CN106058188A - Lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 with core-shell structure and preparation method of lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 - Google Patents

Lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 with core-shell structure and preparation method of lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 Download PDF

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CN106058188A
CN106058188A CN201610554381.7A CN201610554381A CN106058188A CN 106058188 A CN106058188 A CN 106058188A CN 201610554381 A CN201610554381 A CN 201610554381A CN 106058188 A CN106058188 A CN 106058188A
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ion battery
cathode material
lithium ion
composite cathode
lithium
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胡国荣
彭忠东
杜柯
段建国
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Central South University
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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
    • 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
    • H01M4/50—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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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Abstract

The invention discloses a lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 with a core-shell structure and a preparation method of the lithium ion battery composite cathode material LiNi1-x-yMxAlyO2. The preparation method comprises the following steps that precursor powder is dispersed into a reaction still containing a base solution of a certain volume; a sodium metaaluminate solution is added into the reaction still, a precipitator is added at certain flow speed, the reaction conditions are controlled, and aluminum slowly deposits to the surface of the precursor powder; slurry is aged, washed and filtered, and a precursor with the core-shell structure is obtained after drying; the precursor and lithium salt are mixed to be uniform and calcined in oxygen shield to form the composite cathode material LiNi1-x-yMxAlyO2. The method has the advantages of being low in equipment requirement, easy to operate, environmentally friendly, high in element utilization rate, even in coating, good in product quality and the like.

Description

A kind of lithium ion battery composite cathode material LiNi with nucleocapsid structure1-x-yMxAlyO2And preparation method thereof
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, relate to a kind of lithium with nucleocapsid structure from Sub-battery composite anode material LiNi1-x-yMxAlyO2Preparation method.
Background technology
The most prominent feature of nickel system positive electrode is to compare the most popular cobalt acid lithium, and it has inexpensive, low toxicity With advantages such as high specific discharge capacities.But nickelic system positive electrode faces following problem limits its commercial applications: synthesis Nickelic positive electrode is sensitive to ambient humidity and carbon dioxide；Rich nickel based material and acidic electrolysis bath reactivity cause material electrification Learn stability and heat stability is bad.Therefore, material is improved on the premise of the interface of design stability is to ensure that material energy densities Storge quality and the effective way of electrochemically stable performance.
Rich aluminum is coated with mutually and is presently the most commonly used method for coating, as Publication No. CN102244239, The Chinese patent literatures such as CN103872331A, CN104425813A, CN102891301A disclose rich aluminum phase coated lithium ion electricity The method of pond positive electrode, but the method flow used is complicated, technology requires that high, technological process length is unfavorable for controlling, wrapping Covering selected system is that organic system cost is of a relatively high.Simple solid phase method mixing cladding also exists and can not realize the former of coating film Position is compound, the shortcoming that covered effect is the best.
It is aluminum source, titanium dioxide that the Chinese patent literature of Publication No. CN104766960A discloses a kind of employing sodium metaaluminate Carbon is faintly acid precipitant, carries out aluminium hydroxide cladding on lithium nickel lithium manganate cathode material surface and obtain oxygen by temper Change the Modified Nickel manganate cathode material for lithium of aluminum cladding.The method relate to be wrapped by matrix surfactant carry out surface live Change process, ultrasonic disperse also prepare the material modified (LiNi of alumina-coated by tempering process0.5Mn1.5O4/Al2O3) (should Material modified Li/ (Ni+Mn+Al) ≈ 0.5).The model of the method is alumina-coated spinel-type matrix material, the two knot Structure differs greatly, and needs surface activation process could realize oxide cladding.The shortcoming of this method is: surfactant meeting Matrix material bring the adverse effects such as corrosion, the matrix material induction aluminum hydroxide precipitation poor meeting of activity cause carbonation decomposition Later stage forms the generation containing sodium and the Dawsonite Kompensan of carbonate affects purity, aluminium oxide and Spinel architectural difference greatly, Biphase for physical coupling, it is easily peeled off in the course of processing and charge and discharge process and comes off.
In prior art, it is bad to there is cyclical stability in rich nickel system positive electrode, sensitive to ambient moisture and carbon dioxide The shortcoming poor with thermodynamic stability.
Summary of the invention
The cyclical stability that generally there is rich nickel system positive electrode for solution prior art is bad, to ambient moisture and dioxy Changing the shortcomings such as sensitive, the thermodynamic stability difference of carbon, it is desirable to provide a kind of simple, condition is easily controllable, synthesis Material has good processing characteristics, storge quality and the anode material for lithium-ion batteries of excellent chemical property and preparation thereof Method.
A kind of lithium ion battery composite cathode material LiNi with nucleocapsid structure1-x-yMxAlyO2Preparation method, including Following steps:
Step (1): positive electrode material precursor dispersion is obtained dispersion liquid in deionized water；Meta-aluminic acid is added in dispersion liquid Saline solution mixes to obtain alkaline slurry, and described alkaline slurry pH is 11～14；In alkaline slurry, add acid solution or blast acidity PH is down to 9～10.5 by gas, makes to be formed aluminium hydroxide clad on positive electrode material precursor surface；The most aged, washing, It is dried to obtain surface A l (OH)3The composite precursor of cladding；Described positive electrode material precursor is Ni1-a-bM′aAlb(OH)2Or Ni1-v- wM″vAlwOδ；
Described Ni1-a-bM′aAlb(OH)2In, 0≤a≤1,0≤b≤1 and 0≤a+b≤1, M ' is Mn, Co, Al, Ti, Mg, At least one in Ca, Ba, Si, Cr；
Described Ni1-v-wM″vAlwOδIn, 0≤v≤1,0≤w≤1 and 0≤v+w≤1,1≤8≤3, M " for Mn, Co, Al, At least one in Ti, Mg, Ca, Ba, Si, Cr；
Step (2): after being mixed with lithium-containing compound by the composite precursor that step (1) obtains, be placed in the atmosphere containing oxygen Enclose lower 650～850 DEG C of calcinings and obtain Surface L iAlO2The LiNi of cladding1-x-yMxAlyO2Material.
The present invention it is critical only that the positive electrode material precursor described in employing is matrix material, uses acidifying decomposition method system Obtain the composite precursor material of aluminium hydroxide cladding；Coordinated is at the described temperature of step (2) at high-temperature calcination the most again Reason, thus obtain LiAlO in situ2The LiNi of cladding1-x-yMxAlyO2Material (composite positive pole).Inventor finds, described Hydroxide Ni1-a-bM′aAlb(OH)2Or oxide Ni1-v-wM″vAlwOδIt is the good induced material of aluminum hydroxide precipitation, can make For crystal seed induction aluminium hydroxide original position, homoepitaxial cladding；Activate without additional surface and/or aid in ultrasonic cavitation effect Aluminium hydroxide can be realized in described positive electrode material precursor (matrix material) growth in situ above, cladding.The present invention can be effective Avoid surfactant that matrix material brings the adverse effects such as corrosion, also can avoid because aluminum hydroxide precipitation induced by matrix material Activity is poor and causes acidifying to decompose the later stage formation generation containing sodium and the Dawsonite Kompensan of carbonate and affects purity.The present invention In, by described matrix material, and step described in coordinated (1) and the process of step (2), cladding can be prepared firmly, at electricity The aspect performance such as chemical stability and heat stability has the composite positive pole of bigger lifting.Such as, prepared LiAlO2 It is high that the composite positive pole of cladding has specific capacity, insensitive to ambient humidity and carbon dioxide, good processability, stable circulation Property and the thermally-stabilised advantage such as good.
In step (1), positive electrode material precursor dispersed with stirring to water will obtain dispersion liquid, control the pH in dispersion liquid and Temperature；With backward dispersion liquid adds meta-aluminate solution；Positive electrode material precursor is made to be evenly dispersed in meta-aluminate solution In, it is subsequently passed acid solution or sour gas carries out precipitation, make in-stiu coating Al on positive electrode material precursor material (OH)3。
In step (1), after dispersion liquid adds meta-aluminate solution, it is uniformly mixed to obtain alkaline slurry, due to inclined aluminum The pH value of hydrochlorate is the highest, the preferred ＞ of pH 12, so the alkalescence of system (alkaline slurry) is very strong after adding meta-aluminate, and pH value Between 11～14.Add acid solution or sour gas, owing to acid solution or sour gas are known from experience and the OH-effect in alkaline slurry, disappear Consumption hydroxyl, increases the degree of supersaturation of sodium aluminate solution, reduces aluminium hydroxide stability in the solution, when pH value reaches one After definite value, aluminium hydroxide will slowly separate out；Judged the thickness of clad by testing graininess, use and measure system pH judgement The rate of deposition of the aluminium hydroxide in system, such that it is able to judge the reaction terminating time according to granularity or pH value.Coating thickness The difference of the granularity granularity front with cladding for measuring is divided by 2.The inventors discovered that, after being passed through acid solution or sour gas, described When the pH of alkaline slurry is down between 9～10.5, i.e. think that aluminium hydroxide precipitates substantially completely.
Positive electrode material precursor is dispersed in water, obtains dispersion liquid；Wherein, the solid, liquid weight of positive pole precursor material and water Ratio preferably 0.5%～50%.
The pH value of described dispersion liquid is 11～14；Temperature is 20～80 DEG C.Described pH and at a temperature of, can effectively prevent When dispersion liquid mixes with meta-aluminate solution, aluminium hydroxide the most individually becomes karyogenesis alumine hydroxide colloid, be more beneficial for carbon divide heavy Aluminum, aluminium hydroxide are evenly coated at substrate material surface.
Maintain described dispersion liquid pH value and at a temperature of, add meta-aluminate solution.
The described meta-aluminate solution aqueous solution of at least one in sodium metaaluminate, lithium metaaluminate, potassium metaaluminate.
As a example by sodium aluminate solution, sodium aluminate solution is by the one in aluminum nitrate, aluminum sulfate or aluminum acetate or several Plant and be made into, with sodium hydroxide crystal or sodium hydroxide solution effect, the sodium metaaluminate aqueous solution that OH-concentration is 0.01～10mol/L. In described sodium aluminate solution, in addition to OH-and meta-aluminic acid root, also have the nitric acid of free state according to the difference of aluminum feedstock Root, sulfate radical, acetate plasma exist.
As preferably, in meta-aluminate solution, the molar concentration of meta-aluminic acid root is preferably 0.01～2mol/L.
As preferably, in dispersion liquid and meta-aluminate solution mixed process, control positive electrode material precursor and meta-aluminate In solution, the mol ratio of meta-aluminic acid root is 10～10000.In other words, in described alkaline slurry, positive electrode material precursor and inclined aluminum In acid salt solution, the mol ratio of meta-aluminic acid root is 10～10000.
As preferably, in step (1), the pH controlling described alkaline slurry is 12～13.
The particle diameter of positive electrode material precursor is preferably 0.2～50 μm.
As preferably, the Al (OH) of composite precursor3The thickness of clad is 0.001～1 micron.
Described acid solution is the aqueous solution of at least one in sulphuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid；Wherein, in acid solution [H+]=0.1～0.5mol/L.
In the present invention, aluminium hydroxide clad is made uniformly, to be slowly coated on described positive electrode material precursor surface.
Such as, under described preferred acid solution, the flow velocity that adds of described acid solution can be 0.01～2000ml/min.
Described sour gas is at least one in carbon dioxide, chlorine, hydrogen chloride gas, nitrogen dioxide, sulfur dioxide. Such as, the flow of described sour gas is 0.01～2000ml/min.
As preferably, the Al (OH) that in-stiu coating generates3It is 0.001～0.1 with the mol ratio of matrix material.
After being covered to complete the most aged, filter, wash, be dried and to obtain surface A l (OH)3The composite precursor of cladding；As excellent Choosing, in step (1), the product after using the deionized water of 20～80 DEG C to clean ageing, the pH value of cleanout fluid is less than after 10.5 again Product after cleaning is dried process；Baking temperature is 60～150 DEG C；It is dried 6～100h.
After the composite precursor that step (1) obtains uniformly is mixed with lithium-containing compound, it is placed under the atmosphere containing oxygen Calcining obtains Surface L iAlO2The LiNi of cladding1-x-yMxAlyO2Material.
As preferably, in step (2), during mixed lithium, Li add mole be in composite precursor Ni, M and Al mole 1～1.05 times of amount sum.
Composite precursor and lithium salts use ball milling or the direct solid-solid blend of high-speed stirred method, sampling test analysis mixing Show mix homogeneously when thing Li, Ni, M, Al content is consistent with design load and fluctuating error is less than 1 ‰, otherwise continue mixing.
In step (2), described lithium-containing compound be in lithium acetate, lithium sulfate, lithium nitrate, lithium carbonate, Lithium hydrate extremely Few one.
As preferably, in calcination process, oxygen concentration controls more than 95%.
As preferably, calcining heat controls at 700～750 DEG C.
As preferably, in calcination process, programming rate 0.01～10 DEG C/min.
Under described calcining heat, calcination time is preferably 10～30h.
Present invention additionally comprises a kind of lithium ion battery composite cathode material LiNi using described preparation method to prepare1-x- yMxAlyO2, wherein, 0≤x≤1,0 ＜ y≤1 and 0 ＜ x+y≤1, M be in Mn, Co, Al, Ti, Mg, Ca, Ba, Si, Cr at least A kind of.
Covering amount is relevant with thickness, to be coated with gauge in the present invention.In obtained composite positive pole, LiAlO2Bag Covering percetage by weight is 0.1～10%.
Described composite positive pole LiNi1-x-yMxAlyO2In, 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= 0.05、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.M is at least one in Mn, Co, Al, Ti, Mg, Ca, Ba, Si, Cr.
The anode material for lithium-ion batteries prepared by the method, has stable electrochemical property, and energy density is big, The features such as anti-humidity sensitive, security performance are good, can be used to prepare the electrokinetic cell met needed for electronic product and electric tool.
A kind of lithium ion battery composite cathode material LiNi preferably with nucleocapsid structure of the present invention1-x-yMxAlyO2System Preparation Method, comprises the following steps:
Step (a): prepare aluminium hydroxide cladding composite precursor:
Step (a-1): positive electrode material precursor is distributed in deionized water, the solid-to-liquid ratio control of positive pole precursor material and water System, between 0.5%～50%, obtains dispersion liquid；The pH value adjusting dispersion liquid is 11～14, and temperature controls at 20～80 DEG C；Described Positive electrode material precursor is Ni1-a-bM′aAlb(OH)2Or Ni1-v-wM″vAlwOδ；Described Ni1-a-bM′aAlb(OH)2In, 0≤a≤ 1,0≤b≤1 and 0≤a+b≤1, M ' is at least one in Mn, Co, Al, Ti, Mg, Ca, Ba, Si, Cr；
Described Ni1-v-wM″vAlwOδIn, 0≤v≤1,0≤w≤1 and 0≤v+w≤1,1≤δ≤3, M " for Mn, Co, Al, At least one in Ti, Mg, Ca, Ba, Si, Cr；
Step (a-2): add meta-aluminate solution (positive electrode material precursor in the system prepared in step (a-1) With the mol ratio of meta-aluminic acid root is between 10 to 10000, the pH of the alkaline slurry that mix homogeneously obtains is 12-13；Subsequently with 5- 400ml/min flow velocity is passed through [H+]=0.1～the acid solution of 0.5mol/L or sour gas reduce system pH to 9～ 10.5, it is thus achieved that the composite precursor of aluminium hydroxide cladding；Described acid solution is the water-soluble of at least one in sulphuric acid, hydrochloric acid or nitric acid Liquid；Described sour gas is at least one in carbon dioxide, chlorine, hydrogen chloride gas, nitrogen dioxide, sulfur dioxide；
Step (b): the composite precursor obtaining step (a-2) washs, filters and is dried:
Step (b-1): using the deionized water of 20～80 DEG C to clean precipitation, (washing process is collected to control final filtrate Cleaning mixture) pH value is less than 10；
Step (b-2): the powder after step (b-1) being cleaned is placed in air dry oven under the conditions of 60～150 DEG C dry Dry 6～100h；
Step (c): the preparation of aluminum coated lithium ion battery positive electrode:
After composite precursor after step (b) being processed mixes with the lithium salts of metering ratio, it is placed in oxygen atmosphere stove in 700 ～750 DEG C of calcinings 10～30h, it is cooled to room temperature and obtains and cover aluminium profiles LiNi1-x-yMxAlyO2Material.
Positive electrode test process of the present invention is: material is fabricated to CR2025 type button cell and carries out discharge and recharge Loop test.Using coating method to prepare electrode, with METHYLPYRROLIDONE (NMP) as solvent, in mass ratio 8: 1: 1 respectively Weigh active substance, acetylene black and PVDF, after mix homogeneously, be coated on pretreated aluminium foil, put in vacuum drying oven 120 DEG C are dried to obtain positive plate.In the glove box of full argon, with metal lithium sheet as negative pole, 1mol L-1LiPF6It is dissolved in Ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethyl methyl carbonate (EMC) (volume ratio is 1: 1: 1) is electrolyte, Celgard2400 porous polypropylene film is barrier film, is assembled into button cell, carries out electro-chemical test on Land electrochemical instrument.
In the present invention, use highly active hydroxide Ni1-a-bM′aAlb(OH)2Or oxide Ni1-v-wM″vAlwOδAs Positive electrode material precursor (matrix), with meta-aluminate for aluminum source, aids in positive electrode material precursor pair under described acid condition The good inductive effect of aluminum hydroxide precipitation, and then induction aluminium hydroxide growth in situ cladding, precipitation；And due in system pH delay Slow reduction, Al (OH)3Preferential slow crystallization on nickel cobalt aluminum (positive electrode material precursor) spheroidal particle, makes uniformly to be coated with Form one layer of absolutely Al (OH)3Clad, and clad is the thinnest, is evenly coated, overall to positive electrode material precursor Composition influence little.Additionally, by means of described method for calcinating, by surface A l (OH)3Composite precursor one step of cladding is in situ Reaction, prepares LiAlO2The positive electrode LiNi of cladding1-x-yMxAlyO2；Described positive electrode LiNi1-x-yMxAlyO2Model is such as For LiNi1-a-bM′aAlbO2/LiAlO2.During calcination reaction part Al can be diffused in matrix material formation graded elemental divide The transition zone of cloth, in addition LiAlO2The structure of clad and body phase LiNi1-x-yMxAlyO2It is NaFeO2Layer structure, structure phase Big like degree, it is coated with the most firm, can more effectively improve material electrochemical stability and heat stability.
The inventive method is simple, and condition is easily controllable, green high-efficient.The LiAlO prepared2Coated prod (clad) Purity is high, complete crystallization, good physical properties.Owing to active material surface is stable to air ambient and the rich aluminum of electrolyte Phase, the chemical action of the sensitivity of environment and charge and discharge process with electrolyte is substantially inhibited, shows excellent adding by material Work performance, good storge quality (such as, anti-humidity sensitive is obviously improved) and superior chemical property.
Accompanying drawing explanation
Fig. 1 is the SEM comparison diagram in embodiment 1 before presoma cladding and after cladding；
Fig. 2 is embodiment 1 composite and the XRD of embodiment 2 composite；Wherein, a part of Fig. 2 is that embodiment 1 is multiple The XRD figure of condensation material；The XRD figure that b part is embodiment 2 composite of Fig. 2；
Fig. 3 is the SEM comparison diagram in embodiment 2 before presoma cladding and after cladding；
Fig. 4 is product charging and discharging curve and cycle performance curve in embodiment 3；
Fig. 5 embodiment 4 is Al (OH)3The presoma of cladding and finished product TEM figure；Wherein, Fig. 5 a is Al (OH)3Before Bao Fu Drive body TEM figure；Fig. 5 b is LiAlO2The TEM figure of the finished product of cladding.
Specific embodiment
Embodiment 1
Use the method synthesis 5Kg Ni described in Publication No. CN103066257A0.815Co0.15Al0.035(OH)2Presoma (NCA presoma；SEM is shown in a part of Fig. 1).Stopped reaction when product particle size distribution D50=11.4～11.5 microns.Filter Mother solution obtains NCA presoma (Ni0.815Co0.15Al0.035(OH)2).NCA presoma is joined in 50L reactor, add 30Kg Deionized water, uses the mixing speed stirring 30min of 3m/s, and uses sodium hydroxide to control pH=11.50, add 1.09L The sodium aluminate solution of 0.5mol/L, and it is slowly added to the dilution heat of sulfuric acid of 0.2mol/L with the flow velocity of 5ml/min until reacting 9.0≤pH≤10 in still；Subsequently by the slip after acid reaction after 30min is aged, filtrated stock, and with 60 DEG C, 10% Sodium chloride solution cleans 30min, and slip is through washing, filter, obtaining Ni after drying0.815Co0.15Al0.035(OH)2/Al(OH)3 (NCA presoma and Al (OH)3The mol ratio of clad is 100: 1) the presoma b part of embodiment Fig. 1 (SEM see), from SEM It can be seen that cladding is front and after cladding, presoma surface topography differs greatly in figure, Al (OH)3It is distributed in spheroidal particle surface, Define uniform aluminum hydroxide film.By Ni0.815Co0.15Al0.035(OH)2/0.01Al(OH)3Lithium hydrate with metering ratio After (molar ratio of Li/ (Ni+M+Al) is 1) uniformly mixing, it is placed in oxygen atmosphere stove and heats up with the heating rate of 3 DEG C/min To 750 DEG C of calcining at constant temperature 12h, it is cooled to room temperature obtains LiNi0.807Co0.149Al0.044O2Composite positive pole (LiAlO2Bag The composite positive pole covered), XRD detects this composite positive pole and has single layer structure (see a part of embodiment Fig. 2). Detecting this composite positive pole actual nickel cobalt aluminum ratio is 80.7: 14.9: 4.4.It is button prepared by positive pole with this composite positive pole Formula battery is in 2.8～4.3 voltage window discharge and recharges, and under 0.1C multiplying power, discharge capacity is 198mAh/g first, and discharge under 1C specific volume Amount is maintained at 178mAh/g, 1C and circulates 200 weeks capability retention ＞ 80%.
Comparative example 1
The LiAlO prepared by embodiment 12The element proportioning of the composite positive pole of cladding uniformly mixes, is doping to not wrap Cover the material (LiNi of Uniform Doped0.807Co0.149Al0.044O2Material).
The LiAlO that embodiment 1 is prepared2The composite positive pole of cladding and the uncoated material of comparative example 1 carry out humidity, Security performances etc. detect, and result is as follows:
The LiAlO that embodiment 1 prepares2The composite positive pole (clad anode material) of cladding stores under the humidity of 60% Weightening finish in 30 days is only 0.5%, the LiNi of Uniform Doped0.807Co0.149Al0.044O2Material (the uncoated material of comparative example 1) is in phase Under the conditions of Tong, gain in weight reaches 3.68%.Absolutely prove the LiAlO that embodiment 1 prepares2The moisture-resisting of the composite positive pole of cladding Degree sensitivity is improved.With N-methyl pyrrole network alkanone as dispersant, weigh the bag of embodiment 1 synthesis according to mass ratio 96: 2: 2 Coated positive pole material, acetylene black and binding agent (poly-inclined tetrafluoroethene PVDF), be stirred experiment in the environment of humidity is 40%, After test result indicate that cladding, material is stirred 80h under the highest humidity and does not produce fruit jelly；And contrast under the conditions of same Fruit jelly phenomenon is just there is in Uniform Doped material (uncoated material) in 1h.Illustrate further the LiAlO that embodiment 1 prepares2 The composite positive pole of cladding has more preferable anti-moisture sensitivity and processing characteristics.Use LiAlO2The anode composite material of cladding Material and uncoated positive electrode are respectively prepared 1Ah soft-package battery, and are charged to 4.4V and carry out acupuncture experiment, test result indicate that enforcement Covering material LiNi of example 10.807Co0.149Al0.044O2Corresponding battery in acupuncture course, there is not thermal runaway combustion phenomena and Battery prepared by uncoated material there occurs explosive reaction on fire, illustrates that the covering material of embodiment 1 has superior safety Energy.
Embodiment 2
By 5Kg Ni0.9Co0.1(OH)2The presoma a part of Fig. 3 (SEM see) joins in 50L coating reaction still.Add 30Kg deionized water, uses the mixing speed stirring 30min of 3m/s.Use sodium hydroxide to control pH=11.50, add 2.16L The sodium aluminate solution of 0.5mol/L, and it is passed through CO with the flow velocity of 300ml/min2Gas is until solution 9.5≤pH≤10；Subsequently By the slip after acid reaction after 30min is aged, filtrated stock, and clean precipitate, forerunner with 60 DEG C of deionized waters of 30Kg Body is through washing, filter, obtaining Ni after drying0.9Co0.1(OH)2/Al(OH)3(mol ratio is 100: 2) (SEM is shown in composite precursor The b part of Fig. 3), presoma surface topography differs greatly from SEM figure it can be seen that before covering aluminum and after covering aluminum, Al (OH)3Point Cloth, on spheroidal particle surface, defines uniform aluminum hydroxide film.Then by Ni0.9Co0.1(OH)2/0.02Al(OH)3With metering After the uniformly mixing of the Lithium hydrate (mole design proportion of Li/ (Ni+M+Al) is 1) of ratio, it is placed in oxygen atmosphere stove 750 DEG C and forges Burning 12h is cooled to room temperature and obtains LiNi0.882Co0.098Al0.02O2Composite positive pole (LiAlO2The anode composite material of cladding Material).XRD detects this material and has single layer structure (see the b part of embodiment Fig. 2).The composite positive pole prepared is 2.8 ～4.3 voltage window carry out charge-discharge test, under 0.1C, discharge capacity is 220mAh/g first, and under 1C, specific discharge capacity is maintained at 190mAh/g, circulates 200 weeks capability retention ＞ 80%.
Comparative example 2
The LiAlO prepared by embodiment 22The element proportioning of the composite positive pole of cladding uniformly mixes, is doping to not wrap Cover the material (LiNi of Uniform Doped0.882Co0.098Al0.02O2Material).
The LiAlO that embodiment 2 is prepared2The composite positive pole of cladding and the uncoated material of comparative example 2 carry out humidity, Security performances etc. detect, and result is as follows:
The LiAlO that embodiment 2 prepares2The composite positive pole of cladding stores weightening finish in 30 days under the humidity of 60% and is only 0.61%, the LiNi of Uniform Doped0.882Co0.098Al0.02O2Material (the uncoated positive electrode of comparative example 2) is under the same conditions Gain in weight reaches 6.88%.Absolutely prove material (LiAlO after cladding2Cladding composite positive pole) anti-humidity sensitive obtain Promote.With N-methyl pyrrole network alkanone as dispersant, weigh the LiAlO of the 2-in-1 one-tenth of embodiment according to mass ratio 96: 2: 22Cladding Composite positive pole, acetylene black and binding agent (poly-inclined tetrafluoroethene PVDF), be stirred reality in the environment of humidity is 40% Testing, after test result indicate that the cladding of embodiment 2, material is stirred 50h under the highest humidity and does not produce fruit jelly；And with Under the conditions of the Uniform Doped material of contrast in 0.5h, just there is fruit jelly phenomenon.Illustrate further what embodiment 2 prepared LiAlO2The composite positive pole of cladding has more preferable anti-moisture sensitivity and processing characteristics.Use LiAlO2Being combined of cladding Positive electrode and uncoated positive electrode make 1Ah soft-package battery, and are charged to 4.4V and carry out acupuncture experiment, test result indicate that bag Cover material LiNi0.882Co0.098Al0.02O2Corresponding battery in acupuncture course, there is not thermal runaway combustion phenomena and uncoated just Battery prepared by pole material there occurs explosive reaction on fire, and the LiAlO of embodiment 2 is described2The composite positive pole of cladding has Superior security performance.
Embodiment 3
Take 5Kg Ni0.8Co0.2(OH)2Presoma joins in 50L coating reaction still.Add 30Kg deionized water, use The mixing speed stirring 30min of 4m/s.Use sodium hydroxide adds 2.16L 0.5mol/L meta-aluminic acid after controlling pH=11.50 Sodium solution, and it is passed through CO with the flow velocity of 400ml/min2Gas is until solution 9.5≤pH≤10；Subsequently by the slip warp after acidifying After crossing 30min ageing, filtrated stock, and with 60 DEG C, the sodium chloride solution of 10% clean 30min, slip through washing, filtration, Obtain Ni after drying0.80Co0.20(OH)2/Al(OH)3(mol ratio is 100: 2) presoma.Then by Ni0.80Co0.20(OH)2/ 0.02Al(OH)3After uniformly mixing with the Lithium hydrate (mole design proportion of Li/ (Ni+M+Al) is 1) of metering ratio, it is placed in oxygen In gas atmosphere furnace, 750 DEG C of calcining 12h are cooled to room temperature and obtain LiNi0.784Co0.196Al0.02O2Composite positive pole (LiAlO2 The composite positive pole of cladding, LiNi0.784Co0.196Al0.02O2)。
Comparative example 3
The LiAlO prepared by embodiment 32The element proportioning of the composite positive pole of cladding uniformly mixes, is doping to not wrap Cover the material (LiNi of Uniform Doped0.784Co0.196Al0.02O2Material).
The LiAlO that embodiment 3 is prepared2The composite positive pole of cladding and the uncoated material of comparative example 3 carry out humidity, Security performance detects, and result is as follows:
The LiAlO that embodiment 3 prepares2The composite positive pole of cladding stores weightening finish in 30 days under the humidity of 60% and is only 0.42%, the LiNi of Uniform Doped0.784Co0.196Al0.02O2Material (the uncoated positive electrode of comparative example 3；Comparative example 3) in phase Under the conditions of Tong, gain in weight reaches 1.28%.The LiAlO prepared with embodiment 32The composite positive pole of cladding is prepared by positive pole Button cell carries out discharge and recharge in 2.8～4.3 voltage windows, and under 0.1C multiplying power, discharge capacity is 198mAh/g first, under 1C Specific discharge capacity is maintained at 180mAh/g, circulates 180 weeks capability retention ＞ 80% (as shown in Figure 4).
With N-methyl pyrrole network alkanone as dispersant, weigh prepared LiAlO according to mass ratio 96: 2: 22Clad anode material Material, acetylene black and binding agent (poly-inclined tetrafluoroethene PVDF), be stirred experiment, experimental result in the environment of humidity is 60% After showing embodiment 3 cladding, material is stirred 100h under the highest humidity and does not produce fruit jelly, and with under the conditions of contrast Fruit jelly phenomenon is just there is in Uniform Doped material in 1h.Illustrate further material and there is more preferable anti-moisture sensitivity and processing Performance.Use the clad anode material of embodiment 3 and uncoated positive electrode to make 1Ah soft-package battery, and be charged to 4.4V and carry out Acupuncture is tested, and test result indicate that covering material LiNi0.784Co0.196Al0.02O2Corresponding battery does not occurs in acupuncture course Thermal runaway combustion phenomena and battery prepared by uncoated material there occurs explosive reaction on fire, illustrate that covering material has superior Security performance.
Embodiment 4
Preparing concentration of metal ions is 2mol/L, the nickel cobalt mixed solution of Ni: Co=81.5: 15, the inclined aluminum of 0.5mol/L Acid sodium solution.NaOH solution with 10% is as precipitant, and EDTA is chelating agent, cocurrent adding material, controls reactor interior reaction temperature 50 DEG C, pH 11.40～11.50, EDTA concentration is 0.05mol/L, and mixing speed is 400r/min.Control condition makes product grain Degree distribution D50=11.4～11.5, in reactor, solid content is 150 ± 5g/L.Slip the most out is focused on and constantly stirs In the medial launder of the 50L mixed, stop feeding toward this medial launder after slip volume is 40L in medial launder, again adjust mother solution, control PH=11.50, adds appropriate sodium aluminate solution, and is slowly introducing SO2Gas is until detection D50=11.6～11.7 micro- Rice.By slip after 30min is aged, filtrated stock, and precipitate with the deionized water wash of 60 DEG C, slip is through washing, mistake Filter, obtain Ni after drying0.815Co0.15Al0.035(OH)2/xAl(OH)3(mol ratio is 100: x) (TEM is shown in enforcement illustration to presoma 5a), from TEM figure it can be seen that before covering aluminum and cover presoma surface topography after aluminum and change substantially, and the most gluey Grain exists, and illustrates that aluminium hydroxide is successfully coated on ball-shape nickel hydroxide cobalt aluminum surface, defines uniform aluminum hydroxide film.So After by Ni0.815Co0.15Al0.035(OH)2/xAl(OH)3[elementary analysis result is Ni0.803Co0.148Al0.049(OH)2] compare with metering Lithium hydrate (molar ratio of Li/ (Ni+M+Al) is 1) uniformly mixing after, be placed in 750 DEG C of calcining 12h in oxygen atmosphere stove It is cooled to room temperature and obtains LiNi0.803Co0.148Al0.049O2Composite positive pole.The high-resolution TEM figure of this positive electrode is shown in figure Shown in 5b, interpreting blueprints understands, and obvious LiAlO is distributed at material surface2Exist mutually.Detect the actual nickel cobalt of this composite positive pole Aluminum ratio is 80.29: 14.78: 4.926.
Comparative example 4
The LiAlO prepared by embodiment 42The element proportioning of the composite positive pole of cladding uniformly mixes, is doping to not wrap Cover the material (LiNi of Uniform Doped0.803Co0.148Al0.049O2Material).
The LiAlO that embodiment 4 is prepared2The composite positive pole of cladding and the uncoated material of comparative example 4 carry out humidity, Security performance detects, and result is as follows:
The LiAlO that embodiment 4 prepares2The composite positive pole of cladding stores weightening finish in 30 days under the humidity of 60% and is only 0.54%, the LiNi of Uniform Doped0.803Co0.148Al0.049O2Material (the uncoated material of comparative example 4) increases under the same conditions Weight reaches 2.35%.Material is charge and discharge cycles in 2.8～4.3 voltage windows, and under 0.1C multiplying power, discharge capacity is 201 first Under mAh/g, 1C multiplying power, specific discharge capacity is maintained at 185mAh/g, circulates 200 weeks capability retention ＞ 83%.With N-methyl pyrrole network Alkanone is dispersant, weighs the clad anode material of embodiment 4, acetylene black and the binding agent of synthesis according to mass ratio 96: 2: 2 (poly-inclined tetrafluoroethene PVDF), is stirred experiment in the environment of humidity is 60%, test result indicate that the cladding of embodiment 4 Rear material is stirred 100h under the highest humidity and does not produce fruit jelly, and with under the conditions of the Uniform Doped material of contrast at 1h Interior just generation fruit jelly phenomenon.The material illustrating further embodiment 4 has more preferable anti-moisture sensitivity and processing characteristics.Adopt Make 1Ah soft-package battery with the clad anode material of embodiment 4 and the uncoated positive electrode of comparative example 4, and be charged to 4.5V and enter Hand-manipulating of needle thorn experiment, test result indicate that covering material LiNi of embodiment 40.803Co0.148Al0.049O2Corresponding battery is in acupuncture During there is not thermal runaway combustion phenomena and battery prepared by uncoated material there occurs explosive reaction on fire, embodiment is described The covering material of 4 has superior security performance.

Claims (9)

1. a lithium ion battery composite cathode material LiNi with nucleocapsid structure1-x-yMxAlyO2Preparation method, its feature It is, comprises the following steps:
Step (1): positive electrode material precursor dispersion is obtained dispersion liquid in deionized water；Meta-aluminate is added molten in dispersion liquid Liquid mixes to obtain alkaline slurry, and described alkaline slurry pH is 11～14；In alkaline slurry, add acid solution or blast sour gas PH is down to 9～10.5, makes to be formed on positive electrode material precursor surface aluminium hydroxide clad；The most aged, wash, be dried Obtain surface A l (OH)3The composite precursor of cladding；Described positive electrode material precursor is Ni1-a-bM′aAlb(OH)2Or Ni1-v-wM"vAlwOδ；
Described Ni1-a-bM′aAlb(OH)2In, 0≤a≤1,0≤b≤1 and 0≤a+b≤1, M ' is Mn, Co, Al, Ti, Mg, Ca, At least one in Ba, Si, Cr；
Described Ni1-v-wM"vAlwOδIn, 0≤v≤1,0≤w≤1 and 0≤v+w≤1,1≤δ≤3, M " for Mn, Co, Al, Ti, Mg, At least one in Ca, Ba, Si, Cr；
Step (2): after the composite precursor that step (1) obtains is mixed with lithium-containing compound, be placed under the atmosphere containing oxygen 650～850 DEG C of calcinings obtain Surface L iAlO2The LiNi of cladding1-x-yMxAlyO2Material.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that in positive electrode material precursor and meta-aluminate solution, the mol ratio of meta-aluminic acid root is 10～10000.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that described acid solution is the aqueous solution of at least one in sulphuric acid, hydrochloric acid, nitric acid, citric acid, acetic acid；Its In, [the H in acid solution+]=0.1～0.5mol/L；Described sour gas is carbon dioxide, chlorine, hydrogen chloride gas, titanium dioxide At least one in nitrogen, sulfur dioxide.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that the pH value of described dispersion liquid is 11～14；Temperature is 20～80 DEG C.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that the particle diameter of positive electrode material precursor is 0.2～50 μm.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that in step (1), the product after using the deionized water of 20～80 DEG C to clean ageing, the pH of cleanout fluid Value is dried process to the product after cleaning after being less than 10.5 again；Baking temperature is 60～150 DEG C；It is dried 6～100h.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that calcining heat controls at 700～750 DEG C.
There is the lithium ion battery composite cathode material LiNi of nucleocapsid structure the most as claimed in claim 11-x-yMxAlyO2System Preparation Method, it is characterised in that in step (2), described lithium-containing compound is lithium acetate, lithium sulfate, lithium nitrate, lithium carbonate, hydrogen-oxygen Change at least one in lithium.
9. the lithium ion battery composite cathode material LiNi that the preparation method as described in any one of claim 1-8 prepares1-x- yMxAlyO2, it is characterised in that wherein, 0≤x≤1,0 ＜ y≤1 and 0 ＜ x+y≤1, M is Mn, Co, Al, Ti, Mg, Ca, Ba, At least one in Si, Cr.
CN201610554381.7A 2016-07-14 2016-07-14 Lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 with core-shell structure and preparation method of lithium ion battery composite cathode material LiNi1-x-yMxAlyO2 Pending CN106058188A (en)

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Application publication date: 20161026