CN104157844B - High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof - Google Patents
High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof Download PDFInfo
- Publication number
- CN104157844B CN104157844B CN201410409799.XA CN201410409799A CN104157844B CN 104157844 B CN104157844 B CN 104157844B CN 201410409799 A CN201410409799 A CN 201410409799A CN 104157844 B CN104157844 B CN 104157844B
- Authority
- CN
- China
- Prior art keywords
- lithium
- nano
- manganese
- positive electrode
- rich manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007774 positive electrode material Substances 0.000 claims abstract description 40
- 239000010406 cathode material Substances 0.000 claims abstract description 29
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- 239000002073 nanorod Substances 0.000 claims abstract description 20
- 238000001338 self-assembly Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 12
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- 150000002696 manganese Chemical class 0.000 claims abstract description 4
- 150000002815 nickel Chemical class 0.000 claims abstract description 4
- 229910015118 LiMO Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 238000011056 performance test Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940071257 lithium acetate Drugs 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229940099594 manganese dioxide Drugs 0.000 description 2
- 229910001171 0.5LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012741 LiNi0.5Co0.5O2 Inorganic materials 0.000 description 1
- 229910014411 LiNi1/2Mn1/2O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种纳微结构的高倍率富锂锰基正极材料及其制备方法，属于材料合成技术领域。所述正极材料的化学式为aLi2MnO3·(1-a)LiMO2，其中0.3≤a＜1，M＝NixCoyMn1-x-y，0≤x≤0.5，0≤y≤0.5。制备方法为：一、称取锰盐、表面活性剂与氯酸钠均匀混合，进行水热反应得到由二氧化锰纳米棒自组装形成的辐射状空心纳微结构；二、将步骤一得到的纳微结构的二氧化锰与锂盐、钴盐与镍盐均匀混合得到前驱体；三、将前驱体高温煅烧，得到具有纳微结构的富锂锰基正极材料。本发明通过利用具有纳微结构中纳米结构本征载流子扩散路径短的优点，可有效提高材料的倍率容量，同时也可利用微米结构表面能低不易团聚、化学稳定性高等特性，保持材料的循环性能。The invention relates to a high-rate lithium-rich manganese-based cathode material with a nano-microstructure and a preparation method thereof, which belong to the technical field of material synthesis. The chemical formula of the positive electrode material is aLi 2 MnO 3 ·(1-a)LiMO 2 , wherein 0.3≤a<1, M=Nix Co y Mn 1-xy , 0≤x≤0.5, 0≤y≤0.5. The preparation method is as follows: 1. Weigh manganese salt, surfactant and sodium chlorate to mix uniformly, and carry out hydrothermal reaction to obtain a radial hollow nanostructure formed by the self-assembly of manganese dioxide nanorods; 2. Manganese dioxide with nano-microstructure and lithium salt, cobalt salt and nickel salt are uniformly mixed to obtain a precursor; third, the precursor is calcined at high temperature to obtain a lithium-rich manganese-based positive electrode material with nano-microstructure. The present invention can effectively improve the rate capacity of the material by taking advantage of the short diffusion path of the intrinsic carrier in the nanostructure of the nanostructure, and can also use the characteristics of the low surface energy of the microstructure, which is not easy to agglomerate, and high chemical stability, to maintain the material cycle performance.
Description
技术领域technical field
本发明属于材料合成技术领域，涉及一种锂离子电池正极材料及其制备方法，尤其涉及一种纳微结构的高倍率富锂锰基正极材料及其制备方法。The invention belongs to the technical field of material synthesis, and relates to a lithium-ion battery cathode material and a preparation method thereof, in particular to a nano-microstructure high-rate lithium-rich manganese-based cathode material and a preparation method thereof.
背景技术Background technique
锂离子电池是目前二次电池体系中能量密度最高的电池体系，具有无记忆效应、工作电压高、自放电率小等显著优点，其在便携式电子设备领域已得到广泛应用，同时在电动汽车和储能电站等领域也已展现出巨大的应用前景。Lithium-ion battery is currently the battery system with the highest energy density in the secondary battery system. It has significant advantages such as no memory effect, high working voltage, and low self-discharge rate. It has been widely used in the field of portable electronic devices, and it is also used in electric vehicles and Fields such as energy storage power stations have also shown great application prospects.
对于现有的正极材料，LiCoO2由于深度充电时对电解质的强氧化作用及过度脱锂对自身结构的破坏，其实际可用容量只有理论容量的一半左右。以Mn和/或Ni替代LiCoO2中的Co(典型的如LiNi1/3Co1/3Mn1/3O2和LiNi1/2Mn1/2O2)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)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。与上述几种正极材料相比，层状富锂锰基材料的理论容量可超过250mAh/g，将成为下一代锂离子电池的重要候选正极材料之一。但是富锂锰基正极材料电导率偏低，大电流放电以及高倍率性能差，循环过程中容量衰减快，这些缺点已成为限制富锂锰基正极材料应用的技术瓶颈。For the existing positive electrode materials, due to the strong oxidation of the electrolyte during deep charging and the damage to its own structure caused by excessive delithiation , the actual usable capacity of LiCoO2 is only about half of the theoretical capacity. Replacing Co in LiCoO 2 with Mn and/or Ni (typically such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 1/2 Mn 1/2 O 2 ) reduces material cost and toxicity, Significantly improved the safety of the material, but the actual specific capacity (generally less than 180mAh/g) of these layered structure materials has no big breakthrough; spinel structure positive electrode material LiMn 2 O 4 and polyanion positive electrode material (typically such as olive The theoretical specific capacities of LiFePO 4 with stone structure are only 148mAh/g and 170mAh/g respectively, which are far from meeting the performance requirements of high specific energy lithium-ion batteries for cathode materials. Therefore, the positive electrode material has become the bottleneck for the further improvement of the performance of lithium-ion batteries. Compared with the above-mentioned cathode materials, the theoretical capacity of layered lithium-rich manganese-based materials can exceed 250mAh/g, and will become one of the important candidate cathode materials for the next generation of lithium-ion batteries. However, lithium-rich manganese-based cathode materials have low conductivity, poor high-current discharge and high-rate performance, and rapid capacity decay during cycling. These shortcomings have become technical bottlenecks that limit the application of lithium-rich manganese-based cathode materials.
发明内容Contents of the invention
本发明的目的是提供一种纳微结构的高倍率富锂锰基正极材料及其制备方法。通过利用具有纳微结构中纳米结构本征载流子扩散路径短的优点，可有效提高材料的倍率容量，同时也可利用微米结构表面能低不易团聚、化学稳定性高等特性，保持材料的循环性能。The purpose of the present invention is to provide a high-rate lithium-rich manganese-based positive electrode material with a nano-microstructure and a preparation method thereof. By taking advantage of the advantages of short intrinsic carrier diffusion paths of nanostructures in nanostructures, the rate capacity of materials can be effectively improved. At the same time, the characteristics of low surface energy and high chemical stability of microstructures can also be used to maintain the circulation of materials. performance.
一种纳微结构的高倍率富锂锰基正极材料，化学式为aLi2MnO3·(1-a)LiMO2，其中0.3≤a＜1，M＝NixCoyMn1-x-y，0≤x≤0.5，0≤y≤0.5。A high-rate lithium-rich manganese-based cathode material with a nano-microstructure, the chemical formula is aLi 2 MnO 3 ·(1-a)LiMO 2 , where 0.3≤a<1, M=Ni x Co y Mn 1-xy , 0≤ x≤0.5, 0≤y≤0.5.
上述纳微结构的高倍率富锂锰基正极材料的制备方法，采用水热法制备了纳米棒自组装形成的辐射状空心纳微结构的富锂锰基正极材料，具体制备方法如下：The preparation method of the high-rate lithium-rich manganese-based cathode material with a nano-microstructure is to prepare a radial hollow nano-microstructure lithium-rich manganese-based cathode material formed by self-assembly of nanorods by a hydrothermal method. The specific preparation method is as follows:
一、按摩尔比1∶1～1.5∶3～5称取锰盐、表面活性剂与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于150～200℃的烘箱中，控制反应时间为10～16h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为6～8，放置于80～120℃的烘箱中干燥24～48h，得到黑色粉末二氧化锰A，其具有由纳米棒自组装形成的辐射状空心纳微结构；1. Weigh the manganese salt, surfactant and sodium chlorate in a molar ratio of 1:1~1.5:3~5, stir and dissolve with an appropriate amount of deionized water until clear, and transfer the mixed solution into a high-pressure tank lined with polytetrafluoroethylene. Put it in an oven at 150-200°C, control the reaction time for 10-16 hours, wait for the reaction kettle to cool down to room temperature naturally, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 6 ～8, placed in an oven at 80～120°C and dried for 24～48 hours to obtain black powder manganese dioxide A, which has a radial hollow nanostructure formed by self-assembly of nanorods;
二、将锂盐、镍盐、钴盐与步骤一得到具有纳微结构的二氧化锰A均匀混合，得到前驱体B；2. Uniformly mix lithium salt, nickel salt, cobalt salt and manganese dioxide A with nanostructure obtained in step 1 to obtain precursor B;
三、将前驱体B放入马弗炉空气气氛中，以1～5℃/min升温速率从室温升至300～500℃预烧3～8h，再以相同升温速率升温至600～900℃煅烧6～15h，得到具有纳微结构的富锂锰基正极材料。3. Put the precursor B in the air atmosphere of the muffle furnace, raise the temperature from room temperature to 300-500°C at a heating rate of 1-5°C/min for pre-burning for 3-8 hours, and then raise the temperature to 600-900°C at the same heating rate Calcining for 6-15 hours to obtain a lithium-rich manganese-based positive electrode material with a nano-microstructure.
上述制备方法中，所述锰盐化合物为硫酸锰、乙酸锰、草酸锰或硝酸锰中的一种或多种的混合物。In the above preparation method, the manganese salt compound is a mixture of one or more of manganese sulfate, manganese acetate, manganese oxalate or manganese nitrate.
上述制备方法中，所述表面活性剂为聚乙烯吡咯烷酮、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵中的一种。In the above preparation method, the surfactant is one of polyvinylpyrrolidone, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetyltrimethylammonium bromide kind.
上述制备方法中，所述锂盐化合物为氢氧化锂、醋酸锂、硝酸锂、乙醇锂、甲酸锂、碳酸锂中的一种或多种的混合物。In the above preparation method, the lithium salt compound is a mixture of one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, and lithium carbonate.
上述制备方法中，所述镍盐化合物为硫酸镍、乙酸镍、草酸镍或硝酸镍中的一种或多种的混合物。In the above preparation method, the nickel salt compound is a mixture of one or more of nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate.
上述制备方法中，所述钴盐化合物为硫酸钴、乙酸钴、草酸钴或硝酸钴中的一种或多种的混合物。In the above preparation method, the cobalt salt compound is a mixture of one or more of cobalt sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate.
上述制备方法中，所述混合方式为液相混合或固相混合。In the above preparation method, the mixing method is liquid phase mixing or solid phase mixing.
上述制备方法中，所述煅烧气氛为空气。In the above preparation method, the calcination atmosphere is air.
上述制备方法中，所述二氧化锰具有由直径200～400nm的纳米棒自组装形成的直径为10～20μm辐射状空心纳微结构。In the above preparation method, the manganese dioxide has a radial hollow nanostructure with a diameter of 10-20 μm formed by self-assembly of nanorods with a diameter of 200-400 nm.
上述制备方法中，所述富锂锰基正极材料具有由直径200～400nm的纳米棒自组装形成的直径为10～20μm辐射状空心纳微结构。In the above preparation method, the lithium-rich manganese-based positive electrode material has a radial hollow nanostructure with a diameter of 10-20 μm formed by self-assembly of nanorods with a diameter of 200-400 nm.
本发明具有如下有益效果：The present invention has following beneficial effects:
(1)采用本方法制备合成的富锂锰基正极材料具有特殊的、由直径200～400nm的纳米棒自组装形成的直径为10～20μm辐射状空心纳微结构。(1) The lithium-rich manganese-based cathode material synthesized by this method has a special radial hollow nanostructure with a diameter of 10-20 μm formed by self-assembly of nanorods with a diameter of 200-400 nm.
(2)通过利用该富锂锰基正极材料特殊纳微结构中纳米结构本征载流子扩散路径短的优点，可有效提高材料的倍率容量，同时也可利用微米结构表面能低不易团聚、化学稳定性高等特性，保持材料的循环性能，(2) By taking advantage of the short diffusion path of intrinsic carriers in the nanostructure in the special nanostructure of the lithium-rich manganese-based cathode material, the rate capacity of the material can be effectively improved, and the low surface energy of the microstructure is not easy to agglomerate, High chemical stability and other characteristics, maintain the cycle performance of the material,
(3)本发明工艺简单、性能提升明显可靠，制备的富锂锰基正极材料具有较高的倍率容量与优异的循环性能。(3) The process of the present invention is simple, the performance improvement is obvious and reliable, and the prepared lithium-rich manganese-based cathode material has a higher rate capacity and excellent cycle performance.
附图说明Description of drawings
图1是本发明制备的具有纳微结构的二氧化锰的放大倍数为3000的SEM图。Fig. 1 is the SEM image of the magnification of 3000 of manganese dioxide with nano-microstructure prepared by the present invention.
图2是本发明制备的具有纳微结构的二氧化锰的放大倍数为10000的SEM图。Fig. 2 is a SEM image with a magnification of 10,000 of the manganese dioxide with nano-microstructure prepared by the present invention.
图3是本发明制备的具有纳微结构的富锂锰基正极材料的放大倍数为10000的SEM图。Fig. 3 is a SEM image with a magnification of 10,000 of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared by the present invention.
图4是本发明实施例1制备的具有纳微结构的富锂锰基正极材料的XRD图。Fig. 4 is an XRD pattern of the lithium-rich manganese-based cathode material with nano-microstructure prepared in Example 1 of the present invention.
图5是本发明实施例1制备的具有纳微结构的富锂锰基正极材料扣电的倍率性能曲线。Fig. 5 is a charge performance curve of lithium-rich manganese-based positive electrode material with nano-microstructure prepared in Example 1 of the present invention.
图6是本发明实施例1制备的具有纳微结构的富锂锰基正极材料扣电的循环性能曲线。Fig. 6 is a button charge cycle performance curve of the lithium-rich manganese-based cathode material with nano-microstructure prepared in Example 1 of the present invention.
具体实施方式detailed description
下面结合附图对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。The technical solution of the present invention will be further described below in conjunction with the accompanying drawings, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention. within the scope of protection.
实施例1：Example 1:
按摩尔比1∶1.1∶3称取硫酸锰、聚乙烯吡咯烷酮与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于180℃的烘箱中，控制反应时间为12h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构，如图1、2所示；Weigh manganese sulfate, polyvinylpyrrolidone and sodium chlorate in a molar ratio of 1:1.1:3, stir and dissolve with an appropriate amount of deionized water until clear, transfer the mixed solution into a high-pressure reactor lined with polytetrafluoroethylene, and Place in an oven at 180°C, control the reaction time for 12 hours, wait for the reaction kettle to cool down to room temperature naturally, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in an oven at 110°C to dry for 48 hours , the obtained black manganese dioxide powder has a radial hollow nanostructure formed by the self-assembly of nanorods, as shown in Figures 1 and 2;
按摩尔比Li∶Ni∶Mn＝1.2∶0.2∶0.6称取氢氧化锂、乙酸镍、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以2℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至750℃，煅烧10h，得到具有纳微结构的富锂锰基正极材料，化学式为0.5Li2MnO3·0.5LiNi0.5Mn0.5O2。Weigh lithium hydroxide, nickel acetate, and manganese dioxide at a molar ratio of Li:Ni:Mn=1.2:0.2:0.6, and mix them uniformly in a mixed solution of deionized water and ethanol; Raise to 500°C, pre-calcine for 5 hours, then raise the temperature to 750°C at the same heating rate, and calcinate for 10 hours to obtain a lithium-rich manganese-based positive electrode material with nano-microstructure, the chemical formula is 0.5Li 2 MnO 3 ·0.5LiNi 0.5 Mn 0.5 O 2 .
如图3所示，本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径200nm的纳米棒自组装形成的直径10μm辐射状空心结构。如图4所示，本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达261.6mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，如图5所示，0.2、0.5、1、2、5、10C下放电比容量分别约为254、228、204、182、147、112mAh/g；如图6所示，在5C下进行50次循环后放电比容量可达141.2mAh/g，容量保持率为96.1％。As shown in Figure 3, the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, which is specifically manifested as a radial hollow structure with a diameter of 10 μm formed by the self-assembly of nanorods with a diameter of 200 nm. As shown in FIG. 4 , the XRD curve of the lithium-rich manganese-based cathode material with nano-microstructures prepared in this example has superlattice characteristic peaks, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based cathode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V, activated at 0.05C, and the first discharge specific capacity could reach 261.6mAh/g; The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test. As shown in Figure 5, the discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were about 254, 228, 204, 182, 147, 112mAh/g; as shown in Figure 6, after 50 cycles at 5C, the discharge specific capacity can reach 141.2mAh/g, and the capacity retention rate is 96.1%.
实施例2：Example 2:
按摩尔比1∶1∶4称取硝酸锰、聚乙烯吡咯烷酮与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于200℃的烘箱中，控制反应时间为10h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构；Weigh manganese nitrate, polyvinylpyrrolidone and sodium chlorate in a molar ratio of 1:1:4, stir and dissolve with an appropriate amount of deionized water until clear, transfer the mixed solution into a high-pressure reactor lined with polytetrafluoroethylene, and Place in an oven at 200°C, control the reaction time for 10 hours, wait for the reaction kettle to cool down to room temperature naturally, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in an oven at 110°C to dry for 48 hours , the obtained black manganese dioxide powder has a radial hollow nanostructure formed by self-assembly of nanorods;
按摩尔比Li∶Co∶Mn＝1.2∶0.2∶0.6称取乙酸锂、乙酸钴、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以2℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至750℃，煅烧8h，得到具有纳微结构的富锂锰基正极材料，化学式为0.5Li2MnO3·0.5LiCo0.5Mn0.5O2。Weigh lithium acetate, cobalt acetate, and manganese dioxide at a molar ratio of Li:Co:Mn=1.2:0.2:0.6, and mix them uniformly in a mixed solution of deionized water and ethanol; to 500°C, pre-calcined for 5 hours, then raised to 750°C at the same heating rate, and calcined for 8 hours to obtain a lithium-rich manganese-based positive electrode material with a nano-microstructure, with a chemical formula of 0.5Li 2 MnO 3 ·0.5LiCo 0.5 Mn 0.5 O 2 .
本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径200nm的纳米棒自组装形成的直径15μm辐射状空心结构。本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达262.5mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，0.2、0.5、1、2、5、10C下放电比容量分别约为254、233、205、183、151、113mAh/g；在5C下进行50次循环后放电比容量可达142.5mAh/g，容量保持率为94.4％。The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, specifically manifested as a radial hollow structure with a diameter of 15 μm formed by the self-assembly of nanorods with a diameter of 200 nm. The XRD curve of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a superlattice characteristic peak, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based positive electrode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V. The activation was carried out at 0.05C, and the specific capacity of the first discharge could reach 262.5mAh/g; The lithium-rich manganese-based cathode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test, and the discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were respectively about 254, 233, 205, 183, 151, 113mAh/g; after 50 cycles at 5C, the discharge specific capacity can reach 142.5mAh/g, and the capacity retention rate is 94.4%.
实施例3：Example 3:
按摩尔比1∶1∶4称取草酸锰、十六烷基三甲基溴化铵与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于200℃的烘箱中，控制反应时间为10h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构；Weigh manganese oxalate, cetyltrimethylammonium bromide and sodium chlorate in a molar ratio of 1:1:4, stir and dissolve with an appropriate amount of deionized water until clear, and transfer the mixed solution into a polytetrafluoroethylene-lined In a high-pressure reaction kettle, place it in an oven at 200°C, and control the reaction time for 10 hours. After the reaction kettle is naturally cooled to room temperature, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in Dry in an oven at 110°C for 48 hours to obtain a black manganese dioxide powder with a radial hollow nanostructure formed by self-assembly of nanorods;
按摩尔比Li∶Mn∶Ni＝1.13∶0.3∶0.57称取草酸锂、草酸镍、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以2℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至800℃，煅烧8h，得到具有纳微结构的富锂锰基正极材料，化学式为0.3Li2MnO3·0.7LiNi0.5Mn0.5O2。Weigh lithium oxalate, nickel oxalate, and manganese dioxide at a molar ratio of Li:Mn:Ni=1.13:0.3:0.57, and mix them uniformly in a mixed solution of deionized water and ethanol; to 500°C, pre-calcined for 5 hours, and then raised to 800°C at the same heating rate, and calcined for 8 hours to obtain a lithium-rich manganese-based positive electrode material with a nano-microstructure, with a chemical formula of 0.3Li 2 MnO 3 ·0.7LiNi 0.5 Mn 0.5 O 2 .
本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径300nm的纳米棒自组装形成的直径15μm辐射状空心结构。本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达258.5mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，0.2、0.5、1、2、5、10C下放电比容量分别约为252、230、198、178、141、108mAh/g；在5C下进行50次循环后放电比容量可达132.6mAh/g，容量保持率为94.0％。The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, specifically manifested as a radial hollow structure with a diameter of 15 μm formed by the self-assembly of nanorods with a diameter of 300 nm. The XRD curve of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a superlattice characteristic peak, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based cathode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V, activated at 0.05C, and the first discharge specific capacity could reach 258.5mAh/g; The lithium-rich manganese-based cathode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test. The discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were about 252, 230, 198, 178, 141, 108mAh/g; after 50 cycles at 5C, the discharge specific capacity can reach 132.6mAh/g, and the capacity retention rate is 94.0%.
实施例4：Example 4:
按摩尔比1∶1.05∶4称取乙酸锰、十四烷基三甲基溴化铵与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于160℃的烘箱中，控制反应时间为15h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构；Weigh manganese acetate, tetradecyltrimethylammonium bromide and sodium chlorate in a molar ratio of 1:1.05:4, stir and dissolve with an appropriate amount of deionized water until clear, and transfer the mixed solution into a polytetrafluoroethylene-lined Put it in a high-pressure reactor, place it in an oven at 160°C, and control the reaction time for 15 hours. After the reactor is naturally cooled to room temperature, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in Dry in an oven at 110°C for 48 hours to obtain a black manganese dioxide powder with a radial hollow nanostructure formed by self-assembly of nanorods;
按摩尔比Li∶Ni∶Co∶Mn＝1.12∶0.26∶0.26∶0.36称取乙酸锂、乙酸镍、乙酸钴、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以3℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至800℃，煅烧10h，得到具有纳微结构的富锂锰基正极材料，化学式为0.5Li2MnO3·0.5LiNi0.5Co0.5O2。Weigh lithium acetate, nickel acetate, cobalt acetate, and manganese dioxide at a molar ratio of Li:Ni:Co:Mn=1.12:0.26:0.26:0.36, and mix them uniformly in a mixed solution of deionized water and ethanol; min heating rate from room temperature to 500°C, pre-calcined for 5 hours, then raised to 800°C at the same heating rate, and calcined for 10 hours to obtain a lithium-rich manganese-based cathode material with a nano-microstructure, the chemical formula is 0.5Li 2 MnO 3 ·0.5 LiNi 0.5 Co 0.5 O 2 .
本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径200nm的纳米棒自组装形成的直径12μm辐射状空心结构。本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达261.9mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，0.2、0.5、1、2、5、10C下放电比容量分别约为257、236、206、184、146、116mAh/g；在5C下进行50次循环后放电比容量可达138.2mAh/g，容量保持率为94.7％。The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, specifically manifested as a radial hollow structure with a diameter of 12 μm formed by the self-assembly of nanorods with a diameter of 200 nm. The XRD curve of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a superlattice characteristic peak, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based cathode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V, activated at 0.05C, and the first discharge specific capacity could reach 261.9mAh/g; The lithium-rich manganese-based cathode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test, and the discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were about 257, 236, 206, 184, 146, 116mAh/g; after 50 cycles at 5C, the discharge specific capacity can reach 138.2mAh/g, and the capacity retention rate is 94.7%.
实施例5：Example 5:
按摩尔比1∶1.2∶4称取硫酸锰、十二烷基三甲基溴化铵与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于200℃的烘箱中，控制反应时间为12h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构；Weigh manganese sulfate, dodecyltrimethylammonium bromide and sodium chlorate in a molar ratio of 1:1.2:4, stir and dissolve with an appropriate amount of deionized water until clear, and transfer the mixed solution into a polytetrafluoroethylene-lined In a high-pressure reaction kettle, place it in an oven at 200°C, and control the reaction time for 12 hours. After the reaction kettle is naturally cooled to room temperature, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in Dry in an oven at 110°C for 48 hours to obtain a black manganese dioxide powder with a radial hollow nanostructure formed by self-assembly of nanorods;
按摩尔比Li∶Ni∶Co∶Mn＝1.2∶0.136∶0.36∶0.528称取乙酸锂、乙酸镍、乙酸钴、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以3℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至800℃，煅烧10h，得到具有纳微结构的富锂锰基正极材料，化学式为0.5Li2MnO3·0.5LiNi1/3Ni1/3Mn1/3O2。Weigh lithium acetate, nickel acetate, cobalt acetate, and manganese dioxide at a molar ratio of Li:Ni:Co:Mn=1.2:0.136:0.36:0.528, and mix them uniformly in a mixed solution of deionized water and ethanol; min heating rate from room temperature to 500°C, pre-calcined for 5 hours, then raised to 800°C at the same heating rate, and calcined for 10 hours to obtain a lithium-rich manganese-based cathode material with a nano-microstructure, the chemical formula is 0.5Li 2 MnO 3 ·0.5 LiNi 1/3 Ni 1/3 Mn 1/3 O 2 .
本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径200nm的纳米棒自组装形成的直径15μm辐射状空心结构。本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达262.1mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，0.2、0.5、1、2、5、10C下放电比容量分别约为253、232、204、186、145、111mAh/g；在5C下进行50次循环后放电比容量可达139.6mAh/g，容量保持率为96.3％。The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, specifically manifested as a radial hollow structure with a diameter of 15 μm formed by the self-assembly of nanorods with a diameter of 200 nm. The XRD curve of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a superlattice characteristic peak, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based cathode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V, activated at 0.05C, and the specific capacity of the first discharge could reach 262.1mAh/g; The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test. The discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were about 253, 232, 204, 186, 145, 111mAh/g; after 50 cycles at 5C, the discharge specific capacity can reach 139.6mAh/g, and the capacity retention rate is 96.3%.
实施例6：Embodiment 6:
按摩尔比1∶1.1∶4称取硝酸锰、聚乙烯吡咯烷酮与氯酸钠，用适量去离子水搅拌溶解至澄清，将混合溶液转入内衬聚四氟乙烯的高压反应釜中，将其置于200℃的烘箱中，控制反应时间为12h，待反应釜自然冷却至室温，过滤，得到黑色沉淀，用去离子水与乙醇反复清洗至pH为7，放置于110℃的烘箱中干燥48h，得到得黑色二氧化锰粉末具有由纳米棒自组装形成的辐射状空心纳微结构；Weigh manganese nitrate, polyvinylpyrrolidone and sodium chlorate in a molar ratio of 1:1.1:4, stir and dissolve with an appropriate amount of deionized water until clear, transfer the mixed solution into a high-pressure reactor lined with polytetrafluoroethylene, and Place in an oven at 200°C, control the reaction time for 12 hours, wait for the reaction kettle to cool down to room temperature naturally, filter to obtain a black precipitate, wash it repeatedly with deionized water and ethanol until the pH is 7, and place it in an oven at 110°C to dry for 48 hours , the obtained black manganese dioxide powder has a radial hollow nanostructure formed by self-assembly of nanorods;
按摩尔比Li∶Ni∶Co∶Mn＝1.2∶0.136∶0.36∶0.528称取乙酸锂与碳酸锂摩尔比为1∶1混合物、乙酸镍与草酸镍摩尔比为1∶1混合物、乙酸钴与草酸钴摩尔比为1∶1混合物、二氧化锰，并在去离子水与乙醇混合溶液中均匀混合；以2℃/min升温速率从室温升至500℃，预烧5h，再以相同升温速率升至800℃，煅烧10h，得到具有纳微结构的富锂锰基正极材料，化学式为0.5Li2MnO3·0.5LiNi1/3Ni1/3Mn1/3O2。According to the molar ratio Li:Ni:Co:Mn=1.2:0.136:0.36:0.528, weigh the mixture of lithium acetate and lithium carbonate with a molar ratio of 1:1, the mixture of nickel acetate and nickel oxalate with a molar ratio of 1:1, cobalt acetate and oxalic acid The cobalt molar ratio is 1:1 mixture, manganese dioxide, and uniformly mixed in the mixed solution of deionized water and ethanol; the temperature is raised from room temperature to 500 ° C at a heating rate of 2 ° C / min, pre-calcined for 5 hours, and then heated at the same heating rate The temperature was raised to 800°C and calcined for 10 hours to obtain a lithium-rich manganese-based positive electrode material with a nanostructure and a chemical formula of 0.5Li 2 MnO 3 ·0.5LiNi 1/3 Ni 1/3 Mn 1/3 O 2 .
本实施例制备的具有纳微结构的富锂锰基正极材料具有均一的纳微结构，具体表现为由直径500nm的纳米棒自组装形成的直径15μm辐射状空心结构。本实施例制备的具有纳微结构的富锂锰基正极材料的XRD曲线出现超晶格特征峰，说明合成材料为富锂锰基材料。将得到的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池，在2～4.8V区间内进行电化学性能测试，以0.05C活化进行，首次放电比容量可达258.2mAh/g；对本实施例制备的具有纳微结构的富锂锰基正极材料装配模拟锂离子电池进行倍率性能测试，0.2、0.5、1、2、5、10C下放电比容量分别约为251、229、194、173、141、106mAh/g；在5C下进行50次循环后放电比容量可达129.4mAh/g，容量保持率为91.8％。The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a uniform nano-microstructure, specifically manifested as a radial hollow structure with a diameter of 15 μm formed by the self-assembly of nanorods with a diameter of 500 nm. The XRD curve of the lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example has a superlattice characteristic peak, indicating that the synthesized material is a lithium-rich manganese-based material. The obtained lithium-rich manganese-based positive electrode material with nano-microstructure was assembled into a simulated lithium-ion battery, and the electrochemical performance test was carried out in the range of 2-4.8V, activated at 0.05C, and the first discharge specific capacity could reach 258.2mAh/g; The lithium-rich manganese-based positive electrode material with nano-microstructure prepared in this example was assembled to simulate the lithium-ion battery for rate performance test, and the discharge specific capacities at 0.2, 0.5, 1, 2, 5, and 10C were about 251, 229, 194, 173, 141, 106mAh/g; after 50 cycles at 5C, the discharge specific capacity can reach 129.4mAh/g, and the capacity retention rate is 91.8%.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410409799.XA CN104157844B (en) | 2014-08-19 | 2014-08-19 | High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410409799.XA CN104157844B (en) | 2014-08-19 | 2014-08-19 | High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104157844A CN104157844A (en) | 2014-11-19 |
| CN104157844B true CN104157844B (en) | 2016-03-16 |
Family
ID=51883297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410409799.XA Active CN104157844B (en) | 2014-08-19 | 2014-08-19 | High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104157844B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692703B (en) * | 2014-11-24 | 2017-09-08 | 苏州世名科技股份有限公司 | Lithium-rich manganese-based anode material and preparation method thereof and lithium ion battery |
| CN104900866B (en) * | 2015-04-29 | 2017-07-21 | 哈尔滨工业大学 | A kind of lithium-rich anode material of micro-nano hierarchical structure and preparation method thereof |
| CN105047898B (en) * | 2015-06-05 | 2017-03-01 | 吉林大学 | A kind of twin spherical lithium ion secondary battery lithium-rich anode material and preparation method thereof |
| CN105655573B (en) * | 2016-01-29 | 2018-04-03 | 合肥工业大学 | A kind of general preparative methods of the adjustable one-dimensional micro-nano structure manganese base lithium ion battery electrode material of draw ratio |
| CN105742623A (en) * | 2016-04-07 | 2016-07-06 | 华南师范大学 | Nanometer prismatic lithium-rich material and preparation method and application thereof |
| CN106058239B (en) * | 2016-07-25 | 2019-06-11 | 上海电力学院 | A kind of preparation method of nanowire-like lithium-rich manganese-based cathode material |
| CN106784740B (en) * | 2017-02-16 | 2019-08-30 | 盐城工学院 | A kind of hollow spherical cathode material and preparation method thereof |
| CN112701273B (en) * | 2020-12-29 | 2023-05-02 | 国联汽车动力电池研究院有限责任公司 | Preparation method of fluorine-doped lithium-rich manganese-based positive electrode material |
| CN114275827B (en) * | 2021-12-16 | 2023-10-31 | 河源职业技术学院 | Method for preparing ternary composite material by manganese dioxide nanorod precursor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582497A (en) * | 2009-06-18 | 2009-11-18 | 中南大学 | Method for preparing composite anode material of high-capacity lithium ion battery |
| CN102709545A (en) * | 2012-06-11 | 2012-10-03 | 湖南化工研究院 | Lithium manganese oxide cathode material preparation method for lithium ion power battery |
| CN103187566A (en) * | 2013-03-28 | 2013-07-03 | 浙江大学 | Tubular lithium-rich anode material, preparation method and application thereof |
| CN103715416A (en) * | 2013-12-30 | 2014-04-09 | 华南师范大学 | Preparation method of Li[Li0.201Ni0.133Co0.133Mn0.533]O2 for high-capacity lithium-ion battery cathode material |
| CN103943848A (en) * | 2014-04-23 | 2014-07-23 | 合肥工业大学 | Preparation method of positive pole material of cobalt-based lithium ion battery with porous rod-like structure |
-
2014
- 2014-08-19 CN CN201410409799.XA patent/CN104157844B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582497A (en) * | 2009-06-18 | 2009-11-18 | 中南大学 | Method for preparing composite anode material of high-capacity lithium ion battery |
| CN102709545A (en) * | 2012-06-11 | 2012-10-03 | 湖南化工研究院 | Lithium manganese oxide cathode material preparation method for lithium ion power battery |
| CN103187566A (en) * | 2013-03-28 | 2013-07-03 | 浙江大学 | Tubular lithium-rich anode material, preparation method and application thereof |
| CN103715416A (en) * | 2013-12-30 | 2014-04-09 | 华南师范大学 | Preparation method of Li[Li0.201Ni0.133Co0.133Mn0.533]O2 for high-capacity lithium-ion battery cathode material |
| CN103943848A (en) * | 2014-04-23 | 2014-07-23 | 合肥工业大学 | Preparation method of positive pole material of cobalt-based lithium ion battery with porous rod-like structure |
Non-Patent Citations (2)
| Title |
|---|
| "A facile one-pot hydrothermal synthesis of β-MnO2 nanopincers and their catalytic degradation of methylene blue";Gao Cheng,et al.;《Journal of Solid State Chemistry》;20140505;第217卷;第57-63页 * |
| 湿法球磨制备LiCo_(1/3)Mn_(1/3)Ni_(1/3)O_2材料及表征;谭江等;《电源技术》;20091120(第11期) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104157844A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104157831B (en) | Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof | |
| CN104157844B (en) | High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof | |
| CN103227323B (en) | Preparation method of positive pole material (spinel type lithium nickel manganese oxide) of high-voltage lithium ion battery | |
| CN105185979B (en) | A kind of anode material for lithium ion battery of hollow-core construction and preparation method thereof | |
| CN104953110B (en) | Lithium ion battery lithium-rich manganese-based anode material with hollow-core construction and preparation method thereof | |
| CN104868122A (en) | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material | |
| CN103490059B (en) | The preparation method of porous pattern high-voltage lithium nickel manganate anode material | |
| CN103078109A (en) | Gradient coated LiNiO2 material and preparation method | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN102637866A (en) | Method for preparing lithium ion battery anode material with concentration gradient | |
| CN103928664A (en) | A lithium-rich manganese-based positive electrode material with a fast ion conductor cladding layer and a surface heterogeneous structure and its preparation method | |
| CN103682315B (en) | Preparation method of high-capacity, long-life lithium-ion battery lithium manganate cathode material | |
| CN103985854A (en) | A kind of preparation method of nanoscale lithium nickel manganese oxide cathode material | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN102709568A (en) | A kind of preparation method of LiNixCoyMn1-x-yO2 of nickel-cobalt manganese oxide lithium lithium ion battery cathode material | |
| CN107394123A (en) | Lithium-rich manganese-based hollow nano-sphere positive electrode that thin slice is wound in and preparation method thereof | |
| CN103956478A (en) | Preparation method of high-specific-capacity lithium-rich anode material | |
| CN107204426A (en) | A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property | |
| CN106410142A (en) | A kind of cathode material and preparation method thereof coated lithium-rich layered oxide with LaNiO3 | |
| CN103441238A (en) | Mg-doped Li-rich anode material and preparation method for same | |
| CN105390666A (en) | Lithium mixing method for lithium ion positive electrode material synthetic process | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Li1+xMn3/2-yNi1/2-zMy+zO4 for long-life lithium ion battery | |
| CN108735993B (en) | A kind of preparation method of Co, Al co-doped high nickel manganese-based oxide cathode material | |
| CN104900866B (en) | A kind of lithium-rich anode material of micro-nano hierarchical structure and preparation method thereof | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160519 Address after: 150000, room 14955, No. 414, No. 9, enterprise accelerator building, science and technology innovation enterprise, Harbin hi tech Zone, Heilongjiang, China Patentee after: HARBIN BOERTE ENERGY TECHNOLOGY CO., LTD. Address before: 150000 Harbin, Nangang, West District, large straight street, No. 92 Patentee before: Harbin Institute of Technology |