CN1493522A - 一种锂过渡金属氧化物的制备方法 - Google Patents
一种锂过渡金属氧化物的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 23
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 title claims description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 25
- 239000012071 phase Substances 0.000 description 24
- 238000010792 warming Methods 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 21
- 229910012820 LiCoO Inorganic materials 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000010405 anode material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910015645 LiMn Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910013733 LiCo Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
一种锂过渡金属氧化物的制备方法,涉及用作可充放电的锂或锂离子电池正极材料的制备。本发明以Li的氧化物、氢氧化物或其盐和过渡金属Co、Ni、Mn的氧化物、氢氧化物或它们的盐为主原料,以Co、Ni、Mn、Cr、Al、Mg的氧化物、氢氧化物或盐为掺杂元素,并加入一定量的熔融盐,固相混合均匀;加热至所加入的熔融盐熔点以上,恒温焙烧,然后冷却,洗去残余的盐,烘干。该方法不仅保持了固相合成法制造工艺简单的特点,而且由于在反应原料中加入熔融盐,提供液态反应环境,从而有利于离子扩散,加快反应速度,减少反应时间,节约能源。所制备的产品成分均匀,形貌规则,晶型完整,粒度分布均匀,有高比容量和优良的循环性。
Description
技术领域
本发明涉及用于可充放电的锂或锂离子二次电池正极材料的制备方法,特别涉及一种锂过渡金属氧化物的制备方法,属于高能电池技术、电化学技术或无机材料合成技术领域。
背景技术
正极材料的制备是制约可充放电锂离子电池快速发展的关键技术之一。各国都投入大量的人力、物力研制容量大、电位高、循环性好的正极材料。目前常用作锂离子电池正极材料的过渡金属氧化物有LiCoO2、LiNiO2或LiMn2O4。
目前用于工业生产的常规方法为固相合成法。高温固相合成法通常以锂的氧化物、氢氧化物或其盐与过渡金属的氧化物、氢氧化物或盐为原料,固相混合均匀后,在700~950℃高温下长时间煅烧。低温固相合成法则是将锂和过渡金属原料在不同气氛或有机溶剂中长时间研磨,然后仍需一定温度长时间加热。固相合成法工艺流程简单,但因固相反应速度慢,需长时间或反复煅烧,能源消耗大,产品形貌不规则,均匀性差,并且颗粒大,使用前需粉碎。
有人研究了如溶胶一凝胶法、共沉淀法、喷雾干燥法等湿化学合成方法制备正极材料。相对固相合成法,这些方法易得到成分均匀的产品。但湿化学方法一般流程较长,工艺复杂,操作繁琐,因而难以在工业上实施。
发明内容
本发明的目的是针对现有技术的不足,提供一种工艺简单,节约能源,生产重复性好,产品均匀性好,粒度可控的制备方法。
本发明的目的还在于可以使反应在较低温度下进行,获得均匀的纳米晶体正极材料,具有良好的大电流充放性能。
本发明的目的是通过如下技术方案实现的:一种锂过渡金属氧化物的制备方法,其特征在于该方法按如下步骤进行:
1)以Li的氧化物、氢氧化物或其盐和过渡金属Co、Ni、Mn的氧化物、氢氧化物或它们的盐为主原料,以Co、Ni、Mn、Cr、Al、Mg的氧化物、氢氧化物或盐为掺杂元素,按化学式LixM1-yAiBjO2配料,其中0.45≤x≤1.2,0≤i≤1,0≤j≤1,y=i+j,M≠A≠B,然后加入与Li的摩尔比为0.5~6的熔融盐,固相混合均匀;
2)将混合均匀的原料加热至所加入的熔融盐熔点以上至950℃,恒温焙烧0.5~24小时,然后冷却,洗去残余的盐,烘干。
本发明所述的熔融盐采用所述的熔融盐采用硝酸钾、氯化钾、氢氧化钾、硫酸氢钾、醋酸钾、醋酸锂、氢氧化锂、氯化锂、硝酸锂、碳酸锂中的至少一种。
本发明在洗去残余的盐时,可以采用水、乙腈、乙醇或正丁醇中的至少一种溶剂洗涤;其烘干温度应在50~300℃,采用常压或真空干燥。
本发明的技术特征还在于:在反应原料混合时,其中Co、Ni或Mn的化合物与掺杂元素化合物可采用共沉淀得到的混合物形式加入。
在本发明所述的方法中,按化学式LixM1-yAiBjO2配料时,当i=0,j=0,即无掺杂元素时,原料中Li与Co或Ni的摩尔比为0.95~1.15配料;Li与Mn的摩尔比为0.45~0.55配料。
本发明与现有技术相比,具有以下优点及有益效果:本发明不仅保持了固相合成法制造工艺简单的特点,而且由于在反应原料中加入了熔融盐,在熔融盐熔点以上温区反应,提供液态反应环境,从而有利于离子扩散,加快反应速度,减少反应时间,节约能源。加入熔点较低的熔融盐还可明显降低合成温度,有效控制晶粒生长;该方法所制备的产品成分均匀,形貌规则,晶型完整,粒度分布均匀,具有高比容量和优良的循环性能.。例如,按照本发明的制备方法,可以制备颗粒度为50~200nm的LiCoO2,在室温下500mA/g电流密度放电,首次可达120mAh/g,工作电位在2.7~4.3V间,循环20周后,容量衰减小于10%;1000mA/g电流密度放电,首次可达110mAh/g,工作电位在2.5~4.35V间,循环20周后,容量衰减小于15%。按照本发明的制备方法制备出的Li(CoNiMn)1/3O2粒度约为200nm,在室温下1000mA/g电流密度放电,首次可达115mAh/g,工作电位在2.5~4.35V间,循环50周后,容量衰减小于30%。
附图说明
图1:本发明制备的锂离子电池正极材料的LiCoO2的X光衍射图谱(实施例1)。
图2:本发明制备的锂离子电池正极材料的LiCoO2的SEM图(实施例1)。
图3:本发明制备的锂离子电池正极材料的Li(CoNiMn)1/3O2的SEM图(实施例2)。
图4:本发明制备的锂离子电池正极材料的LiCoO2的SEM图(实施例3)。
图5:本发明制备的锂离子电池正极材料的LiCoO2的充放电循环性能图。
具体实施方式
以下结合实施例对本发明作进一步说明,将有助于进一步了解本发明的方法及优点。但是下述实施例仅为理解本发明。
本发明采用以Li的氧化物、氢氧化物或其盐和过渡金属Co、Ni、Mn的氧化物、氢氧化物或它们的盐为主要原料,加入或不加入掺杂元素,按化学式LixM1-yAiBjO2进行配料,其中M=Co、Ni或Mn;A、B为掺杂元素,原料选自Co、Ni、Mn、Cr、Al、Mg的氧化物、氢氧化物或其盐,其中:0.45≤x≤1.2,0≤i≤1,0≤j≤1,y=i+j,M≠A≠B,然后加入与Li的摩尔比为0.5~6的熔融盐,固相混合均匀;将混合均匀的原料加热,升温速率可保持1~100℃/min,需加热至所加熔融盐熔点以上至950℃的范围,然后恒温焙烧,温度一般在400~950℃,时间为0.5~24小时;然后冷却,冷却降温速度1~200℃/min;再采用去离子水、普通水、乙腈、乙醇或正丁醇洗涤,洗去残余的盐;也可先用水洗,再用所述溶剂洗涤;然后在常压或真空干下干燥,干燥温度为50~300℃。
本发明生产出的产品,材料的晶体结构采用X射线衍射法测定,表面形貌由场发射扫描电子显微镜测定。
为了检测本发明制备的锂离子电池正极材料的性能,将其组成试验电池进行测试。正极活性材料70~90%,乙炔黑5~20%,粘结剂聚偏氟乙烯(PVDF)5~10%。对电极为金属锂片,Celgard2300为隔膜,1mol/L LiPF6 EC/DMC为电解液。试验电池在微机控制的自动充放电仪上进行充放电循环测试。
实施例1
将LiOH·H2O、CoO与KNO3按摩尔比为1∶1∶3混匀,于空气氛围中,以5℃/min速度升温至800℃,恒温焙烧1小时,然后随炉自然冷却。先用蒸馏水洗,然后用乙醇洗涤,过滤并于130℃烘干。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度为1~2μm。在2.7~4.3V间充放电,比电流密度为200mA/g,首次充电比容量为141mAh/g,放电比容量为132mAh/g,效率为93.6%,循环性能良好。
实施例2
将Co(NO3)2·6H2O、Ni(NO3)2·6H2O、MnCl2·4H2O按摩尔比为1∶1∶1配成水溶液,滴入过量KOH水溶液中,得到Co、Ni、Mn氢氧化物的混合物(CoNiMn)1/3(OH)2,将沉淀用蒸馏水洗涤至中性,过滤并烘干。
将LiOH·H2O、(CoNiMn)1/3(OH)2与KCl按摩尔比为1.1∶1∶4混匀,于空气氛围中,以10℃/min速度升温至850℃,恒温焙烧6小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,然后用乙醇洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相Li(CoNiMn)1/3O2化合物,材料的颗粒度约为200nm。在2.5~4.35V间充放电,比电流密度为1000mA/g,首次放电可达115mAh/g,循环50周后,容量衰减小于30%。
实施例3
将LiOH·H2O、CoO与KNO3按摩尔比为1.15∶1∶2混匀,于空气氛围中,以1℃/min速度升温至400℃,恒温焙烧24小时,然后以1℃/min速率降到室温。用蒸馏水洗涤,然后用正丁醇洗涤,过滤并于130℃烘干。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度为50~100nm。
实施例4
将LiOH·H2O、CoCO3与KNO3按摩尔比为1∶1∶2混匀,于空气氛围中,以2℃/min速度升温至600℃,恒温焙烧12小时,然后以2℃/min速率降到室温。先用蒸馏水洗,然后用正丁醇洗涤,过滤并于130℃烘干。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度为100~200nm。在2.7~4.3V间充放电,比电流密度为500mA/g,首次放电可达120mAh/g,循环20周后,容量衰减小于10%。在2.5~4.35V间充放电,比电流密度1000mA/g放电,首次放电可达110mAh/g,循环20周后,容量衰减小于15%。
实施例5
将LiOH·H2O、CoO、Ni2O3与KNO3按摩尔比为1.1∶0.8∶0.1∶2混匀,于空气氛围中,以5℃/min速度升温至800℃,恒温焙烧8小时,然后以50℃/min速率降到室温。先用蒸馏水洗,然后用乙醇洗涤,过滤并于200℃烘干。所得产物经XRD分析表明为纯相LiCo0.8Ni0.2O2化合物,材料的颗粒度为1~2μm。在2.7~4.3V间充放电,比电流密度为100mA/g,首次放电可达142mAh/g,循环性能良好。
实施例6
将Li2CO3、Co(OH)2与KCl按摩尔比为1∶2∶6混匀,于空气氛围中,以20℃/min速度升温至900℃,恒温焙烧1小时,然后以10℃/min速率降到室温。先用蒸馏水洗涤,然后用乙醇洗涤,过滤并于300℃烘干。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度为1~2μm。在2.7~4.3V间充放电,比电流密度为100mA/g,首次放电可达138mAh/g,循环性能良好。
实施例7
将Li2O、Co(NO3)2·6H2O与KCl按摩尔比为1∶1∶1混匀,于空气氛围中,以100℃/min速度升温至850℃,恒温焙烧8小时,然后以200℃/min速率降到室温。用蒸馏水洗涤,过滤并于50℃真空干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度为1~6μm。
实施例8
将LiOH·H2O、Ni2O3与KNO3按摩尔比为2.3∶1∶5混匀,于空气氛围中,以50℃/min速度升温至800℃,恒温焙烧8小时,然后以10℃/min速率降到室温。用蒸馏水洗涤,过滤并于120℃烘干。所得产物经XRD分析表明为纯相LiNiO2化合物,材料的颗粒度为1~2μm。
实施例9
将Li2CO3、Ni(NO3)2·6H2O与KNO3按摩尔比为0.98∶2∶4混匀,于空气氛围中,以10℃/min速度升温至700℃,恒温焙烧8小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,然后用正丁醇洗涤,过滤并于120℃烘干。所得产物经XRD分析表明为纯相LiNiO2化合物,材料的颗粒度为200~300nm。
实施例10
将LiOH·H2O、MnO2与KNO3按摩尔比为1.1∶2∶2混匀,于空气氛围中,以5℃/min速度升温至700℃,恒温焙烧10小时,然后随炉自然冷却。用蒸馏水洗涤,然后用正丁醇洗涤,过滤并于120℃烘干。所得产物经XRD分析表明为纯相LiMn2O4化合物,材料的颗粒度为0.5~1μm。
实施例11
将LiOH·H2O、MnO2、Co(NO3)2·6H2O与KNO3按摩尔比为1.02∶1.8∶0.2∶2混匀,于空气氛围中,以8℃/min速度升温至800℃,恒温焙烧6小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,过滤并于150℃烘干。所得产物经XRD分析表明为纯相LiMn1.8Co0.2O4化合物,材料的颗粒度约为1~2μm。
实施例12
将LiOH·H2O、Co(OH)2、Ni(OH)2、Al2O3与KCl按摩尔比为1.15∶0.6∶0.3∶0.05∶2混匀,于空气氛围中,以5℃/min速度升温至850℃,恒温焙烧8小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCo0.6Ni0.3Al0.1O2化合物,材料的颗粒度约为1~5μm。
实施例13
将Li2CO3、Co(NO3)2·6H2O、MgO与KNO3按摩尔比为0.55∶0.9∶0.1∶2混匀,于空气氛围中,以5℃/min速度升温至750℃,恒温焙烧4小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCo0.9Mg0.1O2化合物,材料的颗粒度约为1~2μm。
实施例14
将Li2CO3、MnO2、Ni(NO3)2·6H2O、Cr2O3与KCl按摩尔比为0.55∶1.4∶0.4∶0.1∶1混匀,于空气氛围中,以5℃/min速度升温至850℃,恒温焙烧8小时,然后以10℃/min速率降到室温。用蒸馏水洗,然后用乙腈洗,过滤并于120℃真空干燥。所得产物经XRD分析表明为纯相LiMn1.4Ni0.4Cr0.2O4化合物,材料的颗粒度约为1~5μm。
实施例15
将Li2O、CoO、Ni(NO3)2·6H2O与KNO3按摩尔比为0.55∶0.6∶0.4∶6混匀,于空气氛围中,以5℃/min速度升温至700℃,恒温焙烧6小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCo0.6Ni0.4O2化合物,材料的颗粒度约为0.5~2μm。
实施例16
将LiCl、MnCl2·4H2O与KNO3按摩尔比为1.1∶2∶2混匀,于空气氛围中,以5℃/min速度升温至600℃,恒温焙烧6小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiMn2O4化合物,材料的颗粒度约为200~500nm。
实施例17
将Li2CO3、CoCO3、与0.43LiNO3-0.57KNO3按摩尔比为0.5∶1∶4混匀,于空气氛围中,以5℃/min速度升温至600℃,恒温焙烧10小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为200~500nm。
实施例18
将LiOH·H2O、CoO、与KCH3CO2按摩尔比为1∶1∶2混匀,于空气氛围中,以5℃/min速度升温至500℃,恒温焙烧12小时,然后以10℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为200nm。
实施例19
将LiOH·H2O、Mn(OH)2与0.59LiCl~0.41KCl按摩尔比为0.9∶2∶2混匀,于空气氛围中,以5℃/min速度升温至800℃,恒温焙烧1小时,然后以10℃/min速率降到室温。用蒸馏水洗涤,过滤并于200℃干燥。所得产物经XRD分析表明为纯相LiMn2O4化合物,材料的颗粒度约为0.5~1μm。
实施例20
将Li2CO3、Co(OH)2与KHSO4按摩尔比为0.5∶1∶2混匀,于空气氛围中,以2℃/min速度升温至300℃,恒温焙烧24小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于100℃真空干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为200nm。
实施例21
将LiOH·H2O、CoO与KOH按摩尔比为1∶1∶2混匀,于空气氛围中,以5℃/min速度升温至800℃,恒温焙烧2小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于130℃干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为1~2μm。
[实施例22]
将Li2O、CoO与0.43LiNO3~0.57KOH按摩尔比为1∶2∶20混匀,于空气氛围中,以5℃/min速度升温至500℃,恒温焙烧10小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于130℃干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为200~500nm。
[实施例23]
将LiCl、CoO与Li2CO3按摩尔比为1∶1∶8混匀,于空气氛围中,以5℃/min速度升温至800℃,恒温焙烧6小时,然后以5℃/min速率降到室温。用蒸馏水洗涤,过滤并于130℃干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为2~5μm。
实施例24
将LiOH·H2O、CoO与LiCH3CO2按摩尔比为0.95∶1∶2混匀,于空气氛围中,以5℃/min速度升温至600℃,恒温焙烧8小时,然后以20℃/min速率降到室温。用蒸馏水洗涤,过滤并于130℃干燥。所得产物经XRD分析表明为纯相LiCoO2化合物,材料的颗粒度约为500nm。
Claims (8)
1.一种锂过渡金属氧化物的制备方法,其特征在于该方法按如下步骤进行:
1)以Li的氧化物、氢氧化物或其盐与过渡金属Co、Ni、Mn的氧化物、氢氧化物或其盐为主要原料,以Co、Ni、Mn、Cr、Al、Mg的氧化物、氢氧化物或盐为掺杂元素,按化学式LixM1-yAiBjO2配料,其中0.45≤x≤1.2,0≤i≤1,0≤j≤1,i+j=y,M≠A≠B,然后加入与Li的摩尔比为0.5~6的熔融盐,固相混合均匀;
2)将混合均匀的原料加热至所加入的熔融盐熔点以上至950℃,恒温焙烧0.5~24小时,然后冷却,洗去残余的盐,烘干。
2.按照权利要求1所述的制备方法,其特征在于:所述的熔融盐采用硝酸钾、氯化钾、氢氧化钾、硫酸氢钾、醋酸钾、醋酸锂、氢氧化锂、氯化锂、硝酸锂、碳酸锂中的至少一种。
3.按照权利要求1或2所述的制备方法,其特征在于:所述步骤2)中洗去残余的盐采用水、乙腈、乙醇或正丁醇中的至少一种洗涤。
4.按照权利要求3所述的制备方法,其特征在于:烘干温度为50~300℃,采用常压或真空干燥。
5.按照权利要求1所述的制备方法,其特征在于:所述的步骤1)中反应原料混合时,其中Co、Ni或Mn的化合物与掺杂元素化合物可采用共沉淀得到的混合物形式加入。
6.按照权利要求1所述的制备方法,其特征在于:i=0,j=0时,原料按Li与Co或Ni的摩尔比为0.95~1.15配料。
7.按照权利要求1所述的制备方法,其特征在于:i=0,j=0时,原料按Li与Mn的摩尔比为0.45~0.55配料。
8.按照权利要求1所述的制备方法,其特征在于:所述反应原料加热的升温速度1~100℃/min,恒温焙烧温度为400~950℃,冷却降温速度1~200℃/min。
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CN102683645A (zh) * | 2011-03-17 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | 一种锂离子电池正极材料层状富锂锰基氧化物的制备方法 |
CN102709547A (zh) * | 2012-06-18 | 2012-10-03 | 中国第一汽车股份有限公司 | 一种富锂正极材料的溶液式熔盐制备方法 |
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