CN104966820A - Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof - Google Patents

Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof Download PDF

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CN104966820A
CN104966820A CN201510233146.5A CN201510233146A CN104966820A CN 104966820 A CN104966820 A CN 104966820A CN 201510233146 A CN201510233146 A CN 201510233146A CN 104966820 A CN104966820 A CN 104966820A
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cobalt
nickel
precursor material
salt
manganese
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吴层
谭潮溥
严亮
黄殿华
陈瑞祥
张郑
袁昌杰
骆宏钧
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GUANGZHOU LIBODE NEW MATERIAL Co Ltd
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GUANGZHOU LIBODE NEW MATERIAL 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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

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

Abstract

The present invention relates to a lithium-ion battery positive electrode material precursor material with high-voltage charge and discharge stability, a composite positive electrode material synthetic method and a composite positive electrode material prepared by the method. The precursor material has the advantages of good sphericity, high density, strong lithium source adaptability, gentle mixing environment, and the like, the synthesized composite material has high tap density, compared with ordinary lithium nickel-cobalt-aluminum material, the composite material sensitivity to ambient moisture and carbon dioxide is reduced, and the composite material has good processing performance and storage performance, and exhibits high specific capacity and high stability characteristics when the composite material is charged and discharged in 2.8-4.4V and 2.8-4.5V voltage windows.

Description

Lithium ion battery precursor material, composite positive pole and preparation method thereof
Technical field
The present invention relates to lithium ion battery and manufacture field, relate to lithium ion battery precursor material, composite positive pole and preparation method thereof particularly.
Background technology
Lithium ion battery with its high-energy-density, the life-span is long, self discharge is little, the advantage such as memory-less effect and environmental protection is known as optimal chemical power source by international community, is widely used in the electronic products such as mobile phone, notebook computer, electric tool and camcorder.Meanwhile, lithium ion battery in the peak valley adjustment solving electrical network electricity consumption and the clean energy resource energy storage field of the discontinuity such as wind energy, solar energy and tidal energy play an important role.In addition, larger development space is brought by lithium ion battery in the electric automobile of expanding day, electric bicycle, Aero-Space, the field such as military mobile communication facility and equipment.
The maximization of power lithium-ion battery and large-scale application require that positive electrode improves performance, reduces costs, and wherein improve the power density of material, energy density further and improve the main development direction that security performance becomes current anode material for lithium-ion batteries.LiNiO 2the high and low cost of base anode material specific capacity and have good cycle performance, thus becomes the focus of people's research, such as LiNi 1-xco xo 2the specific capacity of 190mAh/g can have been given play to.But the stability of nickel cobalt binary material does not still reach present stage 3C (household electrical appliances, computer, communication) electronic product and electrokinetic cell to material requirement.
The modification direction of lithium nickelate sill mainly stable crystal structure undergoes phase transition in charge and discharge process to improve its electrochemical stability, suppress and to extenuate it.Main method is bulk phase-doped and Surface coating.What be representative with nickel cobalt aluminum mixes aluminum, LiNi 1-x-yco xal yo 2as LiNiO 2, LiCoO 2and LiAlO 2the isomorphism solid solution of three, has possessed energy density high, Heat stability is good, the advantages such as inexpensive environmental protection simultaneously, has become the high-end energy storage material in 3C field and electrokinetic cell field.But due to niccolic thermodynamic phase, cause NCA (nickel cobalt lithium aluminate material) to synthesize difficulty, bivalent nickel ion is difficult to be oxidized to trivalent, needs could be oxidized under pure oxygen atmosphere completely.In addition, because NCA water absorption is strong, there is the reaction in following formula, battery production needs could normally to produce in the following condition of 10% humidity.Because NCA easily releases O 2, CO 2deng, the easy inflatable of battery, preferably adopts 18650 type cylindrical batteries to produce.
LiNi 1-x-yCo xAl yO 2+H 2O→Ni 1-x-yCo xAl yO+LiOH+O 2
LiOH+CO 2→Li 2CO 3
Li 2CO 3+HF→LiF+CO 2
Architectural characteristic in view of this material itself causes preparing constitutionally stable LiNiCoAlO 2the condition of material and nickel cobalt aluminium lithium battery is very harsh, not only high to the requirement of synthesis material, and very high to the requirement of synthesis condition and battery production environment.LiNi 1-x-yco xal yo 2material still in the face of the carbon dioxide of structural instability also easily and in environment and water function, causes electro-chemical activity to decay.Due to the Li generated 2cO 3electronic conductivity and ionic conductivity very low, be electrochemicaUy inert, Li 2cO 3existence can by mutually isolated for positive electrode particle, cause electronics discontinuity, ion discontinuity and hinder lithium ion motion in the electrolytic solution, the impedance of the positive electrode/electrolyte interface thus increased.Secondly, Li 2cO 3generation captured the Li of 3a position in material surface lattice +, cause the structure and composition of material surface to there occurs change.3rd, Surface L i 2cO 3the safety problem of battery can be caused with the existence of LiOH, under high temperature, LiOH and Li 2cO 3can decompose and release H 2, CO and CO 2deng gas, battery is caused to occur swellingly even to explode.
At present, the nickel cobalt aluminium lithium anode material of domestic production still to exist in charge and discharge process that capacity attenuation is very fast, high rate performance is bad and the defect such as storge quality extreme difference.For this reason, in order to cater to gentle NCA battery production technology, reducing the sensitiveness to humidity, the nickel cobalt aluminum that processability is superior, being necessary the nickel cobalt aluminium presoma of development of new.
Coprecipitation is preparation LiNiCoAlO 2and a kind of simple, the practical method that surface doping is coated.The co-precipitation of Ni, Co and Al, key overcomes Al 3+facile hydrolysis precipitates separately, and difficult and nickel cobalt element forms the presoma of single structure, cannot form high density spherical nickel-cobalt aluminum.For Al 3+facile hydrolysis problem, patent CN103094546A and CN103553152A proposes with aluminium complex solution for aluminium source is prepared separately, prepares the method for spherical nickel-cobalt aluminium with the form of cocurrent adding material and nickel cobalt salt solution, sodium hydroxide solution and ammonia solution by crystallization control.But there are the following problems for the method: 1,5%wt ~ 15%wt sodium hydroxide solution ripening of CN103553152A is conducive to removing of sulphur, but in washing process, often cause the loss of surfaces of aluminum element, cause the material surface of final preparation lack aluminium and reduce the cyclical stability of material; 2, still there is structural instability in the active nickel cobalt lithium aluminate material of coprecipitation, requires the problems such as harsh to synthetic environment and battery production environment; 3, common nickel cobalt lithium aluminate charge and discharge cyclical stability under relatively high voltage is poor.
Summary of the invention
The invention provides a kind of lithium ion battery composite cathode material and preparation method thereof, and prepare the method for the nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material comprised in described positive electrode, to overcome and to avoid the shortcoming and defect of prior art.According to present nickel cobalt lithium aluminate cathode material Problems existing, provide a kind of nickel cobalt lithium aluminate base composite positive pole of modification of excellent electrochemical performance, and simple, the condition of preparing this composite positive pole are easy to the preparation method of control.
According to a first aspect of the invention, provide a kind of lithium ion battery composite cathode material, it is characterized in that, described material comprises coating layer Li 1.2mn 0.54ni 0.13co 0.13o 2with principal phase LiNi 1-x-yco xal yo 2precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1, such as x=0,0.05,0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60,0.65,0.70,0.75,0.80,0.85,0.90,0.95 or 1; Y=0,0.05,0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60,0.65,0.70,0.75,0.80,0.85,0.90,0.95 or 1.
According to a second aspect of the invention, a kind of preparation method of nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material is provided: said method comprising the steps of:
1) coprecipitation is adopted to prepare spherical Ni 1-x-yco xal y(OH) 2precursor material, obtains and comprises the slip of described precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1;
2) nickel cobalt manganese cladded type composite precursor is prepared, comprise: add precipitation reagent to described slip, complexing agent I, the mixed solution of nickel salt I, cobalt salt I and manganese salt, thus making the hydroxide of nickel, cobalt and manganese or carbonate with described precursor material for matrix growth in situ, acquisition principal phase is Ni 1-x-yco xal y(OH) 2, coating layer is Mn 0.675ni 0.1625co 0.1625(OH) 2, or principal phase is Ni 1-x-yco xal y(OH) 2, coating layer is Mn 0.675ni 0.1625co 0.1625cO 3compound precursor material.
According to an embodiment of the present invention, nickel salt I described in described method is one or more in nickelous sulfate, nickel chloride, nickel acetate or nickel nitrate.
According to an embodiment of the present invention, cobalt salt I described in described method is one or more in cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
According to an embodiment of the present invention, manganese salt described in described method is one or more in manganese sulfate, manganese chloride, manganese acetate or manganese nitrate
According to an embodiment of the present invention, the complexing agent I described in described method is one or more in ammoniacal liquor, triethanolamine, citric acid, oxalic acid, sodium ethylene diamine tetracetate and carbonic hydroammonium.
According to an embodiment of the present invention, precipitation reagent described in described method is one or more in NaOH, sodium carbonate or carbonic hydroammonium.
According to an embodiment of the present invention, step 1 described in described method) comprising: the mixed solution of preparation nickel salt II and cobalt salt II, containing aluminium complex solution, complexing agent II solution, sodium hydroxide solution; Add the end liquid containing described complexing agent II in a kettle. in advance; By the mixed solution of described nickel salt II and cobalt salt II, described containing aluminium complex solution, described complexing agent II solution, described sodium hydroxide solution respectively stream adds precipitation reaction in reactor, obtains the slip comprising described precursor material.
According to an embodiment of the present invention, nickel salt II described in described method is one or more in nickelous sulfate, nickel chloride, nickel acetate or nickel nitrate.
According to an embodiment of the present invention, cobalt salt II described in described method is one or more in cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
According to an embodiment of the present invention, the wherein said aluminium salt contained in aluminium complex solution is one or more in aluminum nitrate, aluminum sulfate or aluminum acetate.
According to an embodiment of the present invention, wherein said complexing agent II is one or more in ammoniacal liquor, citric acid, ammonium fluoride, oxalic acid, sodium ethylene diamine tetracetate and NaOH.
According to a third aspect of the invention we, provide a kind of preparation method of lithium ion battery composite cathode material, described positive electrode comprises coating layer Li 1.2mn 0.54ni 0.13co 0.13o 2with principal phase LiNi 1-x-yco xal yo 2precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1, described method comprises:
A) method as described in second aspect is adopted to prepare compound precursor material;
B) described composite precursor cleaning step a) obtained, filtration also drying;
C) dried described composite precursor and lithium hydroxide Homogeneous phase mixing are placed in oxygen atmosphere stove calcine, be cooled to room temperature afterwards, obtain described positive electrode.
According to an embodiment of the present invention, step b described in described method) comprising: 1) by described precursor material with 20 ~ 80 DEG C, concentration is the sodium chloride solution stirring and washing 10 ~ 60min of 3 ~ 30wt%; 2) the washed with de-ionized water precipitation several of 20 ~ 80 DEG C is adopted, to final ph lower than 10; With 3) wet feed after cleaning is placed in dry 6 ~ 60h at 60 ~ 150 DEG C.
According to an embodiment of the present invention, step c described in described method) comprising: by the precursor material after cleaning-drying and lithium hydroxide Homogeneous phase mixing, in 650 ~ 850 DEG C of calcining 10 ~ 30h in oxygen atmosphere stove, after being cooled to room temperature, obtain described positive electrode.
In a word, nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material preparation method provided by the invention, the method of lithium ion battery composite cathode material is prepared and thus obtained lithium ion battery composite cathode material has multiple Advantageous Effects: (1) introduces high manganese compound as surrounding phase based on nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material, first rich manganese material storage and building-up process in the moisture in environment and raw material and carbon dioxide insensitive, to a certain degree weaken material in building-up process to ambient moisture and the carbon dioxide even sensitivity of raw material impurity, (2) rich lithium manganese base solid solution has 2.8 ~ 4.5V window structure stability characteristic (quality) mutually, rich surface manganese can extenuate the nickelic chemical action with electrolyte in high voltage (4.3 ~ 4.5V) charge and discharge process mutually, makes the exploitation of high voltage nickel cobalt lithium aluminate become possibility, (3) surperficial lithium-rich manganese-based phase has extenuated the absorption of material to moisture and carbon dioxide greatly, is beneficial to and improves materials processing performance and memory property, (4) described nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material physical property is excellent, and product purity is high, complete crystallization, has the chemical property of high voltage stable circulation, (5) the NaCl desulfurization washing process that comprises of method of the present invention, removing of objectionable impurities can be improved while the loss reducing effective element in presoma, thus be conducive to synthesizing the lithium ion battery composite cathode material LiNi with high voltage stable charge/discharge 1-x-yco xal yo 2/ Li 1.2mn 0.54ni 0.13co 0.13o 2.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to technological means of the present invention can be better understood, and can be implemented according to the content of specification, and can become apparent, below especially exemplified by the specific embodiment of the present invention to allow above and other objects of the present invention, feature and advantage.
Accompanying drawing explanation
By reading hereafter detailed description of the preferred embodiment, various other advantage and benefit will become cheer and bright for those of ordinary skill in the art.Accompanying drawing only for illustrating the object of preferred implementation, and does not think limitation of the present invention.In the accompanying drawings:
Fig. 1 be in embodiment 1 preparation presoma coated before and coated after SEM comparison diagram.
Fig. 2 is the XRD figure of the composite material of preparation in embodiment 1.
Fig. 3 is positive electrode 0.1C and the 1C cycle performance curve of preparation in embodiment 1
Fig. 4 be in embodiment 2 preparation presoma coated before and coated after SEM comparison diagram.
Fig. 5 is positive electrode 1C charging and discharging curve (2a) and the 1C cycle performance curve (2b) of preparation in embodiment 2.
Fig. 6 be in embodiment 3 preparation presoma coated before and coated after SEM comparison diagram.
Fig. 7 is the positive electrode of preparation in embodiment 3 and the positive electrode cycle performance correlation curve by common nickel cobalt aluminium precursor power.
Embodiment
Illustrative embodiments of the present disclosure will be described in more detail below.Although hereinafter show illustrative embodiments of the present disclosure, however should be appreciated that can realize the disclosure in a variety of manners and not should limit by the execution mode of setting forth here.On the contrary, provide these execution modes to be in order to more thoroughly the disclosure can be understood, and complete for the scope of the present disclosure can be conveyed to those skilled in the art.But achieve the present invention although should be appreciated that those skilled in the art can dream up clearly not describe in this manual or record and be included in various methods, component and the content in spirit of the present invention, principle and scope.The all examples quoted from this specification and conditional language are all for the object illustrated and instruct, principle prior art contributed to help reader understanding inventor and concept, and should be understood to be not limited to these the specifically example of citation and conditions.In addition, in order to be illustrated more clearly in, the detailed description for known method, component and content is eliminated, not obscure description of the invention.Should be understood that unless stated otherwise, the feature in each execution mode described herein can combine mutually.
Embodiment 1:
Prepare the nickel cobalt mixed solution that nickel concentration of cobalt ions is 2mol/L, Ni:Co=80:15, (aluminium and complex solution hydroxy, by Al for the sodium aluminate solution of aluminium content 0.5mol/L 3+: OH -=1:4 is formulated), the NaOH solution of 4mol/L, the ammoniacal liquor of 7mol/L;
In 150L reactor, add the ammonia solution as end liquid in advance, temperature is 50 DEG C, (NH 3h 2o+NH 4 +) concentration be 1mol/L, pH is 11.50 ± 0.02,40L altogether;
By nickel cobalt mixed solution, sodium aluminate solution, NaOH solution and concentrated ammonia liquor respectively stream be dosed in reactor, charging rate is respectively: 20 ± 1mL/min, 4.21 ± 0.05mL/min, 20 ± 5mL/min, 7 ± 1mL/min, controlling reaction temperature is 50 DEG C, pH is 11.40 ~ 11.50, mixing speed is 400r/min, when product particle size distribution D50=11.4 ~ 11.5 micron, stop reaction;
By the material in reactor after standing 1h, drain supernatant.Be 50 DEG C, pH=10.50, (NH by the concentrated ammonia liquor of deionized water, 7mol/L and the NaOH solution of 4mol/L by system furnishing temperature in still 3h 2o+NH 4 +) concentration is the slip of 0.2mol/L.By Mn:Ni:Co=67.5:16.25:16.25 and Ni+Mn+Co be the nickel cobalt manganese solution of 1mol/L, the ammonia spirit of the sodium hydroxide solution of 2mol/l and 7mol/l simultaneously respectively stream add in reactor, charging rate is respectively 10ml/min, 10 ± 2mL/min and 0.6 ± 0.05ml/min, controlling reaction temperature is 50 DEG C, pH=10.50 ± 0.05, adopt pH meter detection architecture pH value in preparation process, adopt (NH in chemical titration detection architecture 3h 2o+NH 4 +) content.Preparation Mn 0.625ni 0.1625co 0.1625(OH) 2coated Ni 0.80co 0.15al 0.05(OH) 2composite precursor, when granularity D50=11.60 ± 0.01 stop charging.
By slip in a kettle. after 30min ageing, filtrated stock, and with 60 DEG C, the sodium chloride solution of 10% cleaning 30min, slip through deionized water washing, filter, obtain Ni after drying 0.80co 0.15al 0.05(OH) 2/ Mn 0.675ni 0.1625co 0.1625(OH) 2composite precursor (its SEM is see Fig. 1, Fig. 1 a, Fig. 1 b be respectively coated before and coated after presoma SEM figure), as can be seen from SEM figure, be spherical with coated rear presoma pattern before coated, but surface topography differ greatly and also coated after presoma surface there is no independent short grained appearance, show that coated source is all distributed in spheric granules surface, define uniform hydroxide film.By Ni 0.80co 0.15al 0.05(OH) 2/ Mn 0.675ni 0.1625co 0.1625(OH) 2composite precursor and the lithium hydroxide Homogeneous phase mixing of metering ratio after, be placed in 750 DEG C, oxygen atmosphere stove calcining 10h and be cooled to room temperature and obtain LiNi 0.80co 0.15al 0.05o 2/ Li 1.2mn 0.54ni 0.13co 0.13o 2composite positive pole, XRD detects this material and has α NaFeO 3structure (its XRD testing result is see Fig. 2).Adopt this positive electrode do button cell prepared by positive pole under 2.8 ~ 4.4 voltage window discharge and recharge 0.1C first discharge capacity be 216mAh/g, under 1C, specific discharge capacity remains on 195mAh/g, and circulate 150 weeks capability retention > 80% (see Fig. 3).
Embodiment 2
Prepare the nickel cobalt mixed solution that nickel concentration of cobalt ions is 2mol/L, Ni:Co=80:10, the Al:EDTA=1:1.05 of aluminium content 0.5mol/L containing aluminium complex solution, the NaOH solution of mass concentration 10%, the EDTA solution of 0.5mol/l;
In 150L reactor, add the EDTA solution as end liquid in advance, temperature is 50 DEG C, and EDTA concentration is 0.02mol/L, pH is 11.50 ± 0.02, and volume is 40L;
By nickel cobalt mixed solution, containing aluminium complex solution, NaOH solution and EDTA solution respectively simultaneously stream be dosed in reactor, charging rate is respectively: 20 ± 1mL/min, 8.89 ± 0.05mL/min, 37 ± 2mL/min, 2.7 ± 0.1mL/min are 50 DEG C in reaction temperature, pH is 11.40 ~ 11.50, mixing speed is successive reaction under the condition of 400r/min, when product particle size distribution D50=11.4 ~ 11.5 micron, stop reaction;
By the material in reactor after standing 1h, drain supernatant.Be 50 DEG C, pH=8.50 with the ammonium bicarbonate soln of deionized water, 1mol/L and the sodium carbonate liquor of 2mol/L by system furnishing temperature in still, ammonium bicarbonate concentration is the slip of 0.1mol/L.Be the nickel cobalt manganese solution of 1mol/L by Mn:Ni:Co=67.5:16.25:16.25, Ni+Mn+Co, the ammonium bicarbonate soln of the sodium carbonate liquor of 2mol/l and 1mol/l simultaneously respectively stream add in reactor, charging rate is respectively 10,5 and 1.67mL/min, control reaction temperature 50 DEG C, pH=8.50 ± 0.05, adopt pH meter detection architecture pH value in preparation process, adopt (NH in chemical titration detection architecture 3h 2o+NH 4 +) content.Preparation Ni 0.80co 0.10al 0.10(OH) 2/ Mn 0.675ni 0.1625co 0.1625cO 3composite precursor, when granularity D50=11.60 ± 0.05 stop charging.
By slip in a kettle. after 30min ageing, filtrated stock, and with 60 DEG C, the sodium chloride solution of 10% cleaning 30min, slip through deionized water washing, filter, obtain Ni after drying 0.80co 0.10al 0.10(OH) 2/ Mn 0.675ni 0.1625co 0.1625cO 3composite precursor (its SEM is see Fig. 4, Fig. 4 a, Fig. 4 b be respectively coated before and coated after presoma SEM figure), as can be seen from SEM figure, coated front and back presoma pattern is spherical, and surface topography differs greatly and coated after presoma surface there is no the appearance of independent nuclear particle, show that coated source is all distributed in spheric granules surface, define uniform carbonate deposition film.By Ni 0.80co 0.10al 0.10(OH) 2/ Mn 0.675ni 0.1625co 0.1625cO 3composite precursor and the lithium hydroxide Homogeneous phase mixing of metering ratio after, be placed in 750 DEG C, oxygen atmosphere stove calcining 10h and be cooled to room temperature and obtain LiNi 0.80co 0.10al 0.10o 2/ Li 1.2mn 0.54ni 0.13co 0.13o 2composite positive pole.Adopt this positive electrode do button cell prepared by positive pole under 2.8 ~ 4.5 voltage window discharge and recharge 0.1C first discharge capacity be 206mAh/g, under 1C, specific discharge capacity remains on 186mAh/g, and circulate 200 weeks capability retention > 80% (as Fig. 5).
Embodiment 3
Prepare the nickel cobalt mixed solution that nickel concentration of cobalt ions is 2mol/L, Ni:Co=80:15, the Al:EDTA=1:1.05 of aluminium content 0.5mol/L containing aluminium complex solution, the NaOH solution of mass concentration 30%, the ammoniacal liquor of 7mol/L;
In 150L reactor, add the ammonia solution as end liquid in advance, temperature is 50 DEG C, (NH 3h 2o+NH 4 +) concentration be 1mol/L, pH is 11.50 ± 0.02, volume is 40L;
By nickel cobalt mixed solution, containing aluminium complex solution, NaOH solution and concentrated ammonia liquor respectively simultaneously stream be dosed in 150L reactor, charging rate is respectively: 20 ± 1mL/min, 4.21 ± 0.05mL/min, 20 ± 5mL/min and 7 ± 1mL/min.Be 50 DEG C in reaction temperature, pH is 11.40 ~ 11.50, and mixing speed is successive reaction under the condition of 400r/min, when product particle size distribution D50=11.4 ~ 11.5 micron, stop reaction;
By the material in reactor after standing 1h, drain supernatant.Be 50 DEG C, pH=10.50, (NH with the NaOH solution of deionized water, 4mol/L and the ammonia spirit of 7mol/L by system furnishing temperature in still 3h 2o+NH 4 +) concentration is the slip of 0.2mol/L.By Mn:Ni:Co=67.5:16.25:16.25, Ni+Mn+Co be the nickel cobalt manganese solution of 1mol/L, 30% sodium hydroxide solution and 7mol/l ammonia spirit simultaneously respectively stream add in reactor, charging rate is respectively 10ml/min, 2.67 ± 0.1 and 0.37 ± 0.1mL/min, control reaction temperature 50 DEG C, pH=10.50 ± 0.05, adopt pH meter detection architecture pH value in preparation process, adopt (NH in chemical titration detection architecture 3h 2o+NH 4 +) content.Preparation Ni 0.80co 0.15al 0.05(OH) 2/ Mn 0.675ni 0.1625co 0.1625(OH) 2composite precursor, when granularity D50=11.60 ± 0.01 stop charging.
By slip in a kettle. after 30min ageing, filtrated stock, and with 60 DEG C, the sodium chloride solution of 10% cleaning 30min, slip through deionized water washing, filter, obtain Ni after drying 0.80co 0.15al 0.05(OH) 2/ Mn 0.675ni 0.1625co 0.1625(OH) 2(its SEM is see Fig. 6 for composite precursor, Fig. 6 a, Fig. 6 b be respectively coated before and coated after presoma SEM figure), as can be seen from SEM figure, differ greatly with coated rear presoma surface topography before coated, there is no the appearance of independent nuclear particle, show that coated source is all distributed in spheric granules surface, define uniform precipitation of hydroxide film.Then by after composite precursor and the lithium hydroxide Homogeneous phase mixing of metering ratio, be placed in 750 DEG C, oxygen atmosphere stove calcining 10h and be cooled to room temperature and obtain LiNi 0.80co 0.15al 0.05o 2/ Li 1.2mn 0.54ni 0.13co 0.13o 2composite positive pole.Adopt this positive electrode do button cell prepared by positive pole under 2.8 ~ 4.4 voltage window discharge and recharge 0.1C first discharge capacity be 220mAh/g, under 1C, specific discharge capacity remains on 206mAh/g, and circulate 150 weeks capability retention > 80% (see accompanying drawing 7).
The present invention will be described instead of limit the invention to it should be noted that above-mentioned execution mode, and those skilled in the art are not when departing from the scope of claims, can design various alternate embodiments.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the increase of helper component, the concrete way choice etc. of component selected by the present invention, all drops within protection scope of the present invention and open scope.

Claims (15)

1. a lithium ion battery composite cathode material, is characterized in that, described material comprises coating layer Li 1.2mn 0.54ni 0.13co 0.13o 2with principal phase LiNi 1-x-yco xal yo 2precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1.
2. a preparation method for nickel cobalt manganese cladded type nickel cobalt aluminium compound precursor material, is characterized in that, said method comprising the steps of:
1) coprecipitation is adopted to prepare spherical Ni 1-x-yco xal y(OH) 2precursor material, obtains and comprises the slip of described precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1;
2) nickel cobalt manganese cladded type composite precursor is prepared, comprise: add precipitation reagent to described slip, complexing agent I, the mixed solution of nickel salt I, cobalt salt I and manganese salt, thus making the hydroxide of nickel, cobalt and manganese or carbonate with described precursor material for matrix growth in situ, acquisition principal phase is Ni 1-x-yco xal y(OH) 2, coating layer is Mn 0.675ni 0.1625co 0.1625(OH) 2, or principal phase is Ni 1-x-yco xal y(OH) 2, coating layer is Mn 0.675ni 0.1625co 0.1625cO 3compound precursor material.
3. method according to claim 2, is characterized in that: described nickel salt I is one or more in nickelous sulfate, nickel chloride, nickel acetate or nickel nitrate.
4. method according to claim 2, is characterized in that: described cobalt salt I is one or more in cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
5. method according to claim 2, is characterized in that: described manganese salt is one or more in manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
6. method according to claim 2, is characterized in that: described complexing agent I is one or more in ammoniacal liquor, triethanolamine, citric acid, oxalic acid, sodium ethylene diamine tetracetate and carbonic hydroammonium.
7. method according to claim 2, is characterized in that: described precipitation reagent is one or more in NaOH, sodium carbonate or carbonic hydroammonium.
8. method according to claim 2, is characterized in that: described step 1) comprising: preparation nickel salt II and cobalt salt II mixed solution, containing aluminium complex solution, complexing agent II solution, sodium hydroxide solution; Add the end liquid containing described complexing agent II in a kettle. in advance; By the mixed solution of described nickel salt II and cobalt salt II, described containing aluminium complex solution, described complexing agent II solution, described sodium hydroxide solution respectively stream adds precipitation reaction in reactor, obtains the slip comprising described precursor material.
9. method according to claim 8, is characterized in that: described nickel salt II is one or more in nickelous sulfate, nickel chloride, nickel acetate or nickel nitrate.
10. method according to claim 8, is characterized in that: described cobalt salt II is one or more in cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
11. methods according to claim 8, is characterized in that: the described aluminium salt contained in aluminium complex solution is one or more in aluminum nitrate, aluminum sulfate or aluminum acetate.
12. methods according to claim 8, is characterized in that: described complexing agent II is one or more in ammoniacal liquor, citric acid, ammonium fluoride, oxalic acid, sodium ethylene diamine tetracetate and NaOH.
The preparation method of 13. 1 kinds of lithium ion battery composite cathode materials, described positive electrode comprises coating layer Li 1.2mn 0.54ni 0.13co 0.13o 2with principal phase LiNi 1-x-yco xal yo 2precursor material, wherein 0≤x≤1,0≤y≤1 and 0≤x+y≤1, described method comprises:
A) method according to any one of claim 2 to 12 is adopted to prepare compound precursor material;
B) described composite precursor cleaning step a) obtained, filtration also drying;
C) dried described composite precursor and lithium hydroxide Homogeneous phase mixing are placed in oxygen atmosphere stove calcine, be cooled to room temperature afterwards, obtain described positive electrode.
14. methods according to claim 13, is characterized in that: described step b) comprising: 1) by described precursor material with 20 ~ 80 DEG C, concentration is the sodium chloride solution stirring and washing 10 ~ 60min of 3 ~ 30wt%; 2) the washed with de-ionized water precipitation several of 20 ~ 80 DEG C is adopted, to final ph lower than 10; With 3) wet feed after cleaning is placed in dry 6 ~ 60h at 60 ~ 150 DEG C.
15. methods according to claim 13 or 14, it is characterized in that: described step c) comprising: by the precursor material after cleaning-drying and lithium hydroxide Homogeneous phase mixing, in 650 ~ 850 DEG C of calcining 10 ~ 30h in oxygen atmosphere stove, after being cooled to room temperature, obtain described positive electrode.
CN201510233146.5A 2015-05-08 2015-05-08 Lithium-ion battery precursor material, composite positive electrode material and preparation method thereof Pending CN104966820A (en)

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