CN102306791B - 一种碳包覆非化学计量比氧化锂铁磷材料的制备方法 - Google Patents
一种碳包覆非化学计量比氧化锂铁磷材料的制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000005253 cladding Methods 0.000 title claims abstract description 22
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 230000002045 lasting effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- -1 lithium halide Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001694 spray drying Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 4
- 239000004005 microsphere Substances 0.000 abstract 3
- 230000002411 adverse Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011164 primary particle Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
发明公开了一种碳包覆非化学计量比氧化锂铁磷材料的制备方法。其化学组成为LiFexPO4，将铁源化合物FexPO4•nH2O（0.96≤x＜1）和碳源化合物混合，喷雾干燥造粒，预烧结得到具有一定粒度分布的一次碳包覆FexPO4微球，将一次碳包覆的FexPO4微球和锂源化合物以及碳源化合物混合，喷雾干燥造粒，二次烧结得到由纳米级LiFexPO4一次粒子组成的二次碳包覆LiFexPO4微球。此方法工艺简单可控，易操作，可以实现工业化批量生产。制备得到的LiFexPO4材料碳包覆效果好，既保持纳米尺寸材料所特有的优异的倍率性能和循环性能，又具有微米尺寸材料所具有的振实密度高、加工性能优良的特性。另外，本合成方法采用水作为溶剂，杜绝了使用有机溶剂存在的安全隐患、回收及成本等不利于生产的因素。
Description
技术领域
本发明涉及一种二次碳包覆非化学计量比氧化锂铁磷材料及其制备方法，特别涉及锂离子二次电池正极材料的制备方法，属能源材料与技术领域。
技术背景
锂离子电池是一种绿色高能电池，具有电压高、能量密度大、循环性能好、工作温度范围宽等优点，在化石能源日益昂贵，环境污染严重的形势下，锂离子电池有着重要的研究价值和良好的应用前景。小型锂离子电池目前已被广泛应用于便携式电动工具、笔记本电脑、移动电话、电子仪表等设备中。大型锂离子电池在电动车和混合动力车中的应用近来也广受关注。
LiCoO2, LiNiO2,
LiMn2O4和LiNi1-xCoxO2等是锂离子电池常用的正极材料。其中LiCoO2的综合性能较好，但价格昂贵且毒性较大；LiNiO2难以合成；LiMn2O4的成本低，安全性好，但循环性能较差。橄榄石结构的LiFePO4以其良好的电化学性能，充放电平台十分平稳，充放电过程中结构稳定，无毒、无污染、安全性能好，原材料来源广泛等优点成为国内外的研究热点。但是LiFePO4材料低的导电性和振实密度、较差的高倍率充放电性能制约了其实际应用。
针对LiFePO4材料导电性能差有多种改善方法，其中碳包覆是普遍采用而且最为有效的提高LiFePO4材料表面电导率的方法之一。另外将材料粒径缩小为纳米级能缩短锂离子在LiFePO4晶粒中的扩散路径，可以解决电池的大电流放电性能差的问题。但低密度的疏松的导电碳包覆层的引入以及材料粒子的纳米化，使得材料的振实密度很低，显示出很差的加工性能，严重限制了LiFePO4材料的商业化应用。
发明内容
本发明的目的是提供一种高倍率放电性能好，加工性能优良的二次碳包覆非化学计量比氧化锂铁磷材料及其制备方法。所制备的材料既具有纳米材料所特有的优异的倍率性能和循环性能，又有微米尺寸材料的加工性能优良和极片填充密度大的优点，并且通过二次导电碳包覆改善材料的导电性能。
本发明首先引入一种非化学计量比氧化锂铁磷材料，其化学组成为LiFexPO4（0.96≤x＜1）。当采用锂、铁、磷元素比为1.0-1.1:1:1的磷酸铁锂材料制作电芯进行长时间循环测试时，电池隔膜上会出现很多小黑点，EDS（图一）分析黑点处的铁含量比别处高很多，排除了电芯测试过程中引入铁杂质的可能性之后，只能认为是锂、铁、磷元素比为1:1:1的磷酸铁锂材料制作电芯进行长时间循环测试时会有微量铁析出。由于析出铁可能造成短路，本发明采用锂、铁、磷元素比为1.0-1.1:0.96-1:1的氧化锂铁磷材料作为电池的正极材料。
本发明的技术方案是：
一种碳包覆非化学计量比氧化锂铁磷材料, 其化学组成为LiFexPO4，要求0.96≤x＜1。
所述的碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于，具体步骤如下：
（1）将FexPO4或者水合FexPO4（FexPO4•nH2O）与碳源按照比例分散于去离子水中，所得分散液置于搅拌磨中持续搅拌1.5-2.5小时，制成平均粒径小于2微米的浆料；
（2）将步骤（1）中得到的浆料进行喷雾干燥，然后在惰性气体保护下高温热处理一段时间制成具有一定粒度分布的碳包覆FexPO4微球，步骤（1）碳源的添加量使得产物中含碳量为1.0-2.0 wt%；
（3）将步骤（2）中得到的碳包覆FexPO4微球与锂源、碳源按照一定比例混合，搅拌，调节固含量后进行二次喷雾干燥，得到前驱体粉末，其中，锂元素与
铁元素的摩尔比为（1.0-1.1）：（0.96-1）；
（4）将步骤（3）中得到的前驱体粉末在惰性气体保护下高温热处理得到二次碳包覆的LiFexPO4微球，碳源的添加量为使最终的成品二次碳包覆的LiFexPO4微球中碳含量为2.0-5.0 wt%。
所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于，所述的锂源选自硝酸锂、氢氧化锂、碳酸锂、氯化锂、醋酸锂、卤化锂中的一种或者多种混合。
所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：步骤（2）中高温热处理的温度为400-600℃，热处理时间为2-4小时。
所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：步骤（4）中高温热处理的具体方法为：首先在400-600 ℃恒温烧结2小时，然后以每分钟2-10 ℃的速率升温至650-750℃，并在650-750
℃恒温烧结10-15小时。
所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：所合成的FexPO4/C微球的平均粒径小于20微米。
所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：所合成的LiFexPO4/C微球的平均粒径为5-25微米。
本发明的有益效果是：
本发明通过喷雾干燥造粒获得微米级球状粒子，通过两次碳包覆法使得添加的碳源分解得到的碳层完整致密地包覆LiFexPO4颗粒表面。因此得到的LiFexPO4材料碳包覆效果及电导率优异，并且既保持纳米尺寸材料所特有的优异的倍率性能和循环性能，又具有微米尺寸材料所具有的振实密度高、加工性能优良的特性。本发明提供的制备方法工艺简单可控，易操作，可以实现工业化批量生产。另外，本合成方法采用水作为溶剂，杜绝了使用有机溶剂存在的安全隐患、回收及成本等不利于生产的因素。
附图说明
图1是由Li、Fe、P化学计量比为1:1:1的材料做成电池进行长期充分循环试验后电池隔膜上黑点的X射线能量散射谱（EDS），插图是隔膜无黑点区域的X射线能量散射谱。
图2是实施例一制得的二次碳包覆LiFe0.98PO4微球的扫描电子显微（SEM）照片和透射电子显微（TEM）照片；
图3是实施例一制得二次碳包覆LiFe0.98PO4微球的X射线衍射（XRD）谱图；
图4是实施例一制得的二次碳包覆LiFe0.98PO4微球的粒度分布曲线；
图5是一次碳包覆LiFe0.98PO4微球与二次碳包覆LiFe0.98PO4微球的充放电曲线；
图6是实施例一制得的二次碳包覆LiFe0.98PO4微球不同倍率的放电曲线；
图7是由实施例一制得二次碳包覆LiFe0.98PO4微球做成的10Ah电芯的循环性能曲线。
具体实施方式
下面是本发明非限定制备实施例，通过这些实施例对本发明作进一步描述。
实施例1
1795.2克Fe0.98PO4•2H2O与碳源以摩尔比1:0.08的比例分散于去离子水中。所得分散液置于10升搅拌磨中持续搅拌2小时，制成平均粒径小于2微米的浆料。调整所得浆料固含量为20-50 %后进行喷雾干燥，并在惰性气体保护下600 ℃高温热处理2小时制成碳包覆Fe0.98PO4微球。产物平均粒径为20微米，比表面积为10-15微米，含碳量为1.0-2.0 wt%。将制得的Fe0.98PO4/C微球与Li2CO3、碳源按照一定比例混合，其中，Li2CO3与Fe0.98PO4/C微球的摩尔比为1.02，碳源的添加量为使最终的成品LiFe0.98PO4/C微球中碳含量为2.0 wt%。混合物经搅拌和调节固含量步骤后进行第二次喷雾干燥得到前驱体粉末。将所得前驱体粉末在惰性气体保护下400 ℃恒温煅烧2小时，之后以每分钟10 ℃的速率升温至700 ℃，并在700 ℃保温12小时得到二次碳包覆的LiFe0.98PO4微球。产物平均粒径为5-25微米，比表面积为20-30微米。
所得产物的形貌如图2所示，二次碳包覆LiFe0.98PO4微球是由一次LiFe0.98PO4纳米粒子组成的微米球体，表面碳包覆均匀完整，且充放电性能比一次碳包覆LiFe0.98PO4微球更为优异（图5）。
XRD证实所得产物为橄榄石结构，磷酸铁锂相纯度很高（图3），振实密度为1.2 g•cm− 3, 比表面积为21.53
m2•g-1，平均粒径为24.0 μm（图4）。电化学测试结果显示其0.2 C条件下放电比容量为152.6 mAh•g-1，并且可以在10 C大电流条件下放电（图6）。将所得二次碳包覆LiFe0.98PO4微球做成10 Ah电芯进行循环测试（图7），测试结果证明LiFe0.98PO4微球具有很好的循环稳定性。
实施例2
1795.2克Fe0.96PO4•2H2O与碳源以摩尔比1:0.095的比例分散于去离子水中。所得分散液置于10升搅拌磨中持续搅拌2小时，制成平均粒径小于2微米的浆料。调整所得浆料固含量为20-50 %后进行喷雾干燥，并在惰性气体保护下400℃高温热处理4小时制成碳包覆Fe0.96PO4微球。产物平均粒径为20微米，比表面积为10-15微米，含碳量为1.0-2.0 wt%。将制得的Fe0.96PO4/C微球与Li2CO3、碳源按照一定比例混合，其中，Li2CO3与Fe0.96PO4/C微球的摩尔比为1.0，碳源的添加量为使最终的成品LiFe0.96PO4/C微球中碳含量为2.5 wt%。混合物经搅拌和调节固含量步骤后进行第二次喷雾干燥得到前驱体粉末。将所得前驱体粉末在惰性气体保护下400 ◦C恒温煅烧2小时，之后以每分钟10 ◦C的速率升温至700 ◦C，并在700
◦C保温12小时得到二次碳包覆的LiFe0.96PO4微球。产物平均粒径为5-25微米，比表面积为20-30微米。
实施例3
1795.2克Fe0.98PO4•4H2O与碳源以摩尔比1:0.15的比例分散于去离子水中。所得分散液置于10升搅拌磨中持续搅拌2小时，制成平均粒径小于2微米的浆料。调整所得浆料固含量为20-50 %后进行喷雾干燥，并在惰性气体保护下500 ◦C高温热处理3小时制成碳包覆Fe0.98PO4微球。产物平均粒径为20微米，比表面积为10-15微米，含碳量为1.0-2.0 wt%。将制得的Fe0.98PO4/C微球与LiOH、碳源按照一定比例混合，其中，LiOH与Fe0.98PO4/C微球的摩尔比为1.07，碳源的添加量为使最终的成品LiFe0.98PO4/C微球中碳含量为5.0 wt%。混合物经搅拌和调节固含量步骤后进行第二次喷雾干燥得到前驱体粉末。将所得前驱体粉末在惰性气体保护下400 ◦C恒温煅烧2小时，之后以每分钟10 ◦C的速率升温至700 ◦C，并在700
◦C保温12小时得到二次碳包覆的LiFe0.98PO4微球。产物平均粒径为5-25微米，比表面积为20-30微米。
实施例4
1795.2克Fe0.98PO4•2H2O与碳源以摩尔比1:0.125的比例分散于去离子水中。所得分散液置于10升搅拌磨中持续搅拌2小时，制成平均粒径小于2微米的浆料。调整所得浆料固含量为20-50 %后进行喷雾干燥，并在惰性气体保护下400 ◦C高温热处理4小时制成碳包覆Fe0.98PO4微球。产物平均粒径为20微米，比表面积为10-15微米，含碳量为1.0-2.0 wt%。将制得的Fe0.98PO4/C微球与LiNO3、碳源按照一定比例混合，其中，LiNO3与Fe0.98PO4/C微球的摩尔比为1.05，碳源的添加量为使最终的成品LiFe0.98PO4/C微球中碳含量为3.0 wt%。混合物经搅拌和调节固含量步骤后进行第二次喷雾干燥得到前驱体粉末。将所得前驱体粉末在惰性气体保护下600 ◦C恒温煅烧2小时，之后以每分钟2 ◦C的速率升温至750 ◦C，并在750
◦C保温10小时得到二次碳包覆的LiFe0.98PO4微球。产物平均粒径为5-25微米，比表面积为20-30微米。
实施例5
1795.2克Fe0.96PO4•2H2O与碳源以摩尔比1:0.11的比例分散于去离子水中。所得分散液置于10升搅拌磨中持续搅拌2小时，制成平均粒径小于2微米的浆料。调整所得浆料固含量为20-50 %后进行喷雾干燥，并在惰性气体保护下600 ℃高温热处理2小时制成碳包覆Fe0.96PO4微球。产物平均粒径为20微米，比表面积为10-15微米，含碳量为1.0-2.0 wt%。将制得的Fe0.96PO4/C微球与Li2CO3、碳源按照一定比例混合，其中，Li2CO3与Fe0.96PO4/C微球的摩尔比为1.1，碳源的添加量为使最终的成品LiFe0.96PO4/C微球中碳含量为4.0
wt%。混合物经搅拌和调节固含量步骤后进行第二次喷雾干燥得到前驱体粉末。将所得前驱体粉末在惰性气体保护下500℃恒温煅烧2小时，以后以每分钟6℃的速率升温至650℃，并在650℃保温15小时得到二次碳包覆的LiFe0.96PO4微球。产物平均粒径为5-25微米，比表面积为20-30微米。
Claims (4)
1.一种碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于： 所述材料的化学组成为LiFexPO4，要求0.96≤x＜1；所述的碳包覆非化学计量比氧化锂铁磷材料的制备方法，具体步骤如下：
（1）将FexPO4或者水合FexPO4（FexPO4·nH2O）与碳源按照比例分散于去离子水中，所得分散液置于搅拌磨中持续搅拌1.5-2.5小时，制成平均粒径小于2微米的浆料；
（2）将步骤（1）中得到的浆料进行喷雾干燥，然后在惰性气体保护下高温热处理一段时间制成具有一定粒度分布的碳包覆FexPO4微球，步骤（1）碳源的添加量使得产物中含碳量为1.0-2.0 wt%，上述高温热处理的温度为400-600℃，热处理时间为2-4小时；
（3）将步骤（2）中得到的碳包覆FexPO4微球与锂源、碳源按照一定比例混合，搅拌，调节固含量后进行二次喷雾干燥，得到前驱体粉末，其中，锂元素与 铁元素的摩尔比为（1.0-1.1）：（0.96-1）；
（4）将步骤（3）中得到的前驱体粉末在惰性气体保护下高温热处理得到二次碳包覆的LiFexPO4微球，碳源的添加量为使最终的成品二次碳包覆的LiFexPO4微球中碳含量为2.0-5.0 wt%；所述高温热处理的具体方法为：首先在400-600 ℃恒温烧结2小时，然后以每分钟2-10 ℃的速率升温至650-750℃，并在650-750 ℃恒温烧结10-15小时。
2.根据权利要求1所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于，所述的锂源选自硝酸锂、氢氧化锂、碳酸锂、醋酸锂、卤化锂中的一种或者多种混合。
3.根据权利要求1所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：所合成的FexPO4/C微球的平均粒径小于20微米。
4.根据权利要求1所述碳包覆非化学计量比氧化锂铁磷材料的制备方法，其特征在于：所合成的LiFexPO4/C微球的平均粒径为5-25微米。
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Address after: 230000 Yaohai Industrial Zone, Hefei New District, Anhui, No. D weft Road, No. 7 Patentee after: Gotion High-tech Co., Ltd. Address before: 230000 Yaohai Industrial Park, Anhui, Hefei No. D weft Road, No. 7 Patentee before: Hefei Guoxuan High-Tech Power Energy Co.,Ltd. |