CN105742624A - Preparation method of spherical lithium nickel manganese oxide material with hollow porous micro-nano level structure - Google Patents

Preparation method of spherical lithium nickel manganese oxide material with hollow porous micro-nano level structure Download PDF

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CN105742624A
CN105742624A CN201610235265.9A CN201610235265A CN105742624A CN 105742624 A CN105742624 A CN 105742624A CN 201610235265 A CN201610235265 A CN 201610235265A CN 105742624 A CN105742624 A CN 105742624A
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nickel
preparation
manganese
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王丽
吴伟
王江峰
梁广川
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Hebei University of Technology
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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
    • 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
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • 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

The invention provides a preparation method of a spherical lithium nickel manganese oxide material with a hollow porous micro-nano level structure. The method comprises the following steps: (1) dissolving a soluble nickel salt, a manganese salt and urea into a mixed solvent and stirring the mixture to obtain a mixed solution; (2) carrying out hydrothermal reaction at 150-190 DEG C for 4-12 hours and carrying out cooling, washing, filtering and drying to obtain an Ni0.25Mn0.75CO3 precursor; and (3) presintering the precursor in air at 450-550 DEG C, putting the product into absolute ethyl alcohol, adding a lithium source compound, heating and stirring until ethanol volatilization, calcining the product in air at 700-900 DEG C, and carrying out cooling to obtain the LiNi0.5Mn1.5O4 material. Any template agent does not need to be used; the spherical lithium nickel manganese oxide material with the hollow porous micro-nano level structure prepared through a simple kirkendall effect combines the advantages of nano primary particles, the porous structure and the hollow structure, and the rate capability and the cycle performance of the material can be significantly improved.

Description

A kind of preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure
Technical field
The invention belongs to technical field of lithium ion, the preparation method particularly relating to a kind of hollow porous level time spherical nickel ion doped material of micro-nano structure.
Background technology
At present, the anode material for lithium-ion batteries of Commercialization application is (such as LiCoO2、LiMn2O4、LiFePO4Deng) energy density all relatively low, it is impossible to meet the application requirement on electric motor car, hybrid electric vehicle and large-scale energy-storage system.Therefore, the important problem that energy density has become as lithium ion battery researcher and manufacturer faces and the challenge of battery are improved.
The energy density of battery is the specific capacity by battery and running voltage together decides on.Considering the problems such as safety, the room for promotion being improved battery energy density by improvement packaging technology is limited.Therefore people always search for the positive electrode of a kind of high-energy-density.Spinel-type nickel ion doped (LiNi0.5Mn1.5O4) material is a kind of high-energy-density positive electrode that at present research is relatively more, it has 4.7V (vs.Li/Li+) high working voltage, theoretical capacity 147mAh/g, three-dimensional lithium ion diffusion admittance so that it is there is higher energy density and good high rate performance.
Although nickel ion doped material has many advantages, but at high temperature poor high rate performance and cycle performance seriously limit its large-scale application.Can by the transformation of material morphology structure be solved for this problem.Such as can be made into the level time micro-nano structure (the secondary micron particle being made up of nanometer primary particle) of hollow, porous, the stress that in hollow structure energy slow release charge and discharge process, change in volume produces so on the one hand, loose structure can increase the contact area of electrode material and electrolyte, and nanometer primary particle can shorten Li+The evolving path in electrode material, thus high rate performance and the cycle performance of material can be improved simultaneously.
The preparation of current hollow structure mainly adopts soft or hard template.Patent CN103474650A is prepared for the nickel ion doped material of hollow structure, first it prepare manganese carbonate, after calcining, its shell becomes manganese dioxide, then manganese carbonate kernel is dissolved with diluted acid, remaining manganese dioxide shell mix with lithium source and nickel source after through high-temperature calcination prepare hollow nickel ion doped material, material list reveal excellence high rate performance and cycle performance.Zhu et al. (RSCAdv.2014,4:10151-10156) first passes through coprecipitation and prepares Mn3Ca1(CO3)4Spherical precursor, first forms MnO 400 DEG C of pre-burning 4h rear sections by it2, it is embedded in CaCO3In template and core is also undecomposed, subsequently with HCl by CaCO3Template and undecomposed core are removed, thus obtaining Porous hollow MnO2Microsphere, calcines 3h at 600 DEG C afterwards and obtains Porous hollow Mn2O3Microsphere, finally by itself and Ni (NO3)2And LiNO3Porous hollow LiNi is prepared through high-temperature calcination after mix homogeneously0.5Mn1.5O4Material.The shortcomings such as visible, these preparation methoies exist complex process, and poor repeatability, product amount are few, thus limiting its extensive use.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of hollow porous level time spherical nickel ion doped material of micro-nano structure.The method, with carbamide for precipitant, prepares the spherical Ni of even particle size distribution by a step hydro-thermal reaction0.25Mn0.75CO3Presoma, in order to make itself and lithium source be sufficiently mixed uniformly, first its pre-burning is obtained loose structure oxide, finally in high-temperature burning process, prepare the hollow porous level time spherical nickel ion doped material of micro-nano structure by simple Kinkendal Effect, thus reaching the purpose not using template also can prepare hollow structure.
The technical solution used in the present invention is as follows:
The preparation method of a kind of hollow porous level time spherical nickel ion doped material of micro-nano structure, comprises the following steps:
(1) soluble nickel salt, manganese salt and carbamide are dissolved in mixed solvent, stir 20~40 minutes, obtain mixed solution;Wherein, mol ratio nickel: manganese=1:3, mol ratio carbamide and metal ion integral molar quantity=1~3:1, mixed solvent is the mixture of deionized water and organic solvent, and in mixed solution, the total concentration of metal ion is 0.05~0.5M;Described metal ion is nickel ion and manganese ion;
(2) mixed solution that step (1) obtains has been transferred in teflon-lined autoclave, it is put in baking oven after sealing and is incubated 4~12 hours in 150~190 DEG C, naturally cool to room temperature, by gained washing of precipitate, filtration, dried, prepare Ni0.25Mn0.75CO3Presoma;
(3) by step (2) gained Ni0.25Mn0.75CO3Presoma is 450~550 DEG C of pre-burning 3~5h in atmosphere, obtain oxide, then this oxide is first put in dehydrated alcohol, add Li source compound, this mixed solution is heated while stirring at 80 DEG C, after ethanol all volatilizees, by gained powder in atmosphere 700~900 DEG C calcine 5~20 hours, namely obtain LiNi after furnace cooling0.5Mn1.5O4Material;
Wherein, mol ratio is the Li in Li source compound: the metal ion integral molar quantity=1~1.1:2 in step (1);The volume of dehydrated alcohol is 10~20 times of oxide volume.
Described soluble nickel salt is one or more in nickel sulfate, Nickel dichloride., nickel nitrate or nickel acetate.
Described soluble manganese salt is one or more in manganese sulfate, manganese chloride, manganese nitrate or manganese acetate.
Described organic solvent is one or both in ethylene glycol and ethanol.
Described Li source compound is one or more in Lithium hydrate, lithium carbonate and lithium nitrate.
In the described mixed solvent in step (1), volume ratio is preferably deionized water: organic solvent=6:1~1:6.
The substantive distinguishing features of the present invention is:
The present invention first passes through hydro-thermal method and prepares Ni0.25Mn0.75CO3Presoma, obtains oxide after its pre-burning, prepares the LiNi of hollow loose structure by high temperature lithiumation0.5Mn1.5O4Material.The preparation of presoma adopts carbamide as precipitant, because it is as a kind of homogeneous precipitation agent, precipitating ion is generated by sluggish, thus uniform degree of supersaturation in solution can be ensured, and then ensures to generate the uniformity of deposit seed.Additionally, water-heat process adopts the mixed solvent of deionized water and organic solvent (ethanol, ethylene glycol etc.), the low-k of organic solvent and steric effect is utilized to reduce grain diameter further.Gained presoma is after pre-burning, due to the CO that carbonate thermal decomposition produces2The effusion of gas causes the loose structure of oxide particle surface, and this structure is conducive to being sufficiently mixed uniformly with lithium source in mixed lithium process subsequently.In order to not destroy the spherical morphology of presoma, liquid phase batch mixing method is adopted to be mixed homogeneously with lithium source by this oxide.And in last high temperature lithiumation process, due to Kinkendal Effect, solid sphere interior nickel atom and manganese atom are very fast to the speed of external diffusion, the speed that in spheroid outside atmosphere, oxygen atom spreads to ball interior is relatively slow, after spheroid and Air Interface vicinity nickel manganese atom and oxygen atom quickly form shell, the nickel manganese atom of ball interior then continues to external diffusion, moves to shell, ultimately forms hollow ball shape structure.
The nickel ion doped material of hollow porous level prepared by the present invention time micro-nano structure is in combination with the advantage of nanometer primary particle, loose structure and hollow structure, thus being remarkably improved high rate performance and the cycle performance of material.
The invention have the benefit that
(1) make carbamide be hydrolyzed slow releasing carbanion at a certain temperature by a step hydro-thermal reaction, precipitate thus realizing nickel manganese ion simultaneously, and obtain the granular precursor of even particle size distribution.By in embodiment 1 it can be seen that gained Ni0.25Mn0.75CO3Granular precursor is spheroidal particle, and uniform particle diameter, all between 1-2 μm.
(2), in the end in high-temperature burning process, can be prepared by the hollow porous level time spherical LiNi of micro-nano structure by simple Kinkendal Effect0.5Mn1.5O4Material, it is not necessary to use any template.The stress that in hollow structure energy slow release charge and discharge process, change in volume produces on the one hand, loose structure can increase the contact area of electrode material and electrolyte, and nanometer primary particle can shorten Li+The evolving path in electrode material, thus high rate performance and the cycle performance of material can be improved simultaneously.The LiNi prepared in embodiment 20.5Mn1.5O4Discharge capacity under material 5C, 10C can reach 122.2 respectively, 121.4mAh/g.The LiNi prepared in embodiment 30.5Mn1.5O4The capability retention after 200 times is circulated up to 96.3% under material 1C multiplying power.And document (Electrochim.Acta2014,115:290-296) adopts ammonium carbonate and ammonium oxalate to be precipitant, by the solid spherical LiNi that co-precipitation-hydro-thermal-high-temperature calcination technique prepares0.5Mn1.5O4The material discharge capacity when 3C is that under 125.1mAh/g, 1C, the capability retention circulated after 200 times is 94.4%.As can be seen here, the hollow porous structure material that the present invention prepares shows better high rate performance and cycle performance.
Accompanying drawing explanation
Fig. 1 is the Ni that embodiment 1 prepares0.25Mn0.75CO3Scanning electron microscope (SEM) figure of presoma;Wherein Fig. 1 a is 5000 times, and Fig. 1 b is 60000 times;
Fig. 2 is the Ni that embodiment 1 prepares0.25Mn0.75CO3Scanning electron microscope (SEM) figure of the oxide that presoma obtains through pre-burning.
Fig. 3 is the LiNi that embodiment 1 prepares0.5Mn1.5O4Scanning electron microscope (SEM) figure of material.Wherein Fig. 3 a is 5000 times, and Fig. 3 b is 40000 times;
Fig. 4 is the LiNi that embodiment 1 prepares0.5Mn1.5O4X-ray diffraction (XRD) figure of material.
Fig. 5 is the LiNi that embodiment 2 prepares0.5Mn1.5O4The high rate performance curve of material.
Fig. 6 is the LiNi that embodiment 3 prepares0.5Mn1.5O4The 1C cyclic curve of material.
Detailed description of the invention
Below in conjunction with Figure of description, the invention will be further described.
Embodiment 1:
Weigh 0.9954g (0.004mol) nickel acetate (Ni (CH respectively3COO)2·4H2O), 2.9411g (0.012mol) manganese acetate (Mn (CH3COO)2·4H2O) being dissolved in the mixed solution of 80mL deionized water and ethylene glycol (volume ratio 5:1) with 1.9219g (0.032mol) carbamide, magnetic agitation makes it be completely dissolved in 30 minutes;This mixed solution is transferred in teflon-lined 100mL autoclave, has been put in baking oven after sealing and reacts 8 hours in 170 DEG C, naturally cool to room temperature, by gained washing of precipitate, filtration, dried, prepared Ni0.25Mn0.75CO3Presoma, its SEM is as shown in Figure 1.By Fig. 1 (a) it can be seen that prepared presoma is spheroidal particle, uniform particle diameter, substantially remain in 1-2 μm;By Fig. 1 (b) it can be seen that presoma surface is comparatively dense.
Obtaining oxide after first for gained presoma 500 DEG C of pre-burning 4h in atmosphere, its SEM is as in figure 2 it is shown, visible material maintains the spherical morphology of presoma substantially, but particle surface exists a lot of hole, and this is by Ni0.25Mn0.75CO3The CO that thermal decomposition produces2The effusion of gas causes.
In order to not destroy the spherical morphology of presoma, gained oxide first being put in dehydrated alcohol 10 times of oxide volume (volume be), then by Li:(Ni+Mn)=1.03:2 (mol ratio) weighs 0.3044gLi2CO3Add wherein, this mixed solution is placed on magnetic stirring apparatus and heats while stirring at 80 DEG C, until ethanol all volatilizees, by gained powder in atmosphere 800 DEG C calcine 10 hours, namely obtain LiNi after furnace cooling0.5Mn1.5O4Material, its SEM is as shown in Figure 3.By Fig. 3 (a) it can be seen that material maintains the spherical morphology of presoma, uniform particle sizes substantially, substantially remain in 1-2 μm;By Fig. 3 (b) it will be seen that granule is entirely the secondary agglomeration body being made up of nanometer primary particle, and presenting hollow-core construction inside granule, surface presents loose structure, thus having reached the purpose of preparation hollow porous level time wiener structure.Fig. 4 is obtained LiNi0.5Mn1.5O4The XRD figure of material.As seen from the figure, all diffraction maximums all match with standard card PDF#80-2162, illustrate that sample is cubic spinel structure, and each diffraction maximum is sharp-pointed by force, and illustrative material degree of crystallinity is higher, and without LixNi1-xO dephasign occurs.
Embodiment 2:
Weigh 0.4977g (0.002mol) nickel acetate (Ni (CH respectively3COO)2·4H2O), 1.4705g (0.006mol) manganese acetate (Mn (CH3COO)2·4H2O) being dissolved in the mixed solution of 80mL deionized water and ethylene glycol (volume ratio 3:1) with 0.8408g (0.014mol) carbamide, magnetic agitation makes it be completely dissolved in 30 minutes;This mixed solution is transferred in teflon-lined 100mL autoclave, has been put in baking oven after sealing and reacts 6 hours in 180 DEG C, naturally cool to room temperature, by gained washing of precipitate, filtration, dried, prepared Ni0.25Mn0.75CO3Presoma,
Oxide is obtained after first for gained presoma 500 DEG C of pre-burning 4h in atmosphere, it first being put in dehydrated alcohol 15 times of oxide volume (volume be), then by Li:(Ni+Mn)=1.05:2 (mol ratio) weighs 0.1552gLi2CO3Add wherein, this mixed solution is placed on magnetic stirring apparatus and heats while stirring at 80 DEG C, until ethanol all volatilizees, by gained powder in atmosphere 850 DEG C calcine 8 hours, namely obtain LiNi after furnace cooling0.5Mn1.5O4Material.This material is mixed with acetylene black, PTFE 80:15:5 in mass ratio ultrasonic rear stirring, roll-in, puts into the insulation of 120 DEG C of baking oven and obtain positive plate half an hour, using metal lithium sheet as to electrode, 1mol/LLiPF6/ DMC+EMC+EC (volume ratio is 1:1:1) is electrolyte, and glove box at full argon is built-in is configured to button cell.Fig. 5 is this battery discharge curve under different multiplying.As seen from the figure, material specific discharge capacity under 0.2C, 1C, 5C, 10C respectively 120.6,122.6,122.2,121.4mAh/g.Document (Electrochim.Acta2014,115:290-296) adopts ammonium carbonate and ammonium oxalate to be precipitant, by the solid spherical LiNi that co-precipitation-hydro-thermal-high-temperature calcination technique prepares0.5Mn1.5O4The material discharge capacity when 3C is 125.1mAh/g.By comparison, the LiNi that this example prepares0.5Mn1.5O4Material list reveals better high rate performance.
Embodiment 3:
Weigh 0.7466g (0.003mol) nickel acetate (Ni (CH respectively3COO)2·4H2O), 2.2058g (0.009mol) manganese acetate (Mn (CH3COO)2·4H2O) being dissolved in the mixed solution of 80mL deionized water and ethylene glycol (volume ratio 2:1) with 1.6216g (0.027mol) carbamide, magnetic agitation makes it be completely dissolved in 30 minutes;This mixed solution is transferred in teflon-lined 100mL autoclave, has been put in baking oven after sealing and reacts 4 hours in 190 DEG C, naturally cool to room temperature, by gained washing of precipitate, filtration, dried, prepared Ni0.25Mn0.75CO3Presoma,
Oxide is obtained after first for gained presoma 500 DEG C of pre-burning 4h in atmosphere, it first being put in dehydrated alcohol 10 times of oxide volume (volume be), then by Li:(Ni+Mn)=1.06:2 (mol ratio) weighs 0.2350gLi2CO3Add wherein, this mixed solution is placed on magnetic stirring apparatus and heats while stirring at 80 DEG C, until ethanol all volatilizees, by gained powder in atmosphere 750 DEG C calcine 12 hours, namely obtain LiNi after furnace cooling0.5Mn1.5O4Material.Button cell is made according to the method in embodiment 2.Fig. 6 is this battery cycle performance curve under 1C multiplying power.As seen from the figure, material under 1C multiplying power, circulate 100 times after capability retention be 97.6%.The solid spherical LiNi that document (Electrochim.Acta2014,115:290-296) is prepared0.5Mn1.5O4Under material 1C, the capability retention circulated after 200 times is 96.3%.By comparison, the LiNi that this example prepares0.5Mn1.5O4Material list reveals better cycle performance.
Unaccomplished matter of the present invention is known technology.

Claims (6)

1. a preparation method for the hollow porous level time spherical nickel ion doped material of micro-nano structure, is characterized by that the method comprises the following steps:
(1) soluble nickel salt, manganese salt and carbamide are dissolved in mixed solvent, stir 20 ~ 40 minutes, obtain mixed solution;Wherein, mol ratio nickel: manganese=1:3, mol ratio carbamide: metal ion integral molar quantity=1 ~ 3:1, mixed solvent is the mixture of deionized water and organic solvent, and in mixed solution, the total concentration of metal ion is 0.05 ~ 0.5M;Described metal ion is nickel ion and manganese ion;
(2) mixed solution that step (1) obtains has been transferred in teflon-lined autoclave, has been put in baking oven after sealing and is incubated 4 ~ 12 hours in 150 ~ 190 DEG C, naturally cool to room temperature, by gained washing of precipitate, filtration, dried, prepared Ni0.25Mn0.75CO3Presoma;
(3) by step (2) gained presoma 450 ~ 550 DEG C of pre-burning 3 ~ 5h in atmosphere, obtain oxide, then this oxide is first put in dehydrated alcohol, add Li source compound, this mixed solution is heated while stirring at 80 DEG C, after ethanol all volatilizees, by gained powder in atmosphere 700 ~ 900 DEG C calcine 5 ~ 20 hours, namely obtain LiNi after furnace cooling0.5Mn1.5O4Material;
Wherein, mol ratio is the Li in Li source compound: the metal ion integral molar quantity=1 ~ 1.1:2 in step (1);The volume of dehydrated alcohol is 10 ~ 20 times of oxide volume.
2. the preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure as claimed in claim 1, is characterized by that described soluble nickel salt is one or more in nickel sulfate, Nickel dichloride., nickel nitrate or nickel acetate.
3. the preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure as claimed in claim 1, is characterized by that described soluble manganese salt is one or more in manganese sulfate, manganese chloride, manganese nitrate or manganese acetate.
4. the preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure as claimed in claim 1, is characterized by that described organic solvent is one or both in ethylene glycol and ethanol.
5. the preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure as claimed in claim 1, is characterized by that described Li source compound is one or more in Lithium hydrate, lithium carbonate and lithium nitrate.
6. the preparation method of the hollow porous level time spherical nickel ion doped material of micro-nano structure as claimed in claim 1, is characterized by that in the mixed solvent in described step (1), volume ratio is preferably deionized water: organic solvent=6:1 ~ 1:6.
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CN106784701A (en) * 2016-12-27 2017-05-31 电子科技大学 A kind of lithium ion battery composite cathode material and preparation method thereof
CN110199412A (en) * 2017-01-12 2019-09-03 嘉里士有限公司 Rechargeable battery and catalyst material and its production method
CN108011096A (en) * 2017-11-22 2018-05-08 桂林电子科技大学 A kind of porous cube anode material of lithium battery nickel ion doped and preparation method thereof
CN108011096B (en) * 2017-11-22 2020-06-23 桂林电子科技大学 Porous cubic lithium battery cathode material lithium nickel manganese oxide and preparation method thereof
CN108565454A (en) * 2018-05-18 2018-09-21 湖北大学 A kind of nickel lithium manganate cathode material and its preparation method and application of three-dimensional desert wave structure
CN109599553A (en) * 2018-11-20 2019-04-09 湘潭大学 A kind of hollow sphere nickel sodium manganate and preparation method thereof, sodium-ion battery positive plate and sodium-ion battery
CN111640923A (en) * 2020-06-01 2020-09-08 广州大学 Lithium nickel manganese oxide positive electrode material and preparation method thereof
CN111668445A (en) * 2020-06-01 2020-09-15 广东轻工职业技术学院 Shape-controllable nickel manganese oxide electrode material and preparation method and application thereof
CN111640923B (en) * 2020-06-01 2021-12-10 广州大学 Lithium nickel manganese oxide positive electrode material and preparation method thereof
CN111613788A (en) * 2020-06-05 2020-09-01 哈尔滨工业大学(威海) Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof

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Application publication date: 20160706