，搅拌分散时间为1.5h，超声分散时间为4h；
实施例4：
制备方法基本与实施例1相同，不同之处为步骤2中的锂源、铁源、磷源的添加量反应后形成的浆料含碳量为5wt％，固含量为50wt％。
实施例5：
制备方法基本与实施例1相同，不同之处为步骤2中的锂源与磷源为同一物质：磷酸二氢锂。
实施例6：
制备方法基本与实施例1相同，不同之处为步骤2中的铁源与磷源为同一物质磷酸铁。
实施例7：
制备方法基本与实施例1相同，不同之处为步骤2的回流温度为110℃，回流时间为10h。
实施例8：
制备方法基本与实施例1相同，不同之处为步骤4的退火温度为800℃，退火时间为10h。
图3为本发明实施例1所制备的碳纳米带包覆磷酸铁锂材料的倍率充电性能图，从图3可以看出，本发明实施例1所制备的碳纳米带包覆磷酸铁锂材料的锂离子电池在1CDischarge、3C Discharge及5C Discharge的情况下均表现出良好的倍率特性；图5为本发明实施例1和实施例4所制备的碳纳米带包覆磷酸铁锂材料的锂离子电池循环性能图，从图5可以看出，本发明实施例1和实施例4所制备的碳纳米带包覆磷酸铁锂材料的锂离子电池在充放电次数逐渐增加的情况下，容量保持率依然在90％以上，具有良好的循环性能。
本发明并不仅仅限于说明书和实施方式中所描述，因此对于熟悉领域的人员而言可容易地实现另外的优点和修改，故在不背离权利要求及等同范围所限定的一般概念的精神和范围的情况下，本发明并不限于特定的细节、代表性的设备和这里示出与描述的图示示例。
Claims (9)
1.一种碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：包括如下步骤：
步骤一：将碳纳米带通过搅拌和超声分散方式充分均匀分散于水溶液中；
步骤二：在惰性气体保护下，向步骤一得到的混合物中按摩尔比为Li：Fe：P＝1：1：1的比加入锂源、铁源及磷源，并加入水搅拌成为浆料并进行回流；
步骤三：洗涤并干燥得到初级的碳纳米带包覆的磷酸铁锂材料；
步骤四：将步骤三得到的初级的碳纳米带包覆的磷酸铁锂材料在5-10v/v％H2的氩气混合气氛中进行高温退火，获得最终的碳纳米带包覆的磷酸铁锂材料；所述步骤一中的碳纳米带的厚度为2-30nm，宽度与厚度的比例为(10-20)：1，宽度与长度的比例为1：(5-25)。
2.如权利要求1所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤一得到的混合物的固含量为2-10wt％。
3.如权利要求2所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤一中的搅拌和超声分散方式为：先搅拌分散0.5-4h，后进行超声分散0.5-4h。
4.如权利要求3所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤二所得的浆料的含碳量为2-5wt％，固含量为35-65wt％。
5.如权利要求4所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤二中的回流温度为90℃-110℃，回流时间为4-12h。
6.如权利要求5所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤四中的退火温度为400-1200℃，退火时间为4-16h。
7.如权利要求1所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤二中的锂源为：碳酸锂或氢氧化锂或磷酸二氢锂。
8.如权利要求1所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤二中的铁源为：氧化铁或磷酸铁或草酸亚铁。
9.如权利要求1所述的碳纳米带包覆磷酸铁锂材料的制备方法，其特征在于：所述步骤二中的磷源为：磷酸二氢铵或磷酸氢二铵或磷酸二氢锂或磷酸铁。
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