CN1564343A - 含磷酸亚铁锂盐－碳的锂离子电池正极复合材料的制备方法 - Google Patents
含磷酸亚铁锂盐－碳的锂离子电池正极复合材料的制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 22
- 229910052799 carbon Inorganic materials 0.000 title claims description 21
- 229910052744 lithium Inorganic materials 0.000 title claims description 17
- 238000000034 method Methods 0.000 title abstract description 10
- 229940116007 ferrous phosphate Drugs 0.000 title abstract description 4
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title abstract description 4
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- -1 Fe3+ compound Chemical class 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 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
- 239000000047 product Substances 0.000 claims description 4
- 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
本发明涉及含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，该方法采用一步固相法将一定比例的锂盐、Fe3+化合物和磷酸盐混合均匀，然后将混合物在惰性气氛中热解，热解前加入一定量的高分子聚合物，得到磷酸亚铁基锂盐—碳正极复合材料。该方法不使用较贵的Fe2+原材料，生产工艺简单、安全、成本低，所得正极复合材料纯度高，导电性能得到改善，电化学性能得到很大提高，比容量高，循环性能优良，具有3.4V左右的稳定放电电压平台。由该方法制备出的锂离子电池材料可广泛应用于移动电话、笔记本电脑、小型摄录像机、电动汽车等领域。
Description
技术领域
本发明涉及一种锂离子电池正极复合材料的制备方法，特别涉及一种磷酸亚铁基锂盐-碳复合材料的制备方法。
背景技术
锂离子电池是20世纪90年代初出现的新型绿色高能可充电电池，目前已成为世界各国竞相研究开发的重点。正极材料是锂离子电池的一个重要组成部分，在锂离子电池充放电过程中，不仅要提供在正负极嵌锂化合物中往复嵌/脱所需要的锂，而且还要负担负极材料表面形成SEI膜所需要的锂，因此，研究和开发高性能的正极材料已成为锂离子电池发展的关键所在。目前的研究主要集中在含锂过渡金属氧化物方面，过渡金属主要为钴、镍、锰。近年来，基于Fe3+/Fe2+氧化还原电对的物质引起人们的极大兴趣，特别是具有橄榄石晶体结构的LiFePO4成为近期研究的最有希望的备选正极材料，与其他正极材料相比，其具有更安全、更环保、更廉价并且相当高比容量等多种优势。
Goodenough[A.K.Padhi，K.S.Nanjundaswarmy，J.B.Goodenough，J.Electrochem.Soc.，144(1997)1188]研究小组合成了一种含铁锂盐LiFePO4，该物质用作锂离子电池正极材料具有较高的理论比容量(170mAh/g)，大于已商品化的LiCoO2的实际放电比容量140mAh/g，所以引起研究者的极大关注。但这种材料的导电性很差，室温下只能在极小倍率下充放电，而且其制备需要Fe2+做铁源，价格较Fe3+盐高且需要多次热处理和研磨，制备工艺复杂，产物纯度不容易控制，从而使成本增加，这些都大大限制了其在实际锂离子电池中的应用。
发明内容
本发明的目的是提供一种制备含磷酸亚铁锂盐一碳的锂离子电池正极复合材料的方法，以简化制备工艺，降低制备成本，提高产物纯度，改善材料导电性能；
本发明的含磷酸亚铁锂盐-碳的锂离子电池正极复合材料的制备方法，包括以下步骤：
1)将锂盐，Fe3+化合物和磷酸盐按比例混合，其中Li∶Fe∶P摩尔比为(0.95-1.1)∶1∶1；
2)研磨混合物，使其充分混合均匀；
3)在混合物中掺入高分子聚合物，高分子聚合物的用量使得产物中碳含量为1-20％，然后放入管式炉中，在流速为5-40升/分钟的惰性气流保护下，于450-900℃温度下热处理8-50小时，降温至室温即可。
本发明中所说的锂盐可选自Li2CO3、LiOH、草酸锂、醋酸锂或磷酸锂等，Fe3+化合物可采用三氧化二铁、四氧化三铁或磷酸铁等含Fe3+的化合物，磷酸盐可选自磷酸铵、磷酸氢铵、磷酸二氢铵或磷酸铁等。所说的惰性气体可以是氮气或氩气。高分子聚合物为碳氢聚合物，以聚丙烯为宜。
通常，为使混合物达到充分混合的效果，可在研磨时加入适量酒精。
本发明采用一步固相法制备了含铁锂盐-碳复合正极活性材料，所采用的原材料来源广泛、易得到、价格低廉，制备方法简单；制得的复合材料不含有Co、Ni等对环境有较大污染的元素，因而对环境友好；该正极复合材料纯度高，正极具有平稳的3.4V左右的充放电电压平台，导电性能和大电流充放电性能优良；该正极复合材料结构稳定，热稳定性能好，循环性能优良。
由该方法制备出的锂离子电池材料可广泛应用于移动电话、笔记本电脑、小型摄录像机、电动汽车等领域。
附图说明
图1是按实施例1所制备的磷酸亚铁基锂盐-碳复合材料的晶体衍射图，采用Rigaku-D/MAX-2550PC型X射线多晶衍射仪(Cu靶Kα射线，波长λ＝0.154056nm)。
图2是按实施例1所制备的模拟锂离子电池充放电曲线图，电压范围2.5-4.2V，电解液为1mol/L LiPF6/EC-DMC(1∶1)，充放电倍率为0.1C，测量温度为30℃±0.5℃。
图3是按实施例1所制备的模拟锂离子电池在不同充放电倍率下的放电曲线，电压范围2.5-4.2V，电解液为1mol/L LiPF6/EC-DMC(1∶1)，充放电倍率分别为0.1C、0.2C、0.5C，测量温度为30℃±0.5℃。
图4是按实施例1所制备的模拟锂离子电池的循环性能图，电压范围2.5-4.2V，电解液为1mol/L LiPF6/EC-DMC(1∶1)，充放电倍率为0.2C，测量温度为30℃±0.5℃。
具体实施方式
实施例1
将0.5摩尔氢氧化锂和0.5摩尔磷酸铁混合，放入尼龙罐中，并加入80ml酒精，在球磨机上混合2小时后，将该混合物掺入14克聚丙烯放入管式炉中，在5升/分钟的氮气氛下，以5℃/分钟的速率升至700℃，并在该温度下恒定10小时，然后降温至室温。
测得所得复合材料中碳含量为2.5％，其XRD谱图见图1，对照标准卡，为晶型完好的橄榄石型LiFePO4，而未观察到碳的衍射峰。
用实施例1所得的复合材料按下述方法制成电极。
以80∶10∶10的质量比分别称取实施例1所得的复合材料∶炭黑∶聚四氟乙烯，研磨均匀后制成电极，配以纯锂片为负极，以溶解在碳酸乙酯+碳酸二甲酯(体积比1∶1)混合溶剂中的1.0mol/L LiPF6为电解液，聚丙稀微孔薄膜为隔膜，组装成模拟锂离子电池。图2为相应电池按0.1C倍率在4.2V-2.5V截至电压时的首次充放电曲线，表明所测电池有3.4V左右的平稳的充放电电压平台，可计算出实施例1复合材料的可逆比容量为164mAh/g。图3为相应电池在不同充放电倍率下的放电曲线。在0.1C-0.5C的放电倍率范围内，正极活性材料的可逆容量介于4145-164mAh/g之间。图4为相应电池在0.2C倍率下的循环性能。其中，比容量以LiFePO4的质量计算，而非LiFePO4-碳复合物的质量，以下实施例中与此相同。
实施例2：
将0.5摩尔氢氧化锂、0.25摩尔的三氧化二铁和0.5摩尔的磷酸二氢铵混合并放入尼龙罐中，加入80ml酒精，在球磨机上充分混合2小时后，将该混合物掺入20克聚丙烯放入管式炉中，在5升/分钟的氮气氛下，以5℃/分钟的速率升至700℃，并在该温度下恒定20小时，然后降温至室温。测得所得复合材料的碳含量为4.6％，同样按实施例1的方法制备电极片，组装成电池后以0.2C倍率充放电，测定可逆容量为157mAh/g。
实施例3：
将0.5摩尔氢氧化锂和0.5摩尔磷酸铁混合，放入尼龙罐中，并加入80ml酒精，在球磨机上混合1小时后，将该混合物掺入25克聚乙烯放入管式炉中，在5升/分钟的氮气氛下，以5℃/分钟的速率升至500℃，并在该温度下恒定24小时，然后降温至室温。测得所得复合材料的碳含量为3.1％，并按实施例1的方法制备电极片，组装成电池后以0.5C倍率充放电，测定可逆容量为148mAh/g。
实施例4：
将0.25摩尔碳酸锂，0.25摩尔的三氧化二铁和0.5摩尔的磷酸氢铵混合，放入尼龙罐中，并加入80ml酒精，在球磨机上混合1小时后，将该混合物掺入25克聚丙烯放入管式炉中，在5升/分钟的氮气氛下，以5℃/分钟的速率升至600℃，并在该温度下恒定48小时，然后降温至室温。测得所得复合材料的碳含量为7.6％，并按实施例1的方法制备电极片，组装成电池后以1C倍率充放电，测定可逆容量为125mAh/g。
Claims (6)
1.含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，包括以下步骤：
1)将锂盐，Fe3+化合物和磷酸盐按比例混合，其中Li∶Fe∶P摩尔比为(0.95-1.1)∶1∶1；
2)研磨混合物，使其充分混合均匀；
3)在混合物中掺入高分子聚合物，高分子聚合物的用量使得产物中碳含量为1-20％，然后放入管式炉中，在流速为5-40升/分钟的惰性气流保护下，于450-900℃温度下热处理8-50小时，降温至室温即可。
2.根据权利要求1所述的含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，其特征在于所述的锂盐选自Li2CO3、LiOH、草酸锂、醋酸锂或磷酸锂。
3.根据权利要求1所述的含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，其特征在于所述的Fe3+化合物选自三氧化二铁、四氧化三铁或磷酸铁。
4.根据权利要求1所述的含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，其特征在于所述的磷酸盐选自磷酸铵、磷酸氢铵、磷酸二氢铵或磷酸铁。
5.根据权利要求1所述的含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，其特征在于所述的惰性气体选自氮气或氩气。
6.根据权利要求1所述的含磷酸亚铁锂盐—碳的锂离子电池正极复合材料的制备方法，其特征在于所述的高分子聚合物为碳氢聚合物或聚丙烯。
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| CN1332462C (zh) * | 2005-11-15 | 2007-08-15 | 厦门大学 | 磷酸铁锂正极材料及其制备方法 |
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