WO2018121101A1 - Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material - Google Patents

Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material Download PDF

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WO2018121101A1
WO2018121101A1 PCT/CN2017/110595 CN2017110595W WO2018121101A1 WO 2018121101 A1 WO2018121101 A1 WO 2018121101A1 CN 2017110595 W CN2017110595 W CN 2017110595W WO 2018121101 A1 WO2018121101 A1 WO 2018121101A1
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lithium
lithium manganate
cycle
mol
positive electrode
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徐茂龙
黄红如
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徐茂龙
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

A method for preparing a high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material, comprising the following steps: (1) mixing and drying an aqueous solution of manganese salt and an aqueous solution of carbonate to obtain spherical manganese carbonate; (2) obtaining spherical manganese dioxide; (3) mixing the spherical manganese dioxide with lithium hydroxide for roasting to obtain Li2MnO4; (4) adding the Li2MnO4 to a manganese chloride solution, stirring evenly, adding Al2O3, Sc2O3, and CeO2 powder, stirring evenly and drying to obtain a precursor product; and (5) sintering to obtain the modified lithium-rich lithium manganate positive electrode material. The method for preparing a high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material has the characteristics of high efficiency, high speed and energy saving, the modified lithium-rich lithium manganate positive electrode material prepared using the preparing method has the advantages of high capacity, high-temperature stability, good cycle performance, high compaction density, high charging speed, etc., and the method has a simple technology, is environmentally friendly, and is suitable for large-batch industrial production.

Description

一种高循环、高电压改性富锂锰酸锂正极材料的制备方法Preparation method of high cycle and high voltage modified lithium lithium manganate cathode material 技术领域Technical field
本发明涉及一种正极材料制备方法,具体涉及一种高循环、高电压改性富锂锰酸锂正极材料的制备方法.。The invention relates to a preparation method of a cathode material, in particular to a preparation method of a high cycle and high voltage modified lithium lithium manganate cathode material.
背景技术Background technique
锰基正极材料具有价格低,绿色无污染等优点,是锂离子电池的研究重点。在锰基正极材料中,研究得较多的有尖晶石Li2MnO3、层状LiMnO2和层状固溶体正极材料,纯的富锂锰酸锂Li2MnO3亦可表示为Li(Li1/3Mn2/3)O2,具有层状结构,Li出现在过渡金属层中,与Mn(按照Li:Mn=1:2)形成了超点阵的结构,由于其中的Mn已为+4价,在正常的充放电范围内(2.0-4.4V),Mn4+很难再继续升价,Li2MnO3呈现出非电化学活性。但当充放电的范围扩展为2.0-4.8V时,Li2MnO3可表现出电活性,但在首次充电时,O伴随着Li+一起脱出,Li2MnO3的理论比容量可达到438mAh/g,且具有良好的热稳定性,但由于充放电机理特殊,材料首次不可逆容量大,循环性能较差,导电性和倍率性能差,不适合单独使用,因此有待进一步的改进。Manganese-based cathode materials have the advantages of low price, no pollution, and are the focus of research on lithium-ion batteries. Among the manganese-based cathode materials, spinel Li 2 MnO 3 , layered LiMnO 2 and layered solid solution cathode materials have been studied, and pure lithium lithium manganate Li 2 MnO 3 can also be expressed as Li (Li). 1/3 Mn 2/3 )O 2 , with a layered structure, Li appears in the transition metal layer, and Mn (according to Li:Mn=1:2) forms a superlattice structure, since Mn is already +4 valence, in the normal charge and discharge range (2.0-4.4V), Mn 4+ is difficult to continue to increase the price, and Li 2 MnO 3 exhibits non-electrochemical activity. However, when the range of charge and discharge is extended to 2.0-4.8V, Li 2 MnO 3 can exhibit electrical activity, but on the first charge, O is accompanied by Li + together, and the theoretical specific capacity of Li 2 MnO 3 can reach 438 mAh / g, and has good thermal stability, but due to the special charging and discharging mechanism, the material has large irreversible capacity for the first time, poor cycle performance, poor conductivity and rate performance, and is not suitable for use alone, so further improvement is needed.
发明内容Summary of the invention
本发明所要解决的技术问题是针对上述现有技术的不足而提供一种高效的长寿命、高循环动力型锰酸锂正极材料的制备方法。The technical problem to be solved by the present invention is to provide a high-efficiency long-life, high-cycle dynamic lithium manganate cathode material preparation method in view of the above-mentioned deficiencies of the prior art.
本发明提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,包括如下步骤:The invention provides a preparation method of a high cycle and high voltage modified lithium lithium manganate cathode material, comprising the following steps:
(1)将浓度为0.05mol/L~3mol/L锰盐的水溶液和浓度为2mol/L~8mol/L的碳酸盐的水溶液混合,搅拌反应15min,分离、洗涤、干燥后得到球形碳酸锰;(1) mixing an aqueous solution having a concentration of 0.05 mol/L to 3 mol/L of manganese salt and an aqueous solution of a carbonate having a concentration of 2 mol/L to 8 mol/L, stirring the reaction for 15 minutes, separating, washing, and drying to obtain spherical manganese carbonate. ;
(2)将步骤(1)中所得球形碳酸锰分散于水中得到分散液,向所述分散液中滴加浓度为3mol/L的高锰酸钾溶液,搅拌1~3min滴加稀酸,反应1~3min, 分离、洗涤、干燥后得到球形二氧化锰;(2) Dispersing the spherical manganese carbonate obtained in the step (1) in water to obtain a dispersion, adding a potassium permanganate solution having a concentration of 3 mol/L to the dispersion, and adding a dilute acid by stirring for 1 to 3 minutes. 1 to 3 minutes, After separation, washing and drying, spherical manganese dioxide is obtained;
(3)将球形二氧化锰于氢氧化锂混合进行焙烧,得到Li2MnO4(3) The spherical manganese dioxide lithium hydroxide mixing calcined to obtain Li 2 MnO 4;
(4)将步骤(3)中所得到Li2MnO4加入到氯化锰溶液中,搅拌均匀,同时加入Al2O3、Sc2O3和Ce O2粉末,并搅拌均匀,烘干得到前驱体产物,(4) Adding Li 2 MnO 4 obtained in the step (3) to the manganese chloride solution, stirring uniformly, simultaneously adding Al 2 O 3 , Sc 2 O 3 and Ce O 2 powder, stirring uniformly, and drying Precursor product,
(5)将步骤(4)中得到的前驱体体产物进行烧结得到改性富锂锰酸锂正极材料。(5) The precursor product obtained in the step (4) is sintered to obtain a modified lithium-rich lithium manganate cathode material.
进一步地,步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:Li2(Mn wAlz Scy Cex)O4,其中6w+4x+3y+3z=6。Further, the modified lithium-rich lithium manganate cathode material obtained in the step (4) conforms to the chemical formula: the modified lithium-rich lithium manganate cathode material obtained in the step (4) conforms to the chemical formula: Li 2 (Mn w Alz Sc y Ce x ) O 4 , where 6w+4x+3y+3z=6.
本发明的有益效果在于:The beneficial effects of the invention are:
本发明提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法具有高效、快速、节能的特点,且通过该合成方法合成的改性富锂锰酸锂正极材料具有容量高、高温稳定、循环性能好、压实密度高、充电速度快等优点,且该方法工艺简单、环境友好、适合大批量工业产生。The invention provides a high-cycle, high-voltage modified lithium lithium manganate cathode material preparation method with high efficiency, rapidity and energy saving, and the modified lithium lithium manganate cathode material synthesized by the synthesis method has high capacity. The utility model has the advantages of high temperature stability, good cycle performance, high compaction density and fast charging speed, and the method is simple in process, environmentally friendly, and suitable for mass production.
具体实施方式detailed description
下面结合附图具体阐明本发明的实施方式,附图仅供参考和说明使用,不构成对本发明专利保护范围的限制。The embodiments of the present invention are exemplified in the following with reference to the accompanying drawings, which are for the purpose of illustration and description.
实施例1Example 1
本实施例提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,包括如下步骤:The embodiment provides a method for preparing a high cycle, high voltage modified lithium lithium manganate cathode material, comprising the following steps:
(1)将浓度为0.05mol/L~3mol/L锰盐的水溶液和浓度为2mol/L~8mol/L的碳酸盐的水溶液混合,搅拌反应15min,分离、洗涤、干燥后得到球形碳酸锰;(1) mixing an aqueous solution having a concentration of 0.05 mol/L to 3 mol/L of manganese salt and an aqueous solution of a carbonate having a concentration of 2 mol/L to 8 mol/L, stirring the reaction for 15 minutes, separating, washing, and drying to obtain spherical manganese carbonate. ;
(2)将步骤(1)中所得球形碳酸锰分散于水中得到分散液,向所述分散液中滴加浓度为3mol/L的高锰酸钾溶液,搅拌1~3min滴加稀酸,反应1~3min,分离、洗涤、干燥后得到球形二氧化锰;(2) Dispersing the spherical manganese carbonate obtained in the step (1) in water to obtain a dispersion, adding a potassium permanganate solution having a concentration of 3 mol/L to the dispersion, and adding a dilute acid by stirring for 1 to 3 minutes. After 1 to 3 minutes, the spherical manganese dioxide is obtained after separation, washing and drying;
(3)将球形二氧化锰于氢氧化锂混合进行焙烧,得到Li2MnO4(3) mixing spherical manganese dioxide in lithium hydroxide to obtain Li 2 MnO 4 ;
(4)将步骤(3)中所得到Li2MnO4加入到氯化锰溶液中,搅拌均匀,同时加入Al2O3、Sc2O3和CeO2粉末,并搅拌均匀,烘干得到前驱体产物,(4) Adding Li 2 MnO 4 obtained in the step (3) to the manganese chloride solution, stirring uniformly, simultaneously adding Al 2 O 3 , Sc 2 O 3 and CeO 2 powder, stirring uniformly, and drying to obtain a precursor Body product,
(5)将步骤(4)中得到的前驱体体产物进行烧结得到改性富锂锰酸锂正极材料。(5) The precursor product obtained in the step (4) is sintered to obtain a modified lithium-rich lithium manganate cathode material.
本实施例中,步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:步骤(4)中得到的改性富锂锰酸锂正极材料Li2(Mn 0.5Al0.1Sc0.1Ce0.6)O4In this embodiment, the modified lithium-rich lithium manganate cathode material obtained in the step (4) conforms to the chemical formula: the modified lithium-rich lithium manganate cathode material Li 2 (Mn 0.5 Al 0.1 Sc 0.1 Ce obtained in the step (4) 0.6 )O 4 .
测试结果表明,在充放电电压2.0-4.75V,充放电倍率为0.5C条件下,首次放电比容量为220mAh/g,循环500次容量保持率达80%;The test results show that under the condition of charge-discharge voltage of 2.0-4.75V and charge-discharge rate of 0.5C, the first discharge specific capacity is 220mAh/g, and the capacity retention rate of cycle 500 times reaches 80%;
在充放电倍率为1C的条件下,首次放电比容量为210mAh/g,循环500次容量保持率达81%;Under the condition of 1C of charge and discharge, the first discharge specific capacity is 210mAh/g, and the capacity retention rate of cycle 500 times is 81%;
在充放电倍率为4C的条件下,首次放电比容量为205mAh/g,循环500次容量保持率达78%。Under the condition of a charge-discharge rate of 4C, the first discharge specific capacity was 205 mAh/g, and the capacity retention rate of the cycle was 78%.
实施例2Example 2
本实施例提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,包括如下步骤:The embodiment provides a method for preparing a high cycle, high voltage modified lithium lithium manganate cathode material, comprising the following steps:
(1)将浓度为0.05mol/L~3mol/L锰盐的水溶液和浓度为2mol/L~8mol/L的碳酸盐的水溶液混合,搅拌反应15min,分离、洗涤、干燥后得到球形碳酸锰;(1) mixing an aqueous solution having a concentration of 0.05 mol/L to 3 mol/L of manganese salt and an aqueous solution of a carbonate having a concentration of 2 mol/L to 8 mol/L, stirring the reaction for 15 minutes, separating, washing, and drying to obtain spherical manganese carbonate. ;
(2)将步骤(1)中所得球形碳酸锰分散于水中得到分散液,向所述分散液中滴加浓度为3mol/L的高锰酸钾溶液,搅拌1~3min滴加稀酸,反应1~3min,分离、洗涤、干燥后得到球形二氧化锰;(2) Dispersing the spherical manganese carbonate obtained in the step (1) in water to obtain a dispersion, adding a potassium permanganate solution having a concentration of 3 mol/L to the dispersion, and adding a dilute acid by stirring for 1 to 3 minutes. After 1 to 3 minutes, the spherical manganese dioxide is obtained after separation, washing and drying;
(3)将球形二氧化锰于氢氧化锂混合进行焙烧,得到Li2MnO4(3) mixing spherical manganese dioxide in lithium hydroxide to obtain Li 2 MnO 4 ;
(4)将步骤(3)中所得到Li2MnO4加入到氯化锰溶液中,搅拌均匀,同时加入Al2O3、Sc2O3和CeO2粉末,并搅拌均匀,烘干得到前驱体产物,(4) Adding Li 2 MnO 4 obtained in the step (3) to the manganese chloride solution, stirring uniformly, simultaneously adding Al 2 O 3 , Sc 2 O 3 and CeO 2 powder, stirring uniformly, and drying to obtain a precursor Body product,
(5)将步骤(4)中得到的前驱体体产物进行烧结得到改性富锂锰酸锂正极材料。(5) The precursor product obtained in the step (4) is sintered to obtain a modified lithium-rich lithium manganate cathode material.
本实施例中,步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:步 骤(4)中得到的改性富锂锰酸锂正极材料Li2(Mn 0.5Al0.2Sc0.2Ce0.45)O4In the present embodiment, the modified lithium-rich lithium manganate cathode material obtained in the step (4) is in accordance with the chemical formula: the modified lithium-rich lithium manganate cathode material Li 2 (Mn 0.5 Al 0.2 Sc 0.2 Ce obtained in the step (4). 0.45 )O 4 .
测试结果表明,在充放电电压2.0-4.75V,充放电倍率为0.5C条件下,首次放电比容量为300mAh/g,循环500次容量保持率达95%;The test results show that under the condition of charge-discharge voltage of 2.0-4.75V and charge-discharge rate of 0.5C, the first discharge specific capacity is 300mAh/g, and the capacity retention rate of cycle 500 times reaches 95%;
在充放电倍率为1C的条件下,首次放电比容量为280mAh/g,循环500次容量保持率达81%;Under the condition of 1C of charge and discharge, the first discharge specific capacity is 280mAh/g, and the capacity retention rate of cycle 500 times is 81%;
在充放电倍率为4C的条件下,首次放电比容量为260mAh/g,循环500次容量保持率达78%。Under the condition of a charge-discharge rate of 4C, the first discharge specific capacity was 260 mAh/g, and the capacity retention rate of the cycle was 78%.
实施例3Example 3
本实施例提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,包括如下步骤:The embodiment provides a method for preparing a high cycle, high voltage modified lithium lithium manganate cathode material, comprising the following steps:
(1)将浓度为0.05mol/L~3mol/L锰盐的水溶液和浓度为2mol/L~8mol/L的碳酸盐的水溶液混合,搅拌反应15min,分离、洗涤、干燥后得到球形碳酸锰;(1) mixing an aqueous solution having a concentration of 0.05 mol/L to 3 mol/L of manganese salt and an aqueous solution of a carbonate having a concentration of 2 mol/L to 8 mol/L, stirring the reaction for 15 minutes, separating, washing, and drying to obtain spherical manganese carbonate. ;
(2)将步骤(1)中所得球形碳酸锰分散于水中得到分散液,向所述分散液中滴加浓度为3mol/L的高锰酸钾溶液,搅拌1~3min滴加稀酸,反应1~3min,分离、洗涤、干燥后得到球形二氧化锰;(2) Dispersing the spherical manganese carbonate obtained in the step (1) in water to obtain a dispersion, adding a potassium permanganate solution having a concentration of 3 mol/L to the dispersion, and adding a dilute acid by stirring for 1 to 3 minutes. After 1 to 3 minutes, the spherical manganese dioxide is obtained after separation, washing and drying;
(3)将球形二氧化锰于氢氧化锂混合进行焙烧,得到Li2MnO4(3) mixing spherical manganese dioxide in lithium hydroxide to obtain Li 2 MnO 4 ;
(4)将步骤(3)中所得到Li2MnO4加入到氯化锰溶液中,搅拌均匀,同时加入Al2O3、Sc2O3和Ce O2粉末,并搅拌均匀,烘干得到前驱体产物,(4) Adding Li 2 MnO 4 obtained in the step (3) to the manganese chloride solution, stirring uniformly, simultaneously adding Al 2 O 3 , Sc 2 O 3 and Ce O 2 powder, stirring uniformly, and drying Precursor product,
(5)将步骤(4)中得到的前驱体体产物进行烧结得到改性富锂锰酸锂正极材料。(5) The precursor product obtained in the step (4) is sintered to obtain a modified lithium-rich lithium manganate cathode material.
本实施例中,步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:步骤(4)中得到的改性富锂锰酸锂正极材料Li2(Mn0.5Al0.3Sc0.3Ce0.3)O4In this embodiment, the modified lithium-rich lithium manganate cathode material obtained in the step (4) conforms to the chemical formula: the modified lithium-rich lithium manganate cathode material Li 2 (Mn 0.5 Al 0.3 Sc 0.3 Ce obtained in the step (4). 0.3 )O 4 .
测试结果表明,在充放电电压2.0-4.75V,充放电倍率为0.5C条件下,首次放电比容量为350mAh/g,循环500次容量保持率达96%;The test results show that under the condition of charge-discharge voltage of 2.0-4.75V and charge-discharge rate of 0.5C, the first discharge specific capacity is 350mAh/g, and the capacity retention rate of cycle 500 times reaches 96%;
在充放电倍率为1C的条件下,首次放电比容量为330mAh/g,循环500次容量保持率达94%; Under the condition of 1C of charge and discharge rate, the first discharge specific capacity is 330mAh/g, and the capacity retention rate of cycle 500 times reaches 94%;
在充放电倍率为4C的条件下,首次放电比容量为300mAh/g,循环500次容量保持率达790%。Under the condition of a charge-discharge rate of 4C, the first discharge specific capacity was 300 mAh/g, and the capacity retention rate of the cycle was 790%.
本发明提供一种高循环、高电压改性富锂锰酸锂正极材料的制备方法具有高效、快速、节能的特点,且通过该合成方法合成的高循环、高电压改性富锂锰酸锂正极材料具有容量高、高温稳定、循环性能好、压实密度高、充电速度快等优点。The invention provides a high cycle, high voltage modified lithium lithium manganate cathode material preparation method with high efficiency, rapidity and energy saving, and the high cycle and high voltage modified lithium lithium manganate synthesized by the synthesis method The positive electrode material has the advantages of high capacity, high temperature stability, good cycle performance, high compaction density, and fast charging speed.
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。 The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplifications should all be equivalent replacements and are included in the scope of the present invention.

Claims (2)

  1. 一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,其特征在于,包括如下步骤:The invention discloses a preparation method of a high cycle and high voltage modified lithium lithium manganate cathode material, which comprises the following steps:
    (1)将浓度为0.05mol/L~3mol/L锰盐的水溶液和浓度为2mol/L~8mol/L的碳酸盐的水溶液混合,搅拌反应15min,分离、洗涤、干燥后得到球形碳酸锰;(1) mixing an aqueous solution having a concentration of 0.05 mol/L to 3 mol/L of manganese salt and an aqueous solution of a carbonate having a concentration of 2 mol/L to 8 mol/L, stirring the reaction for 15 minutes, separating, washing, and drying to obtain spherical manganese carbonate. ;
    (2)将步骤(1)中所得球形碳酸锰分散于水中得到分散液,向所述分散液中滴加浓度为3mol/L的高锰酸钾溶液,搅拌1~3min滴加稀酸,反应1~3min,分离、洗涤、干燥后得到球形二氧化锰;(2) Dispersing the spherical manganese carbonate obtained in the step (1) in water to obtain a dispersion, adding a potassium permanganate solution having a concentration of 3 mol/L to the dispersion, and adding a dilute acid by stirring for 1 to 3 minutes. After 1 to 3 minutes, the spherical manganese dioxide is obtained after separation, washing and drying;
    (3)将球形二氧化锰于氢氧化锂混合进行焙烧,得到Li2MnO4(3) mixing spherical manganese dioxide in lithium hydroxide to obtain Li 2 MnO 4 ;
    (4)将步骤(3)中所得到Li2MnO4加入到氯化锰溶液中,搅拌均匀,同时加入Al2O3、Sc2O3和Ce O2粉末,并搅拌均匀,烘干得到前驱体产物,(4) Adding Li 2 MnO 4 obtained in the step (3) to the manganese chloride solution, stirring uniformly, simultaneously adding Al 2 O 3 , Sc 2 O 3 and Ce O 2 powder, stirring uniformly, and drying Precursor product,
    (5)将步骤(4)中得到的前驱体体产物进行烧结得到改性富锂锰酸锂正极材料。(5) The precursor product obtained in the step (4) is sintered to obtain a modified lithium-rich lithium manganate cathode material.
  2. 如权利要求1所述的一种高循环、高电压改性富锂锰酸锂正极材料的制备方法,其特征在于:步骤(4)中得到的改性富锂锰酸锂正极材料符合化学式:Li2(MnwAlzScyCex)O4,其中6w+4x+3y+3z=6。 The method for preparing a high cycle, high voltage modified lithium lithium manganate cathode material according to claim 1, wherein the modified lithium lithium manganate cathode material obtained in the step (4) conforms to a chemical formula: Li 2 (Mn w AlzSc y Ce x )O 4 , wherein 6w+4x+3y+3z=6.
PCT/CN2017/110595 2016-12-30 2017-11-10 Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material WO2018121101A1 (en)

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