CN1547273A - 一种采用微波法制备LiFePO4材料的方法 - Google Patents
一种采用微波法制备LiFePO4材料的方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052493 LiFePO4 Inorganic materials 0.000 title 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910010710 LiFePO Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000012774 insulation material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000007144 microwave assisted synthesis reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019838 diammonium phosphate Nutrition 0.000 abstract 1
- 238000007600 charging Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- -1 phosphoric acid hydrogen Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
本发明提供了一种采用微波法制备LiFePO4材料的方法，其特征在于：采用微波合成技术，用活性炭作为微波接收体加热原材料，合成LiFePO4材料。具体工艺为：将Li2CO3和草酸亚铁(FeC2O4·2H2O)，磷酸氢二氨((NH4)2HPO4)按生成物LiFePO4化学计量比(Li∶Fe∶PO4＝1∶1∶1)配比，装入玛瑙球磨罐中，用丙酮作分散剂球磨，球磨4～12小时，混合好的料干燥、压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中，频率2.45GHz，调节功率为低档～中档，时间3～30分钟，获得合成产物。本发明的优点在于：与固相合成等传统方法相比，加热迅速，合成时间短，较好地防止了晶粒的长大；降低能耗。
Description
技术领域
本发明属于锂离子电池复合阴离子正极材料制备技术领域，特别是提供了一种采用微波法制备LiFePO4材料的方法，可用做锂离子电池复合阴离子正极材料。
技术背景
近年来，围绕着城市的环保与电动车的研发，为了解决锂离子电池的安全性和价格问题，人们一直进行着新材料的探索研究。1997年Goodenough小组开发研究了具有橄榄石结构的复合阴离子材料。这是一类很优秀的锂离子电池正极候选材料，它廉价、无毒、对环境无污染，具有代表性的LiFePO4材料理论容量可达170mAh/g，较小电流的情况下的可逆容量达140mAh/g。与目前已商业化的锂离子电池正极材料LiCoO2相比，除了价格低廉外，还大大提高了使用过程的安全性。因此在锂离子电池正极材料的研究中，复合阴离子材料的研究引起了人们广泛的重视，尤其是对LiFePO4正极材料的研究。
目前LiFePO4的合成方法基本采用高温固相合成，如专利CN1401559是将一定比例的锂盐、亚铁盐和磷酸盐混合均匀，在惰性气氛保护下进行热处理，所得正极材料的可逆容量大于95mAh/g。或溶胶-凝胶法合成，专利CN1410349，是采用湿化学方法先制成LiFePO4的预聚体，然后在惰性气氛保护下进行热处理，得到LiFePO4粉体。高温固相合成温度600-800℃，要在氮气保护下保温时间24小时以上。它对合成温度要求较严，合成过程中处理温度过低会造成Fe3+还原不完全，Fe3+的存在不仅降低了LiFePO4的比容量，而且使LiFePO4结构不稳定，而温度过高会导致粉体粒度过大，这也会导致它的高倍率放电性能较差，这些都阻碍了LiFePO4的实际应用，尤其是在大的动力电池上的应用。
目前在发表的文章和专利中尚未见到采用与本发明相同原材料及方法合成该材料的报道。
发明内容
本发明在于解决：合成LiFePO4正极材料过程中Fe2+的氧化，晶粒的不正常长大，及降低能耗。
本发明采用微波合成技术，用活性炭作为微波接收体加热原材料，在3-30分钟即可完成LiFePO4材料的合成，并无需惰性气体保护，与高温固相合成及溶胶-凝胶法合成相比大大降低了材料的合成过程中的能耗，降低了材料成本。与M.Higuchi，Synthesis of LiFePO4 cathode material by microwave processing，J.ofpower sources 119-121(2003)258-261，微波法合成LiFePO4不同的是，我们采用了更便宜的原材料，而且不用惰性气体保护。
本发明采用微波技术合成LiFePO4材料的具体工艺为：
将Li2CO3和草酸亚铁即FeC2O4·2H2O，磷酸氢二氨即(NH4)2HPO4按生成物LiFePO4化学计量比(Li∶Fe∶PO4＝1∶1∶1)配比，装入玛瑙球磨罐中，用丙酮作分散剂球磨，球磨4-12小时，混合好的料干燥、压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中(频率2.45GHz)，调节功率为低档-中档，时间3-30分钟，可制备获得合成产物。
本发明的优点在于：与固相合成等传统方法相比，加热迅速，合成时间短，较好的防止了晶粒的长大；由于合成时间短，无需惰性气体保护，大大降低了合成过程的能耗；实验中作为吸波载体的活性炭，高温下部分碳氧化为CO，防止了Fe2+的氧化，提高了LiFePO4材料的纯度。
附图说明
图1为本发明微波合成的LiFePO4的XRD图，低火三档，九分钟。横坐标为2θ角，纵坐标为强度。
图2为本发明微波合成的LiFePO4的比容量-电压曲线，低火三档，九分钟，充放电电流密度10mA/g，充放电电压范围4.5-2V。横坐标为比容量，纵坐标为电压。
图3为本发明微波合成的LiFePO4的XRD图，低火二档，九分钟。横坐标为2θ角，纵坐标为强度。
图4为本发明微波合成的LiFePO4的比容量-电压曲线，低火二档，九分钟充放电电流密度40mA/g，充放电电压范围4.2-2.5V)。横坐标为比容量，纵坐标为电压。
图5为本发明微波合成的LiFePO4的XRD图，中低火一档，三分钟。横坐标为2θ角，纵坐标为强度。
具体实施方式
将化学纯Li2CO3和草酸亚铁(FeC2O4·2H2O)及分析纯磷酸氢二氨((NH4)2HPO4)按生成物化学计量比配比，装入玛瑙球磨罐中，用丙酮作分散剂球磨，球磨6小时，混合好的料干燥待用。
例1
将干燥料压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中(频率2.45GHz)，调节功率为低火三档，微波辐射9分钟。所得试样的物相分析结果见图1。由XRD图可见，合成产物为橄榄石型的LiFePO4，无杂质相。
将合成材料加导电剂，粘结剂(分别为20％和5％)粘压成膜，与金属锂组成试验电池，进行恒电流充放电实验，充放电电流为10mA/g，充放电电压范围控制在2.0-4.5V之间。图2给出第12次充放电曲线，比容量可达100mAh/g以上。
例2
将干燥料压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中(频率2.45GHz)，调节功率为低火二档，微波辐射9分钟。所得试样的物相分析结果见图3。由XRD图可见，合成产物为橄榄石型的LiFePO4，基本无杂质相。
将合成材料加导电剂，粘结剂(分别为20％和5％)粘压成膜，与金属锂组成试验电池，进行恒电流充放电实验，充放电电流为10mA/g，充放电电压范围控制在2.5-4.2V之间。图4给出第2-7次充放电曲线，比容量可达70mAh/g以上。
例3
将干燥料压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中(频率2.45GHz)，调节功率为中低火一档，微波辐射3分钟。所得试样的物相分析结果见图5。由XRD图可见，合成产物为橄榄石型的LiFePO4，无杂质相。
Claims (1)
1、一种采用微波法制备LiFePO4材料的方法，其特征在于：采用微波合成技术，用活性炭作为微波接收体加热原材料，合成LiFePO4材料；具体工艺为：
将Li2CO3和草酸亚铁即FeC2O4·2H2O，磷酸氢二氨即(NH4)2HPO4按生成物LiFePO4化学计量比为Li∶Fe∶PO4＝1∶1∶1配比，装入玛瑙球磨罐中，用丙酮作分散剂球磨，球磨4-12小时，混合好的料干燥、压片，放入装有活性炭及保温材料的氧化铝坩埚中，然后将坩埚置于家用微波炉中，频率2.45GHz，调节功率为低档～中档，时间3～30分钟，获得合成产物。
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371239C (zh) * | 2006-03-20 | 2008-02-27 | 清华大学 | 微波加热制备高密度磷酸铁锂的方法 |
| CN100418252C (zh) * | 2005-01-28 | 2008-09-10 | 比亚迪股份有限公司 | 锂离子二次电池正极活性材料磷酸亚铁基锂盐的制备方法 |
| WO2009127672A1 (en) | 2008-04-17 | 2009-10-22 | Basf Se | Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials |
| WO2010023194A1 (en) | 2008-08-26 | 2010-03-04 | Basf Se | Synthesis of lifepo4 under hydrothermal conditions |
| WO2010076265A2 (en) | 2008-12-29 | 2010-07-08 | Basf Se | Synthesis of lithium-metal-phosphates under hydrothermal conditions |
| WO2010106035A2 (en) | 2009-03-17 | 2010-09-23 | Basf Se | Synthesis of lithium-iron-phosphates |
| WO2010149681A1 (en) | 2009-06-24 | 2010-12-29 | Basf Se | Process for the preparation of lifepo4-carbon composites |
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| US9147877B2 (en) | 2008-04-17 | 2015-09-29 | Basf Se | Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials |
| JP2016052996A (ja) * | 2009-08-07 | 2016-04-14 | 株式会社半導体エネルギー研究所 | リン酸遷移金属リチウムの作製方法 |
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| CN100418252C (zh) * | 2005-01-28 | 2008-09-10 | 比亚迪股份有限公司 | 锂离子二次电池正极活性材料磷酸亚铁基锂盐的制备方法 |
| CN100371239C (zh) * | 2006-03-20 | 2008-02-27 | 清华大学 | 微波加热制备高密度磷酸铁锂的方法 |
| WO2009127672A1 (en) | 2008-04-17 | 2009-10-22 | Basf Se | Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials |
| US9147877B2 (en) | 2008-04-17 | 2015-09-29 | Basf Se | Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials |
| US8673497B2 (en) | 2008-04-17 | 2014-03-18 | Basf Se | Process for the preparation of crystalline lithium-, iron- and phosphate-comprising materials |
| US8586241B2 (en) | 2008-08-26 | 2013-11-19 | Basf Se | Synthesis of LIFEPO4 under hydrothermal conditions |
| WO2010023194A1 (en) | 2008-08-26 | 2010-03-04 | Basf Se | Synthesis of lifepo4 under hydrothermal conditions |
| WO2010076265A2 (en) | 2008-12-29 | 2010-07-08 | Basf Se | Synthesis of lithium-metal-phosphates under hydrothermal conditions |
| US9156693B2 (en) | 2008-12-29 | 2015-10-13 | Basf Se | Synthesis of lithium-metal-phosphates under hydrothermal conditions |
| US9023523B2 (en) | 2009-03-17 | 2015-05-05 | Basf Se | Synthesis of lithium-iron-phosphates under hydrothermal conditions |
| WO2010106035A2 (en) | 2009-03-17 | 2010-09-23 | Basf Se | Synthesis of lithium-iron-phosphates |
| WO2010149681A1 (en) | 2009-06-24 | 2010-12-29 | Basf Se | Process for the preparation of lifepo4-carbon composites |
| US9209461B2 (en) | 2009-06-24 | 2015-12-08 | Basf Se | Process for the preparation of LiFePO4-carbon composites |
| JP2016052996A (ja) * | 2009-08-07 | 2016-04-14 | 株式会社半導体エネルギー研究所 | リン酸遷移金属リチウムの作製方法 |
| US9809456B2 (en) | 2009-08-07 | 2017-11-07 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method for positive electrode active material |
| CN104402059A (zh) * | 2014-11-13 | 2015-03-11 | 沈阳化工大学 | 一种微波烧结合成二元金属复合氧化物的方法 |
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