CN104009221B - 溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法 - Google Patents
溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000009841 combustion method Methods 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010405 anode material Substances 0.000 claims abstract description 25
- 239000011572 manganese Chemical class 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000002485 combustion reaction Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910052748 manganese Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000013522 chelant Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 6
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- 239000012467 final product Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 3
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- 238000012216 screening Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002956 ash Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
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- 230000005518 electrochemistry Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
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- 150000002696 manganese Chemical class 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229910006235 Li1+xM1-xO2 Inorganic materials 0.000 description 1
- 229910006255 Li1+xM1−xO2 Inorganic materials 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本发明是一种溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法。属于锂电池原材料的制造方法。该方法按以下步骤进行：将锂、镍、锰的盐类溶于醇类试剂中配制成溶液A，然后将溶液A置于一定温度的恒温水浴锅中在搅拌的条件下蒸发为胶状螯合物前驱体B，并转移入坩埚中，置于马弗炉内于一定温度下使其自蔓延燃烧生成灰烬物质C，物质C经研磨后置于马弗炉内于高温下在氧气氛围中煅烧数小时，研磨过筛后即得富锂正极材料。本发明采用的溶胶凝胶法不经过凝胶完全干燥过程即可进行自蔓延燃烧反应，合成的一次颗粒为亚微米级粒子，粒径小，锂离子扩散路径短，利于锂离子的脱嵌，改善了富锂材料的不足。
Description
技术领域
本发明属于锂离子电池正极材料的领域，具体涉及一种容量高、化学计量比好、纯度高、倍率性能的锂离子电池正极材料Li（Li0.08Ni0.38Mn0.54）O2的制备方法。
背景技术
随着人们对能源需求的日益增长和对社会与经济可持续发展重要性认识的不断深化，以绿色环保和高效高能为特点的锂离子电池越来越受到人们的重视。大中型电动工具、储能电站、电动车、智能电网等应用对锂离子电池的安全性、能量密度、功率密度、循环寿命、价格、环境友好等方面都提出了更高要求。目前锂离子电池负极材料的比容量通常在300mAh/g以上，而正极材料的比容量则始终徘徊在150mAh/g左右。由于深度充电时电极材料对有机电解质的强氧化作用及过度脱锂对材料自身结构的破坏，LiCoO2的实际可利用容量只有理论容量的一半左右。而镍钴锰三元材料虽然降低了材料成本和毒性，明显提高了材料的安全性，但这些层状结构材料的实际比容量（一般小于180mAh/g）并没有大的突破。尖晶石结构正极材料LiMn2O4和聚阴离子正极材料（典型的如橄榄石结构的LiFePO4）的理论比容量也分别只有148mAh/g和170mAh/g，远不能满足高比能锂离子电池对正极材料的性能要求。因此，正极材料成为锂离子电池性能进一步提高的瓶颈。
富锂层状结构正极材料Li1+xM1-xO2（M为Ti，Cr，Fe，Co，Ni，Mn等）的理论比容量超过300mAh/g，实际可利用容量大于200mAh/g，成为发展能量密度大于300Wh/kg锂离子电池的重要候选正极材料，近年来受到人们的广泛关注。
合成富锂材料的方法主要有高温固相法、共沉淀法、溶胶凝胶法、水热法和喷雾干燥法等。共沉淀法是用来合成复合正极材料前驱体最常用的方法，此法可实现原子级的混合，但是，实际中不同种类阳离子不同时沉淀，沉淀存在先后顺序，金属离子沉淀不完全，化学计量比不容易精确控制，沉淀不完全的重金属还造成环境污染，且耗水量大。溶胶凝胶法不仅可以实现原子级的混合，而且合成的材料化学计量比精确、金属元素分布均匀、纯度高,自蔓延燃烧反应快速省时，颗粒粒径分布均匀，工艺过程简单。
发明内容
本发明的目的在于提供一种溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，本方法工艺流程简单、化学计量比好、纯度高、倍率性能好，可以改善现有富锂材料由于存在Li2MnO3 组分导致材料导电性差，倍率性能差的不足。
本发明的技术方案如下：
一种溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，所述富锂正极材料为Li（Li0.08Ni0.38Mn0.54）O2，其特征在于该方法按以下步骤进行：
（1）将锂、镍、锰的盐类溶于醇类试剂中配制成溶液A，
（2）然后将溶液A置于一定温度的恒温水浴锅中在搅拌的条件下蒸发为胶状螯合物前驱体B，
（3）将前驱体B转移入坩埚中，置于马弗炉内于一定温度下使其自蔓延燃烧生成灰烬物质C，
（4）将物质C经研磨后置于马弗炉内于高温下在氧气氛围中煅烧数小时，研磨过筛后即得富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2。
作为优选，所述锂盐为硝酸锂、醋酸锂中的至少一种锂盐；所述镍盐为硝酸镍、醋酸镍中的至少一种镍盐；所述锰盐为硝酸锰、醋酸锰中的至少一种为醋酸盐。作为优选，所述水浴温度为50-100℃，搅拌方式为机械搅拌或磁力搅拌。
作为优选，所述的燃烧温度为300-500℃，燃烧时间为0.1-2h。
作为优选，所述的煅烧温度为750-950℃，煅烧时间为6-24h。
本发明采用的溶胶凝胶法不经过凝胶完全干燥过程即可进行自蔓延燃烧反应，操作简便且省时。合成的一次颗粒为亚微米级粒子，粒径小，锂离子扩散路径短，利于锂离子的脱嵌，改善了富锂材料的不足。
附图说明
图1为实施案例1中富锂正极材料的SEM图。
图2为实施例1中富锂正极材料的首次充放电曲线图。
图3为实施例1中富锂正极材料的循环性能图。
具体实施方式
下面通过实施案例进一步对本发明进行说明，但这并非是对本发明的限制，本领域技术人员可根据本发明的基本思路，做出相应的改进，只要不脱离本发明的思路，均在本发明的范围以内。
一种溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，所述富锂正极材料为Li（Li0.08Ni0.38Mn0.54）O2，其特征主要包含以下步骤：
1)将锂、镍、锰的盐类溶于醇类试剂中配制成溶液A，
2)然后将溶液A置于一定温度的恒温水浴锅中在搅拌的条件下蒸发为胶状螯合物前驱体B，
3)将前驱体B转移入坩埚中，置于马弗炉内于一定温度下使其自蔓延燃烧生成灰烬物质C，
4)将物质C经研磨后置于马弗炉内于高温下在氧气氛围中煅烧数小时，研磨过筛后即得富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2。
根据所述的方法溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，其特征在于，所述锂盐为硝酸锂、醋酸锂中的至少一种锂盐；所述镍盐为硝酸镍、醋酸镍中的至少一种镍盐；所述锰盐为硝酸锰、醋酸锰中的至少一种为醋酸盐。
根据所述的溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，其特征在于，步骤2）中所述水浴温度为50-100℃，搅拌方式为机械搅拌或磁力搅拌。
根据所述的溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，其特征在于，步骤3）中所述的燃烧温度为300-500℃，燃烧时间为0.1-2h。
根据所述的溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，其特征在于，步骤4）中所述的煅烧温度为750-950℃，煅烧时间为6-24h。
本发明采用先溶胶凝胶法合成出纯度高、化学计量比好的胶状螯合物前驱体，再自蔓延燃烧的方法使其初步生成富锂材料，再经过高温处理得到颗粒均匀的富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2。
实施案例1
制备富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2，按照目标产物中Li、Ni、Mn各元素的化学计量比准确称取相应的硝酸锂、硝酸镍及醋酸锰，按照金属盐总质量：乙醇质量=1：8，配制溶液，常温下进行搅拌溶解后置于80oC恒温水浴锅中进行机械搅拌蒸发，待其成为胶状透明物质后转移至坩埚内，将坩埚置于马弗炉内于350℃下灼烧1h，使其发生自蔓延燃烧反应，将燃烧后的灰烬经研磨后置于马弗炉内在氧气氛围下850℃煅烧16h。研磨并过400目筛得Li（Li0.08Ni0.38Mn0.54）O2正极材料。
将合成的Li（Li0.08Ni0.38Mn0.54）O2正极材料、乙炔黑、粘结剂聚偏二氟乙烯（PVDF）按质量比85：10：5混匀作为正极，以金属锂为负极，1mol/L LiPF6-EC/DMC为电解液组装扣式电池，于25oC环境中，在2.0–4.5V的电压范围内，0.1C倍率下（1C=200mA/g）进行电化学测试，电池放电比容量为265mAh/g；循环50周后容量保持率为96%。
实施案例2
制备富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2，按照目标产物中Li、Ni、Mn各元素的化学计量比准确称取相应的醋酸锂、醋酸镍及醋酸锰，按照金属盐总质量：乙醇质量=1：9，配制溶液，常温下进行搅拌溶解后加入磁子，置于90oC恒温水浴锅中进行磁力搅拌蒸发，待其成为胶状透明物质后转移至坩埚内，将坩埚置于马弗炉内于400℃下灼烧0.5h，使其发生自蔓延燃烧反应，将燃烧后的灰烬经研磨后置于马弗炉内在氧气氛围下900℃煅烧12h。研磨并过400目筛得Li（Li0.08Ni0.38Mn0.54）O2正极材料。
将合成的Li（Li0.08Ni0.38Mn0.54）O2正极材料、乙炔黑、粘结剂聚偏二氟乙烯（PVDF）按质量比85：10：5混匀作为正极，以金属锂为负极，1mol/L LiPF6-EC/DMC为电解液组装扣式电池，于25oC环境中，在2.0–4.5V的电压范围内，0.1C倍率下（1C=200mA/g）进行电化学测试，电池放电比容量为263mAh/g。
实施案例3
制备富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2，按照目标产物中Li、Ni、Mn各元素的化学计量比准确称取相应的硝酸锂、醋酸镍及硝酸锰，按照金属盐总质量：乙醇质量=1：10，配制溶液，常温下进行搅拌溶解后置于75oC恒温水浴锅中进行搅拌蒸发，待其成为胶状透明物质后转移至坩埚内，将坩埚置于马弗炉内于350℃下灼烧2h，使其发生自蔓延燃烧反应，将燃烧后的灰烬经研磨后置于马弗炉内在氧气氛围下800℃煅烧24h。研磨并过400目筛得Li（Li0.08Ni0.38Mn0.54）O2正极材料。
将合成的Li（Li0.08Ni0.38Mn0.54）O2正极材料、乙炔黑、粘结剂聚偏二氟乙烯（PVDF）按质量比85：10：5混匀作为正极，以金属锂为负极，1mol/L LiPF6-EC/DMC为电解液组装扣式电池，于25oC环境中，在2.0–4.5V的电压范围内，0.1C倍率下（1C=200mA/g）进行电化学测试，电池放电比容量为260mAh/g。
Claims (1)
1.一种溶胶凝胶自蔓延燃烧法制备富锂正极材料的方法，所述富锂正极材料为Li（Li0.08Ni0.38Mn0.54）O2，主要包含以下步骤：（1）、将锂、镍、锰的盐类溶于醇类试剂中配制成溶液A，其特征是，还包括以下步骤， (2)、将溶液A置于一定温度的恒温水浴锅中在搅拌的条件下蒸发为胶状螯合物前驱体B，步骤（2）中所述水浴温度为50-100℃，搅拌方式为机械搅拌； (3)、将前驱体B转移入坩埚中，置于马弗炉内于一定温度下使其自蔓延燃烧生成灰烬物质C，燃烧温度为300-500℃，燃烧时间为0.1-2h；(4)、将物质C经研磨后置于马弗炉内于高温下在氧气氛围中煅烧数小时，煅烧温度为750-950℃，煅烧时间为6-24h，研磨过筛后即得富锂正极材料Li（Li0.08Ni0.38Mn0.54）O2。
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