CN113860281A - 一种以聚合硫酸铁为铁源制备锂离子电池正极材料磷酸铁锂的方法 - Google Patents
一种以聚合硫酸铁为铁源制备锂离子电池正极材料磷酸铁锂的方法 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 title claims abstract description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 8
- 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 8
- 239000007774 positive electrode material Substances 0.000 title description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910012453 Li3Fe2(PO4)3 Inorganic materials 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 6
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012153 distilled water Substances 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
- 239000000463 material Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract 1
- 159000000002 lithium salts Chemical class 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000011888 foil Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 229910012437 Li3Fe2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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Abstract
本发明公开了一种以聚合硫酸铁为铁源制备锂离子电池正极材料磷酸铁锂的方法。先将廉价的聚合硫酸铁与磷源化合物溶解于水中,然后用氨水调节混合溶液的pH值,形成悬浮液,然后通过洗涤、抽滤得到无定形磷酸铁,再将无定形磷酸铁与锂盐、磷源化合混合均匀,并通过空气气氛条件下的高温固相反应制得Li3Fe2(PO4)3。本发明制备方法无需惰性气体或氧气,工艺简单、易操作、能耗低、生产成本低,所制备的锂离子电池正极材料Li3Fe2(PO4)3材料具有优异的电化学性能。
Description
技术领域
本发明属于新能源材料技术领域,特别涉及一种以聚合硫酸铁为铁源制备锂离子电池正极材料磷酸铁锂(Li3Fe2(PO4)3)的方法。
背景技术
传统的化石燃料等一次性能源储量有限,且使用过程中易带来环境污染等一系列的问题,已难以满足现代文明社会可持续发展的需求,因此,发展新能源及节能技术,已成为世界各国的发展战略。而新能源技术的发展离不开高效的储能技术,化学电源作为一种高效、稳定、低成本的储能技术,在储能应用领域中应用广泛并具有重要的地位。
近年来,随着化学电源应用领域不断拓宽,在化学电源中具有主导地位的锂离子电池因其具有电压高、循环寿命长、安全性好、自放电小等优点,成为化学电源储能技术的研究重点。而成本低、循环性能良好的锂离子电池成为对电池能量密度要求不高的储能电站的优选储能电源。正极材料是电池的关键材料之一,对电池的电化学性能起着决定性作用。常用商品化磷酸亚铁锂正极材料(LiFePO4)由于其循环性能优异,在化学电源领域应用比较广泛,但由于其在实际生产过程中需要惰性气氛且材料性能一致不容易控制,导致LiFePO4的生产成本及技术门槛仍然偏高。而另一种聚磷酸铁盐正极材料Li3Fe2(PO4)3由于其结构稳定、循环性能优异,且在生产过程无需惰性气氛,制备过程简单、易控制,因而成本比LiFePO4更低,成为储能电站应用领域潜在的重点材料。
本发明针对目前对Li3Fe2(PO4)3研究较少的现状,开发一种制备Li3Fe2(PO4)3的新技术,以廉价的聚合硫酸铁为铁源,通过无需保护气体的固相烧结法制备锂离子电池正极材料Li3Fe2(PO4)3。本发明可显著削减产能过剩的聚合硫酸铁的堆积,对Li3Fe2(PO4)3电池的发展和产能过剩材料的处理均具有较重要的意义。
发明内容
本发明的目的在于提供一种以聚合硫酸铁为铁源制备锂离子电池正极材料Li3Fe2(PO4)3的方法,通过空气气氛条件下的高温烧结得到生长均匀的晶体。
具体步骤为:
(1)按摩尔比Fe∶P=1∶(1+x)(其中0≤x≤0.2)称量聚合硫酸铁、磷源化合物,溶于蒸馏水并形成澄清溶液,然后用分析纯氨水调节溶液pH值为1~3,并将溶液在60~80℃条件下搅拌1~4小时,得到悬浊液。
(2)将步骤(1)得到的悬浊液反复洗涤、抽滤各3次,得到产物为无定形磷酸铁的滤渣,并将滤渣烘干。
(3)按摩尔比Li∶Fe∶P=3~3.05∶2∶3称量烘干后的滤渣、锂源化合物和磷源化合物,并混合均匀,然后将混合物置于马弗炉中,以2~15℃/min的升温速率升至800~950℃,并保温10~20小时,冷却后得到目标产物Li3Fe2(PO4)3。
所述磷源化合物为磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸锂、磷酸二氢锂和磷酸氢二锂中的一种或多种。
所述锂源化合物为氢氧化锂、碳酸锂、醋酸锂、磷酸锂、磷酸二氢锂和磷酸氢二锂中的一种或多种。
所述以正极材料Li3Fe2(PO4)3组装成的锂离子电池由锂离子电池正极片、负极片、隔膜、电解液组装而成,其中正极片由锂离子电池正极材料与导电剂和粘结剂混合后制成,负极片为金属锂,隔膜为多孔聚丙乙烯膜,电解液为1M的LiPF6电解质溶于有机混合溶剂EC/DMC(体积比为1∶1)形成的溶液。
本发明先将聚合硫酸铁、磷源化合物在去离子水中溶解、混合均匀,在适宜的温度、pH条件下,使反应物在水溶液中达到分子水平上的均匀混合,获得颗粒尺寸较小的无定形磷酸铁前驱体;然后将纳米无定形磷酸铁前驱体与锂源化合物、磷源化合物混合均匀,并通过温度较低的空气气氛条件下的固相烧结,实现制备纳米Li3Fe2(PO4)3晶体的目标,从而获得电化学性能优良的Li3Fe2(PO4)3材料。
本发明制备方法无需惰性气体或氧气,工艺简单、易操作、能耗低、生产成本低,所制备的锂离子电池正极材料Li3Fe2(PO4)3材料具有优异的电化学性能。
附图说明
图1是本发明实施例1、实施例2、实施例3制备的Li3Fe2(PO4)3的X-射线衍射图。
图2是本发明实施例1制备的Li3Fe2(PO4)3扫描电镜图。
图3是本发明实施例1制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的首次充放电曲线。
图4是本发明实施例1制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的循环性能图。
图5是本发明实施例2制备的Li3Fe2(PO4)3扫描电镜图。
图6是本发明实施例2制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的首次充放电曲线。
图7是本发明实施例2制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的循环性能图。
图8是本发明实施例3制备的Li3Fe2(PO4)3扫描电镜图。
图9是本发明实施例3制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的首次充放电曲线。
图10是本发明实施例3制备的Li3Fe2(PO4)3作为锂离子电池正极材料在1.5~4.2V的电压范围内以及电流密度为0.1C条件下的循环性能图。
具体实施方式
下面对本发明实施案例作进一步说明。
实施例1:
(1)称量0.0375mol聚合硫酸铁、0.0825mol磷酸二氢铵,将其全部加入到500mL的烧杯中,加入300mL去离子水,搅拌1小时,并用分析纯氨水将溶液调节pH为2,在70℃水浴条件下搅拌1小时,形成悬浮液。
(2)将步骤(1)所得悬浊液用去离子水进行反复洗涤、抽滤各3次,然后将所得滤渣烘干。
(3)将步骤(2)烘干后的滤渣与0.02813mol碳酸锂、0.01875mol磷酸二氢铵混合均匀,并放入马弗炉中,以5℃/min的升温速率加热至850℃,恒温12小时,冷却至室温,即得到目标产物Li3Fe2(PO4)3。所制得的Li3Fe2(PO4)3的X-射线衍射图见图1,图2为该材料的扫描电镜图。
将制备所得Li3Fe2(PO4)3、乙炔黑和PVDF按质量比为8∶1∶1的比例研磨混合均匀,滴加适量的NMP制成电极浆料,磁力搅拌24小时,然后再将浆料在铝箔上涂磨均匀,置于110℃真空干燥箱中充分,裁成直径为15mm的箔片,用对辊机压实,即可得锂离子电池正极片。将制备所得正极片作为正极,金属锂片为负极,多孔聚丙乙烯膜为隔膜,1M的LiPF6溶解在EC/DMC(体积比为1∶1)中的溶液作为电解液,在充满干燥的高纯氩气的手套箱(水分和氧气含量都小于0.1ppm)中组装成CR2016型纽扣电池。将扣式电池置于电池测试系统上,测试其在室温充放电性能。当电流密度为0.1C及充放电电压范围为1.5~4.2V的条件下,首次放电容量为87.6mAh·g-1,循环25次后容量仍保持为87.0mAh·g-1。图3和图4分别在该材料的首次充放电曲线及循环性能曲线。
实施例2:
(1)称量0.04mol聚合硫酸铁、0.088mol磷酸二氢铵,将其全部加入到500mL的烧杯中,加入350mL去离子水,搅拌0.5小时,并用分析纯氨水将混合溶液调节pH至2。将混合溶液在75℃恒温水浴条件下搅拌2小时,得到悬浮液。
(2)将步骤(1)所得悬浊液用去离子水进行反复洗涤、抽滤各3次,然后将所得滤渣烘干。
(3)将步骤(2)烘干后的滤渣与0.030mol碳酸锂、0.02mol磷酸铵混合均匀,并放入马弗炉中,以5℃/min的升温速率加热至850℃,恒温18小时,冷却至室温,即得到目标产物Li3Fe2(P04)3。所制得的Li3Fe2(PO4)3的X-射线衍射图见图1,图5为该材料的扫描电镜图。
将制备所得Li3Fe2(PO4)3、乙炔黑和PVDF按质量比为8∶1∶1的比例研磨混合均匀,滴加适量的NMP制成电极浆料,磁力搅拌24小时,然后再将浆料在铝箔上涂磨均匀,置于110℃真空干燥箱中充分,裁成直径为15mm的箔片,用对辊机压实,即可得锂离子电池正极片。将制备所得正极片作为正极,金属锂片为负极,多孔聚丙乙烯膜为隔膜,1M的LiPF6溶解在EC/DMC(体积比为1∶1)中的溶液作为电解液,在充满干燥的高纯氩气的手套箱(水分和氧气含量都小于0.1ppm)中组装成CR2016型纽扣电池。将扣式电池置于电池测试系统上,测试其在室温充放电性能。当电流密度为0.1C及充放电电压范围为1.5~4.2V的条件下,首次放电容量为78.5mAh·g-1,循环25次后容量仍保持为78mAh·g-1。图6和图7分别在该材料的首次充放电曲线及循环性能曲线。
实施例3:
(1)称量0.025mol聚合硫酸铁、0.050mol磷酸氢二铵,并加入到500mL的烧杯中,加入400mL去离子水,搅拌1.5小时,并用分析纯氨水将混合溶液调节pH至3。在80℃恒温水浴条件下搅拌1小时,得到悬浮液。
(2)将步骤(1)所得悬浊液用去离子水进行反复洗涤、抽滤各3次,然后将所得滤渣烘干。
(3)将步骤(2)烘干后的滤渣与0.0375mol醋酸锂、0.0125mol磷酸二氢铵混合均匀,并放入马弗炉中,以5℃/min的升温速率加热至950℃,恒温20小时,冷却至室温,即得到目标产物Li3Fe2(PO4)3。所制得的Li3Fe2(PO4)3的X-射线衍射图见图1,图8为该材料的扫描电镜图。
将制备所得Li3Fe2(PO4)3、乙炔黑和PVDF按质量比为8∶1∶1的比例研磨混合均匀,滴加适量的NMP制成电极浆料,磁力搅拌24小时,然后再将浆料在铝箔上涂磨均匀,置于110℃真空干燥箱中充分,裁成直径为15mm的箔片,用对辊机压实,即可得锂离子电池正极片。将制备所得正极片作为正极,金属锂片为负极,多孔聚丙乙烯膜为隔膜,1M的LiPF6溶解在EC/DMC(体积比为1∶1)中的溶液作为电解液,在充满干燥的高纯氩气的手套箱(水分和氧气含量都小于0.1ppm)中组装成CR2016型纽扣电池。将扣式电池置于电池测试系统上,测试其在室温充放电性能。当电流密度为0.1C及充放电电压范围为1.5~4.2V的条件下,首次放电容量为60.6mAh·g-1,循环25次后容量仍保持为59.3mAh·g-1。图9和图10分别在该材料的首次充放电曲线及循环性能曲线。
本发明的实施方案较多,在此不一一枚举,在不背离本发明的精神及其实质的情况下,熟悉本领域的技术人员可根据本发明做出适当的调整,但这些相应的调整都应属于本发明所附的权利要求的保护范围。
Claims (1)
1.一种以聚合硫酸铁为铁源制备锂离子电池正极材料磷酸铁锂的方法,其特征在于磷酸铁锂分子式为Li3Fe2(PO4)3,其制备方法具体步骤为:
(1)按摩尔比Fe:P =1:(1+x),其中0≤x≤0.2,称量聚合硫酸铁、磷源化合物,溶于蒸馏水并形成澄清溶液,然后用分析纯氨水调节溶液pH值为1~3,并将溶液在60~80℃条件下搅拌1~4小时,得到悬浊液;
(2)将步骤(1)得到的悬浊液反复洗涤、抽滤各3次,得到产物为无定形磷酸铁的滤渣,并将滤渣烘干;
(3)按摩尔比Li:Fe:P=3~3.05:2:3称量烘干后的滤渣、锂源化合物和磷源化合物,并混合均匀,然后将混合物置于马弗炉中,以2~15℃/min的升温速率升至800~950℃,并保温10~20小时,冷却后得到锂离子电池正极材料磷酸铁锂即Li3Fe2(PO4)3;
所述磷源化合物为磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸锂、磷酸二氢锂和磷酸氢二锂中的一种或多种;
所述锂源化合物为氢氧化锂、碳酸锂、醋酸锂、磷酸锂、磷酸二氢锂和磷酸氢二锂中的一种或多种。
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