CN100398434C - 一种高性能锂离子电池正极材料磷酸铁锂的制备方法 - Google Patents
一种高性能锂离子电池正极材料磷酸铁锂的制备方法 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 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 229960001708 magnesium carbonate Drugs 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229960000816 magnesium hydroxide Drugs 0.000 claims description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 2
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 229940062993 ferrous oxalate Drugs 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
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- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 229910010710 LiFePO Inorganic materials 0.000 description 7
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 2
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- 235000021317 phosphate Nutrition 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
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- 239000011718 vitamin C Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
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Abstract
一种高性能锂离子电池正极材料磷酸铁锂的制备方法，将自制包含掺杂元素的磷酸二氢锂、草酸亚铁或乙酸亚铁、导电剂或导电剂的前驱体按照一定的比例混合均匀，然后将混合物放入惰性气氛保护的微波反应炉中煅烧和热处理，最后冷却至室温，便制得锂离子电池正极材料磷酸铁锂。本发明方法避免了氨气、一氧化碳等污染性气体产生，有利环境保护，工艺简单易行，适宜于工业化生产，而且所制备的磷酸铁锂电化学性能优良。
Description
技术领域
本发明涉及一种电池材料，具体涉及一种高性能锂离子电池正极材料磷酸铁锂的制备方法。
背景技术
自1997年Goodenough研究小组报导LiFePO4具有脱锂嵌锂的功能以来，橄榄石结构的磷酸盐材料LiMPO4(M＝Fe2+、Co2+、Ni2+、Mn2+)因为其具有非常稳定的热力学特性而备受关注。其中LiFePO4具有原料来源广泛、价格低廉、作为锂离子电池正极材料高温性能卓越而被认为是一种较为理想的锂离子二次动力电池正极材料。
目前合成LiFePO4的方法主要有高温固相法、水热法、溶胶-凝胶法、液相氧化还原法、固相微波法。
被广大科研工作者所采用的高温固相法是将二价铁的草酸盐或乙酸盐，与磷酸氢铵和锂盐混合，然后在惰性气氛氩气或氮气保护下经过高温煅烧获得产品。这种方法烧结过程中会产生氨气、水和二氧化碳，它们在炉膛内经过冷却的过程中会产生碳酸氢铵晶体颗粒而造成产品的污染，此外氨气的产生不利于环保，进一步增加尾气处理设备。
水热法是以可溶性亚铁盐、锂盐和磷酸为原料在水热条件下直接合成LiFePO4，由于氧气在水热体系中的溶解度很小，水热体系为LiFePO4的合成提供了一个优良的惰性环境。因此水热合成不再需要惰性气体保护Yang等[YangS，Song Y，Zavalij PY，et al.Reactivity，Stability and electrochemicalbehavior of lithium iron phosphates[J]，Electrochem Comm，2002，4：239-244.]以可溶性的二价铁盐、LiOH和H3PO4为原料在120℃下采用水热法短时间(5h)内合成了LiFePO4。XRD分析和氧化-还原滴定结果表明所合成的材料为单一的LiFePO4相。虽然水热法具有物相均一、粉体粒径小、过程简单等优点。但只限于少量的粉体制备，若要扩大其制备量，却受到诸多限制，特别是大型的耐高温高压反应器的设计制造难度大，造价也高。
用溶胶-凝胶法合成磷酸铁锂的工艺首先是以铁的醇盐、锂盐和磷酸盐为原料，以有机化合物为螯合物、醇作为溶剂，制备均质的溶胶凝胶，经干燥后，于300～800℃煅烧数小时，便可得到磷酸铁锂粉末。Sol-gel法主要特征有：前驱体溶液化学均匀性好(可达分子级水平)、凝胶热处理温度低、粉体颗粒粒径小且分布窄、粉体烧结性能好、反应过程易于控制、设备简单。但干燥收缩大、工业化生产难度较大、合成周期较长。此外金属醇盐价格昂贵，且醇盐的常用溶剂通常有毒。
Pier Paolo等人[Pier Paolo etc.Synthetic route for preparingLiFePO4 with enhanced electrochemical performance[J].Journal of theElectrochemical Society，2002，149(7)A886-890]先用H2O2氧化Fe(II)的化合物制得FePO4，然后再用LiI还原制备LiFePO4，经过热处理制得磷酸铁锂晶体。F.Croce等人[F.Crose，Epifanio A D，Hassoun J，et al.A novelconcept for the synthesis of an improved LiFePO4 lithium battery cathode[J].Electrochemical and solide-states Letters，2002，5(3)：47-50]用维生素C酸还原Fe(III)制得磷酸铁锂。在这些制备方法中用了H2O2、LiI、维生素C酸等试剂，从而增加了产品的成本和工艺的复杂性，因此不适合大工业生产。
Masashi Higuchia等人[Masashi Higuchi，Keiichi Katayama，YasuoAzuma，etc.Synthesis of LiFePO4 cathode material by microwaveprocessing.Journal of Power Sources，2003，119-121：258-261]用以碳酸锂、草酸亚铁和磷酸二氢铵为原料通过微波合成的方法快速容易地制备了电化学性能良好的磷酸铁锂，通过此方法合成的活性物质，在60℃下，首次放电容量达到125mAh/g。他所使用的原料在微波反应过程中仍然不可避免地产生氨气而不利于环保或者通过处理尾气而增加工艺的复杂性。
发明内容
本发明所要解决的技术问题是：针对上述现有技术的不足，而提供一种全新环保高效的锂离子电池正极材料磷酸铁锂的制备方法，整个工艺过程避免氨气、一氧化碳等污染气体产生，有利于环境保护，工艺简单易行，反应时间短，容易控制，适宜于工业化生产，而且所制备的磷酸铁锂电化学性能优良。
本发明采用的技术方案是：这种高性能锂离子电池正极材料磷酸铁锂的制备方法是：将自制包含掺杂元素的磷酸二氢锂、草酸亚铁或乙酸亚铁、导电剂或导电剂的前驱体按照一定的比例混合均匀，然后将混合物放入惰性气氛保护的微波反应炉中，于400℃--900℃煅烧和热处理10-60min，最后冷却至室温，便得到锂离子电池正极材料磷酸铁锂。
上述组份的配比为：自制包含掺杂元素的磷酸二氢锂与草酸亚铁或乙酸亚铁的摩尔比为0.98-1.05∶1，包含掺杂元素的磷酸二氢锂与导电剂或导电剂前驱体的重量比为1∶0.06-0.14，或者：导电剂或导电剂前驱体的加入量为磷酸铁锂生成量的5-25％。
上述包含掺杂元素的磷酸二氢锂的制备方法为：将单水氢氧化锂或碳酸锂或乙酸锂和掺杂元素的化合物置于球磨机中，加入适量的水进行球磨制成锂盐料浆，固液的质量比为1∶1-5，然后控制流量将锂盐料浆和浓度为0.1-5.0mol/L的磷酸溶液一起并流加入到反应槽中，边反应边搅拌，溢流出来的溶液经过浓缩结晶便制得掺杂的磷酸二氢锂，其中所用原料的摩尔比为：单水氢氧化锂或乙酸锂或碳酸锂∶磷酸∶掺杂元素的化合物＝0.475-1.05∶1∶0.005-0.1；其中单水氢氧化锂或乙酸锂∶磷酸∶掺杂元素的化合物＝0.95-1.05∶1∶0.005-0.1，碳酸锂∶磷酸∶掺杂元素的化合物＝0.475-0.525∶1∶0.005-0.1。
上述掺杂元素的化合物选择碳酸镁、乙酸镁、氢氧化镁、草酸镁、氢氧化铝、二氧化锆、二氧化钛中的一种或几种，其用量与磷酸的摩尔比为0.005-0.1∶1。
上述导电剂或导电剂前驱体选择乙炔黑、鳞片石墨、蔗糖、葡萄糖、聚乙烯醇中的一种或几种。
本发明的锂离子电池正极材料磷酸铁锂的制备方法具有以下几个显著特点：
(1)通过液相法制备掺杂的磷酸二氢锂，将磷元素、锂元素和掺杂元素组成一种化合物，而且在高温煅烧的过程中避免了传统高温固相法或微波固相法中使用磷酸二氢铵或磷酸一氢铵为原料而产生氨气不利于工作环境问题。
(2)本发明将微波合成技术应用于磷酸铁锂生产，因而具有反应时间短，过程容易控制，制备的磷酸铁锂产品具有纯度高，电化学性能优良的特点。应用本发明所制备的磷酸铁锂正极材料与锂片组成模拟电池，以0.2C倍率充放电可逆比容量达到162mAh/g，以2C倍率充放电比容量达到140mAh/g，而且表现出优良的循环性能。
本发明合成磷酸铁锂方法具有工艺简单、反应时间短、所制备的磷酸铁锂电化学性能优良的特点，而且整个过程中没有氨气、一氧化碳等污染性气体产生，适合于工业化生产。
附图说明
图1为本发明实施例1所制备的含Mg2+的磷酸二氢锂XRD图
图2为本发明实施例4所制备的掺Zr4+的磷酸铁锂的XRD图
图3为本发明实施例1、2、3、4、5所制备的掺Mg2+、Al3+、Ti4+、Zr4+、Nb5+的磷酸铁锂的首次充电曲线图
图4为本发明实施例4所制备的分别掺杂Zr4+的磷酸铁锂的循环性能图
具体实施方式
实施例1
将含LiOH·H2O 4.11克或Li2CO3 3.69克或乙酸锂6.59克和Mg(OH)20.0583克或乙酸镁0.142克或碳酸镁0.084克或MgC2O4·2H2O 0.148克的10克料浆注入含32.67克磷酸溶液(含磷酸9.8克，浓度30％)的反应槽中，反应1-10h后浓缩结晶制得含有Mg2+的磷酸二氢锂晶体。所制备的含有Mg2+的磷酸二氢锂的XRD图，如附图1。将含有Mg2+的磷酸二氢锂10.17克与二水合草酸亚铁18.02克或乙酸亚铁17.40克，同时加入蔗糖15克，一起进行球磨混合，然后放入微波炉中，在充满Ar2或N2的惰性气氛保护下进行微波合成反应，反应条件为800℃，反应时间为15分钟，然后待微波炉冷却至室温将样品取出，制得含有掺杂金属离子Mg2+的LiFePO4/C复合材料。
实施例2
将含LiOH·H2O 4.11克或Li2CO3 3.69克或乙酸锂6.59克和A1(OH)30.0781克的10克料浆注入含32.67克磷酸溶液含磷酸9.8克，浓度30％的反应槽中，反应1-10h后浓缩结晶制得含有Al3+的磷酸二氢锂晶体。将含有Al3+的磷酸二氢锂10.24克与二水合草酸亚铁18.02克或乙酸亚铁17.40克，同时加入蔗糖15克，一起进行球磨混合，然后放入微波炉中，在充满Ar2或N2的惰性气氛保护下进行微波合成反应，反应条件为800℃，反应时间为15分钟，然后待微波炉冷却至室温将样品取出，制得含有掺杂Al3+金属离子的LiFePO4/C复合材料。
实施例3
将含LiOH·H2O 4.11克或Li2CO3 3.69克或乙酸锂6.59克和TiO20.0799克的10克料浆注入含32.67克磷酸溶液含磷酸9.8克，浓度30％的反应槽中，反应1-10h后浓缩结晶制得含有Ti4+的磷酸二氢锂晶体。将含有Ti4+的磷酸二氢锂10.31克与二水合草酸亚铁18.02克或乙酸亚铁17.40克，同时加入蔗糖15克，一起进行球磨混合，然后放入微波炉中，在充满Ar2或N2的惰性气氛保护下进行微波合成反应，反应条件为800℃，反应时间为15分钟，然后待微波炉冷却至室温将样品取出，制得含有掺杂Ti4+金属离子的LiFePO4/C复合材料。
实施例4
将含LiOH·H2O 4.11克或Li2CO3 3.69克或乙酸锂6.59克和ZrO2 0.123克的10克料浆注入含32.67克磷酸溶液含磷酸9.8克，浓度30％的反应槽中，反应1-10h后浓缩结晶制得含有Zr4+的磷酸二氢锂晶体。将含有Zr4+的磷酸二氢锂10.35克，与二水合草酸亚铁18.02克或乙酸亚铁17.40克，同时加入蔗糖15克，一起进行球磨混合，然后放入微波炉中，在充满Ar2或N2的惰性气氛保护下进行微波合成反应，反应条件为800℃，反应时间为15分钟，然后待微波炉冷却至室温将样品取出，制得含有掺杂Zr4+金属离子的LiFePO4/C复合材料。
实施例5
将含LiOH·H2O 4.11克或Li2CO3 3.69克或乙酸锂6.59克和Nb2O5 0.133克的10克料浆注入含32.67克磷酸溶液含磷酸9.8克，浓度30％的反应槽中，反应1-10h后浓缩结晶制得含有Nb5+的磷酸二氢锂晶体。将含有Nb5+的磷酸二氢锂10.35克与二水合草酸亚铁18.02克或乙酸亚铁17.40克，同时加入蔗糖15克，一起进行球磨混合，然后放入微波炉中，在充满Ar2或N2的惰性气氛保护下进行微波合成反应，反应条件为800℃，反应时间为15分钟，然后待微波炉冷却至室温将样品取出，制得含有掺杂Nb5+金属离子的LiFePO4/C复合材料。
Claims (4)
1.一种高性能锂离子电池正极材料磷酸铁锂的制备方法，其特征在于将自制包含掺杂元素的磷酸二氢锂、草酸亚铁或乙酸亚铁、导电剂或导电剂的前驱体按照一定的比例混合均匀，然后将混合物放入惰性气氛保护的微波反应炉中，于400℃-900℃煅烧和热处理10-60min，最后冷却至室温，便得到锂离子电池正极材料磷酸铁锂，包含掺杂元素的磷酸二氢锂的制备方法为：将单水氢氧化锂或碳酸锂或乙酸锂和掺杂元素的化合物置于球磨机中，加入适量的水进行球磨制成锂盐料浆，固液的质量比为1∶1-5，然后控制流量将锂盐料浆和浓度为0.1-5.0mol/L的磷酸溶液一起并流加入到反应槽中，边反应边搅拌，溢流出来的溶液经过浓缩结晶便制得掺杂的磷酸二氢锂，其中所用原料的摩尔比为：单水氢氧化锂或乙酸锂∶磷酸∶掺杂元素的化合物＝0.95-1.05∶1∶0.005-0.1，或碳酸锂∶磷酸∶掺杂元素的化合物＝0.475-0.525∶1∶0.005-0.1。
2.根据权利要求1所述的高性能锂离子电池正极材料磷酸铁锂的制备方法，其特征在于组份的配比为：自制包含掺杂元素的磷酸二氢锂与草酸亚铁或乙酸亚铁的摩尔比为0.98-1.05∶1，包含掺杂元素的磷酸二氢锂与导电剂或导电剂前驱体的重量比为1∶0.06-0.14；或者：导电剂或导电剂前驱体的加入量为磷酸铁锂生成量的5-25％。
3.根据权利要求1所述的高性能锂离子电池正极材料磷酸铁锂的制备方法，
其特征在于掺杂元素的化合物选择碳酸镁、乙酸镁、氢氧化镁、草酸镁、氢氧化铝、二氧化锆、二氧化钛中的一种或几种，其用量与磷酸的摩尔比为0.005-0.1∶1。
4.根据权利要求1所述的高性能锂离子电池正极材料磷酸铁锂的制备方法，其特征在于导电剂或导电剂前驱体选择乙炔黑、鳞片石墨、蔗糖、葡萄糖、聚乙烯醇中的一种或几种。
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