CN103078109A - Gradient coated LiNiO2 material and preparation method - Google Patents

Gradient coated LiNiO2 material and preparation method Download PDF

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CN103078109A
CN103078109A CN2013100163678A CN201310016367A CN103078109A CN 103078109 A CN103078109 A CN 103078109A CN 2013100163678 A CN2013100163678 A CN 2013100163678A CN 201310016367 A CN201310016367 A CN 201310016367A CN 103078109 A CN103078109 A CN 103078109A
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nickel
gradient
solution
lithium nickelate
lithium
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CN2013100163678A
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胡国荣
杜柯
黄金龙
彭忠东
曹雁冰
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中南大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method for gradient coated LiNiO2 for lithium ion battery positive pole material, so as to solve the problem of bad circulating performance of conventional LiNiO2. The molecular formula of the LiNiO2 is LiNi 1-xMxO2, wherein, the x is less than or equal to 0.3 and greater than 0, the M is adulterated metal ions and is one or more selected from magnesium, nickel, Fe, titanium, zinc, Co, manganese, aluminum, Nb and vanadium, the gradient coat refers to that concentration gradient hydroxide coprecipitate provided with nickel and other metallic elements is coated on the surfaces of spherical nickelous hydroxide material, and then the precursor is mixed with lithium-source material and roasted under high temperature in an oxygen atmosphere furnace, so as to obtain high-performance modified LiNiO2. The gradient coated LiNiO2 obtained in the invention has the characteristics of high specific capacity, excellent circulating performance, excellent high-temperature property and the like, and is suitable for the application field of high- capacity lithium ion batteries.

Description

A kind of Gradient Coated lithium nickelate material and preparation method thereof
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of special Gradient Coated lithium nickelate material preparation method.The white certain radius of nickel content place from inside to outside reduces and the content that coats element raises gradually gradually in this special lithium nickelate material.
Background technology
Lithium ion battery is as a kind of green secondary cell, has lightweight, the advantage such as volume is little, discharge platform is high, capacity is large, have extended cycle life, memory-less effect, be widely used in the mobile electronic electrical equipment such as mobile phone, camera, notebook computer, also be used for just more and more simultaneously the fields such as artificial satellite, Aero-Space, electric automobile.
In the lithium ion battery, positive electrode is the key of performance and cost, the LiNiO of its laminate 2Owing to possess very high specific discharge capacity and cheap cost advantage, be considered to most possibly substitute the most successful LiCoO of present commercialization 2One of material.LiNiO 2Electrochemical reaction mechanism relate to three first order phase changes between three six side's phases and the monoclinic phase, three charge and discharge platform on corresponding the charging and discharging curve.LiNiO 2Because the electrochemistry cycle performance of its extreme difference and the extensive utilization that thermodynamic stability has limited this material.A kind of effective ways that solve this defective go part to substitute LiNiO with cobalt atom exactly 2Nickle atom on the lattice can improve the cycle performance of nickel-base material greatly.Afterwards, find again Li[Ni 0.8Co 0.15Al 0.05] O 2Can further improve the thermodynamic stability of material.But, although nickel cobalt binary and doped series material thereof relative LiNiO on chemical property and thermodynamic property 2Larger improvement is arranged, but its cycle performance and high-temperature behavior still can not satisfy people's demand.
2008, Korea S Han Yang University Yang-Kook Sun has developed novel gradient lithium ion battery material, the kernel of this material is the higher nickel-cobalt-manganese ternary material of nickel content, the coating layer of outside also is the nickel-cobalt-manganese ternary material, but nickel cobalt manganese content wherein changes continuously, nickel content reduces gradually, and other constituent content increases gradually.The positive electrode of this particular design has shown high-energy, long-life and good security performance.This seminar has prepared the nickel-base composite material of a series of Gradient Coated: Li[Ni 0.67Co 0.15Mn 0.18] O 2, Li 1.2[Mn 0.62Ni 0.38] 0.8O 2, Li[Ni 0.81Co 0.06Mn 0.13] O 2, Li[Ni 0.82Co 0.04Mn 0.14] O 2And Li[Ni 0.83Co 0.07Mn 0.10] O 2Etc..Yet in their work, kernel is the nickel-cobalt-manganese ternary material, therefore belongs to the modification to ternary material.The ratio that nickel accounts for transition metal in the last composite material does not all have to surpass 90%.The electrochemical reaction mechanism of this ternary material is that lithium embeds and deviates from single six sides solid solution behavior mutually, and what show discharges and recharges the curve that is characterized as continuously smooth.With the reaction mechanism of LiNiO2 obvious difference is arranged.
Summary of the invention
The invention provides a kind of lithium nickelate material and preparation method thereof, and make by the success of material of the present invention, can effectively solve the problems such as the fast and thermodynamic stability of existing lithium nickelate capacity attenuation is poor.
The present invention solves this technical problem the technical scheme that adopts:
The invention provides a kind of Gradient Coated lithium nickelate material, described material kernel is lithium nickelate, and molecular formula is: LiNi 1-xM xO 2, 0<x≤0.3 wherein, described M is the metal ion that mixes; Nickel content from inside to outside reduces gradually from the radius r place and the content of M raises gradually, and 0<r<R(R is the product particle radius); (tangent plane constituent content relation is seen Fig. 5-Fig. 8).M is one or more in magnesium, nickel, iron, titanium, zinc, cobalt, manganese, aluminium, niobium, vanadium preferably.
M can represent a kind of doped metal ion of coating, also is expressed as the doped metal ion of multiple different coating, when M represents multiple doped metal ion, and the M in the general formula xFor a plurality of, the LiNi among the embodiment 2 for example 0.90Co 0.04Mn 0.04Al 0.02O 2, i.e. mix the simultaneously situation of Co, Mn and Al of expression, doping is determined according to the addition of raw material x.
Gradient Coated lithium nickelate material preparation method of the present invention, concrete steps are:
1) preparation reaction solution
The preparation nickel sulfate solution; Preparation coats the M saline solution, the metal ion of M for coating, and M is selected from one or more in magnesium, nickel, iron, titanium, zinc, cobalt, aluminium, niobium, the vanadium; The preparation sodium hydroxide solution; The preparation ammonia spirit; The concentration of the described nickel ion aqueous solution is preferably 0.4-4mol/L; The concentration of M saline solution is preferably 0.5 ~ 2mol/L; The concentration of sodium hydrate aqueous solution is 0.5 ~ 6mol/L; The concentration of ammoniacal liquor is 0.05 ~ 1mol/L.
2) the preparation spherical gradient coats presoma Ni 1-xM x(OH) 2
First with 1) nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor of step preparation input in the reactor simultaneously by dosing pump, keep 20 ~ 90 ℃ of continuous stirring of reaction temperature, control simultaneously pH value 9-13, reaction generation green Ni (OH) 2After the precipitation; With 1) the coating M salting liquid of step preparation is continuously in the remaining nickel sulfate solution of input, and the new mixed ion solutions that stirs and evenly mixs formation is inputted continuously and continued precipitation in the reactor; Precipitation obtains having the hydroxide presoma Ni that gradient concentration coats after ageing, washing and drying 1-xM x(OH) 2Nickel content from inside to outside reduces gradually from the radius r place and the content of M raises gradually in this presoma, and 0<r<R, described R are the granular precursor radius;
3) preparation Gradient Coated material LiNi 1-xM xO 2
With step 2) the coating presoma Ni that obtains 1-xM x(OH) 2With lithium salts Li:(Ni+M in molar ratio)=1 ~ 1.05:1 ball milling of preparing burden; Under 500 ℃ ~ 1000 ℃, in the air or oxygen atmosphere, be sintered to 4h ~ 72h again, obtain final products.
The aqueous solution of nickel ion described in the step 1) is the water-soluble formed solution of soluble nickel salt; Described soluble nickel salt is one or more in nickelous sulfate, manganese chloride, nickel acetate, nickel nitrate and nickel oxalate preferably.
The described precipitation temperature of step 1) is preferably 40 ~ 70 ℃.
Step 2) described adding speed is preferably 1L/h-1.5L/h, and control pH is preferably 10-12.
Step 2) the remaining nickel sulfate solution described in accounts for 5 ~ 25% of the nickelous sulfate quality that all need add.
The described lithium salts of step 3) is one or more in lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate preferably.
In the step 3) preferably at 650 ℃ ~ 850 ℃ lower high temperature sintering 10-24h.
In the step 3) preferably under oxygen atmosphere sintering obtain final products.
Material after the present invention coats, its surface component belongs to the material (nickel content is lower, contains other element) of similar ternary.But the charging and discharging curve of material has kept LiNiO 2The feature of a plurality of charge and discharge platform has effectively been improved its cycle performance.
Below the present invention will be further explained and the explanation:
The present invention adopts the standby spherical gradient of liquid phase crystallization control legal system to coat presoma, in coating layer, coats element and is from the inside to the outside the gradient shape distribution that concentration increases gradually along radial direction, and preparing is the lithium nickelate material with Gradient Coated feature.Coat by effective surface, avoid contacting of pure nickel acid lithium material and electrolyte, improved its cycle performance and thermodynamic stability.Simultaneously, by gradually changing continuously of nickel element in the coating layer, so that the coating layer maintenance is similar to the fertile material lattice, thereby the crystal lattice stress that material is produced in charge and discharge process obtains well slowly discharging, and has avoided coming off of coating layer.Another advantage of this Gradient Coated structure is: the kernel at material is lithium nickelate, is conducive to the electrochemistry capacitance that keeps material high; And at the material surface that recurring structure that occur directly to contact with electrolyte and the easiest changes, the content that coats element increases, and plays effective stabilizing material effect.
The lithium nickelate of the present invention preparation reaches simultaneously and mixes and the dual modified purpose of surface coating modification, meanwhile, has avoided again the problems such as the inhomogeneous and surperficial coating of doping is not tight.
Positive electrode test process of the present invention is: material is made into CR2025 type button cell carries out the charge and discharge cycles test.Adopt coating method to prepare electrode, take METHYLPYRROLIDONE (NMP) as solvent, 8:1:1 takes by weighing respectively active material, acetylene black and PVDF in mass ratio, after mixing, be coated on the pretreated aluminium foil, put into vacuum drying chamber and obtain positive plate 120 ℃ of dryings.In being full of the glove box of argon gas, take metal lithium sheet as negative pole, 1molL-1LiPF 6Being dissolved in ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethyl-methyl carbonic ester (EMC) (volume ratio is 1:1:1) is electrolyte, the Celgard2400 porous polypropylene film is barrier film, be assembled into button cell, carry out electro-chemical test at Land electrochemistry instrument.
Compared with prior art, advantage of the present invention is:
1, by the Gradient Coated material preparation, both guaranteed the high power capacity of composite material by the lithium nickelate kernel, the clad material by good stability solves lithium nickelate material unsettled problem in cyclic process again.
2, because the concentration of nickel element and coating element all is (the seeing Fig. 6-8) that gradually changes continuously, the crystal structure of material has good compatibility, lattice dilatation and contraction deformation that material is produced in charge and discharge process are controlled effectively, thereby have avoided coming off of coating layer.
3, technical process of the present invention simple, be easy to control, the specific capacity height of gained lithium nickelate material, good cycle, Thermodynamically stable are suitable for the high-capacity lithium ion cell application.
Description of drawings
Fig. 1 is the XRD figure that the spherical gradient that obtains of embodiment 1 coats presoma;
Fig. 2 is the SEM figure that the spherical gradient that obtains of embodiment 1 coats presoma;
Fig. 3 is the SEM figure that the spherical gradient that obtains of embodiment 1 coats lithium nickelate;
Fig. 4 is the tangent plane SEM figure that the spherical gradient that obtains of embodiment 1 coats lithium nickelate;
Fig. 5 is the tangent plane linear scan figure that the spherical gradient that obtains of embodiment 1 coats lithium nickelate;
Fig. 6 is the tangent plane Ni constituent content linear scan figure of Fig. 5, and nickel element content reduces from inside to outside gradually along radial direction in the coating layer as can be known;
Fig. 7 is the tangent plane Co constituent content linear scan figure of Fig. 5, as can be known in the coating layer cobalt element along radial direction from inside to outside content increase gradually;
Fig. 8 is the tangent plane Mn constituent content linear scan figure of Fig. 5, as can be known in the coating layer manganese element along radial direction from inside to outside content increase gradually;
Fig. 9 is that the spherical gradient that embodiment 1 obtains coats lithium nickelate at the first charge-discharge curve of 0.1C;
Figure 10 is that the spherical gradient that embodiment 1 obtains coats the 0.1C cyclic curve of lithium nickelate under 25 ℃ and 55 ℃;
Figure 11 is the curve of double curvature that the spherical gradient that obtains of embodiment 2 coats lithium nickelate;
Figure 12 is 1C high temperature (55 ℃) cyclic curve that the spherical gradient that obtains of embodiment 3 coats lithium nickelate;
Figure 13 is the normal temperature cyclic curve that the spherical gradient that obtains of embodiment 4 coats lithium nickelate.
Embodiment
The present invention is described further below in conjunction with drawings and Examples.
Embodiment 1:
Prepare respectively the nickel sulfate solution of 0.5mol/L, the cobaltous sulfate manganese solution of 0.8mol/L (cobalt manganese is than being 1:1), 3molL -1Sodium hydroxide solution and 0.5molL -1Ammonia spirit.Adopt peristaltic pump with the flow velocity of 1.5L/h nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor to be inputted in the reactor simultaneously by dosing pump, keeping reaction temperature is 30 ℃ and continuous stirring, and simultaneously control reaction is in pH=12.The reaction beginning just has a large amount of green Ni (OH) 2Precipitation generates.Reaction continues for some time, and treats 90% NiSO 4After the solution consumption, cobaltous sulfate manganese mixed ion solutions is inputted in the nickel sulfate solution continuously, and stirred and evenly mixed.The new mixed ion solutions that then will form is inputted reactor continuously, continues precipitation.After solution to be mixed dropwises, continued reaction aging 10 hours.The precipitated product that reaction is obtained washs 3 times through deionized water.Be placed in the constant temperature oven of 60 ° of C dry 24 hours after the filtration, finally obtain nickel cobalt manganese hybrid ionic hydroxide presoma.The chemical formula of presoma is Ni 0.92Co 0.04Mn 0.04(OH) 2Can find out the structure of this presoma and Ni (OH) from its XRD figure (Fig. 1) 2Unanimously.Can find out that from its SEM figure (Fig. 2) this presoma is the sphere of reunion, the later particle diameter of reuniting is about 5 ~ 10 μ m.Take lithium carbonate as the lithium source, by Li:(Ni+Mn+Co)=1.05:1 joins lithium, and then ball milling disperses.The mixture that obtains 750 ℃ of roastings in oxygen atmosphere obtained Gradient Coated lithium nickelate positive electrode in 12 hours, and (chemical formula is LiNi 0.92Co 0.04Mn 0.04O 2).The SEM figure (Fig. 3) of this lithium nickelate material shows that it is the agglomerated particle of 5 ~ 10 μ m.This lithium nickelate material has been carried out tangent plane scanning (Fig. 4), and as seen this product has core-shell structure.Further carry out the tangent plane various element linear scans that directly make progress, result such as Fig. 5-shown in Figure 8, can find out to only have nickel element in the nuclear of this product inside, and in shell, nickel, cobalt and three kinds of units of manganese calculate and present graded.Wherein the content of nickel reduces in shell from the inside to the outside gradually, and the content of manganese and cobalt then raises gradually.The continuous gradient of having realized doped chemical in persursor material changes.The first charge-discharge curve (Fig. 9) of this gradient lithium nickelate has embodied the feature of lithium nickelate material, illustrates that the gradient lithium nickelate has kept the electrochemical characteristic of lithium nickelate material, is the material modified of a kind of lithium nickelate.This gradient lithium nickelate has shown outstanding electrochemistry cycle performance (Figure 10): the charging and discharging currents with 0.1C carries out loop test at normal temperatures, discharge capacity can reach 209.5mAh/g after three activation, circulating, capacity is 203.3mAh/g after 50 times, and capability retention reaches 97.0%.The first discharge capacity that the lower 0.1C of high temperature (55 ℃) discharges and recharges is 226.2mAh/g, circulates that capacity is 212.3mAh/g after 50 times, and capability retention is 93.8%.
Embodiment 2:
Prepare at first respectively the nickel sulfate solution of 1mol/L, the cobaltous sulfate manganese aluminum solutions of 0.7mol/L (cobalt manganese aluminum ratio is 1:1:1:0.5), 1molL -1Sodium hydroxide solution and 0.5molL -1Ammonia spirit.Adopt peristaltic pump with the flow velocity of 1.5L/h nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor to be inputted in the reactor simultaneously by dosing pump, keeping reaction temperature is 40 ℃ and continuous stirring, and simultaneously control reaction is in pH=11.The reaction beginning just has a large amount of green Ni (OH) 2Precipitation generates.Reaction continues for some time, and treats 70% NiSO 4After the solution consumption, cobaltous sulfate manganese aluminium mixed ion solutions is inputted in the nickel sulfate solution continuously, and stirred and evenly mixed.The new mixed ion solutions that will form is simultaneously inputted reactor continuously, continues precipitation.After solution to be mixed dropwises, continued reaction aging 10 hours.The precipitated product that reaction is obtained washs 3 times through deionized water.Be placed in the constant temperature oven of 60 ° of C dry 24 hours after the filtration, finally obtain nickel cobalt manganese aluminium hybrid ionic hydroxide presoma.The chemical formula of presoma is Ni 0.78Co 0.088Mn 0.088Al 0.044(OH) 2Take lithium hydroxide as the lithium source, by Li:(Ni+Mn+Co+Al)=1.03:1 joins lithium, and then ball milling disperses.The mixture that obtains obtained spherical gradient coating lithium nickelate positive electrode in 12 hours in 750 ℃ of roastings, and (chemical formula is LiNi 0.78Co 0.088Mn 0.088Al 0.044O 2).Such as Figure 11, this gradient lithium nickelate carries out loop test at high temperature (55 ℃) with the charging and discharging currents of 1C, and discharge capacity reaches 212.2mAh/g first, circulates that capacity is 177.6mAh/g after 100 times, and capability retention reaches 83.69%.
Embodiment 3:
Prepare at first respectively the nickel sulfate solution of 2mol/L, the cobaltous sulfate manganese solution of 0.5mol/L (cobalt manganese is than being 1:2), 1molL -1Sodium hydroxide solution and 0.1molL -1Ammonia spirit.Adopt peristaltic pump with the flow velocity of 1.5L/h nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor to be inputted in the reactor simultaneously by dosing pump, keeping reaction temperature is 30 ℃ and continuous stirring, and simultaneously control reaction is in pH=10.The reaction beginning just has a large amount of green Ni (OH) 2Precipitation generates.Reaction continues for some time, and treats 50% NiSO 4After the solution consumption, cobaltous sulfate manganese mixed ion solutions is inputted in the nickel sulfate solution continuously, and stirred and evenly mixed.The new mixed ion solutions that will form is simultaneously inputted reactor continuously, continues precipitation.After solution to be mixed dropwises, continued reaction aging 10 hours.The precipitated product that reaction is obtained washs 3 times through deionized water.Be placed in the constant temperature oven of 60 ° of C dry 24 hours after the filtration, finally obtain nickel cobalt manganese hybrid ionic hydroxide presoma.The chemical formula of presoma is Ni 0.73Co 0.09Mn 0.18(OH) 2Take lithium hydroxide as the lithium source, by Li:(Ni+Mn+Co)=1.01:1 joins lithium, and then ball milling disperses.The mixture that obtains obtained spherical gradient coating lithium nickelate positive electrode in 12 hours in 750 ℃ of roastings, and (chemical formula is LiNi 0.73Co 0.09Mn 0.18O 2).Such as Figure 12, this gradient lithium nickelate carries out loop test with the charging and discharging currents of 0.1C, 0.2C, 0.5C, 1C, 2C respectively, 0.1 discharge capacity reaches 202.1mAh/g first, 0.2C, specific discharge capacity can reach 196.6mAh/g respectively under 0.5C, 1C, the 2C multiplying power, 186.8mAh/g, 175.2mAh/g and 167.1mAh/g.Return the 0.1C circulation behind the 2C multiplying power discharging and can reach 199.2mAh/g, illustrative material is less because of the capacity of electrochemical reaction loss at material behind high-multiplying power discharge.
Embodiment 4:
Prepare at first respectively the nickel sulfate solution of 3mol/L, the manganese sulfate vanadium aluminum solutions of 0.5mol/L (manganese vanadium aluminum ratio is 1:1:1), 0.8molL -1Sodium hydroxide solution and 0.8molL -1Ammonia spirit.Adopt peristaltic pump with the flow velocity of 1.5L/h nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor to be inputted in the reactor simultaneously by dosing pump, keeping reaction temperature is 30 ℃ and continuous stirring, and simultaneously control reaction is in pH=11.The reaction beginning just has a large amount of green Ni (OH) 2Precipitation generates.Reaction continues for some time, and treats 20% NiSO 4After the solution consumption, manganese sulfate vanadium aluminium mixed ion solutions is inputted in the nickel sulfate solution continuously, and stirred and evenly mixed.The new mixed ion solutions that will form is simultaneously inputted reactor continuously, continues precipitation.After solution to be mixed dropwises, continued reaction aging 10 hours.The precipitated product that reaction is obtained washs 3 times through deionized water.Be placed in the constant temperature oven of 60 ° of C dry 24 hours after the filtration, finally obtain nickel manganese vanadium aluminium hybrid ionic hydroxide presoma.The chemical formula of presoma is Ni 0.81Mn 0.063V 0.063Al 0.063(OH) 2Take lithium hydroxide as the lithium source, by Li:(Ni+Mn+V+Al)=1.05:1 joins lithium, and then ball milling disperses.The mixture that obtains obtained spherical gradient coating lithium nickelate positive electrode in 12 hours in 750 ℃ of roastings, and (chemical formula is LiNi 0.81Mn 0.063V 0.063Al 0.063O 2).Such as Figure 13, this gradient lithium nickelate the 0.1C charging and discharging currents carry out loop test first discharge capacity reach 220.5mAh/g, first discharge specific capacity can reach 200.4mAh/g respectively under the 1C multiplying power, circulates after 150 times, specific discharge capacity still reaches 166.1mAh/g, and capability retention is 82.88%.
Embodiment 5: prepare at first respectively the nickel sulfate solution of 4mol/L, the cobaltous sulfate niobium solution of 0.8mol/L (the cobalt niobium is than being 1:1), 1molL -1Sodium hydroxide solution and 1molL -1Ammonia spirit.Adopt peristaltic pump with the flow velocity of 1.5L/h nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor to be inputted in the reactor simultaneously by dosing pump, keeping reaction temperature is 30 ℃ and continuous stirring, and simultaneously control reaction is in pH=12.The reaction beginning just has a large amount of green Ni (OH) 2Precipitation generates.Reaction continues for some time, and treats 95% NiSO 4After the solution consumption, sulfuric acid niobium cobalt mixed ion solutions is inputted in the nickel sulfate solution continuously, and stirred and evenly mixed.The new mixed ion solutions that will form is simultaneously inputted reactor continuously, continues precipitation.After solution to be mixed dropwises, continued reaction aging 10 hours.The precipitated product that reaction is obtained washs 3 times through deionized water.Be placed in the constant temperature oven of 60 ° of C dry 24 hours after the filtration, finally obtain nickel cobalt niobium hybrid ionic hydroxide presoma.The chemical formula of presoma is Ni 0.94Co 0.03Nb 0.03(OH) 2Take lithium hydroxide as the lithium source, by Li:(Ni+Co+Nb)=1.05:1 joins lithium, and then ball milling disperses.The mixture that obtains obtained spherical gradient coating lithium nickelate positive electrode in 12 hours in 750 ℃ of roastings, and (chemical formula is LiNi 0.94Co 0.03Nb 0.03O 2).This gradient lithium nickelate the 0.1C charging and discharging currents carry out loop test first discharge capacity reach 208.3mAh/g, specific capacity is 192.0mAh/g after 40 discharge cycles, capability retention is 92.2%.

Claims (10)

1. a Gradient Coated type lithium nickelate material is characterized in that described material kernel is lithium nickelate, and molecular formula is: LiNi 1-xM xO 2, 0<x≤0.3 wherein, described M is the metal ion that mixes; Nickel content from inside to outside reduces gradually from the radius r place and the content of M raises gradually, 0<r<R, and wherein R is the lithium nickelate particle radius.
2. a kind of Gradient Coated type lithium nickelate material according to claim 1 is characterized in that M is selected from one or more in magnesium, nickel, iron, titanium, zinc, cobalt, manganese, aluminium, niobium, the vanadium.
3. a Gradient Coated type lithium nickelate material preparation method is characterized in that, may further comprise the steps:
1) preparation reaction solution
The preparation nickel sulfate solution; Preparation coats the M saline solution, the metal ion of M for mixing; The preparation sodium hydroxide solution; The preparation ammonia spirit; The concentration of the described nickel ion aqueous solution is 0.4-4mol/L; The concentration of M saline solution is 0.5 ~ 2mol/L; Naoh concentration is 0.5 ~ 6mol/L; Ammonia concn is 0.05 ~ 2mol/L
2) the preparation spherical gradient coats presoma Ni 1-xM x(OH) 2
First with 1) nickelous sulfate, NaOH and three kinds of solution of ammoniacal liquor of step preparation input in the reactor simultaneously by dosing pump, keep 20 ~ 90 ℃ of continuous stirring of reaction temperature, control simultaneously pH value 9-13, reaction generation green Ni (OH) 2After the precipitation; With 1) the coating M salting liquid of step preparation is continuously in the remaining nickel sulfate solution of input, and the new mixed ion solutions that stirs and evenly mixs formation is inputted continuously and continued precipitation in the reactor; Precipitation obtains having the hydroxide presoma Ni that gradient concentration coats after ageing, washing and drying 1-xM x(OH) 2Nickel content from inside to outside reduces gradually from the radius r place and the content of M raises gradually in this presoma, and 0<r<R, described R are the granular precursor radius;
3) preparation Gradient Coated material LiNi 1-xM xO 2
With step 2) the coating presoma Ni that obtains 1-xM x(OH) 2With lithium salts Li:(Ni+M in molar ratio)=1 ~ 1.05:1 ball milling of preparing burden; Under 500 ℃ ~ 1000 ℃, be sintered to 4h ~ 72h in the air or oxygen atmosphere again, obtain final products.
4. described Gradient Coated type lithium nickelate material preparation method according to claim 3 is characterized in that M is selected from one or more in magnesium, nickel, iron, titanium, zinc, cobalt, aluminium, niobium, the vanadium.
5. described Gradient Coated type lithium nickelate material preparation method according to claim 4 is characterized in that the aqueous solution of nickel ion described in the step 1) is the water-soluble formed solution of soluble nickel salt; Described soluble nickel salt is selected from one or more in nickelous sulfate, nickel chloride, nickel acetate, nickel nitrate and the nickel oxalate.
6. according to claim 3,4 or 5 described Gradient Coated type lithium nickelate material preparation methods, it is characterized in that the described precipitation temperature of step 1) is 40 ~ 70 ℃.
7. described Gradient Coated type lithium nickelate material preparation method according to claim 6 is characterized in that step 2) described in the adding speed of preparation reaction solution be 1L/h-1.5L/h; And control pH is 10-12.
8. according to claim 3,4 or 5 described Gradient Coated type lithium nickelate material preparation methods, it is characterized in that the described lithium salts of step 3) is selected from one or more in lithium carbonate, lithium hydroxide, lithium acetate and the lithium nitrate.
9. according to claim 3,4 or 5 described Gradient Coated type lithium nickelate material preparation methods, it is characterized in that step 3) obtains final products at 650 ℃ ~ 850 ℃ lower high temperature sintering 12-24h.
10. according to claim 3,4 or 5 described Gradient Coated type lithium nickelate material preparation methods, it is characterized in that step 2) described in remaining nickel sulfate solution account for 5 ~ 25% of the nickelous sulfate quality that all need add.
CN2013100163678A 2013-01-16 2013-01-16 Gradient coated LiNiO2 material and preparation method CN103078109A (en)

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CN104241638A (en) * 2014-08-29 2014-12-24 中南大学 Application of nickel based material
CN104710302A (en) * 2015-01-22 2015-06-17 北大先行科技产业有限公司 Gradient-doped manganese iron oxalate precursor and preparation method thereof
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