CN104600285B - Method for preparing spherical lithium nickel manganese oxide positive pole material - Google Patents

Method for preparing spherical lithium nickel manganese oxide positive pole material Download PDF

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CN104600285B
CN104600285B CN201510026782.0A CN201510026782A CN104600285B CN 104600285 B CN104600285 B CN 104600285B CN 201510026782 A CN201510026782 A CN 201510026782A CN 104600285 B CN104600285 B CN 104600285B
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nickel
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lithium
spherical
salt
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CN104600285A (en
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王丽
郅晓科
刘贵娟
陈丹
梁广川
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Hebei University of Technology
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Hebei University of Technology
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    • H—ELECTRICITY
    • H01—BASIC 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
    • H—ELECTRICITY
    • H01—BASIC 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—BASIC 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

Abstract

The invention discloses a method for preparing a spherical lithium nickel manganese oxide positive pole material. The method comprises the following steps: (1) weighing soluble nickel salt and manganese salt, dissolving the salt in deionized water, thereby obtaining a mixed solution; (2) adding urea into the mixed solution in the step (1), performing ultrasonic dispersion for 30 minutes, adding PEG-2000 and CTAB, performing ultrasonic treatment for 30 minutes, transferring the solution into a high-pressure reactor, carrying out hydrothermal reaction for 8-20 hours, and naturally cooling to room temperature, thereby obtaining a precursor; and (3) pre-sintering the precursor obtained in the step (2) at the temperature of 500 DEG C for 2-4 hours, uniformly mixing with a lithium source compound, calcining at the temperature of 700-950 DEG C for 5-20 hours, annealing at the temperature of 550-700 DEG C for 6-15 hours, naturally cooling and grinding, thereby obtaining the product. According to the method disclosed by the invention, the PEG-2000 and CTAB are taken as double template agents, spherical precursor particles with uniform particle size distribution can be obtained by virtue of a one-step hydrothermal reaction, and the 1C discharge capacity of the lithium nickel manganese oxide material prepared by high-temperature lithiation can be 131.4mAh/g.

Description

A kind of preparation method of spherical nickel-lithium manganate anode material
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of preparation of spherical nickel-lithium manganate anode material Method.
Background technology
Lithium ion battery, as one of the most promising power supply of portable type electronic product, also shows in electric automobile field Huge application prospect, have developed various anode material for lithium-ion batteries for this, such as linio2、limn2o4And lini1/3mn1/ 3co1/3o2Deng.However, because these materials are limited to low energy densities or structural stability, spinel-type lini0.5mn1.5o4Material Material causes researcher and more pays close attention to, because it has 4.7v (vs.li/li+) high working voltage, in the high electricity of electric automobile Battery serial number being reduced during pressure application, thus reducing the conforming difficulty of battery cell, being conducive to improving energy density.
At present, the preparation method of nickel ion doped mainly have high temperature solid-state method, sol-gel process, coprecipitation, hydro-thermal method, Spray drying method, molten-salt growth method etc..Wherein coprecipitation is usually carbonate, hydrogen with the acetate of ni and mn, sulfate as raw material Oxide, oxalic acid etc. are precipitant, prepare product with lithium salts mixed calcining again after preparing precipitation.Patent 103579610a adopts Oxalates and hydroxide, simultaneously as precipitant, prepare nickel ion doped by coprecipitation and solid sintering technology.Patent 102386394b is obtained the precipitation of nickeliferous manganese with carbonate for precipitant, obtains nickeliferous Mn oxide after calcining, then with Lioh high-temperature calcination after hydrothermal pretreatment is obtained nickel ion doped material.And this add Direct precipitation agent method easily cause The uneven problem of solution local concentration, leads to product grain size uneven.And sluggish precipitation is anti-using a certain chemistry The configurational ion in solution should be made lentamente, equably to be discharged by solution.Now, the precipitant of addition be not at once with Precipitated component reacts, but so that precipitant is slowly generated in whole solution by chemical reaction.One of its advantage is The degree of supersaturation of configurational ion ratio in whole solution is more uniform, so sedimentary granule is uniformly fine and close, is easy to diafiltration Wash.Meanwhile, it can avoid the co-precipitation of impurity, and the particle diameter so obtaining is evenly distributed.Carbamide is a kind of most typical Homogeneous precipitation agent, when it is added to niso4And mnso4Mixed solution in and be heated to during uniform temperature occurring to react as follows: niso4+3mnso4+4co(nh2)2+8h2o→4ni0.25mn0.75co3+4nh4hso4+4nh3.And hydro-thermal reaction refers in sealing In pressure vessel, with water as solvent, the chemical reaction that carries out under conditions of High Temperature High Pressure.It is characterized in that particle purity is high, divide Scattered property is good, good crystalline and controllable.Based on these advantages of hydro-thermal reaction, if carbamide decomposes required temperature conditionss by hydro-thermal Reaction, to provide, so combines hydro-thermal method and the advantage of sluggish precipitation by single step reaction, can obtain epigranular, divide Dissipate, powder granule that degree of crystallinity is high.
In order to obtain spherical morphology, the present invention uses addition Polyethylene Glycol peg-2000 and 16 in water-heat process The method of alkyl trimethyl ammonium bromide ctab double template.The addition of template has certain regulating and controlling effect to the pattern of product, Its synergetical principle is as shown in Figure 1.As anionic surfactant ctab and non-ionic macromolecule compound peg- After 2000 are mixed to form micelle according to a certain percentage, non-ionic macromolecule compound peg-2000 is intercalated into anionic surface So that the electrical repulsion between the molecule hydrophilic group of original ion weakens between the ionic molecule of activating agent ctab, so that The charge density of micelle reduces, and structure becomes more stable.Because anionic surfactant ctab has long alkyl chain And non-ionic macromolecule compound peg-2000 has longer strand, they easily form after being mutually wound around in system Ball of string structure, so that ni0.25mn0.75co3Precipitation is using it as template growth, and then obtains spherical precursor granule.With During high temperature lithiumation afterwards, the spherical morphology of presoma also will not be destroyed, thus obtaining spherical nickel-lithium manganate anode material. So combine carbamide homogeneous precipitation agent and the collective effect of double template, particle diameter distribution be can get by a step hydro-thermal reaction equal Even spherical nickel-lithium manganate granule.
Content of the invention
The purpose of the present invention is the deficiency for current techniques, provides a kind of preparation side of spherical nickel-lithium manganate anode material Method, with carbamide for homogeneous precipitation agent, peg-2000 and ctab is double template to the method, is prepared spherical by a step hydro-thermal reaction ni0.25mn0.75co3Presoma, then spherical nickel-lithium manganate anode material is obtained through high temperature lithiumation.
The technical solution used in the present invention is as follows:
A kind of preparation method of spherical nickel-lithium manganate anode material, comprises the following steps:
(1) according to material lini0.5mn1.5o4Stoichiometric equation in ratio weigh soluble nickel salt and manganese salt, be dissolved in Mixed solution is made, metal ion in solution total concentration is 0.5～2.0m in deionized water；
(2) add carbamide in the mixed solution of step (1), wherein carbamide and the mol ratio of metal ion are 1～8:1, Ultrasonic disperse added peg-2000 and ctab after 30 minutes, was transferred to reaction under high pressure by after this mixed solution more ultrasonic 30 minutes In kettle, sealing, after 160～190 DEG C of hydro-thermal reactions 8～20 hours, naturally cools to room temperature, and gained pelleting centrifugation washs, After drying, prepared ni0.25mn0.75co3Presoma；Wherein peg-2000 and ctab mass ratio are 3:1～1:2, and the two gross mass is ni0.25mn0.75co3The 1%～6% of theoretical generation quality；
(3) by step (2) gained ni0.25mn0.75co3Presoma first after 500 DEG C of pre-burnings 2～4 hours, then by itself and lithium After source compound mix homogeneously, calcine 5～20 hours at 700～950 DEG C in atmosphere, continue afterwards to move back at 550～700 DEG C Fire 6～15 hours, obtains final product described lini after natural cooling grinds0.5mn1.5o4Positive electrode；Wherein, Li source compound and nickel Manganese presoma ni0.25mn0.75co3Mol ratio during mixing is li:(ni+mn)=(1～1.1): 2.
Described soluble nickel salt is one or more of nickel sulfate, nickel nitrate and nickel acetate.
Described solubility manganese salt is one or more of manganese sulfate, manganese nitrate and acetate.
Described Li source compound is the mixture of one or more of Lithium hydrate, lithium carbonate and lithium nitrate.
The invention has the benefit that
(1) homogeneous precipitation agent is made using carbamide, the powder granule of even particle size distribution can be obtained, and particle diameter distribution is uniform Property has a major impact to the chemical property of material.By in embodiment 3 as can be seen that gained nickel ion doped material 1c electric discharge specific volume Amount is up to 131.4mah/g；
(2) water-heat process and coprecipitation process can be completed by a step hydro-thermal reaction simultaneously, and combine two processes Advantage, simplifies the technological process of production；
(3) to be controlled for double template using peg-2000 and ctab and to obtain spheroidal particle, spheroidal particle is conducive to improving The tap density of material is (up to 2.6g/cm3), and then improve its energy density, improve drawing abillity simultaneously.
Brief description
Fig. 1 is peg-2000 and ctab double template action principle figure.
Fig. 2 is the ni corresponding to embodiment 10.25mn0.75co3Scanning electron microscope (sem) figure of presoma；
Fig. 3 is scanning electron microscope (sem) figure of the nickel ion doped material corresponding to embodiment 1；
Fig. 4 is the X-ray diffraction pattern of the nickel ion doped material corresponding to embodiment 2；
Fig. 5 is the 1c rate charge-discharge curve of the nickel ion doped material corresponding to embodiment 3.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, following embodiments are merely to illustrate the present invention, but simultaneously It is not used in the practical range limiting the present invention.
Embodiment 1:
By 248.9g (1mol) nickel acetate (ni (ch3coo)2·4h2O) with 519.0g (3mol) manganese acetate (mn (ch3coo)2) be dissolved in 4000ml deionized water and make mixed solution, metal ion in solution total concentration be 1.0m, by carbamide with The mol ratio of metal ion adds 480.5g (8mol) carbamide for 2:1, adds 6g peg-2000 and 2g after ultrasonic 30 minutes Ctab, this mixed solution ultrasonic disperse is transferred in autoclave after 30 minutes, and sealing is little after 170 DEG C of hydro-thermal reactions 15 When, naturally cool to room temperature, gained pelleting centrifugation washs, after being dried, prepared ni0.25mn0.75co3Presoma.Its pattern is such as Shown in Fig. 2, it is the spherical second particle being made up of lamellar primary particle.
By gained ni0.25mn0.75co3Presoma first after 500 DEG C of pre-burnings 3 hours, then by itself and lioh h2O presses li: (ni+mn), after=1.05:2 (mol ratio) mix homogeneously, calcine 15 hours at 800 DEG C in atmosphere, continue afterwards at 600 DEG C Annealing 10 hours, obtains final product described lini after natural cooling grinds0.5mn1.5o4Positive electrode.Its pattern is as shown in figure 3, serve as reasons The spherical aggregate of octahedra primary particle composition.
Embodiment 2:
By 657.1g (2.5mol) nickel sulfate (niso4·6h2O) with 1132.5g (7.5mol) manganese sulfate (mnso4) be dissolved in Mixed solution is made, metal ion in solution total concentration is 2.0m, by rubbing of carbamide and metal ion in 5000ml deionized water You add 1501.5g (25mol) carbamide than for 2.5:1, add 16g peg-2000 and 8g ctab after ultrasonic 30 minutes, will This mixed solution ultrasonic disperse was transferred in autoclave after 30 minutes, and sealing is after 180 DEG C of hydro-thermal reactions 12 hours, natural It is cooled to room temperature, gained pelleting centrifugation washs, after being dried, prepared ni0.25mn0.75co3Presoma.
By gained (ni0.25mn0.75)co3Presoma first after 500 DEG C of pre-burnings 3 hours, then by itself and li2co3By li:(ni+ Mn after)=1.03:2 (mol ratio) mix homogeneously, calcine 12 hours at 850 DEG C in atmosphere, continue annealing at 650 DEG C afterwards 8 hours, after natural cooling grinds, obtain final product described lini0.5mn1.5o4Positive electrode.Its X-ray diffraction pattern is as shown in figure 4, institute Have diffraction maximum all with standard lini0.5mn1.5o4The diffraction maximum of (jcpds card number 80-2162) is consistent, illustrates that sample is cube point Spinel structure, fd-3m space group, each diffraction maximum is relatively strong and sharp, illustrative material well-crystallized, and no lixni1-xO dephasign goes out Existing.
Embodiment 3:
By 654.3g (2.25mol) nickel nitrate (ni (no3)2·6h2O) with 1687.6g (6.75mol) manganese nitrate (mn (no3)2·4h2O) it is dissolved in 6000ml deionized water and makes mixed solution, metal ion in solution total concentration is 1.5m, by urine Element adds 810.8g (13.5mol) carbamide with the mol ratio of metal ion for 1.5:1, adds 15g peg- after ultrasonic 30 minutes 2000 and 5g ctab, this mixed solution ultrasonic disperse is transferred in autoclave after 30 minutes, and sealing is after 165 DEG C of water Thermal response 20 hours, naturally cools to room temperature, and gained pelleting centrifugation washs, after being dried, prepared ni0.25mn0.75co3Forerunner Body.
By gained ni0.25mn0.75co3Presoma first after 500 DEG C of pre-burnings 3 hours, then by itself and lino3By li:(ni+ Mn after)=1.07:2 (mol ratio) mix homogeneously, calcine 16 hours at 750 DEG C in atmosphere, continue annealing at 700 DEG C afterwards 8 hours, after natural cooling grinds, obtain final product described lini0.5mn1.5o4Positive electrode.This material is pressed matter with acetylene black, ptfe Stir after amount is more ultrasonic than 80:15:5 mixing, roll-in, putting into 120 DEG C of baking oven insulation half an hour obtains positive plate, is made with metal lithium sheet It is to electrode, 1mol/l lipf6/ dmc+emc+ec (volume ratio is 1:1:1) is electrolyte, in the glove box full of argon Button cell is made in assembling.Fig. 5 is charging and discharging curve under 1c multiplying power for this battery, and 1c specific discharge capacity is up to 131.4mah/ g.
Unaccomplished matter of the present invention is known technology.

Claims (4)

1. a kind of preparation method of spherical nickel-lithium manganate anode material, it is characterized by comprising the following steps:
(1) according to material lini0.5mn1.5o4Stoichiometric equation in ratio weigh soluble nickel salt and manganese salt, be dissolved in deionization Mixed solution is made, metal ion in solution total concentration is 0.5 ~ 2.0 m in water；
(2) add carbamide in the mixed solution of step (1), wherein carbamide and the mol ratio of metal ion are 1 ~ 8:1, ultrasonic point Add peg-2000 and ctab after dissipating 30 minutes, be transferred to after this mixed solution more ultrasonic 30 minutes in autoclave, Sealing, after 160 ~ 190 DEG C of hydro-thermal reactions 8 ~ 20 hours, naturally cools to room temperature, and gained pelleting centrifugation washs, after being dried, Prepared ni0.25mn0.75co3Presoma, the secondary micron-size spherical granular precursor being made up of lamellar primary particle；Wherein Peg-2000 and ctab mass ratio are 3:1 ~ 1:2, and the two gross mass is ni0.25mn0.75co3The 1% ~ 6% of theoretical generation quality；
(3) by step (2) gained ni0.25mn0.75co3Presoma first after 500 DEG C of pre-burnings 2～4 hours, then by itself and lithium source After compound mix homogeneously, calcine 5 ~ 20 hours at 700 ~ 950 DEG C in atmosphere, continue to anneal 6 ~ 15 afterwards at 550 ~ 700 DEG C Hour, obtain final product described lini after natural cooling grinds0.5mn1.5o4Positive electrode is that is, tight by nanometer octahedron primary particle Pile up the spherical secondary micron particles of composition；Wherein, Li source compound and nickel manganese presoma ni0.25mn0.75co3During mixing Mol ratio is li:(ni+mn)=(1 ~ 1.1): 2.
2. the preparation method of spherical nickel-lithium manganate anode material as claimed in claim 1, it is characterized by described soluble nickel Salt is one or more of nickel sulfate, nickel nitrate and nickel acetate.
3. the preparation method of spherical nickel-lithium manganate anode material as claimed in claim 1, it is characterized by described soluble manganese Salt is one or more of manganese sulfate, manganese nitrate and acetate.
4. the preparation method of spherical nickel-lithium manganate anode material as claimed in claim 1, it is characterized by described lithium source chemical combination Thing is the mixture of one or more of Lithium hydrate, lithium carbonate and lithium nitrate.
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CN105826532B (en) * 2016-03-25 2018-06-05 河北路博顺新能源汽车科技有限公司 A kind of hierarchical structure positive composite material of lithium battery and preparation method thereof and lithium battery
CN105742624A (en) * 2016-04-14 2016-07-06 河北工业大学 Preparation method of spherical lithium nickel manganese oxide material with hollow porous micro-nano level structure
CN106486664A (en) * 2016-09-20 2017-03-08 苏州宇量电池有限公司 Positive electrode material precursor preparation method and sintering method and lithium ion battery
CN106711441B (en) * 2017-02-24 2018-04-06 中南大学 A kind of 5V anode material for lithium-ion batteries and preparation method thereof, a kind of lithium ion battery
CN110885100A (en) * 2018-09-07 2020-03-17 湖北大学 Preparation method of novel lithium nickel manganese oxide positive electrode material with hierarchical structure
CN110061235A (en) * 2019-03-29 2019-07-26 桂林理工大学 The method of the tertiary cathode material of excellent chemical property is prepared by the structure regulating of soft template
CN111435745B (en) * 2019-12-26 2022-05-27 蜂巢能源科技有限公司 Binary lithium-rich carbonate precursor 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

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CN101807692B (en) * 2010-04-30 2012-05-02 湖南格林新能源有限公司 Preparation method of lithium ion battery positive material of ferric metasilicate lithium
CN102569776B (en) * 2011-12-30 2014-07-02 合肥国轩高科动力能源股份公司 Preparation method of spinel type lithium manganese oxide for spherical high-voltage anode material
CN103825014B (en) * 2014-01-09 2016-03-02 北京理工大学 A kind of preparation method of high-voltage anode material of lithium ion batteries lithium nickel manganese composite oxide
CN103985854A (en) * 2014-04-14 2014-08-13 江苏中欧材料研究院有限公司 Preparation method of nanoscale nickel lithium manganate positive pole material

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