CN103794787A - 一种高能效锂离子电池正极复合材料的制备方法 - Google Patents
一种高能效锂离子电池正极复合材料的制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 239000010955 niobium Substances 0.000 claims abstract description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910008572 Li2O—B2O3-SiO2 Inorganic materials 0.000 claims abstract description 5
- 229910008585 Li2O—B2O3—SiO2 Inorganic materials 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000002905 metal composite material Substances 0.000 claims description 4
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
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- 230000000694 effects Effects 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 230000002427 irreversible effect Effects 0.000 description 2
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- 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 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- -1 sulphur compound Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
本发明涉及一种高能效锂离子电池正极复合材料的制备方法，该方法包括如下步骤：（1）该活性物质料的化学式为Li1-xMgxFe1-yNby（P1-zO4），其中：x=0.1-0.125，y=0.15-0.20，z=0.02-0.0.07，按照上述化学式中的Li、Mg、Fe、Nb、P的摩尔量称取氢氧化锂、氯化镁、硫酸亚铁、硝酸铌、磷酸氢二铵制备活性物质颗粒；（2）将导电玻璃材料Li2O-LiCl、Li2O-B2O3-SiO2和石墨烯混合后球磨成均匀粉末得到导电材料，备用；（3）在去离子水中将所述活性物质颗粒、所述导电材料材料混合；充分搅拌后，蒸发掉水份；将蒸发水份后的残留物在氩气氛围下焙烧，得到产品。本发明制备的正极复合材料，使用Mg和Nb对活性物质，改性提高材料的活性，并在其表面包覆粘附性良好的混合导电材料，提高其导电性能和循环稳定性。
Description
所属技术领域
本发明涉一种高能效锂离子电池正极复合材料的制备方法。
背景技术
随着电池行业的迅速发展，为了解决电池的使用寿命、能量密度、自放电或者质量等诸多问题，出现了各种类型的电池。目前，由于锂电池具有能量密度高、使用寿命长、质量轻、自放电小等优点，现已经成为了通讯设备、笔记本电脑等便携式设备的首选电源，并且也开始应用到电动车、国防等中大型的设备中。
锂二次电池通常使用碳质材料作为负极活性材料。另外，已经考虑使用锂金属、硫化合物等作为负极活性材料。同时，锂二次电池通常使用锂钴复合氧化物(LiCoO2)作为正极活性材料。此外，已经考虑使用锂锰复合氧化物如具有层状晶体结构的LiMnO2、具有尖晶石晶体结构的LiMn2O4和锂镍复合氧化物(LiNiO2)作为正极活性材料。
由于钴资源少，价格高，虽然合成容易也不利于锂离子电池的推广应用，特别是在动力电池大规模应用方面更受到限制；而其他正极材料，镍酸锂在使用时由于循环过程中结构不稳定等缺陷，不能很好地得到应用；锰酸锂存在着比容量低，高温性能差等问题；而橄榄石型磷酸铁锂作为锂离子二次电池新型正极材料则兼具上述各种材料的优点，特别是其安全性和热稳定性方面，性能优越，价格便宜又无污染，充放电效率高，成为近来研究的热题。在橄榄石结构化合物中，与锂(Li)相比，LiFePO4具有约3.5V的高输出电压和170mAh/g的高理论容量，与钴(Co)相比，其表现出优异的高温稳定性，且LiFePO4利用廉价的Fe，因此非常适合作为锂二次电池用正极活性材料。然而，这种橄榄石型LiFePO4具有约100％的工作效率，因而使得难以控制负极的工作效率。在通用的碳质负极活性材料的情况中，在包含首次充电的初始充放电时产生约10％～20％的不可逆容量，且其可逆容量仅为约80％～90％。因此，当使用具有100％的效率材料作为正极活性材料时，以与约10％～20％的不可逆容量成正比的方式不利地浪费了电极材料。此外，当使用具有相对低效率的负极活性材料时，应根据正极的更高效率增加负极活性材料的量，这不利地需要增加制造成本。
发明内容
针对上述问题，本发明提供一种高能效锂离子电池正极复合材料的制备方法，使用该方法制备的正极材料，具有较高的首次充放电容量和并可在较长的使用寿命中保持高可逆容量。
为了实现上述目的，本发明提供的一种高能效锂离子电池正极复合材料的制备方法，该方法包括如下步骤：
（1）制备活性物质
该活性物质料的化学式为Li1-xMgxFe1-yNby（P1-zO4），其中：x=0.1-0.125，y=0.15-0.20，z=0.02-0.0.07，按照上述化学式中的Li、Mg、Fe、Nb、P的摩尔量称取氢氧化锂、氯化镁、硫酸亚铁、硝酸铌、磷酸氢二铵；
将上述原材料溶于去离子水中和足够量的氨水进行初步混合以沉淀Mg、Fe和Nb的氢氧化物，得到混合物；
将超临界水与上述混合物进行二次混合以合成锂金属复合氧化物，并对其进行干燥，其中所述超临界水为在300-450bar的压力下、具有400-500℃的水；
对干燥后的物体进行烧结，煅烧温度为900-1100℃，冷却后，球磨得到活性物质颗粒；
（2）制备导电材料
将导电玻璃材料Li2O-LiCl、Li2O-B2O3-SiO2和石墨烯按照质量比1:1-3：2-3的比例混合后球磨成均匀粉末，备用；
（3）在去离子水中将所述活性物质颗粒、所述导电材料材料按照质量比100:3-5混合，水的用量应可完全浸没固体材料；
充分搅拌后，蒸发掉水份；
将蒸发水份后的残留物在氩气氛围下、400-600℃焙烧，得到产品。
本发明制备的正极复合材料，使用Mg和Nb对活性物质，改性提高材料的活性，并在其表面包覆粘附性良好的混合导电材料，提高其导电性能和循环稳定性。因此该复合材料在用于锂离子电池时，具有较高的比容量以及较长的使用寿命。
具体实施方式
实施例一
活性物质料的化学式为Li0.9Mg0.1Fe0.85Nb0.15（P0.98O4），按照上述化学式中的Li、Mg、Fe、Nb、P的摩尔量称取氢氧化锂、氯化镁、硫酸亚铁、硝酸铌、磷酸氢二铵。
将上述原材料溶于去离子水中和足够量的氨水进行初步混合以沉淀Mg、Fe和Nb的氢氧化物，得到混合物；将超临界水与上述混合物进行二次混合以合成锂金属复合氧化物，并对其进行干燥，其中所述超临界水为在300bar的压力下、具有400℃的水；对干燥后的物体进行烧结，煅烧温度为900℃，冷却后，球磨得到活性物质颗粒。
将导电玻璃材料Li2O-LiCl、Li2O-B2O3-SiO2和石墨烯按照质量比1:1：2的比例混合后球磨成均匀粉末得到导电材料，备用；在去离子水中将所述活性物质颗粒、所述导电材料材料按照质量比100:3混合，水的用量应可完全浸没固体材料；充分搅拌后，蒸发掉水份；将蒸发水份后的残留物在氩气氛围下、400℃焙烧，得到产品。
实施例二
活性物质料的化学式为Li0.875Mg0.125Fe0.8Nb0.2（P0.093O4），按照上述化学式中的Li、Mg、Fe、Nb、P的摩尔量称取氢氧化锂、氯化镁、硫酸亚铁、硝酸铌、磷酸氢二铵。
将上述原材料溶于去离子水中和足够量的氨水进行初步混合以沉淀Mg、Fe和Nb的氢氧化物，得到混合物；将超临界水与上述混合物进行二次混合以合成锂金属复合氧化物，并对其进行干燥，其中所述超临界水为在450bar的压力下、具有500℃的水；对干燥后的物体进行烧结，煅烧温度为1100℃，冷却后，球磨得到活性物质颗粒。
将导电玻璃材料Li2O-LiCl、Li2O-B2O3-SiO2和石墨烯按照质量比1:3：3的比例混合后球磨成均匀粉末得到导电材料，备用；在去离子水中将所述活性物质颗粒、所述导电材料材料按照质量比100:5混合，水的用量应可完全浸没固体材料；充分搅拌后，蒸发掉水份；将蒸发水份后的残留物在氩气氛围下、600℃焙烧，得到产品。
比较例
称取31.8g多壁碳纳米管（CNTs）加入100mL无水乙醇中，在超声环境中分散30min，分别称取2.780kg的FeSO4·7H2O和1.196kg的NH4H2PO4，分别加入纯水配成0.8mol/L的溶液，将上述分散好的CNTs分散液加入硫酸亚铁溶液中，在50℃水浴条件下800r/min搅拌，然后逐渐加入NH4H2PO4溶液，反应一段时间后，加入700mLH2O2，立即有大量白色沉淀生成，用NH3·H2O调节pH值到2，继续反应2h时间，陈化10h后反复过滤、洗涤，直到检测没有SO4 2-存在为止，80℃干燥后得到含结晶水的FePO4·xH2O/CNTs。
对得到的FePO4·xH2O/CNTs以2℃/min的升温速度从室温升到550℃进行热处理，保温2h，除掉结晶水，得到不含结晶水的FePO4/CNTs；采用得到的FePO4/CNTs，同时称取0.362kgLi2CO3、16.00gTiO2、397.50g葡萄糖，加入到6L的无水乙醇中，在高能研磨机中分散搅拌4h，经减压干燥处理除掉乙醇得到前驱体粉末。此粉末在高纯氮气气氛下以8℃/min的升温速度从室温升到700℃进行高温焙烧，保温5h，自然降温到室温，经气流粉碎机粉碎分级，得到0.5～5μm的磷酸铁锂电池材料，其结构表达为Li0.98Ti0.02FePO4/CNTs/C。
将上述实施例一、二以及比较例所得产物与导电炭黑和粘合剂聚偏氟乙烯以质量比80∶10∶10的比例混合，制作成同样规格的测试电池。参比电极为金属锂，电解液为1mol/l LiPF6的EC/DEC/DMC(体积比1∶1∶1)。在测试温度为25℃下进行电性能测试，经测试该实施例一和二的材料与比较例的产物相比，首次充放电容量提高了35-40%，可逆容量衰减到70%时，使用寿命时间提高到1.3倍以上。
Claims (1)
1.一种高能效锂离子电池正极复合材料的制备方法，该方法包括如下步骤：
（1）制备活性物质
该活性物质料的化学式为Li1-xMgxFe1-yNby（P1-zO4），其中：x=0.1-0.125，y=0.15-0.20，z=0.02-0.0.07，按照上述化学式中的Li、Mg、Fe、Nb、P的摩尔量称取氢氧化锂、氯化镁、硫酸亚铁、硝酸铌、磷酸氢二铵；
将上述原材料溶于去离子水中和足够量的氨水进行初步混合以沉淀Mg、Fe和Nb的氢氧化物，得到混合物；
将超临界水与上述混合物进行二次混合以合成锂金属复合氧化物，并对其进行干燥，其中所述超临界水为在300-450bar的压力下、具有400-500℃的水；
对干燥后的物体进行烧结，煅烧温度为900-1100℃，冷却后，球磨得到活性物质颗粒；
（2）制备导电材料
将导电玻璃材料Li2O-LiCl、Li2O-B2O3-SiO2和石墨烯按照质量比1:1-3：2-3的比例混合后球磨成均匀粉末，备用；
（3）在去离子水中将所述活性物质颗粒、所述导电材料材料按照质量比100:3-5混合，水的用量应可完全浸没固体材料；
充分搅拌后，蒸发掉水份；
将蒸发水份后的残留物在氩气氛围下、400-600℃焙烧，得到产品。
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