CN111777051A - 一种片状的磷酸铁锂电极材料的制备方法 - Google Patents
一种片状的磷酸铁锂电极材料的制备方法 Download PDFInfo
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 77
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 8
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229910010710 LiFePO Inorganic materials 0.000 claims abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052742 iron Inorganic materials 0.000 claims abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 2
- 239000011574 phosphorus Substances 0.000 claims abstract 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052603 melanterite Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 abstract 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 abstract 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- C01B25/00—Phosphorus; Compounds thereof
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Abstract
本发明公开了一种片状的磷酸铁锂电极材料制备方法。该方法具体步骤为:以七水合硫酸亚铁、磷酸、一水合氢氧化锂为铁源,磷源和锂源,再为以少量抗坏血酸为还原剂,然后以乙二醇作为一种液体表面活性剂,控制乙二醇的用量,溶剂热法首先合成LiFePO4前驱体;离心洗涤,干燥过夜;得到的前驱体在管式炉中烧结得到磷酸铁锂。本发明的工艺过程简单,原料来源广泛,控制形貌效果明显,有利于大规模工业生产;制备的锂离子电池正极材料具有良好的的倍率充放电性能和优异的循环使用寿命,且材料的容量较高。
Description
技术领域
本发明属于新能源材料制备技术领域,特别是涉及一种片状的磷酸铁锂电极材料的制备方法。
背景技术
随着经济的发展以及国际竞争日趋激烈,资源匮乏能源短缺问题愈发严重,这就使得越来越多的科学工作者投入到新能源的开发中。20世纪末,锂离子电池的出现很大程度上解决了能源利用率低的问题。锂离子电池通过锂离子的脱出和嵌入实现能量的转化,具有效率高,安全,绿色环保等优点,广泛适用于笔记本电脑,智能手机等小型家电,诸如特斯拉,比亚迪等公司也将锂离子电池应用于新能源汽车。锂离子电池的正极材料一般是锂的金属氧化物,常用的有钴酸锂,磷酸铁锂,镍钴锰三元材料等,负极材料可以是碳材料的多种形式,金属氧化物等等。钴酸锂是早期常用正极材料,比容量高,但钴的毒性大,不符合绿色环保的要求,因此逐渐被市场所淘汰;镍钴锰三元材料是一种新型的材料,比容量很高,循环性能好,但存在安全隐患,近些年来三元材料起火事件频发;磷酸铁锂是一种绿色环保的材料,安全性能好,是一种可靠的能源材料,但它存在着倍率性能差,振实密度低等缺点,还有很大的提升空间。
磷酸铁锂的缺陷究其本质是因为其导电性差,锂离子迁徙速度慢,针对这两个问题,常用的改性方法有碳包覆,金属掺杂,粒径控制等。磷酸铁锂的制备方法有高温固相法,溶胶凝胶法,水热法等,高温固相法常用于工厂大批量生产,能源消耗较大;溶胶凝胶法和水热法常用于实验室制备研究,更容易调控磷酸铁锂的形貌。一般调控形貌的方法都是使用表面活性剂,Bo Pei.等人通过调节表面活性剂SDBS的量制备纳米粒,纳米棒,纳米片状的磷酸铁锂,其中SDBS添加量为0.2g时,磷酸铁锂的形貌为纳米片,电化学性能最好,在0.1C下比容量为162.9mAh/g,在10C的条件下比容量为107.9mAh/g;Shiliu Yang等人通过调节PEG的量制备出了纳米粒,纳米片,微米片状的磷酸铁锂,其中纳米粒的磷酸铁锂电化学性能最好,在0.1C条件下为155mAh/g。以上均说明磷酸铁锂的形貌与电化学性能有非常大的联系。
发明内容
本发明为了更简单控制磷酸铁锂的形貌,提高其循环性能和充放电稳定性以及放电容量特提供了一种片状的磷酸铁锂电极材料的制备方法。
实现本发明的目的的技术解决方案是:
一种片状的磷酸铁锂电极材料的制备方法,包括下列步骤:
(1)以H3PO4、FeSO4·7H2O、LiOH·H2O,少量抗坏血酸为原料,以乙二醇作为一种液体表面活性剂,控制乙二醇的用量,溶剂热法首先合成LiFePO4前驱体;
(2)用适量磷酸将pH调至7,水热合成LiFePO4前驱体,将前驱体用去离子水和乙醇多次洗涤后干燥;
(3)将干燥后的LiFePO4前驱体研磨,随后在管式炉中烧结。
上述步骤(1)中,FeSO4·7H2O、LiOH·H2O的物质的量比为3:1.1(氢氧化锂稍过量),将FeSO4·7H2O、LiOH·H2O分别溶于30ml去离子水中,抗坏血酸量为0.4g,乙二醇的添加量分别为0ml,10ml,20ml。
上述步骤(2)中,将磷酸滴加到氢氧化锂溶液中至pH为7,水热反应时间是12h,水热反应温度是180℃,升温速度为3℃/min。
上述步骤(3)中,烧结温度为500℃,烧结时间为6h,升温速度为3℃/min,在N2氛围下烧结。
与现有技术相比,本发明的积极效果是:(1)以少量抗坏血酸为还原剂,防止二价铁离子在制备及水热的过程中被氧化;(2)用乙二醇作为一种液体表面活性剂,形成的颗粒结构完整,尺寸大小均已,形貌粒径可调节,方法简便;(3)水热反应12h,水热温度为180℃,可以促进材料生长的同时防止材料过度团聚和结晶,控制一定尺寸;(4)烧结升温速度缓慢减少二价铁离子的氧化,可以使晶体结构更加稳定;(5)本工艺发明过程简单,原料来源广泛,控制形貌效果明显,有利于大规模工业生产;所制备的锂离子电池正极材料具有良好的的倍率充放电性能和优异的循环使用寿命,且材料的容量较高。
附图说明
图1是制备的不同形貌磷酸铁锂的TEM图,图a(EG=0ml),图b(EG=10ml),图c(EG=20ml)。
图2是标准LiFePO4PDF卡片所对应的,制备出的不同形貌磷酸铁锂的XRD图。
图3是制备的不同形貌的磷酸铁锂在0.1C倍率下首次充放电曲线图。
图4是制备的不同形貌的磷酸铁锂在0.2C倍率下循环充放电50次的衰减图。
图5是制备的不同形貌的磷酸铁锂在不同倍率倍率下循环充放电70次的衰减图。
具体实施方式
下面结合附图对本发明的实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
实施例
本发明目标产物不同形貌的磷酸铁锂通过以下步骤制得:
(1)水热法合成稳定的磷酸铁锂前驱体:按物质的量比例为3:1.1称取3.6142g的FeSO4·7H2O和1.7182g的LiOH·H2O,称取0.4g的抗坏血酸,以上药品共称量三份,将LiOH·H2O溶于30ml去离子水中,FeSO4·7H2O与抗坏血酸粉末混合溶于30ml去离子水中。将85%的磷酸滴加到氢氧化锂溶液中,有磷酸锂白色沉淀生成,滴加的过程中搅拌,至溶液的pH为7停止滴加。将磷酸锂溶液置于磁力搅拌器上搅拌,将配置好的硫酸亚铁抗坏血酸混合溶液转移到恒压漏斗中,滴加到白色溶液中。滴加完毕,在三个烧杯中分别加入0ml,10ml,20ml,乙二醇;
(2)将加入乙二醇的溶液搅拌一小时后,转移到100ml水热釜中;在马弗炉中加热,温度为180℃,时间为12h,升温时间为3℃/min,得到磷酸铁锂前驱体;
(3)将水热釜中上清液倒掉,收集沉淀,沉淀为白色,用去离子水和酒精多次离心洗涤。得到的沉淀在80℃的烘箱中干燥过夜。将干燥后的沉淀研磨至细小粉末状,于管式炉中在N2氛围下烧结,烧结温度为500℃,时间为6h,升温速率为3℃/min,都得到的棕色粉末即为磷酸铁锂成品。
采用透射电镜TEM对产物的形貌进行观察和分析,附图1是不同形貌磷酸铁锂的TEM图。从图中可以看出,不添加乙二醇合成的LiFePO4是柱状,长为600-800nm;当乙二醇添加量为10ml时样品的长度略有缩小,分布比较均匀,较不添加乙二醇的样品更薄;当乙二醇的添加量为20ml时,柱状磷酸铁锂的长度和厚度继续减小,平均长度在300-500nm。磷酸铁锂的电化学性与形貌有着极大的关系,颗粒越小,锂离子脱出嵌入的路程就越短,与电解液接触越充分,但颗粒过于薄也会导致结构不稳定,容易影响电池的循环性能。图2是标准LiFePO4PDF卡片所对应的,合成的不同形貌磷酸铁锂的XRD图。可以看到,合成的不同形貌的磷酸铁锂的XRD所对应的的峰和标准的LiFePO4PDF卡片所对应的峰一一对应,证明合成的确实是LiFePO4,无明显的杂峰,随着乙二醇加入的量增加,XRD峰强度逐渐减弱,说明乙二醇的添加会使磷酸铁锂晶体的结晶度降低,说明乙二醇可以抑制磷酸铁锂在反应过程中团聚成更大的颗粒,起到了表面活性剂的作用;将得到的复合材料制作成电极片作为纽扣电池的正极,以锂片作为负极,对其进行充放电测试和循环性能测试,见附图3和附图4。测试结果显示,在0.1C的倍率条件下,不同形貌磷酸铁锂制备出的电池都能有较好的充放电平台,充放电电压稳定平顺,在低倍率电流条件下,乙二醇添加量为20ml制备出的磷酸铁锂首次充放电比容量最大,接近LiFePO4理论值的比容量(170mAh/g),添加乙二醇量为10ml制备出的样品比容量较低,而不添加乙二醇最低,仅能达到120mAh/g左右。进行0.2C倍率下50次充放电循环后,材料的比容量有所衰减,其中乙二醇添加量为10ml制备出的样品虽然初始比容量不是最优,但衰减最为缓慢,说明稳定性最优。图5为不同倍率下合成的不同形貌的磷酸铁锂充放电70次循环图,随着倍率的增加,比容量衰减,但回到小倍率条件充放电,容量与初始条件下充放电相差不大,说明材料结构稳定,乙二醇添加量为0的初始容量都低,说明颗粒体积过大不利于磷酸铁锂的充放电。添加乙二量为10ml的样品循环性能和倍率性能都是最优的,这是最优的合成磷酸铁锂的条件。本发明的此方法制备出的磷酸铁锂有不同的形貌,在最优条件下制备的磷酸铁锂作为锂离子电池阳极材料具有较好的结构稳定性和优异的电化学性能,可以开展深入研究以广泛开发应用。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (7)
1.一种片状的磷酸铁锂电极材料制备的方法,其特征在于,以H3PO4、FeSO4·7H2O、LiOH·H2O作为磷源,铁源及锂源,抗坏血酸为原料,乙二醇作为液体表面活性剂,并控制乙二醇的用量和水热时间,控制水热温度为180℃,水热时间为12h,水热法首先合成LiFePO4前驱体,离心洗涤,干燥过夜;得到的前驱体烧结得到磷酸铁锂。
2.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,FeSO4·7H2O、LiOH·H2O的物质的量比为3:1.1。
3.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,用磷酸将pH调到7,抗坏血酸的量为产量的20wt%。
4.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,将LiOH·H2O,FeSO4·7H2O分别溶于去离子水中,搅拌混合后,将乙二醇作为液体表面活性剂最后补加,乙二醇和去离子水体积的比例分别为0:60。
5.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,将LiOH·H2O,FeSO4·7H2O分别溶于去离子水中,搅拌混合后,将乙二醇作为液体表面活性剂最后补加,乙二醇和去离子水体积的比例分别为10:60。
6.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,将LiOH·H2O,FeSO4·7H2O分别溶于去离子水中,搅拌混合后,将乙二醇作为液体表面活性剂最后补加,乙二醇和去离子水体积的比例分别为20:60。
7.根据权利要求1所述的片状的磷酸铁锂电极材料制备的方法,其特征在于,前驱体在管式炉中烧结,烧结温度为500℃,烧结时间为6h。
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