CN105762352B - Positive electrode material precursor and preparation method thereof and positive electrode and preparation method thereof - Google Patents

Positive electrode material precursor and preparation method thereof and positive electrode and preparation method thereof Download PDF

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CN105762352B
CN105762352B CN201610101162.3A CN201610101162A CN105762352B CN 105762352 B CN105762352 B CN 105762352B CN 201610101162 A CN201610101162 A CN 201610101162A CN 105762352 B CN105762352 B CN 105762352B
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positive electrode
nano
presoma
particle
primary particle
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CN105762352A (en
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赛喜雅勒图
刘兆平
夏永高
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Ningbo Fuli Battery Material Technology Co Ltd
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Ningbo Fuli Battery Material Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of preparation methods of positive electrode material precursor, comprising the following steps: mixes by nickel compound containing, cobalt compound and containing manganese compound, obtains mixed solution；The mixed solution, complexing agent, precipitating reagent are mixed with metallic colloid presoma, positive electrode material precursor is obtained after reaction.During above-mentioned preparation positive electrode material precursor, pass through coprecipitation reaction, nano metallic colloid is set to form electric double layer on presoma surface, inhibit the growth of presoma primary particle thickness, reduce the interlamellar spacing of primary particle lamellar structure, prepare by hexagonal plate structured aggregate at precursor of lithium ionic cell positive material.Present invention also provides a kind of positive electrodes being prepared by positive electrode material precursor.The hexagonal plate primary particle that the application prepares positive electrode has smaller lithium ion mobility path, more preferably electrolyte wellability, and the high rate performance of positive electrode can be improved, be particularly suitable for the manufacture of lithium-ion-power cell.

Description

Positive electrode material precursor and preparation method thereof and positive electrode and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of positive electrode material precursor, preparation method with A kind of positive electrode and preparation method thereof.
Background technique
Lithium ion battery is widely used in electronics and communications industry, and is gradually applied to electric tool, electronic The power batteries such as vehicle and hybrid vehicle field, the battery safety and high rate performance of lithium ion battery also increasingly draw Play the concern of people.Studies have shown that lithium ion cell electrode reaction occurs in electrode/electrolyte interface, so improving positive material The effective ways of material chemical property are to carry out surface covering cladding to material.
Application No. is 201410081429.8 Chinese patents to disclose a kind of high-voltage lithium nickel manganate of core-shell structure just Pole material and preparation method thereof, the core layer material of the material are to contain a small amount of Mn3+LiNi0.5-xMn1.5+xO4, Shell Materials are The Mn be free of3+LiNi0.5Mn1.5O4, shell with a thickness of 0.01~2 μm, the mass fraction that Shell Materials account for core layer material is 2 ~30%.Material made from the method can occur in prolonged charge and discharge cycles Mn element valence variation, cause stratum nucleare and The cycle performance of the phase counterdiffusion of Shell Materials, material can gradually degrade.
Application No. is 201110380626.6 Chinese patents to disclose a kind of anode material for lithium-ion batteries and its preparation Method and lithium ion battery, by LiNi0.5Mn1.5O4Positive electrode active materials particle is added in trivalent silicon source solution and forms solid-liquid Mixture；It adds in a Fluorine source solution and reacts, a fluorination aluminium layer can be formed in the surface of positive electrode active material；At overheat The positive electrode active materials particle that surface has fluorination aluminium layer is obtained after reason.The clad that the method is formed is in material secondary particle table Face does not form effective clad between the primary particle of material, influences the effect of coating modification；And the presence of clad The conductivity that material can be reduced reduces the high rate performance of material.This application provides a kind of lithium ion cell positive materials as a result, Material, anode material for lithium-ion batteries provided by the present application have excellent cycle performance and high rate performance.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of cycle performance and the excellent positive electrode of high rate performance.
In view of this, this application provides a kind of positive electrode material precursor, as presoma and nanogold as shown in formula (I) Belonging to colloid composition, the presoma is that the spherical shape formed is stacked by primary particle, and the primary particle has hexagonal plate pattern, The nano metallic colloid is filled in the surface and lamellar structure gap of the primary particle；
NixCoyMn1-x-y(OH)2(Ⅰ)；
Wherein, 0≤x≤0.35；0≤y≤0.35.
Preferably, the nano metallic colloid is selected from one of nano aluminum colloid, nanometer colloidal magnesium and nano-titanium colloid Or it is a variety of.
Preferably, the primary particle with a thickness of 0.01~1 μm.
Present invention also provides a kind of preparation methods of positive electrode material precursor, comprising the following steps:
It is mixed by nickel compound containing, cobalt compound, containing manganese compound with water, obtains mixed solution, the nickeliferous chemical combination The cobalt ions in nickel ion, cobalt compound in object and the molar ratio containing the manganese ion in manganese compound are x:y:(1-x-y), Wherein, 0≤x≤0.35,0≤y≤0.35；
The mixed solution, complexing agent, precipitating reagent are mixed with metallic colloid presoma, before obtaining positive electrode after reaction Drive body；The metallic colloid presoma forms nano metallic colloid in the mixed solution.
Preferably, the ion summation of nickel ion, cobalt ions and manganese ion in the mixed solution, complexing agent, precipitating reagent with The molar ratio of metallic colloid presoma is 1:0.02~0.5:1.9~2.5:0.001~0.1, and preferred molar ratio is 1:0.05 ~0.2:1.95~2.1:0.001~0.01.
Preferably, the metallic colloid presoma is selected from one kind of the aluminate of salt containing aluminium, hydroxide and solubility Or a variety of, one of salt and hydroxide containing magnesium or one of a variety of or titaniferous salt and acid or a variety of；The metal Colloid presoma be preferably selected from aluminium chloride, magnesium chloride, aluminum sulfate, magnesium sulfate, aluminum nitrate, magnesium nitrate, titanyl sulfate, metatitanic acid and partially One of metatitanic acid is a variety of；
The precipitating reagent is selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of；
The complexing agent is selected from ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, nitric acid One of ammonium and urea are a variety of.
Present invention also provides a kind of positive electrodes, as the active particle as shown in formula (II) and nano-metal-oxide grain Son composition, the active particle is that the spherical shape formed is stacked by hexagonal plate, and the nano-metal-oxide is particle-filled in institute State surface and the hexagonal plate structure interval of active particle；
Li1+zNixCoyMn1-x-yO2(Ⅱ)；
Wherein, 0≤x≤0.35,0≤y≤0.35, -0.5≤z≤0.5.
Preferably, the nano-metal-oxide particle is selected from one of aluminium oxide, magnesia and titanium oxide or a variety of.
Present invention also provides a kind of preparation methods of positive electrode, comprising the following steps:
It will be described in above scheme or positive electrode material precursor prepared by preparation method described in above scheme and lithium salts It is heat-treated after mixing, obtains positive electrode；
The positive electrode material precursor and the molar ratio of the lithium salts are 1:(1+z), -0.5≤z≤0.5.
Present invention also provides a kind of lithium ion batteries, including described in above scheme or preparation side described in above scheme Positive electrode prepared by method.
This application provides a kind of preparation methods of positive electrode material precursor, have prepared nickel compound containing first, containing cobalt Compound and the mixed solution containing manganese compound, then it is reacted with complexing agent, precipitating reagent with metallic colloid presoma, During this, mixed solution reacts the primary particle for generating hexagonal plate with precipitating reagent, in the process of hexagonal plate particles generation Middle addition metallic colloid presoma, metallic colloid presoma is reacted with precipitating reagent generates positively charged nano metallic colloid, receives Rice metallic colloid is formd the electric double layer with positive electricity by the sheet surfaces that charge effect is deposited on hexagonal plate primary particle, The growth for inhibiting hexagonal plate grain thickness reduces the interlamellar spacing of primary particle lamellar structure, under the action of complexing agent Several single lamella primary particles are combined by Van der Waals force and form sandwich structure presoma primary particle, then are stacked and to be formed this The invention precursor of lithium ionic cell positive material.
The positive electrode material precursor that the application obtains is heat-treated after mixing again with lithium salts, the Nano sol particle in presoma It is reacted with oxygen and generates nano-metal-oxide particle, can formed and be protected on the surface of each positive electrode primary particle Layer, prevents the dissolution of metal ion in positive electrode, and the corrosion of electrolyte improves the structural stability of positive electrode, improves The cycle performance of positive electrode；The reduction of positive electrode primary particle interlamellar spacing, increases the specific surface area of material, reduces Interface internal resistance in cyclic process, improves the high rate performance of positive electrode.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of the precursor of lithium ionic cell positive material prepared in the embodiment of the present invention 1；
Fig. 2 is the stereoscan photograph of the anode material for lithium-ion batteries prepared in the embodiment of the present invention 1；
Fig. 3 is the stereoscan photograph of the anode material for lithium-ion batteries prepared in comparative example 2 of the present invention；
Fig. 4 is that 20,000 times of scanning electron microscope of the precursor of lithium ionic cell positive material prepared in the embodiment of the present invention 2 are shone Piece；
Fig. 5 is that 5000 times of scanning electron microscope of the precursor of lithium ionic cell positive material prepared in comparative example 1 of the present invention are shone Piece；
Fig. 6 is the precursor of lithium ionic cell positive material of the filling Nano sol particle prepared in the embodiment of the present invention 1 The schematic diagram without Nano sol particle precursor prepared with comparative example 1；
Fig. 7 is the lithium ion battery circulating ratio curve prepared in the embodiment of the present invention 10 and comparative example 2.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.
The embodiment of the invention discloses a kind of positive electrode material precursors, as presoma and nano metal as shown in formula (I) Colloid composition, the presoma is that the spherical shape formed is stacked by primary particle, and the primary particle has hexagonal plate pattern, institute State surface and lamellar structure gap that nano metallic colloid is filled in the primary particle；
NixCoyMn1-x-y(OH)2(Ⅰ)；
Wherein, 0≤x≤0.35；0≤y≤0.35.
This application provides a kind of positive electrode material precursors, as presoma and nano metallic colloid as shown in formula (I) Composition；Wherein the pattern of the presoma as shown in formula (I) is specially that several hexagonal plate primary particles are stacked, Form spherical structure.The thickness of the primary particle is preferably 0.01~1 μm, more preferably 0.02~0.5 μm, preferred thick Degree is 0.05~0.1 μm.The nano metallic colloid is filled in the gap of the primary particle lamellar structure, while it is also distributed In the surface of primary particle.Herein described primary particle refers both to non-aggregated particle.
The nano metallic colloid is colloid well known to those skilled in the art, is not particularly limited to this application, But as positive electrode, in order to not influence the property of lithium ion battery, the nano metallic colloid be preferably nanometer colloidal magnesium, One of nano aluminum colloid and nano-titanium colloid are a variety of.
It is described herein to have in presoma shown in formula (I), preferably, 0≤x≤0.30；0≤y≤ 0.05, it is furthermore preferred that 0.2≤x≤0.25,0≤y≤0.01.
Present invention also provides a kind of preparation methods of positive electrode material precursor, comprising the following steps:
It is mixed by nickel compound containing, cobalt compound, containing manganese compound with water, obtains mixed solution, the nickeliferous chemical combination The cobalt ions in nickel ion, cobalt compound in object and the molar ratio containing the manganese ion in manganese compound are x:y:(1-x-y), Wherein, 0≤x≤0.35,0≤y≤0.35.
The mixed solution, complexing agent, precipitating reagent are mixed with metallic colloid presoma, before obtaining positive electrode after reaction Drive body；The metallic colloid presoma forms nano metallic colloid in the mixed solution.
During preparing positive electrode material precursor, the application is first by nickel compound containing, cobalt compound, containing manganese It closes object to be dissolved in deionized water, obtains mixed solution.Herein described nickel compound containing is well known to those skilled in the artization Close object, preferably, the nickel compound containing be preferably one of nickel sulfate, nickel nitrate, nickel oxalate and nickel chloride or It is a variety of；The cobalt compound is compound well known to those skilled in the art, and preferably, the cobalt compound is excellent It is selected as one of cobaltous sulfate, cobalt nitrate, cobalt oxalate and cobalt chloride or a variety of；The manganese compound that contains is those skilled in the art Well known compound, preferably, it is described containing manganese compound in manganese sulfate, manganese nitrate, manganese oxalate and manganese chloride It is one or more.The cobalt ions in nickel ion, the cobalt compound in the nickel compound containing contains manganese compound with described In manganese ion molar ratio be x:y:(1-x-y), wherein 0≤x≤0.35,0≤y≤0.35, preferably, 0≤x ≤0.30,0≤y≤0.05；It is furthermore preferred that x, y value are 0.2≤x≤0.25,0≤y≤0.01.
Then the application mixes the mixed solution, complexing agent, precipitating reagent with metallic colloid presoma, coprecipitation reaction Afterwards, positive electrode material precursor is obtained.During mixing, complexing agent and precipitating reagent are preferably dissolved in deionization by the application respectively After water, then mix with mixed solution, metallic colloid presoma.During this, mixed solution is reacted with precipitating reagent generates hexagonal The primary particle of sheet, during hexagonal plate particles generation be added metallic colloid presoma, metallic colloid presoma with Precipitating reagent reaction generates positively charged nano metallic colloid, and nano metallic colloid is deposited on hexagonal plate one by charge effect The sheet surfaces of secondary particle form the electric double layer with positive electricity, it is suppressed that the growth of hexagonal plate grain thickness reduces one The interlamellar spacing of secondary particle splat structure, several single lamella primary particles pass through Van der Waals force combination shape under the action of complexing agent At sandwich structure presoma primary particle, then stacks and to form precursor of lithium ionic cell positive material of the present invention.
Herein described metallic colloid presoma is the substance that nano metallic colloid is formed in the mixed solution, excellent One or more, one of salt and hydroxide containing magnesium of salt, hydroxide selected from aluminium and the aluminate of solubility Or the salt and one of acid or one of a variety of these three types of substances or a variety of of a variety of and titaniferous；The metallic colloid forerunner Body is more preferably selected from aluminium chloride, magnesium chloride, aluminum sulfate, magnesium sulfate, aluminum nitrate, magnesium nitrate, titanyl sulfate, metatitanic acid and metatitanic acid It is one or more；It is furthermore preferred that the metallic colloid presoma is selected from one of aluminium chloride, magnesium chloride, metatitanic acid, metatitanic acid Or it is a variety of.Mole of the ion total mole number of nickel ion, cobalt ions and manganese ion, complexing agent in herein described mixed solution Number, the molal quantity of precipitating reagent and metallic colloid presoma molal quantity ratio for 1:0.02~0.5:1.9~2.5:0.001~ 0.1, preferred molar ratio is 1:0.05~0.2:1.95~2.1:0.001~0.01.
Present invention also provides a kind of positive electrodes, as the active particle as shown in formula (II) and nano-metal-oxide grain Son composition, the active particle is that the spherical shape formed is stacked by hexagonal plate, and the nano-metal-oxide is particle-filled in institute State surface and the hexagonal plate structure interval of active particle；
Li1+zNixCoyMn1-x-yO2(Ⅱ)；
Wherein, 0≤x≤0.35,0≤y≤0.35, -0.5≤z≤0.5.
This application provides a kind of positive electrodes, as the active particle as shown in formula (II) and nano-metal-oxide grain Son composition；Wherein the pattern of the active particle as shown in formula (II) is specially that several hexagonal plate primary particles are stacked on It is formed together spherical structure, the nano-metal-oxide is particle-filled in the hexagonal plate primary particle lamellar structure Gap, while its surface for being also distributed in hexagonal plate primary particle.Above-mentioned hexagonal plate primary particle interlamellar spacing is smaller, increases The specific surface area of material, reduces the interface internal resistance in cyclic process, in favor of improving the high rate performance of positive electrode.As Preferred embodiment, the hexagonal plate particle, with a thickness of 0.01~1 μm, preferably with a thickness of 0.02~0.5 μm, more preferably With a thickness of 0.05~0.1 μm.In the herein described active particle as shown in formula (II), 0≤x≤0.35,0≤y≤0.35 ,- 0.5≤z≤0.5；Preferably, 0≤x≤0.30；0≤y≤0.05, -0.5≤z≤0.2；It is furthermore preferred that 0.2≤x≤0.25,0 ≤ y≤0.01, -0.5≤z≤- 0.45.
Herein described nano-metal-oxide particle is metal oxide particle well known to those skilled in the art, in order to The performance of positive electrode is improved, the nano-metal-oxide particle is preferably selected from one in aluminium oxide, magnesia and titanium oxide Kind is a variety of.
Present invention also provides a kind of preparation methods of positive electrode, comprising the following steps:
It will be described in above scheme or positive electrode material precursor prepared by preparation method described in above scheme and lithium salts It is heat-treated after mixing, obtains positive electrode；The positive electrode material precursor and the molar ratio of the lithium salts are 1:(1+z).
During preparing positive electrode, the process for preparing positive electrode material precursor is identical as above scheme, herein not It is repeated again.According to the present invention, after obtaining positive electrode material precursor, then it is heat-treated after mixing it with lithium salts, Obtain positive electrode；The positive electrode material precursor and the molar ratio of the lithium salts are 1:(1+z), -0.5≤z≤0.5, preferably , -0.5≤z≤0.2；It is furthermore preferred that -0.5≤z≤- 0.45.During this, heat after positive electrode material precursor is mixed with lithium salts It handles, the oxygen decomposed after the nano metallic colloid and positive electrode material precursor heat treatment in presoma, which reacts, generates nano metal Oxide particle can form protective layer on the surface of each positive electrode primary particle, prevent in positive electrode metal from The dissolution of son, the corrosion of electrolyte improve the structural stability of positive electrode, improve the cycle performance of positive electrode.
Herein described lithium salts is lithium salts well known to those skilled in the art, and preferably, the lithium salts is selected from hydrogen One of lithia, lithium carbonate, lithium nitrate and lithium oxalate are a variety of.Mole of the positive electrode material precursor and the lithium salts Than for 1:(1+z), -0.5≤z≤0.5；Preferably, the value of z is -0.5~0.2；It is furthermore preferred that the value of z is -0.5~-0.45. Depending on the specific positive electrode material precursor of the temperature-visualized of the heat treatment and lithium source, preferably, the heat treatment Temperature is preferably 650 DEG C~1150 DEG C.
Metallic colloid presoma is added in the present invention during precursor preparation, and metallic colloid presoma is reacted with complexing agent Positively charged nano metal sol particles are generated, nano metal sol particles are deposited on the single lamella of presoma primary particle Surface forms the electric double layer with positive electricity, reduces binding force of the primary particle in thickness direction of sheet, thus before inhibiting Drive body primary particle thickness direction growth, reduce the interlamellar spacing of primary particle lamellar structure；Several single lamellas are primary Particle by Van der Waals force combine form sandwich structure presoma primary particle, then be stacked to be formed it is of the present invention Precursor of lithium ionic cell positive material.
Further, gained presoma is heat-treated after mixing with lithium salts, and the Nano sol particle and oxygen in presoma are anti- Nano-metal-oxide particle should be generated, protective layer can be formed on the surface of each positive electrode primary particle, prevented just The dissolution of metal ion in the material of pole, the corrosion of electrolyte improve the structural stability of positive electrode, improve positive electrode Cycle performance.The reduction of positive electrode primary particle interlamellar spacing, increases the specific surface area of material, reduces in cyclic process Interface internal resistance, improve the high rate performance of positive electrode.
The experimental results showed that contain hexagonal plate primary for the precursor of lithium ionic cell positive material that the present invention is prepared Particle stacks the presoma and nano metal sol particles constituted, and nano metal sol particles are filled in the lamella knot of primary particle Structure gap, the surface for being coated on primary particle, several single lamella primary particles are combined by Van der Waals force and form sandwich knot Structure.There is the positive electrode that the present invention is prepared hexagonal plate primary particle to stack the active material particle constituted and nanogold Belong to oxide particle, the particle-filled lamellar structure gap in hexagonal plate primary particle of nano-metal-oxide is coated on six The surface of cornual plate shape primary particle.
Experiment shows that the anode material for lithium-ion batteries that the present invention is prepared has excellent cycle performance and forthright again Energy.
For a further understanding of the present invention, below with reference to embodiment to positive electrode material precursor provided by the invention, its system Preparation Method and positive electrode and preparation method thereof are described in detail, and protection scope of the present invention is not by the limit of following embodiment System.
Raw material in following embodiment is commercial product.
Embodiment 1
1.1 weigh the manganese sulfate of the nickel sulfate of 0.5mol, 1.5mol, are dissolved in 1L deionized water, are made into mixed solution；Claim It takes the sodium hydroxide of 4mol to be dissolved in 1L deionized water, is made into precipitating reagent；The ammonium hydroxide for weighing 0.1mol is dissolved in 1L deionized water, It is made into complexing agent, weighs 0.001mol aluminium chloride and 0.001mol magnesium chloride, obtains metallic colloid presoma；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 1.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
1.3 obtain the coprecipitated product containing nanometer Al, nanometer Mg sol particles after washing, drying Ni0.25Mn0.75(OH)2Presoma；
After 1.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.51:1, it is heat-treated at 850 DEG C 16 hours, natural cooling obtained the Li containing nano aluminium oxide, nano magnesia after being ground up, sieved0.51Ni0.25Mn0.75O2Lithium Ion battery positive electrode.
Precursor of lithium ionic cell positive material obtained in embodiment 1 is analyzed using scanning electron microscope, obtains it Stereoscan photograph, as shown in Figure 1, as shown in Figure 1, before the anode material for lithium-ion batteries that the embodiment of the present invention 1 is prepared Body is driven to have the feature that including stacking the spherical Ni constituted by hexagonal plate primary particle0.25Mn0.75(OH)2Presoma and Nano aluminum, nanometer Mg sol particles, the particle-filled lamellar structure gap in primary particle of the Nano sol coat simultaneously On the surface of primary particle, measure hexagonal plate presoma with a thickness of 0.25 μm.
Anode material for lithium-ion batteries obtained in embodiment 1 is analyzed using scanning electron microscope, obtains its scanning electricity Mirror photo, as shown in Fig. 2, as can be seen from FIG. 2, the anode material for lithium-ion batteries that the embodiment of the present invention 1 is prepared has such as Lower feature: including stacking the spherical Li constituted by hexagonal plate primary particle0.51Ni0.25Mn0.75O2It active material particle and receives Rice aluminium oxide, magnesia particle, the nano-particles filled primary particle lamellar structure gap, simultaneously be coated on it is primary The surface of particle.Measure hexagonal plate lithium ion anode material primary particle with a thickness of 0.45 μm.
Embodiment 2
2.1 weigh the manganese sulfate of the nickel sulfate of 0.48mol, the cobalt chloride of 0.02mol, 1.5mol, are dissolved in 1L deionized water In, it is made into mixed solution；The sodium hydroxide for weighing 5mol is dissolved in 1L deionized water, is made into precipitating reagent；Weigh the ammonia of 0.15mol It is water-soluble in 1L deionized water, be made into complexing agent；0.002mol aluminum sulfate and 0.001mol metatitanic acid are weighed, before obtaining metallic colloid Drive body；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 2.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
2.3 obtain the coprecipitated product after washing, drying containing nanometer Al, Ti sol particles Ni0.24Co0.01Mn0.75(OH)2Presoma；
After 2.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.50:1, it is heat-treated at 900 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved0.50Ni0.24Co0.01Mn0.75O2 Anode material for lithium-ion batteries.
Precursor of lithium ionic cell positive material obtained in embodiment 2 is analyzed using scanning electron microscope, obtains it Stereoscan photograph, as shown in Figure 3, Figure 4, according to Fig. 3, Fig. 4 it is found that the lithium ion battery that the embodiment of the present invention 2 is prepared Positive electrode material precursor has the feature that including stacking the Ni constituted by hexagonal plate primary particle0.24Co0.01Mn0.75 (OH)2Presoma and nano aluminum, nano-titanium sol particles, the particle-filled lamellar structure in primary particle of the Nano sol Gap, the surface for being coated on primary particle simultaneously.
Embodiment 3
3.1 weigh the manganese nitrate of the nickel nitrate of 0.33mol, the cobalt nitrate of 0.33mol, 0.34mol, are dissolved in 2L deionized water In, it is made into mixed solution；The sodium hydroxide for weighing 4.5mol is dissolved in 2L deionized water, is made into precipitating reagent；Weigh 0.05mol's Diammonium phosphate (DAP) is dissolved in 0.5L deionized water, is made into complexing agent；0.003mol titanium sulfate is weighed, metallic colloid presoma is obtained；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 3.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
3.3 obtain the coprecipitated product after washing, drying containing nanometer Ti sol particles Ni0.33Co0.33Mn0.34(OH)2Presoma；
After 3.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 1.06:1, it is heat-treated at 920 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved1.06Ni0.33Co0.33Mn0.34O2 Anode material for lithium-ion batteries.
Embodiment 4
4.1 weigh the manganese sulfate of the nickel sulfate of 0.16mol, the cobalt chloride of 0.16mol, 0.68mol, are dissolved in 1.5L deionization In water, it is made into mixed solution；The sodium hydroxide for weighing 6mol is dissolved in 2L deionized water, is made into precipitating reagent；Weigh 0.8mol's Urea is dissolved in 2L deionized water, is made into complexing agent；0.001mol aluminum nitrate is weighed, metallic colloid presoma is obtained；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 4.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
4.3 obtain the coprecipitated product after washing, drying containing nanometer Al sol particles Ni0.16Co0.16Mn0.68(OH)2Presoma；
After 4.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 1.4:1, it is heat-treated at 870 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide after being ground up, sieved1.4Ni0.16Co0.16Mn0.68O2Lithium-ion electric Pond positive electrode.
Embodiment 5
5.1 weigh the manganese sulfate of the nickel sulfate of 0.50mol, the cobaltous sulfate of 0.02mol, 1.48mol, are dissolved in 1L deionized water In, it is made into mixed solution；The potassium hydroxide for weighing 4.5mol is dissolved in 1L deionized water, is made into precipitating reagent；Weigh 0.12mol's Diammonium hydrogen phosphate is dissolved in 0.5L deionized water, is made into complexing agent；0.001mol magnesium sulfate and 0.001mol metatitanic acid are weighed, is obtained To metallic colloid presoma；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 5.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
5.3 obtain the coprecipitated product after washing, drying containing nanometer Mg, Ti sol particles Ni0.25Co0.01Mn0.74(OH)2Presoma；
After 5.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.53:1, it is heat-treated at 800 DEG C 18 hours, natural cooling obtained the Li containing nano magnesia, nano-titanium oxide after being ground up, sieved0.53Ni0.25Co0.01Mn0.74O2 Anode material for lithium-ion batteries.
Embodiment 6
6.1 weigh the manganese sulfate of the nickel sulfate of 0.49mol, 1.51mol, are dissolved in 1L deionized water, are made into mixed solution； The sodium hydroxide for weighing 4mol is dissolved in 1L deionized water, is made into precipitating reagent；The ammonium hydroxide for weighing 0.2mol is dissolved in 1L deionized water In, it is made into complexing agent；0.002mol nano aluminium oxide, 0.002mol magnesium chloride are weighed, metallic colloid presoma is obtained；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 6.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
6.3 obtain the coprecipitated product after washing, drying containing nanometer Al, Mg sol particles Ni0.245Mn0.755(OH)2Presoma；
After 6.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.50:1, it is heat-treated at 950 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved0.50Ni0.245Mn0.755O2's Anode material for lithium-ion batteries.
Embodiment 7
7.1 weigh the manganese nitrate of the cobalt chloride of 0.02mol, 1.98mol, are dissolved in 0.8L deionized water, and it is molten to be made into mixing Liquid；The sodium hydroxide for weighing 2mol is dissolved in 0.4L deionized water, is made into precipitating reagent；The ammonium hydroxide for weighing 0.2mol is dissolved in 0.5L and goes In ionized water, it is made into complexing agent, weighs 0.005mol aluminium chloride, obtains metallic colloid presoma；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 7.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
The coprecipitated product is obtained the Co containing nanometer Al sol particles by 7.3 after washing, drying0.01Mn0.99 (OH)2Presoma；
After 7.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.54:1, it is heat-treated at 900 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved0.54Co0.01Mn0.99O2Lithium Ion battery positive electrode.
Embodiment 8
8.1 weigh the manganese sulfate of the nickel sulfate of 0.52mol, 1.48mol, are dissolved in 2L deionized water, are made into mixed solution； The sodium hydroxide for weighing 2.5mol is dissolved in 3L deionized water, is made into precipitating reagent；The ammonium hydroxide for weighing 0.3mol is dissolved in 2L deionization In water, it is made into complexing agent；0.001mol titanium sulfate, 0.001mol metatitanic acid are weighed, metallic colloid presoma is obtained；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 8.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
The coprecipitated product is obtained the Ni containing nanometer Ti sol particles by 8.3 after washing, drying0.26Mn0.74 (OH)2Presoma；
After 8.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.53:1, it is heat-treated at 900 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved0.53Ni0.26Mn0.74O2Lithium Ion battery positive electrode.
Embodiment 9
9.1 weigh the manganese sulfate of the nickel sulfate of 0.50mol, 1.5mol, are dissolved in 1L deionized water, are made into mixed solution； The sodium hydroxide for weighing 3mol is dissolved in 0.4L deionized water, is made into precipitating reagent；The ammonium hydroxide for weighing 1.0mol is dissolved in 5L deionization In water, it is made into complexing agent；0.001mol aluminium hydroxide, 0.002mol aluminium chloride are weighed, metallic colloid presoma is obtained；
Reaction vessel is added in mixed solution, precipitating reagent, complexing agent and metallic colloid presoma by 9.2 simultaneously, is carried out coprecipitated It forms sediment and reacts, obtain coprecipitated product；
The coprecipitated product is obtained the Ni containing nanometer Al sol particles by 9.3 after washing, drying0.25Mn0.75 (OH)2Presoma；
After 9.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.51:1, it is heat-treated at 900 DEG C 20 hours, natural cooling obtained the Li containing nano aluminium oxide, nano-titanium oxide after being ground up, sieved0.51Ni0.25Mn0.75O2Lithium Ion battery positive electrode.
Embodiment 10
10.1 by anode material for lithium-ion batteries obtained in 9g embodiment 1,0.5g acetylene black, 0.5g Kynoar and 30gN~methyl pyrrolidone is mixed to form slurry at normal temperatures and pressures, is coated uniformly on aluminium foil surface and pole piece is made.
10.2 pole piece obtained in 10.1 is dried at 80 DEG C after compress, being cut into area is 1.32cm2Circle it is thin Piece is as anode, using pour lithium slice as cathode, with the LiPF of 1mol/L6Ethylene carbonate (EC) and dimethyl carbonate (DMC) it is molten Liquid is that the volume ratio of electrolyte, wherein EC and DMC is 1:1, is then assembled into lithium ion battery in the glove box full of argon gas.
Comparative example 1
11.1 weigh the manganese sulfate of the nickel sulfate of 0.5mol, 1.5mol, are dissolved in the mixed solution being made into 1L deionized water； The sodium hydroxide for weighing 4mol is dissolved in 1L deionized water, the precipitating reagent being made into；The ammonium hydroxide for weighing 0.1mol is dissolved in 1L deionization In water, it is made into complexing agent；
Reaction vessel is added in mixed solution, precipitating reagent and complexing agent by 11.2 simultaneously, is carried out coprecipitation reaction, is obtained coprecipitated Shallow lake product；
11.3 Ni for obtaining the coprecipitated product after washing, drying0.25Mn0.75(OH)2Presoma；
After 11.4 mix lithium carbonate and above-mentioned precursor product according to the ratio of molar ratio 0.51:1, at 850 DEG C of heat Reason 16 hours, natural cooling obtains Li after being ground up, sieved0.51Ni0.25Mn0.75O2Anode material for lithium-ion batteries.
Anode material for lithium-ion batteries obtained in comparative example 1 is analyzed using scanning electron microscope, obtains its scanning electricity Mirror photo, as shown in figure 5, as can be seen from FIG. 5, the anode material for lithium-ion batteries that comparative example 1 of the present invention is prepared is by eight The Li that the primary particle aggregation of face bodily form looks is constituted0.51Ni0.25Mn0.75O2Active material particle.Measure hexagonal plate primary particle With a thickness of 3 μm.
Comparative example 2
12.1 by anode material for lithium-ion batteries obtained in 9g comparative example 1,0.5g acetylene black, 0.5g Kynoar and 30g N~methyl pyrrolidone is mixed to form slurry at normal temperatures and pressures, is coated uniformly on aluminium foil surface and pole piece is made.
12.2 pole piece obtained in 12.1 is dried at 80 DEG C after compress, being cut into area is 1.32cm2Circle it is thin Piece is as anode, using pour lithium slice as cathode, with the LiPF of 1mol/L6Ethylene carbonate (EC) and dimethyl carbonate (DMC) it is molten Liquid is that the volume ratio of electrolyte, wherein EC and DMC is 1:1, is then assembled into lithium ion battery in the glove box full of argon gas.
Electrochemical property test is carried out to lithium ion battery obtained in 10.2 using electrochemical property test instrument, charging is cut Only voltage is 4.95V, discharge cut-off voltage 3.0V, obtains its chemical property curve, as shown in fig. 7, wherein curve 1 is real The chemical property curve of lithium ion battery obtained in example 10 is applied, curve 2 is the electricity of lithium ion battery obtained in comparative example 2 Chemical property curve.As shown in Figure 7, the cycle performance for the anode material for lithium-ion batteries that embodiment 1 is prepared and forthright again It can be preferably.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (6)

1. a kind of positive electrode material precursor is made of the presoma as shown in formula (I) with nano metallic colloid, the presoma is The spherical shape formed is stacked by primary particle, the primary particle has hexagonal plate pattern, and the nano metallic colloid is filled in The surface and lamellar structure gap of the primary particle；
NixCoyMn1-x-y(OH)2(I)；
Wherein, 0≤x≤0.35；0≤y≤0.35.
2. positive electrode material precursor according to claim 1, which is characterized in that the nano metallic colloid is selected from nano aluminum One of colloid, nanometer colloidal magnesium and nano-titanium colloid are a variety of.
3. positive electrode material precursor according to claim 1, which is characterized in that the primary particle with a thickness of 0.01~ 1μm。
4. a kind of positive electrode is made of the active particle as shown in formula (II) with nano-metal-oxide particle, the activity Particle is that the spherical shape formed is stacked by hexagonal plate, the particle-filled surface in the active particle of the nano-metal-oxide With hexagonal plate structure interval；
Li1+zNixCoyMn1-x-yO2(Ⅱ)；
Wherein, 0≤x≤0.35,0≤y≤0.35, -0.5≤z≤0.5；The nano-metal-oxide particle be selected from aluminium oxide, One of magnesia and titanium oxide are a variety of.
5. a kind of preparation method of positive electrode, comprising the following steps:
It is heat-treated after the described in any item positive electrode material precursors of claims 1 to 3 are mixed with lithium salts, obtains positive material Material；
The positive electrode material precursor and the molar ratio of the lithium salts are 1:(1+z), -0.5≤z≤0.5.
6. a kind of lithium ion battery, made including preparation method described in positive electrode as claimed in claim 4 or claim 5 Standby positive electrode.
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