CN108649186B - 一种富含富锂锰基的复合正极片的制备方法及其应用 - Google Patents
一种富含富锂锰基的复合正极片的制备方法及其应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 32
- 239000011572 manganese Substances 0.000 title claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006256 anode slurry Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
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- DGQGEJIVIMHONW-UHFFFAOYSA-N [O-2].[Ta+5].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[Zr+4].[La+3].[Li+] DGQGEJIVIMHONW-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000005520 cutting process Methods 0.000 abstract description 5
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- 229910003002 lithium salt Inorganic materials 0.000 abstract description 3
- 159000000002 lithium salts Chemical class 0.000 abstract description 3
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- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 4
- 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 3
- 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 description 3
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- PYUKXGCMRFTISX-UHFFFAOYSA-N [O].[Ta].[Zr].[La].[Li] Chemical compound [O].[Ta].[Zr].[La].[Li] PYUKXGCMRFTISX-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 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 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
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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
本发明公开了一种富含富锂锰基的复合正极片的制备方法，其特征在于：将有机碳源溶解在去离子水中；将富锂锰基与溶解好的碳源溶液加入到水热反应釜中，将抽滤后的粉体干燥；取包覆了有机碳源的富锂锰基粉体，导电剂，粘结剂，快离子导体以及锂盐混合均匀后分散在N‑甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；用涂布机将复合正极浆料涂布在导电涂层铝箔上，再在真空烘烤箱中进行干燥，最后分切得到复合正极片。优点是：水热法制备的粉体结晶性与分散性好，且低能耗、低污染、低投入，产量较高，设备单一，工艺流程简单，具备大规模生产的可能。
Description
技术领域
本发明涉及新能源锂电池领域，涉及了一种富含富锂锰基的复合正极片的制备方法，还涉及一种富含富锂锰基的复合正极片的应用。
背景技术
传统锂离子电池采用有机液体电解液，在过度充电、内部短路等异常的情况下，电池容易发热，造成电解液气胀、自燃甚至爆炸，存在严重的安全隐患。20世纪50年代发展起来的基于固体电解质的全固态锂电池，由于采用固体电解质，不含易燃、易挥发组分，彻底消除电池因漏液引发的电池冒烟、起火等安全隐患，被称为最安全电池体系。
全固态锂离子电池面临的主要问题是电极材料与固态电解质相匹配以降低其界面阻抗并保证界面的稳定性，要解决该问题，除需要研究开发新型的固态电解质和对界面采取一些特殊手段(如在界面加缓冲物质降低界面阻抗)以外，还亟需开发新型的正极材料，以大幅改善全固态锂离子电池的电化学性能。富锂锰基正极材料xLi2MnO3﹒(1-x)LiMO2(M＝Ni，Co，Mn)是一种过渡金属以锰为主并掺杂了其它元素的锂锰基复合氧化物，由Li2MnO3和LiMO2两种成分按不同比例复合而成，结构类似于α-NaFeO2层状结构。虽然商业化的富锂锰基正极材料具有较高的放电比容量，但仍存在以下几个问题：一是首次不可逆容量损失较大；二是倍率性能和循环寿命较差；三是循环过程电压衰减较快。
发明内容
本发明的目的是：针对上述不足，提供一种富含富锂锰基的复合正极片的制备方法及其应用。
为达到上述目的，本发明采用的技术方案是：
一种富含富锂锰基的复合正极片的制备方法，此制备方法包括如下步骤：步骤一：将2-5质量份的有机碳源溶解在去离子水中；
步骤二：将100质量份的富锂锰基与溶解好的碳源溶液加入到水热反应釜中，加热温度为120-180℃，加热4-12h；
步骤三：取出降温后的混合溶液抽滤，将抽滤后的粉体在70-90℃干燥4-12h；
步骤四：取80-90质量份的包覆了有机碳源的富锂锰基粉体，1-5质量份的导电剂，2-5质量份的粘结剂，2-15质量份的快离子导体以及3-10质量份的锂盐混合均匀后分散在N-甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；
步骤五：用涂布机将复合正极浆料涂布在厚度为15-17μm的导电涂层铝箔上，涂布速度为500-800mm/min，涂布厚度为160-200μm，收卷后的极片再在100-110℃的真空烘烤箱中进行干燥，干燥时间为12-24h，对极片进行辊压，压实密度控制在3-3.4mg/cm3，最后分切得到复合正极片。
所述有机碳源包括葡萄糖，蔗糖，柠檬酸等。
所述导电材料包括Surpe-P，乙炔黑，KS-6，CNT，石墨烯等。
所述粘结剂包括聚偏氟乙烯，聚偏氟乙烯-六氟丙烯，聚四氟乙烯等
所述快离子导体包括锂镧锆氧(LLZO)，锂镧钛氧(LLTO)，锂镧锆钽氧(LZTO)。
所述锂盐包括LiTFSI，LiClO4，LiBF4，LiPF6，LiAsF6。
一种富含富锂锰基的复合正极片的应用，将得到的富锂锰基复合正极片与聚氧化乙烯基锂离子导体固体电解质、锂箔进行叠片，组装得到固态锂离子电池，将得到的固态锂离子电池在60℃、0.2C充放电，充放电截止电压2.5-4.6V的条件下进行充放电循环测试，结果显示放电比容量为175mAh/g-195mAh/g，循环300周后，容量保持率为85％-90％。
与现有技术相比，本发明所达到的技术效果是：采用水热法对富锂锰基正极材料进行表面碳包覆是一种行之有效的方法，在特制的密闭反应容器里，采用水溶液作为反应介质，通过对反应容器加热，创造一个高温、高压反应环境，使得碳源在富锂锰基正极材料表面溶解并且重结晶，水热法制备的粉体结晶性与分散性好，且低能耗、低污染、低投入，产量较高，设备单一，工艺流程简单，具备大规模生产的可能。
附图说明
图1为富含富锂锰基的复合正极片的扣电循环图。
具体实施方式
下面结合附图及实施例对本发明作进一步描述：
实施例一：
一种富含富锂锰基的复合正极片的制备方法，此制备方法包括如下步骤：步骤一：将2质量份的葡萄糖溶解在去离子水中；
步骤二：将100质量份的富锂锰基与溶解好的葡萄糖溶液加入到水热反应釜中，加热温度为120℃，加热4h；
步骤三：取出降温后的混合溶液抽滤，将抽滤后的粉体在70℃干燥4h；
步骤四：取80质量份的包覆了有机碳源的富锂锰基粉体，2质量份的Surpe-P，2质量份的聚偏氟乙烯，2质量份的锂镧锆氧(LLZO)以及3质量份的LiTFSI混合均匀后分散在N-甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；
步骤五：用涂布机将复合正极浆料涂布在厚度为16μm的导电涂层铝箔上，涂布速度为800mm/min，涂布厚度为160μm，收卷后的极片再在105℃的真空烘烤箱中进行干燥，干燥时间为24h，对极片进行辊压，压实密度控制在3-3.4mg/cm3，最后分切得到复合正极片。
一种富含富锂锰基的复合正极片的应用，将得到的富锂锰基复合正极片与聚氧化乙烯基锂离子导体固体电解质、锂箔进行叠片，组装得到固态锂离子电池，将得到的固态锂离子电池在60℃、0.2C充放电，充放电截止电压2.5-4.6V的条件下进行充放电循环测试，结果显示放电比容量为195mAh/g，循环300周后，容量保持率为87％。
实施例二：
一种富含富锂锰基的复合正极片的制备方法，此制备方法包括如下步骤：步骤一：将4质量份的蔗糖溶解在去离子水中；
步骤二：将100质量份的富锂锰基与溶解好的蔗糖溶液加入到水热反应釜中，加热温度为150℃，加热4h；
步骤三：取出降温后的混合溶液抽滤，将抽滤后的粉体在80℃干燥8h；
步骤四：取85质量份的包覆了有机碳源的富锂锰基粉体，2质量份的乙炔黑，3质量份的聚偏氟乙烯-六氟丙烯，3质量份的锂镧钛氧(LLTO)以及3质量份的LiClO4混合均匀后分散在N-甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；
步骤五：用涂布机将复合正极浆料涂布在厚度为16μm的导电涂层铝箔上，涂布速度为800mm/min，涂布厚度为166μm，收卷后的极片再在105℃的真空烘烤箱中进行干燥，干燥时间为24h，对极片进行辊压，压实密度控制在3-3.4mg/cm3，最后分切得到复合正极片。
一种富含富锂锰基的复合正极片的应用，将得到的富锂锰基复合正极片与聚氧化乙烯基锂离子导体固体电解质、锂箔进行叠片，组装得到固态锂离子电池，将得到的固态锂离子电池在60℃、0.2C充放电，充放电截止电压2.5-4.6V的条件下进行充放电循环测试，结果显示放电比容量为180mAh/g，循环300周后，容量保持率为90％。
实施例三：
一种富含富锂锰基的复合正极片的制备方法，此制备方法包括如下步骤：步骤一：将5质量份的柠檬酸溶解在去离子水中；
步骤二：将100质量份的富锂锰基与溶解好的柠檬酸溶液加入到水热反应釜中，加热温度为180℃，加热6h；
步骤三：取出降温后的混合溶液抽滤，将抽滤后的粉体在80℃干燥8h；
步骤四：取90质量份的包覆了有机碳源的富锂锰基粉体，3质量份的石墨烯，4质量份的聚四氟乙烯，6质量份的锂镧锆钽氧(LZTO)以及6质量份的LiPF6混合均匀后分散在N-甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；
步骤五：用涂布机将复合正极浆料涂布在厚度为16μm的导电涂层铝箔上，涂布速度为800mm/min，涂布厚度为170μm，收卷后的极片再在110℃的真空烘烤箱中进行干燥，干燥时间为24h，对极片进行辊压，压实密度控制在3-3.4mg/cm3，最后分切得到复合正极片。
一种富含富锂锰基的复合正极片的应用，将得到的富锂锰基复合正极片与聚氧化乙烯基锂离子导体固体电解质、锂箔进行叠片，组装得到固态锂离子电池，将得到的固态锂离子电池在60℃、0.2C充放电，充放电截止电压2.5-4.6V的条件下进行充放电循环测试，结果显示放电比容量为175mAh/g，循环300周后，容量保持率为87％。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
Claims (2)
1.一种富含富锂锰基材料的复合正极片在固态锂离子电池中的应用，其特征在于：包括如下步骤：
步骤一：将5质量份的柠檬酸溶解在去离子水中；
步骤二：将100质量份的富锂锰基与溶解好的柠檬酸溶液加入到水热反应釜中，加热温度180℃，加热6h；
步骤三：取出降温后的混合溶液抽滤，将抽滤后的粉体在80℃干燥8h；
步骤四：取90质量份的包覆了有机碳源的富锂锰基粉体，3质量份的石墨烯，4质量份的聚四氟乙烯，6质量份的锂镧锆钽氧以及6质量份的LiPF6混合均匀后分散在N-甲基吡咯烷酮溶剂之中，用真空行星搅拌机充分搅拌均匀以得到复合正极浆料；
步骤五：用涂布机将复合正极浆料涂布在厚度为16μm的导电涂层铝箔上，涂布速度为800mm/min，涂布厚度为170μm，收卷后的极片再在110℃的真空烘烤箱中进行干燥，干燥时间为24h，对极片进行辊压，压实密度控制在3-3.4mg/cm3，最后分切得到复合正极片；
步骤六：将得到的富锂锰基复合正极片与聚氧化乙烯基锂离子导体固体电解质、锂箔进行叠片，组装得到固态锂离子电池。
2.如权利要求1所述的应用，其特征在于：所述固态锂离子电池在60℃、0.2C充放电，充放电截止电压2.5-4.6V的条件下进行充放电循环测试，结果显示放电比容量为175mAh/g，循环300周后，容量保持率为87％。
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