CN102449024A - 一种诱导有机导电聚合物聚合的方法 - Google Patents
一种诱导有机导电聚合物聚合的方法 Download PDFInfo
- Publication number
- CN102449024A CN102449024A CN2010800242161A CN201080024216A CN102449024A CN 102449024 A CN102449024 A CN 102449024A CN 2010800242161 A CN2010800242161 A CN 2010800242161A CN 201080024216 A CN201080024216 A CN 201080024216A CN 102449024 A CN102449024 A CN 102449024A
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- China
- Prior art keywords
- lithium
- lifepo
- alkali metal
- mxo
- metal phosphate
- Prior art date
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Links
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract
本发明涉及一种在作为聚合引发剂的部分脱锂的碱金属磷酸盐存在下诱导有机导电聚合物聚合的方法。
Description
本申请要求于2009年6月1日提交的美国临时申请61/183,063的优先权，在此通过援引的方式并入其全部内容。
技术领域
本发明涉及一种在作为聚合引发剂的部分脱锂的碱金属磷酸盐存在下诱导有机导电聚合物聚合的方法。
背景技术
已知锂离子电池在自90年代初索尼基于嵌锂电极的初步工作以来有引人注目的技术成功和商业发展，主要是由J.B.古迪纳夫(J.B.Goodenough)发明的高电压钴氧化物阴极和使用焦化或石墨化的碳质材料的碳阳极。
在90年代中期，古迪纳夫(见US 5,910,382和US 6,391,493)提出聚阴离子磷酸盐结构，即钠超离子导体(nasicons)和橄榄石，可以提高此前一直与嵌入的低电压相关连的低成本并且环境相容的过渡金属，诸如铁，的氧化还原电位。例如已知LiFePO4在3.45V电压表现可逆的嵌入和解嵌入(insert-deinsert)锂离子，相对于与两相反应有关的锂阳极。此外，在磷酸盐聚阴离子中共价结合的氧原子消除了在完全充电的层状氧化物中观察到阴极的不稳定性，使锂离子电池内在更加安全。
如古迪纳夫(US 5,910,382和US 6,514,640)中指出的，一个与在LiFePO4阴极材料中共价结合的聚阴离子有关的缺点是低的电子导电率和Li+在所述材料中的有限扩散。将LiFePO4颗粒减小到纳米级作为解决上述问题的一个方法已有记载，同样通过其他金属或阴离子对铁金属或磷酸盐聚阴离子进行部分补充也已有记载。
使用有机碳前体实现了对复合金属氧化物阴极粉末和更具体的金属磷酸盐的低电子导电率问题的显著改善，所述有机碳前体热解到阴极材料或其前体上，以在阴极粒子水平上改善电场[Ravet(US6,963,666，US6,855,273，WO 02/027824和WO 02/027823)]。
具有导电聚合物(ECP)的复合金属氧化物的复合阴极的制备也可以克服复合金属氧化物的低电子导电率问题，如Wang等人[An investigation ofpolypyrrole-LiFePO4 composite cathode materials for lithium-ion batteries(用于锂离子电池的聚吡咯-磷酸铁锂复合阴极材料为的调查)，Electrochimica Acta，50(2005)4649-4654]的证明]。Wang发现通过在LiFePO4和作为共存阴离子(counter-anion)的对甲苯磺酸钠的水分散液中利用FeCl3化学引发吡咯的聚合来进行LiFePO4聚吡咯复合阴极的制备。古迪纳夫等还在WO 06/130766中公开了通过吡咯的电聚合获得的热解碳包覆的LiFePO4(C-LiFePO4)和吡咯的合成物。
在工业规模，电聚合不是一个简便的制备LiFePO4-ECP合成物的方法并且已知的制备LiFePO4-ECP合成物的化学方法还不尽人意。
找到一个简便的并且允许大规模制备经导电聚合物表面改性的锂金属磷酸盐还存在问题。
发明内容
为了克服现有的经导电聚合物表面改性的锂金属磷酸盐的制备方法的局限，本发明人改进了诱导有机导电聚合物聚合的方法，该方法将在下文进行描述。
按照广泛的方面，本发明涉及一种在由通式A1-XMXO4表示的部分脱锂的碱金属磷酸盐存在下诱导有机导电聚合物聚合的方法，其中A表示Li，被至多10％的Na或K原子单独或部分取代，0＜x≤1，M包括铁和/或锰，并且XO4表示PO4，被至多10％的选自SO4和SiO4的至少一个基团单独或部分取代，其特征在于，所述部分脱锂的碱金属磷酸盐作为不饱和单体(或其混合物)的聚合引发剂，所述不饱和单体(或其混合物)用作所述导电聚合物的前体。
按照广泛的方面，本发明还涉及一种通过利用所选择的氧化剂进行处理获得所述部分脱锂的碱金属磷酸盐的简便方法。
根据一个具体实施例，上述方法可以应用于锂金属磷酸盐和/或碳包覆锂金属磷酸盐。在一个实施具体实施例中，所述碳包覆锂金属磷酸盐可通过有机碳前体在阴极材料或阴极材料前体上的热解获得。
在一个实施例中，所述导电聚合物至少部分接枝在所述碱金属磷酸盐的表面上。
在阅读以下的结合附图对本发明的具体实施例的描述后，本发明的这些和其他方面和特点将对本领域技术人员是明显的。
附图说明
下面参考附图，仅通过示例的方式，详细描述本发明的具体实施例，其中：
图1表示C-LiFePO4(生命动力P1，购自Phostech Lithium)的X射线衍射图(CoKα)(曲线A)，实施例1制备的通过C-LiFePO4的脱锂获得C-FePO4的磷铁锰矿(heterosite)(曲线B)和部分脱锂的C-LiFePO4(曲线C)。
图2表示Li/1M LiPF6 EC∶DEC 3∶7/LiFePO4-PEDOT型电池在60℃的C/4恒电循环曲线。左边的纵坐标表示所述电池的容量(mAh/gLiFePO4-PEDOT)，右边的纵坐标表示库伦效率(库伦充电/库仑放电)，横坐标表示循环次数。在第一次放电循环过程慢扫描伏安法获得的LiFePO4-PEDOT阴极的容量为144.5mAh/g。
具体实施方式
本发明的目的是通过通式A1-XMXO4的至少部分脱锂的碱金属磷酸盐引发不饱和单体的氧化聚合，以形成具有p型掺杂特性的π电子共轭体系的导电聚合物，其中A表示Li，被最多10％的Na或K原子单独或部分取代，0＜x≤1，M包括铁和/或锰，并且其中XO4表示PO4，被最多10％的选自SO4和SiO4的至少一个基团单独或部分取代。在一个实施例中，所述导电聚合物形成在所述碱金属磷酸盐的表面。
在一个非限制性的例子中，可用于本发明的聚合物包括含有共轭区的，或完全由重复单元组成的聚合物，所述重复单元为经取代的或非经取代的苯胺，噻吩，吡咯，苯基硫醇，呋喃，聚苯胺，聚噻吩，聚吡咯，聚(P-聚苯硫醚)，聚呋喃以及这些聚合物的共聚物。在一个非限制性的例子，可用于本发明的聚合物还包括经环取代任何一个所述相应单体的聚合物，其中所述单体是经一个或多个直链或支链烷基，烯基，氧杂烷基，氧杂烯基，氮杂烷基，氮杂烯基，硫代烷基，硫代烯基，硅烷基，硅烯基，芳基，芳基烷基，烷基芳基，烯基芳基，二烷氨基和二烷基偶氮自由基环取代的，所述取代基可以包含从1到约30个碳原子。至少两个自由基可以连接成环。也可认识到，在本发明的物质组成中包含的聚合物也可以是任意一个或多个上述单体与其他具有不饱和乙烯基共聚单体的共聚物。
根据一个具体的优选实施例，聚噻吩化合物(具有含噻吩骨架重复单元的高分子化合物(噻吩或其衍生物))是在本发明中形成具有p型掺杂特性的π电子共轭化合物的导电聚合物。
所述聚噻吩化合物包括含有由下列式(I)所示的重复单元的噻吩化合物：
在式(I)中，R1和R2独立为氢或具有1-4个碳原子的烷基，或可相互连接形成具有1-4个碳原子的烯烃基，1，2-环己烯基或邻二甲苯基，其可被取代。在这些噻吩化合物中，PEDOT是特别优选的。这些噻吩化合物通过部分脱锂的LiMPO4引发的，由下式(II)所示的噻吩化合物的氧化聚合获得：
在式(II)中，R1和R2与式(I)中的R1和R2分别具有相同的含义。优选的由式(II)所示的所述噻吩化合物的例子为3，4-乙烯二氧噻吩(EDOT)。
在式(I)，当其中R1和R2相互连接形成具有1-4个碳原子的烯烃基时，在所述烯烃基上进行取代的基团例子为C1-C14的烷基，苯基，羟甲基，-CH2O-(CH2CH2)S-TTF基团(其中TTF是从四硫富瓦烯化合物衍生的单价基团，同样适用于下列情况下)，-CH2O-(CH2CH2O)5-CH2CH2-TTF基团，-CH2O-(CH2CH2)S-S-TTF基团，-CH2O-(CH2CH2O)5-CH2CH2-S-TFT基团，和-CH2O(CH2)3SO3 -Na+基团。更具体地说，所述聚噻吩化合物包括含有由下列式(III)所示的重复单元的聚合物：
在式(III)中，R0表示-(CH2)2-，-CH2CH(CH3)-，-CH2CH(C6H13)-，-CH2CH(C10H21)-，-CH2CH(C14H29)-，-CH2CH(苯基)-，-(CH2)3-，-CH2CH(CH3)CH2-，-(CH2)4-，邻二甲苯，-CH2CH(OH)-，-CH2CH(CH2O-(CH2CH2)3-S-三甲硫基四硫富瓦烯)-，或-CH2CH(CH2O-(CH2CH2O)5-CH2CH2-S-三甲硫基四硫富瓦烯)-，或
-CH2CH(CH2O(CH2)3SO3 -Na+)-。
作为在本发明中形成的π电子共轭材料的导电聚合物，也可使用以下物质的氧化聚合所制得的聚合物：(E)-1，2-二(2-(3，4-亚乙二氧)噻吩基)乙炔，1，4-二(2-(3，4-亚乙二氧)噻吩基)苯，4，4′-二(2-(3，4-亚乙二氧)噻吩基)联苯，2，5-二(2-(3，4-亚乙二氧)噻吩)呋喃，2，5-二(2-(3，4-亚乙二氧)噻吩基)噻吩，或2，2′：5′，2″-三(3，4-亚乙二氧)噻吩。
根据一个具体实施例，本发明的部分脱锂的聚合引发剂是一种对应通式A1-XMXO4的化合物，所述化合物具有橄榄石结构，在所述通式A1-XMXO4中：
-0＜x≤1
-A表示Li，被最多10％的Na或K原子单独或部分取代；
-M包括至少50％的Fe(II)或Mn(II)或它们的混合物；
-XO4表示PO4，被最多10mol％的选自SO4和SiO4的至少一个基团单独或部分取代。
在一个实施例中，通式A1-XMXO4包括0.02＜X≤0.4。
在第一个具体实施例中，本发明的聚合引发剂是一种对应通式A1-XMXO4的化合物，所述化合物具有橄榄石结构，在所述通式A1-XMXO4中：
-0＜x≤1
-A表示Li，被最多10％的Na或K原子单独或部分取代；
-M选自Fe(II)，Mn(II)及它们的混合物，被最多50％的选自Ni和Co的一种或多种其他金属的原子，和/或被至少15％的一种或多种除了Ni或Co的异价或等价的金属的原子，和/或被最多5％的Fe(III)单独或部分取代；
-XO4表示PO4，被最多10mol％的选自SO4和SiO4的至少一个基团单独或部分取代。
在第二个具体实施例中，本发明的聚合引发剂是一种对应通式A1-XMXO4的化合物，所述化合物具有橄榄石结构，在所述通式A1-XMXO4中：
-0＜x≤1
-A表示Li，被最多10％的Na或K原子单独或部分取代；
-M选自Fe(II)，Mn(II)及它们的混合物，被最多50％的选自Ni和Co的一种或多种其他金属的原子，和/或被最多15％的一种或多种选自Mg，Mo，Nb，Ti，Al，Ta，Ge，La，Y，Yb，Cu，Sm，Ce，Hf，Cr，Zr，Bi，Zn，Ca，B和W异价或等价的金属的原子，和/或被最多5％的Fe(III)单独或部分取代；
-XO4表示PO4，被最多10mol％的选自SO4和SiO4的至少一个基团单独或部分取代。
在第三个具体实施例中，本发明的聚合引发剂是一种对应通式Li1-xFeyMn1-yPO4的化合物，所述化合物具有橄榄石结构，其中0＜X≤1和0≤y≤1。
在第四个具体实施例中，本发明的聚合引发剂是一种对应通式Li1-xFePO4的化合物，所述化合物具有橄榄石结构，其中0＜X≤1。
通式意味着所述材料的化学计量比可能由于取代或出现在结构上的其他缺陷而变化几个百分点。
可选的，本发明的具有橄榄石结构的A1-xMXO4的部分脱锂的聚合引发剂，可在其至少部分的表面上承载有热解碳沉积膜，表示为C-A1-XMXO4。碳沉积可以表现出或多或少均匀的，粘着的和非粉状的沉淀。所述沉淀高达15％(以重量计)，优选0.5-5％(以重量计)，相比于材料的总重量。部分脱锂A1-XMXO4和/或C-A1-XMXO4的合成，可通过，但不限于，使用化学氧化剂对AMXO4和/或C-AMXO4进行脱锂来实现。例如Lemos等人[A new insightinto the LiFePO4 delithiation process，Solid State lonics(对于LiFePO4脱锂方法的一个新的见解，固态离子)，177(2006)1021-1025]，C M.Julien等人[Structural and Magnetic Properties of LiFePO4 and Lithium Extraction Effects(LiFePO4的结构和磁特性和锂提取物的效应)，Z Anorg.AIIg Chem.，632(2006)1598-1605]或Meng等人[Intermittent X-Ray diffraction study of kinetics ofdelithiation in nano-scale LiFePO4，Journal of Power Sources(纳米级LiFePO4脱锂的动力学间歇X-射线衍射研究，电源杂志)，189(2009)702-705]所述的方法。Lemos和Julien分别公开了通过使用过硫酸钾(K2S2O8)的水溶液对LiM0.03Fe0.97PO4(M＝Cr，Cu，Al或Ti)进行化学脱锂，以及通过使用过硫酸钠(Na2S2O8)的水溶液对LiFePO4进行化学脱锂。Meng公开了使用NO2BF4氧化剂的乙腈溶液进行LiFePO4的化学脱锂。
制备AMXO4和/或C-AMXO4化合物的方法是众所周知的。它们可以，例如，通过水热法，通过固态热法或通过熔体法得到。可以在AMXO4或其前体上通过有机碳前体的热解进行碳沉积。
大量氧化剂可供选择来进行化学脱锂，诸如，但不局限于，氯(Cl2)，溴(Br2)，碘(I2)，高锰酸盐(如高锰酸钾)，过氧化物(如过氧化氢或OxoneTM)，硝酰阳离子(例如NO2BF4)或过硫酸盐(例如过氧焦硫酸盐K2S2O8)，本领域技术人员能够通过有限次实验确定合适的氧化剂并不脱离本发明。
化学脱锂一般在溶液中进行，优选，但不局限于，在水溶液中。
优选过氧化氢作为氧化剂，其允许受控制的脱锂在水性溶液中进行，并有最少的副产物，可选地存在缓冲液，诸如，但不局限于，乙酸(CH3COOH)，以避免溶液最终酸化，否则可能导致的锂金属磷酸盐AMXO4和/或C-AMXO4部分分解。
本发明人还出乎意料的发现化学脱锂可以通过气相方法有效进行，例如，氮氧化物气体，尤其是二氧化氮NO2。例如，将LiFePO4暴露在二氧化氮气体中能够制备脱锂的磷酸铁锂Li1-xFePO4，0＜X≤1。
因此，在另一广泛方面，本发明还涉及到使用包括NO2的气相进行AMXO4和/或C-AMXO4化合物脱锂。
根据一个具体实施例，在通过二氧化氮脱锂的过程中从AMXO4和/或C-AMXO4结构中提取的锂阳离子作为沉积在AMXO4和/或C-AMXO4表面的硝酸锂被回收，如脱锂化合物的红外光谱所示。
因此，在另一广泛方面，本发明还涉及一种包括LiNO3沉淀物的式A1-XMXO4和/或C-A1-XMXO4的复合材料。
锂假定作为硝酸锂被定量提取。
因此，在另一广泛方面，本发明还涉及式(LiNO3)X·A1-XMXO4和/或(LiNO3)X·C-A1-XMXO4的复合材料。
根据一个具体实施例，通过用不饱和单体接触部分脱锂A1-XMXO4和/或C-A1-XMXO4进行聚合，优选存在至少一种盐作为p型掺杂导电聚合物共存阴离子源。
根据一个具体实施例，盐优选包括碱盐(Li，Na或K)，并且最优选是锂盐。可选择这些盐的阴离子为，但不局限于，卤化物(F-，Cl-，Br-或I-)，硫酸盐(SO4 2-)，磺酸盐(CH3SO3 -，TsO-，FSO3 -，CF3SO3 -，苯乙烯磺酸盐，聚苯乙烯磺酸盐)，醋酸(CH3CO2 -，CF3CO2 -)，亚胺((CH3SO2)2N-，(FSO2)2N-，(CF3SO2)2N-)，高氯酸盐(CIO4 -)，硼酸(BF4 -，双(草酸)硼酸阴离子，二氟(草酸)硼酸阴离子)，和磷酸盐(PF6 -)。
根据一个具体实施例，聚合可在溶剂或混合溶剂中进行，诸如，但不局限于，水，酒精(甲醇，乙醇，丁醇，丙醇，异丙醇)，乙腈，四氢呋喃，醋酸乙酯，丙酮，二甲基甲酰胺，二甲基亚砜。本领域技术人员能够通过有限次实验确定合适的溶剂并不脱离本发明。
根据一个具体实施例，聚合也可以在使A1-XMXO4和/或C-A1-XMXO4暴露于不饱和单体蒸汽条件下进行。对于气相聚合，优选使A1-XMXO4和/或C-A1-XMXO4与碱盐混合，优选是锂盐，作为导电聚合物共存阴离子源。
在A1-XMXO4和/或C-A1-XMXO4的表面聚合的导电聚合物的量可根据参数进行修改，诸如，但不局限于，脱锂的比例，单体浓度，反应温度，或溶剂。优选的，所述导电聚合物的量代表着高达20％(以重量计)，优选从0.5％至10％(以重量计)，相比于材料的总重量。在团聚体的具体实施例中，所述导电聚合物可以同时作为电子导体和粘合剂，以提高当作为锂离子电池正极使用时所述材料的循环寿命(cyclability)。
根据一个具体实施例，C-A1-XMXO4为特定的形式或纳米粒子的团聚体，且在C-A1-XMXO4上的碳沉积是沉积在所述粒子的表面上或所述纳米粒子的团聚体的内部。
根据一个具体实施例，本发明的方法可以在初级粒子，初级粒子的团聚体，片状，纤维状，薄膜沉积状的形式在A1-XMXO4和/或C-A1-XMXO4上进行，而不脱离本发明的范围。
根据一个具体实施例，本发明的所述方法可以在添加剂的存在下进行，诸如，但不局限于，表面活性剂，聚合物，碳粒子，碳纤维，碳纳米管，金属氧化物，或金属粉末。
这里所公开和要求保护的所有的合成物和/或方法都可根据本发明进行有限次的实验进行制备或实施。虽然优选实施例中已描述本发明的合成物和方法，但是，可在不脱离本发明的内容，精神和范围内对所述合成物和/或方法，以及下文描述的这些方法的步骤或步骤的顺序进行改变，这对本领域技术人员是显而易见的。所有对本领域技术人员显而易见的相似替换和修改应视为在由随附的权利要求所限定的本发明的内容，精神和范围内。
前后文中所有的参考文献以全文纳入的方式在此引用。
实施例1：C-LiFePO4的化学脱锂
将6.5克C-LiFePO4(生命动力
P1，购自Phostech Lithium公司，加拿大)在搅拌的条件下分散在250毫升蒸馏水中，在其中缓慢加入250毫升30wt％的双氧水(购自西格玛-奥德里奇公司；美国)。搅拌30分钟后，过滤回收部分脱锂的C-Li1-XFePO4，用清水洗涤，然后在环境温度真空干燥24小时。通过对液相中Li+离子的原子吸收分析测定C-Li0.59FePO4合成物。使用C-LiFe0.98Mg0.02PO4代替C-LiFePO4重复所述实验以得到C-Li0.63Fe0.98Mg0.02PO4。
实施例2：纳米级别的LiFePO4化学脱锂
由US2007/054187公开的沉淀方法制备的6.5克纳米级别的LiFePO4(D50≈0.6μm)(由加拿大Phostech Lithium公司提供)，按照实施例1中的方法进行处理，但只有30毫升30wt％的双氧水。通过对液相中Li+离子原子吸收分析测定Li0.42FePO4合成物。使用LiFe0.7Mn0.3PO4代替LiFePO4重复所述实验以得到Li0.56Fe0.7Mn0.3PO4。
实施例3：纳米级别的LiFePO4化学脱锂
2毫升的冰乙酸(Alfa Aesar)和5毫升ACS级别29.0-32.0％的过氧化氢(EMD化学)加入到100毫升的水中。将根据US2007/054187公开的沉淀方法制备的LiFePO4(10.18g)(D50＝0.6μm)(由加拿大Phostech Lithium公司提供)加入到上述溶液中。用力搅拌所述悬浮液15分钟。随后对所述悬浮液进行过滤并用水进行清洗。在60℃真空箱中过夜干燥所述Li1-XFePO4。通过原子发射法分析所述溶液用于锂脱嵌(desinsertion)的定量测定。结果提供在下表中。
实施例4：通过气态氧化剂进行纳米级别的LiFePO4化学脱锂
装置由两个反应容器构成，通过塑料管和含有无水硫酸钙的玻璃管连接。第一反应容器除了与管连接的开口，其他部分是气密封的。所述容器，在冰水中冷却，装有铜粉，逐滴加入浓硝酸。产生的气体随着所述管流过硫酸钙进入到第二容器当中，所述第二容器对环境空气开放，并含有187毫克的C-LiFePO4生命动力P1。所述的气体具有特征颜色，因此容易判断容器是否填满。所述110毫升的容器被填满后，保持关闭30分钟。移去样品并通过ATR-FTIR光谱分析其接近完全脱锂。
用实施例2中的纳米级别的LiFePO4代替C-LiFePO4重复相同的实验。移去样品并通过ATR-FTIR光谱分析其接近完全脱锂，且在其表面含有硝酸锂的沉淀物。
用实施例2中的纳米级别的LiFePO4重复相同的实验，但是减少曝光时间到5分钟。除去样本，特征为Li0.59FePO4。
实施例5：纳米级别的LiFePO4的化学脱锂
在30毫升的干乙腈中，用3.9克的亚磺酰苯1，1-双乙酸盐(购自西格玛-奥德里奇公司，美国)处理由US2007/054187公开的沉淀方法制得的6.3克的纳米级别(D50≈0.6μm)(由加拿大Phostech Lithium公司提供)的LiFePO4。搅拌24小时后，通过过滤回收部分脱锂的Li1-xFePO4，用水洗涤，然后在环境温度真空干燥24小时。通过对液相中Li+离子原子吸收分析测定Li0.71FePO4的合成物。用LiFe0.99Nb0.01PO4代替LiFePO4重复所述实验以得到Li0.68Fe0.99Nb0.01PO4。
实施例4：通过脱锂的C-LiFePO4对EDOT进行聚合
将2.37克根据实施例1得到的脱锂的C-LiFePO4和1.75克(CF3SO2)2NLi(FluoradTM锂HQ-115，购自3MTM；美国)加入到25毫升甲醇中，然后加入溶在15毫升丁醇中的0.38克3，4-乙撑二氧噻吩(购自西格玛-奥德里奇公司，美国)。50℃搅拌加热分散液两天，使用旋转蒸发器去除溶剂，然后最终产生的粉末用30毫升的甲醇洗涤三次，并用30毫升的乙腈洗涤三次，然后在60℃的真空干燥12小时。可用C-Li0.63Fe0.98Mg0.02PO4重复所述实验。
实施例5：通过脱锂的LiFePO4对EDOT进行聚合
将4.81克根据实施例2制得的脱锂的LiFePO4和4.95克(CF3SO2)2NLi(FluoradTM锂HQ-115，购自3MTM；美国)加入到30毫升甲醇/丁醇(3∶5体积)中，随后加入溶在50毫升甲醇/丁醇(3∶5体积)中的0.88克3，4-乙撑二氧噻吩(购自西格玛-奥德里奇公司，美国)。然后50℃搅拌加热分散液一天，使用旋转蒸发器去除溶剂。最终产生的粉末用30毫升的甲醇洗涤三次，并用30毫升的乙腈洗涤三次，然后在60℃真空干燥12小时。可用Li0.56Fe0.9Mn0.1PO4重复所述实验。相似的实验也可用喷雾干燥步骤代替上述去除溶剂的步骤来执行。
实施例6：通过脱锂的LiFePO4对EDOT进行聚合
在培养皿中，将3.10克的LiTFSI(FluoradTM锂HQ-115，购自3M；美国)溶解在25毫升的甲醇中。然后，将0.51克的3，4-乙撑二氧噻吩(奥德里奇公司)和由实施例3得到的4.68克的Li0.7FePO4加入到所述溶液中。将培养皿放置在60℃的烘箱中2小时。在溶剂蒸发后会出现蓝色。过滤所述混合物并用甲醇和乙腈清洗后，将PEDOT-LiFePO4(LFP-1)在60℃的真空烘箱过夜干燥。
实施例7：通过气相的脱锂LiFePO4对EDOT进行聚合
将1.48克的LiTFSI(FluoradTM锂HQ-115，购自3M；美国)和在实施例3获得的1.5克的Li0.5FePO4混合，然后放置于锥形烧瓶中。接着，0.27克的3，4-乙撑二氧噻吩(奥德里奇公司)加入到一个小烧瓶中，所述小烧瓶置于所述锥形烧瓶中并形成真空。然后将所述锥形烧瓶放置在60℃的烘箱中2天。过滤所述混合物并用甲醇和乙腈清洗后，将PEDOT-LiFePO4(LFP-2)在60℃的真空烘箱过夜干燥。
实施例8通过脱锂的LiFePO4对EDOT进行聚合以形成膜
将1.27克的LiTFSI(FluoradTM锂HQ-115，购自3M；美国)和在实施例3中获得的1.5克的Li0.5FePO4、0.24克的3，4-乙撑二氧噻吩和1.5毫升的甲醇混合，将混合物涂到铝板上，并放置在60℃的烘箱中2小时。在用甲醇清洗过程中，将PEDOT-LiFePO4薄膜从基板上移除。过滤所述混合物并用甲醇和乙腈清洗，将PEDOT-LiFePO4膜在60℃的真空烘箱过夜干燥。
实施例9：测量电导率
LFP 1-2的电导率通过挤压颗粒测量电阻的方法得到，这三种粉末呈现＞0.1S.cm的较高电导率，而未处理的粉末为＜10-7S.cm。
实施例10：在脱锂的阴极上进行EDOT聚合
在实施例2得到的纳米级的LiFePO4和PVdF-HFP共聚物(由Atochem提供)小心的与N-甲基吡咯烷酮混合以获得LiFePO4/PVdF-HFP(80/20重量混合)组成的分散物。上述得到的混合物随后使用
设备沉积在具有碳处理包覆层(由Intellicoat提供)的铝板上，并且所述沉积膜在80℃的真空干燥24小时，而后存储在手套式操作箱中。
这种膜的10cm2的样本(4.3mg/cm2负载)然后在20毫升的30wt％的双氧水水中处理10分钟，用水洗净，然后在环境温度真空干燥24小时。随后，将膜放置在一个含有10ml的甲醇/丁醇(1∶1体积)，200mg(CF3SO2)2NLi(FluoradTM锂HQ-115，购自3MTM；美国)和50毫克3，4-乙撑二氧噻吩的培养皿中。将培养皿放置在60℃的烘箱中2小时，用甲醇和乙腈洗净，然后在60℃真空干燥12小时(LFP-3)。
实施例11：电池的特性
使用实施例6中制备的LFP-1，EBN1010(高级石墨公司的产品)作为导电介质以及PVdF-HFP(Arkema的产品)作为粘合剂，比例为80/10/10wt，制备复合阴极电极。在室温下检查纽扣电池的阴极涂层的电化学性能，所述纽扣电池使用金属锂作为阳极，并以在EC∶DMC(1∶1)中的1M的LiClO4作为电解液，所述EC∶DMC(1∶1)浸透在25μm的聚丙烯(CelgardTM)中。阴极表面为1.5cm2具有3.97mg/cm2LFP-1负载。
在环境温度下，使用VMP2多通道稳压器(potensiostat)(生物逻辑-科学仪器的产品)，电压在3.0V-3.7V之间，相对于Li+/Li0，进行第一次慢扫描伏安法(20mV/h)。进一步通过恒电势(intentiostatic)实验进行功率测试，比率由从第一次慢扫描伏安法获得的特定的容量值(144.5mAh/g)计算得到。在1C放电容量为134mAh/g，在10C放电容量为112mAh/g。
随后将电池进行在60℃下的C/4恒电流循环。曲线如图2所示。
采用实施例10获得的LFP-3作为涂层装配另一个电池，在环境温度下进行慢扫描伏安法测定146mAh/g的容量，然后进行60℃下的C/4恒电流循环，在50个周期后，容量＞146mAh/g。
上述具体实施例不应以限制的方式进行解释，因为在本发明的精神和范围内，可以进行其他的变化，修改和完善。本发明的范围通过随附的权利要求及它们的等效物进行限定。
Claims (21)
1.一种在由通式A1-XMXO4表示的部分脱锂的碱金属磷酸盐存在下合成有机导电聚合物的方法，所述方法包括：
使用化学反应物接触所述部分脱锂的碱金属磷酸盐，所述化学反应物包括不饱和单体或多种不饱和单体混合物；以及
使用所述部分脱锂的碱金属磷酸盐引发所述不饱和单体或多种不饱和单体混合物的聚合以形成导电聚合物；其中
0＜x≤1
A表示至少90％Li；
M包括至少50％的Fe(II)或Mn(II)或Fe(II)和Mn(II)的混合物；
XO4表示PO4，被最多10％的选自SO4和SiO4的至少一个基团单独或部分取代。
2.根据权利要求1所述的方法，其中所述导电聚合物至少部分接枝到所述碱金属磷酸盐的表面。
3.根据权利要求2所述的方法，其中所述M包括至少90％的Fe(II)或Mn(II)或Fe(II)和Mn(II)的混合物。
4.根据权利要求2所述的方法，其中所述不饱和单体包括取代的或未取代的吡咯、噻吩、苯胺或其任意混合物。
5.根据权利要求4所述的方法，其中所述不饱和单体包括3，4-乙烯二氧噻吩。
6.根据权利要求1所述的方法，其中所述A1-XMXO4通过AMXO4的部分脱锂获得。
7.根据权利要求6所述的方法，其中所述部分脱锂通过氧化剂进行。
8.根据权利要求7所述的方法，其中所述氧化剂包括H2O2、Br2、I2、过硫酸盐、过氧焦硫酸盐或其任意混合物。
9.根据权利要求8所述的方法，其中所述部分脱锂在水介质中进行。
10.根据权利要求1所述的方法，其中所述聚合在溶液中进行。
11.根据权利要求10所述的方法，其中所述溶液包括乙醇。
12.根据权利要求1所述的方法，其中所述聚合在所述单体的蒸汽相进行。
13.根据权利要求1所述的方法，其中所述聚合在气相进行。
14.根据权利要求10-13任一项所述的方法，其中所述聚合在碱性盐存在下进行。
15.根据权利要求14所述的方法，其中所述碱性盐包括选自卤化物，硫酸盐、磺酸盐、醋酸盐、亚胺、高氯酸盐、硼酸盐和磷酸盐组成的阴离子。
16.根据权利要求14所述的方法，其中所述碱性盐为锂盐。
16、根据权利要求14所述的方法，其中所述碱性盐包括(CF3SO2)2NLi。
17.根据权利要求1-16任一项所述的方法，其中所述碱金属磷酸盐具有LiFePO4的通式。
18.根据权利要求1-17任一项所述的方法，其中所述部分脱锂的碱金属磷酸盐作为基本粒子或粒子的团聚体存在。
19.根据权利要求1-18任一项所述的方法，其中0.02＜x≤0.4。
20.根据权利要求1-19任一项所述的方法，其中A1-XMXO4包括通过有机前体的热解获得的沉积碳。
21.根据权利要求6所述的方法，其中所述部分脱锂通过包括NO2的气态氧化剂进行。
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| CN110739458A (zh) * | 2018-07-18 | 2020-01-31 | 华为技术有限公司 | 一种具有热敏特性的导电聚合物碱金属盐及其制备方法和应用 |
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| ES2537588B1 (es) * | 2013-12-05 | 2016-09-28 | Abengoa Research, S.L. | Batería de iones alcalinos y método para producir la misma |
| CN104332597B (zh) * | 2014-10-20 | 2016-10-05 | 北京化工大学 | 一种多酸/聚苯胺/碳纳米管电极材料及其制备方法和应用 |
| JP2018081830A (ja) * | 2016-11-16 | 2018-05-24 | 株式会社リコー | 電極活物質、蓄電素子用電極、および蓄電素子 |
| US10593946B2 (en) | 2016-12-11 | 2020-03-17 | StoreDot Ltd. | LFP as initiator of in-battery polymerization of conducting polymers for high-rate-charging cathodes |
| US9831488B1 (en) | 2016-12-11 | 2017-11-28 | StoreDot Ltd. | In-battery polymerization of conducting polymers for high-rate charging cathodes |
| CN107828009B (zh) * | 2017-10-29 | 2020-06-09 | 山东森久生物材料有限公司 | 一种含正极材料的导电树脂的制备方法 |
| KR101992027B1 (ko) * | 2017-11-28 | 2019-06-21 | 고려대학교 산학협력단 | 전도성 고분자가 코팅된 리튬이차전지용 양극 및 그 제조방법 |
| WO2021053514A1 (en) | 2019-09-16 | 2021-03-25 | InCoR Lithium | Selective lithium extraction from brines |
| EP3846248A1 (en) * | 2019-12-31 | 2021-07-07 | Imec VZW | Conductive polymer coating onto a cathode active material |
| CA3171115A1 (en) * | 2020-03-09 | 2021-09-16 | William C. Mays | Processes for delithiating transition metal oxides |
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| US20120136136A1 (en) | 2012-05-31 |
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| CN102449024B (zh) | 2014-01-15 |
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