CN109326781A - A kind of preparation method of high voltage lithium cobalt oxide anode - Google Patents
A kind of preparation method of high voltage lithium cobalt oxide anode Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of high voltage lithium cobalt oxide anode: (1) by cobaltosic oxide, lithium source, the M containing doped chemical of the M containing doped chemical ' oxide, grain refiner and fluxing agent mix, obtain mixed once material；(2) mixed once material is sintered, crushed, obtain once sintered powder；(3) once sintered powder is mixed with coating, obtains secondary mixed material；(4) secondary mixed material is sintered, crushed, obtain lithium cobaltate cathode material.Present invention doping is divided into pre- blending dry method and is mixed into two ways and solves the problems, such as in product that doped chemical is distributed to be segregated on a microscopic scale；Solve the problems, such as that different material isolates when mixing using plough coulter type hybrid technology；Grain refiner and fluxing agent are used in combination to the material of synthesis mixing pattern；Using technologies such as the double effects of the catalysis of doped chemical surface crystallization and coating；So that the performance of high voltage cobalt acid lithium improves significantly.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries more particularly to a kind of preparation sides of high voltage lithium cobalt oxide anode
Method.
Background technique
With the fast development of electronics technology, the update of 3C Product is more and more frequent, and exploitation energy density is higher, follows
The better anode material for lithium-ion batteries of ring performance becomes the target that lithium electricity industry is mutually chased.Cobalt acid lithium (LiCoO2) have than
The advantages that capacity is high, compacted density is high, volume energy density is high and simple production process, is widely used in smart phone, puts down
The consumer electronics products such as plate computer and notebook, become and are commercialized one of most common anode material for lithium-ion batteries at present.
The theoretical capacity of cobalt acid lithium is 274mAh/g, and in conventional use process, only abjection, insertion reaction, institute occur for the lithium of half
There was only 145mAh/g or so with actual capacity.As the requirement to high-capacity battery is more more and more urgent, performance requirement is higher and higher,
Battery manufacturers gradually use high voltage cobalt acid lithium (4.4V, 4.45V or higher voltage) substitution 4.2V routine cobalt acid lithium to be used to make
Make battery.This is primarily due under higher voltage, and more lithiums are had in cobalt acid lithium and participate in abjection, insertion reaction, thus
Higher specific capacity can be provided.If cobalt acid lithium charge cutoff voltage is increased to 4.45V, specific discharge capacity be can be improved
180mAh/g or so, therefore improving charging voltage is to improve the effective way of cobalt acid lithium specific discharge capacity.
Although the specific capacity of cobalt acid lithium can be significantly improved by improving charging voltage, its cycle performance is but with charging electricity
The raising of pressure and reduce, main cause is there are two aspect.It on the one hand is the LiCoO when charge cutoff voltage is greater than 4.2V2In
Li+Can a large amount of deintercalations, make in structure+trivalent Co ion transit at the Co ion of+4 valences weakens cobalt to form oxygen defect
With the binding force of oxygen, the layered crystal structure for eventually leading to material is collapsed and is destroyed, when charge and discharge Li ion can not normal deintercalation,
The capacity of material is set faster decaying occur.On the other hand, in the state of high voltage charge and discharge, Co ion is easy to dissolve to electricity
It solves in liquid, and the Co ion of+4 valences has stronger oxidisability, will lead to electrolyte oxidation decomposition, that shortens battery uses the longevity
Life.
In order to solve the problems, such as structural collapse and cobalt dissolution of the lithium cobaltate cathode material in high voltage charge and discharge, use at present
Modified means solve, and are mainly doped to cobalt acid lithium material and surface cladding.Many researchers have done a large amount of work
Make, it is bulk phase-doped in often adulterate the compound containing Al, Zr, Ti, Mg etc., the M-O key of the higher bond energy of dependence stablizes cobalt acid lithium knot
Structure；Surface is coated frequently with TiO2、MgO、ZrO2、Al2O3、SiO2Equal oxides or metal phosphate wrap cobalt acid lithium particle
It covers, inhibits erosion of the electrolyte to cobalt acid lithium surface under high voltages, reduce cobalt dissolution, improve the stability of structure.But it mixes
Still there are many needs of work to improve for miscellaneous and cladding.Such as: the dopant of the research work high voltage appearance cobalt acid lithium of the prior art
Cobalt acid lithium particle inside phenomenon unevenly distributed is easily occurred in mix with the continuous improvement of cobalt acid lithium charge cutoff voltage
The phenomenon that miscellaneous amount is gradually increased, and this dopant is segregated is more obvious.In addition, current cladding work is mainly in cobalt acid lithium
Particle shows to coat one layer of oxide or metal phosphate, inhibits electrolyte to the erosion on cobalt acid lithium surface and reduce cobalt dissolution.
But these cladding work all ignore a problem, since there are some Li more than needed on cobalt acid lithium surface+, and Li+Chemical property is living
It sprinkles, material appearance activity is excessive under high voltages in this way, itself decomposition and other and electrolyte side reaction will occur, influence
The stability of material.
The uniformity of high voltage cobalt acid lithium doping will directly affect the structural stability of positive electrode under high voltage, Jin Erying
Ring the chemical property of material.Traditional process is carried out using the method for solid phase mixing, i.e. lithium source, cobalt oxide and dopant
It is mixed under the form of solid phase, is then sintered realization doping at high temperature.Therefore, the uniformity of doping is by dopant
Form and mixing state influence, while in pyroreaction, thermal diffusion is influenced by metal ion.Doped metal ion
Spreading with lithium ion is a competition process in insertion oxidation cobalt phase, and lithium ion has higher as a kind of light-weight metal ion
Diffusion rate is initially formed the cobalt acid lithium object phase of a small amount of metal ion mixing during the reaction, and remaining metal ion expands later
It is dissipated in cobalt acid lithium object phase.Cobalt acid lithium object phase once being formed, metal-doped ion diffusion hindered, doped metal ion tend to
The surface enrichment of grain.Therefore, to realize that material Uniform Doped often has certain difficulty using traditional process, especially
As cobalt acid lithium charge cutoff voltage is constantly soaring, more dopants are needed to stablize cobalt acid lithium structure, so using tradition
Technique realizes that the difficulty of Uniform Doped is bigger.
In addition, the pattern of high voltage cobalt acid lithium is also high voltage cobalt acid lithium at present one of an important factor for influencing its performance
Pattern control there are two types of trend, one is monocrystalline pattern, another kind is class monocrystalline pattern.The high voltage cobalt acid of monocrystalline pattern
Lithium, usually once sintered to pass through high temperature (1050 DEG C of >), long-time (> 12h)) be sintered to obtain, the list that this kind of method obtains
Brilliant material, the smaller and side reaction with electrolyte of specific surface area are reduced, and have the improvement using cycle performance；But because of individual particle diameter
It is larger and make material have poor multiplying power and lower coulombic efficiency for the first time, reduce the capacity usage ratio of material.And class monocrystalline
The high voltage cobalt acid lithium of pattern, it is usually once sintered by lower temperature (1000 DEG C of <), the short period (< 8h) sintering come
Obtain, this kind of method obtain class monocrystal material, the secondary ball being made of big primary particle, due to primary particle granularity compared with
It is small, thus material has preferable multiplying power and higher coulombic efficiency for the first time；But its specific surface area is larger and the pair with electrolyte is anti-
It should increase, simultaneously because secondary ball particle, is easy to split, causes the deterioration of cycle performance when grade piece roll-in.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
The preparation method of kind high voltage lithium cobalt oxide anode.
In order to solve the above technical problems, technical solution proposed by the present invention is as follows:
A kind of preparation method of high voltage lithium cobalt oxide anode, comprising the following steps:
(1) mixing: by cobaltosic oxide, lithium source, the M containing doped chemical of the M containing doped chemical ' compound, crystal grain
Fining agent and fluxing agent are mixed, and mixed once material is obtained；
(2) once sintered: the mixed once material being sintered, is crushed, once sintered powder is obtained；
(3) rerolling: the once sintered powder is mixed with coating, obtains secondary mixed material；
(4) double sintering: the secondary mixed material is sintered, is crushed to get high voltage lithium cobalt oxide anode is arrived.
In the present invention, once sintered main function is the basic structure to form cobalt acid lithium, completes doping；Double sintering
Main function is to form the clad to shield on the surface of cobalt acid lithium, while repairing to surface.And it directly will packet
Object and other raw materials is covered only to carry out once sintered being that the technology effect that high voltage cobalt acid lithium had not only been adulterated but also coated cannot be achieved together
Fruit.
In the present invention, granularity D10 is 10.0~12.0 μm after crushing in step (2), and D50 is 17.0~19.0 μm, and D90 is
26.0~28.0 μm.The once sintered powder of this size distribution, granularity can slightly increase after the double sintering of step (4)
(2.0~3.0 μm bigger on the whole than once sintered powder) is able to maintain and once sintered powder substantially after separating twice
Identical size distribution.This size distribution of finished product, is conducive to the promotion of compacted density when battery production, while controlling micro-
The quantity of powder and bulky grain is conducive to the promotion of high-temperature behavior and high rate performance.
Above-mentioned preparation method, it is preferred that the preparation method of the cobaltosic oxide of the M containing doped chemical includes following step
It is rapid:
(S1) soluble ingredient (cobalt source) containing cobalt is added in aqueous solution and is tuned into pulpous state, being then added includes doped chemical
The soluble ingredient (source M) of M, stirs to get mixed slurry；
(S2) in the mixed slurry after precipitating reagent and complexing agent to be sequentially added to step (S1), control reaction process stirring turns
Speed be 100~900rmp, temperature be 20 DEG C~90 DEG C, the time be 5~40h, pH value be 6~11, solid-liquid mass ratio be 1:(3~
7), reaction obtains the cobalt hydroxide slurry of the M containing doped chemical；
(S3) in the cobalt hydroxide slurry after oxidant to be added to step (S2), the speed of agitator of reaction process is controlled
For 300~1300rmp, temperature is 30 DEG C~90 DEG C, and the time is 2~15h, and reaction obtains the cobaltosic oxide of the M containing doped chemical
Slurry；
(S4) the cobaltosic oxide slurry filtration after step (S3) to filter cake aqueous 20%~60% is dried again, is dried
Dry temperature is 80 DEG C~400 DEG C, and drying time is 1~30h, obtains the cobaltosic oxide of the M containing doped chemical.
Using the cobaltosic oxide of the M containing doped chemical as important source material, which is prepared the present invention by wet process；Pass through
Suitable technological parameter is adjusted, so that the coprecipitation reaction of the soluble ingredient of the soluble ingredient containing cobalt and the M containing doped chemical
It can be carried out simultaneously in aqueous solution, so that cobalt element and doped chemical M are able to achieve atomic level in the product of hydroxide
Uniform mixing, in the high voltage cobalt acid lithium product being finally synthesizing, doped chemical M is evenly distributed completely on a microscopic scale, has
Conducive to the promotion of properties of product.
Above-mentioned preparation method, it is preferred that in the step (S1) soluble ingredient containing cobalt be cobalt chloride, cobalt nitrate,
One or more of cobaltous sulfate；Soluble ingredient comprising doped chemical M is sulfate, in nitrate, acetate, chlorate
One or more.
In the preparation method of the cobaltosic oxide of the M containing doped chemical of the invention, doped chemical M is additive, mainly
Play rock-steady structure, usual doped chemical M is non-chemically active substance, and additive amount need to be controlled in the scope of the present invention
It is interior, if it exceeds the scope of the present invention, can reduce the capacity for the high voltage cobalt acid lithium material prepared, if lower than of the invention
Range, and do not have the effect of rock-steady structure.
Above-mentioned preparation method, it is preferred that precipitating reagent described in the step (S2) is sodium hydroxide；The precipitating reagent adds
The molar ratio of dosage and Co, M total amount is n (precipitating reagent): n (Co+M)=(2~3): 1；The complexing agent is ammonium hydroxide；The complexing
Agent concentration is 0.05~1mol/L.
When not adding ammonium hydroxide or ammonia concn to be lower than the scope of the present invention in system, precipitated product primary particle size is very tiny,
Loose, the irregular globoid of shape is mutually agglomerated between particle.With the rising of ammonia concn, Co's and M is molten in system
Xie Du is dramatically increased, and co-precipitation system degree of supersaturation strongly reduces therewith, and crystal nucleation speed substantially reduces, rate of crystalline growth
Then constantly accelerate, gained precipitated product partial size is gradually increased.On the other hand, with the raising of ammonia concn, what is originally generated is thin
Small precipitate particles are also easier to dissolution and in large particle surface Precipitations again, so that bulky grain partial size is constantly grown up, light
It is sliding.When ammonia concn is higher than the scope of the present invention in system, the new core in reaction process is less, brilliant substantially without little particle
The formation of core only accounts for seldom ratio, and big total ammonia density dissolves small particle in the solution, big particle surface after
It is continuous to grow up；But excessive precursor particle makes the particle of sintered battery material also excessive, can reduce the electrochemistry of material
Rate discharge characteristic.Therefore, the concentration control by complexing agent ammonium hydroxide in mixed slurry is within the scope of the invention, available
The spherical particle that partial size is appropriate, surface is smooth, and the sphericity of spheric granules and compactness are larger, good dispersion between particle.
Above-mentioned preparation method, it is preferred that oxidant is air, oxygen, one in hydrogen peroxide in the step (S3)
Kind is several；It is furthermore preferred that oxidant is compressed air, blasted by conduit from the bottom of reaction vessel, gas is from below to up
It is flowed in reaction vessel, can play the role of being stirred to react slurry to which accelerated oxidation is reacted；Meanwhile in step (S3)
Stirring can realize by installing baffle and agitating paddle in reactor vessel wall, and the turbulent flow that when stirring is formed is conducive to oxidant
It is uniformly mixed with hydroxide slurry, accelerated oxidation reaction.
It is calculated by the cobaltosic oxide of every kilogram of M containing doped chemical, the oxidant additive amount is 80~350g/kg.When
When the additive amount of oxidant is lower than the scope of the present invention, hydroxide slurry cannot be fully oxidized；And it is higher than model of the invention
When enclosing, production cost will increase；When only oxidant additive amount being controlled within the scope of the invention, cost could reduced
It fully ensures that simultaneously and hydroxide slurry is oxidized to oxide.
Above-mentioned preparation method, it is preferred that reaction temperature is 50 DEG C~70 DEG C in the step (S2).Reaction temperature is to determine
Determine the key factor of Chemical Kinetics, reaction rate is increased with the raising of reaction temperature.Reaction temperature is too low to be will lead to
Reaction speed is slow, low efficiency；And reaction temperature is excessively high, energy consumption of reaction is increase accordingly, and the product withdraw of ammonium salt decomposition more collects
In, cause operating environment poor.
Above-mentioned preparation method, it is preferred that drying temperature is 150 DEG C~250 DEG C in the step (S4).
The preparation method of the cobaltosic oxide of the M containing doped chemical of the invention is theoretically carried out by following reaction process
, wherein (0.995~0.9) x:y=: (0.005~0.1).
(1) source cobalt source+M+H2O+ precipitating reagent+complexing agent → (CoxMy)(OH)2；
(2)(CoxMy)(OH)2+O2→(CoxMy)3O4；
Firstly, the reaction process as shown in formula (1) occurs, in the metal ion and precipitating reagent in cobaltosic oxide and the source M
Hydroxyl reaction generate the hydroxide precipitating of cobalt and M, and complexing agent can reduce the cobalt ions in reaction system in system
With the concentration of M ion, play the role of control coprecipitation reaction during nucleation rate and crystal coarsening rate.
Secondly, the reaction process as shown in formula (2) occurs.In (CoxMy)(OH)2When oxidation, oxide (CoxMy)3O4It is
In (CoxMy)(OH)2Surface nucleation is grown up, and the evolution of the volume contraction, reaction heat, water of product causes oxide (CoxMy)3O4Surface it is discontinuous, loose so that constantly having unoxidized (Co with the progress of oxidation reactionxMy)(OH)2Fresh surface
Exposure, so that oxidation reaction quickly, can be carried out persistently, until oxidation reaction terminates.
Above-mentioned preparation method, it is preferred that in the step (3), coating is Co (OH)2And TiO2；The weight of coating
Account for 0.005~5wt% of high voltage lithium cobalt oxide anode weight.The cobalt acid lithium particle synthesized by high temperature solid-state method, it is radial
Li+There are a certain concentration gradients, in particle by the region far from surface to surface region, Li+Concentration is gradually increased, thus surface
In rich Li+State, such LiCoO2It is excessive that positive electrode will appear activity, occurs itself to decompose and other with electrolyte pair
Reaction, influences the performance of material.Therefore, for the present invention during cladding, richness can be consumed by being added into the cobalt acid lithium adulterated
Remaining Li+Addition of C o (OH)2And TiO2, through Overheating Treatment, Li+With Co (OH)2Reaction forms active cobalt acid lithium, also
The Co (OH) of some2One layer of clad is formed in particle surface after Overheating Treatment.By Co (OH)2Consume Li+Mistake
Journey, Li+The state that redistributes and tend towards stability inside cobalt acid lithium blapharoplast is being adulterated, is realizing n (Li)/n (Co) in material
Accuracy controlling；Furthermore Co (OH)2Absorb Li+Can not only structure inside stable particle, while forming one layer of cobalt in particle surface
Oxide clad, completely cut off Co in high potential4+Contact with electrolyte can improve the surface stability of particle.In addition,
Pass through heat treatment, coating TiO2The Li more than needed with surface in the cobalt acid lithium adulterated+Reaction, generates Li4Ti5O12Cladding
Layer, clad electrochemical diffusion coefficient (2 × 10 with higher-8cm 2s-1) and structural stability, it is brilliant in charge and discharge process
Body structure hardly happens variation, is excellent coating, material impedance is reduced after cladding, improves capacity, improves and follows
Ring performance.Therefore, by Co (OH)2And TiO2Two kinds of coatings are used in combination, and effect, which is significantly greater tnan, is used alone a kind of coating
Effect: Co (OH)2Coating have consumption Li more than needed+With the double effects for playing oxide cladding layers, and TiO2Coating
There is consumption Li more than needed+With formation Li4Ti5O12The double effect of clad, in this way to high voltage cobalt acid lithium product capacity and cyclicity
The promotion of energy plays the role of very important.
Above-mentioned preparation method, it is preferred that the metallic element M adulterated in the cobaltosic oxide be Ga, Mo, Al, Ni,
One of Mn, Zn, Zr or a variety of.
Above-mentioned preparation method, it is preferred that the weight of doped metallic elements M is high voltage lithium cobalt oxide anode weight
0.01~5wt%.
Above-mentioned preparation method, it is preferred that the lithium source is one in lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate
Kind is several；In elemental lithium and cobaltosic oxide in the lithium source molar ratio of cobalt element be n (Li): n (Co)=(1.1~
0.9):1.Elemental mole ratios determine lattice constant, oxygen defect quantity, particle size and the cobalt element average valence of agglomerated material,
And then electrochemical discharge capacity, coulombic efficiency and the cycle performance of material are influenced, the molar ratio of lithium, cobalt element is controlled in this hair
The optimal high voltage lithium cobalt oxide anode of comprehensive performance can be prepared in bright range.
Above-mentioned preparation method, it is preferred that doped metallic elements M ' be Al, La, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu, Y, Nb, Tc, Ru, Rh, Pd, Ag, Cd or a variety of, the doping of M ' are high voltage lithium cobalt oxide anode weight
0.005~5wt% of amount.
Dopant is added in two portions and (admixes in Primary batching system and be added in advance in cobaltosic oxide) in the present invention, this is mainly
Depending on entering the complexity of cobalt acid lithium lattice and the feasibility of wet process co-precipitation according to the difference of doping, Doped ions.Four
The metallic element M (Ga, Mo, Al, Ni, Mn, Zn, Zr) adulterated in Co 3 O is since doping is larger, Doped ions enter cobalt
Sour lithium lattice is more difficult, therefore selection is mixed in advance in cobaltosic oxide.
Compound containing doped metallic elements M ' also acts as in high voltage lithium cobaltate cathode dusty material crystallization process
The effect of catalyst can carry out surface crystallization catalysis, and divalent cobalt ion is promoted to convert to trivalent cobalt ions, so preparation is just
Co exists substantially in the form of three valence states in the material of pole, and three valence state cobalt contents are higher, and cyclical stability is better, and capacity is got over for the first time
It is high.Therefore it is catalyzed by surface crystallization, is conducive to the crystalline perfection for improving cobalt acid lithium, improves the structural intergrity of material, together
When can effectively promote the discharge capacity of material.In addition, crystallization after the completion of, lithium cobaltate cathode powder body material surface will form to
Few inertia protective layer containing catalytic elements oxide or composite oxides prevents cobalt dissolution and cyclic process in charge and discharge process
Side reaction between middle cobalt and electrolyte occurs, and is effectively improved positive electrode cycle performance and security performance under high voltage.
Above-mentioned preparation method, it is preferred that in order to which the height for preferably obtaining the mixing of monocrystalline pattern and class monocrystalline pattern is electric
Cobalt acid lithium is pressed, joined grain refiner and fluxing agent in the present invention, the grain refiner is the oxygen of Ti, Nb, V, Al and Zr
One or more of compound；The grain refiner additional amount be high voltage lithium cobalt oxide anode weight 0.01~
5wt%；
The fluxing agent is one or more of the oxide of B, Ba, Bi, Pb, Mo, W, Li, K, Na, Ca and Mg；It is helped
Flux additional amount is 0.01~5wt% of high voltage lithium cobalt oxide anode weight.
Above-mentioned preparation method, it is preferred that it is once sintered to be carried out under air or oxygen-enriched atmosphere in the step (2), one
The detailed process of secondary sintering are as follows: by mixed once material from room temperature to 500 DEG C~900 DEG C, keep the temperature 2~10 hours, then
After being warming up to 900 DEG C~1150 DEG C, heat preservation 5~20 hours, with furnace natural cooling.
Above-mentioned preparation method, it is preferred that in the step (4), double sintering is under air or oxygen-enriched atmosphere, secondary burning
The detailed process of knot are as follows: by secondary mixed material from room temperature to 800 DEG C~1100 DEG C, keep the temperature 5~20 hours, then certainly with furnace
It is so cooling.
Above-mentioned preparation method, once sintered to have carried out ladder-elevating temperature sintering, this is primarily due at 500 DEG C~900 DEG C
Within the temperature range of, mixed once material will do it the reaction such as dehydration and degassing, heat preservation is carried out 2~10 hours in the temperature section,
The side reactions such as dehydration and degassing are sufficiently completed；And the basic knot of cobalt acid lithium is mainly formed at 900 DEG C~1150 DEG C
Structure completes doping.Since the main function of double sintering is to form the clad to shield on the surface of cobalt acid lithium, simultaneously
Surface is repaired, and the stylish amount that coating is added of second batch is fewer (general < 5%), so that side reaction is also few,
So double sintering does not need generally to carry out ladder-elevating temperature sintering, directly it is sintered.
Above-mentioned preparation method, it is preferred that in the step (2) and (4), crushing, which refers to, first breaks sintering feed by Hubei Province formula
After broken machine and twin rollers coarse crushing, crushed using airslide disintegrating mill；
In the step (1) and (3), mixing is carried out using coulter type mixer.Coulter type mixer is by circular cylinder body, biography
Motivation structure, colter, four part of fly cutter composition；Colter is set to move in a circle when mixing, material is split into two by colter knife face
A direction forms bidirectional material stream, shunts the material to come with two sides colter and intersects to form convection current, when material flows through high speed
It is sheared and is shed by high speed fly cutter blade again when fly cutter, to reach uniform mixing within a short period of time.Coulter type mixer is answered
High voltage lithium cobalt oxide anode industry is used, to overcome the problems, such as that fused glass inside and material ask the corrosion of coulter type mixer
Topic.Accurate adjustment colter overcomes the problems, such as fused glass inside at a distance from coulter type mixer inner wall；In colter, fly cutter and mixing machine
Wall is all made of corrosion resistant stainless steel and prepares the etching problem for overcoming material to coulter type mixer.
Compared with the prior art, the advantages of the present invention are as follows:
(1) difference of the present invention according to doped metal ion doping and the complexity into cobalt acid lithium lattice etc. are special
Point, doping, which is divided into when preparing cobaltosic oxide, to be admixed the dry method in a mixing in advance and is mixed into both modes.The element mixed in advance
It is relatively difficult into cobalt acid lithium lattice since doping is larger, therefore when wet process prepares cobaltosic oxide, pass through co-precipitation
The metallic element that method makes cobalt element and mixes in advance is able to achieve the uniform mixing of atomic level in the product, therefore uses this method
In the high voltage cobalt acid lithium product prepared, cobalt element and the distribution for mixing metallic element in advance are distributed completely on a microscopic scale
It is even, to solve the problems, such as that distributions of metallic elements is segregated on a microscopic scale in product, be conducive to the promotion of product electrical property.And
And the mixed doped metallic elements of dry method since doping is smaller are easily accessible cobalt acid lithium lattice, wet process in a mixing
The difficulty of co-precipitation is big, therefore the mode of dry mixed is selected to mix, and simplifies the complexity for preparing material.
(2) present invention carries out the pre- of raw material and mixes, and wet processing ensure that cobalt element and the metallic element mixed in advance is distributed in
Substantially uniformity on micro-scale solves the problems, such as that different metal Elemental redistribution is segregated on a microscopic scale in product；It adopts simultaneously
With mixing is carried out in the few coulter type mixer of lithium electricity positive electrode industrial application, mixed-precision is high, makes in mixture
Different material does not generate isolation, solves lithium source, cobaltosic oxide, the doped chemical of dry-mixed addition, grain refiner and fluxing
The problem of agent etc. isolates, these dual effects eliminate the segregation on micro-scale so that the component of sintered product is consistent, from
And improve the chemical property of product.
(3) grain refiner and fluxing agent are effectively combined use by the present invention, on the one hand ensure that synthesis in solid state process
It coming into full contact between middle compound and reacts, crystal structure is more complete；On the other hand sintering temperature is reduced, reduces energy
Consumption obtains the high voltage cobalt acid lithium of monocrystalline pattern and the mixing of class monocrystalline pattern, gives full play to the high voltage cobalt acid of two kinds of patterns
The advantage of lithium prepares the material for taking into account compacting, for the first time coulombic efficiency, capacity, multiplying power and cycle performance.
(4) present invention utilizes the catalytic action of doped metallic elements surface crystallization, promotes divalent cobalt ion to trivalent cobalt ions
Conversion, while inertia protective layer also is formed on lithium cobaltate cathode material surface, the electric discharge that on the one hand can effectively promote material is held
On the other hand amount also improves positive electrode cycle performance and security performance under high voltage.
(5) present invention selection Co (OH)2And TiO2Through Overheating Treatment as coating, primary burning on the one hand can be consumed
Tie surface Li more than needed+, while oxide cladding layers are yet formed, lithium cobaltate cathode material surface can be both reduced in this way
Activity can also form the clad with excellent properties, improve the security performance of material.
(6) preparation method process of the invention is simple, reacts easily controllable, can significantly improve the consistency of product, thus
Guarantee that the quality of different batches of product is stablized；And product composition is uniform, quality is stable, physical and chemical performance and electrical property show it is excellent
It is different.
Detailed description of the invention
Fig. 1 is the SEM photograph of the high voltage lithium cobalt oxide anode prepared in the embodiment of the present invention 1.
Fig. 2 is the SEM photograph for the high voltage lithium cobalt oxide anode that comparative example 1 of the present invention is prepared.
Fig. 3 is the SEM photograph of the high voltage lithium cobalt oxide anode prepared in the embodiment of the present invention 2.
Fig. 4 is the SEM photograph for the high voltage lithium cobalt oxide anode that comparative example 2 of the present invention is prepared.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of high voltage lithium cobalt oxide anode of the invention, comprising the following steps:
(1) by the cobaltosic oxide adulterated comprising Al uniform ion, lithium carbonate, lanthana, grain refiner TiO2With help
Flux Mg (OH)2Ingredient is carried out, is mixed using coulter type mixer, obtains mixed once material；Wherein in cobaltosic oxide
The amount of the Al metallic element of doping is the 0.50wt% of lithium cobaltate cathode material weight, elemental lithium and four oxidations three in lithium carbonate
The molar ratio of cobalt element is n (Li): n (Co)=1.07:1 in cobalt, and the doping of La is lithium cobaltate cathode material weight
0.1wt%, grain refiner TiO2Additional amount is the 0.1wt%, fluxing agent Mg (OH) of lithium cobaltate cathode material weight2Additional amount
For the 0.2wt% of lithium cobaltate cathode material weight；The cobaltosic oxide of the doping of uniform ion containing Al is by following preparation method system
For what is obtained:
(S1) cobaltous sulfate is added in aqueous solution and is tuned into pulpous state, aluminium chloride is then added, stirs to get mixed slurry；
(S2) in the mixed slurry after sodium hydroxide and ammonium hydroxide to be sequentially added to step (S1), control reaction process stirring turns
Speed is 700rmp, and temperature is 55 DEG C, time 20h, pH value 10, solid-liquid mass ratio 1:5, and reaction obtains the cobalt of the element containing Al
Hydroxide slurry；Wherein, the concentration of ammonium hydroxide is 0.5mol/L, the additive amount of precipitating reagent sodium hydroxide and rubbing for Co, Al total amount
You are than n (precipitating reagent): n (Co2++Al3+)=2.1:1；
(S3) it in the cobalt hydroxide slurry after oxidant air to be added to step (S2), is stirred, speed of agitator
For 1000rmp, reaction temperature is 60 DEG C, reaction time 10h, and reaction obtains mixing the cobaltosic oxide slurry of aluminium；Wherein, by every
The cobaltosic oxide for kilogram mixing aluminium calculates, and air additive amount is 200g/kg；
(S4) by the cobaltosic oxide slurry filtration after step (S3) to filter cake aqueous 40%, the item for being 200 DEG C in temperature
15h is dried under part, obtains the cobaltosic oxide of the doping of uniform ion containing Al.
(2) the mixed once material that step (1) obtains is placed in air and is sintered: first by mixed material from room temperature
To 700 DEG C, and 2 hours are kept the temperature, then heat to 1030 DEG C, 10 hours is kept the temperature, finally with furnace natural cooling；It then will be acquired
Block-like primary sintered material crushes to obtain powdery using airslide disintegrating mill after jaw crusher and twin rollers coarse crushing
Once sintered powder, D50 be 17.45 μm.
(3) the once sintered powder for obtaining step (2) and Co (OH)2、TiO2Mixing, mixed process are mixed using plough coulter type
Conjunction machine is mixed, and secondary mixed material is obtained；Wherein, Co (OH)2For the 3wt% of lithium cobaltate cathode material weight, TiO2For cobalt acid
The 0.05wt% of lithium anode material weight.
(4) secondary mixed material that step (3) obtains is placed in air and is sintered: by secondary mixed material from room temperature
To 920 DEG C, and 10 hours are kept the temperature, then with furnace natural cooling；Then broken by Hubei Province formula by acquired block-like double sintering material
After broken machine and twin rollers coarse crushing, crushed using airslide disintegrating mill to get high voltage cobalt acid lithium material product is arrived.
The SEM photograph for the high voltage lithium cobalt oxide anode that the present embodiment is prepared is as shown in Figure 1, can from figure
Out, which is the mixing of monocrystalline pattern and class monocrystalline pattern, and compacted density can arrive 4.1g/cm when making battery3, the anode material
The D50 of material is 17.59 μm, specific surface area 0.21m2/g。
Comparative example 1:
The preparation method of this comparative example high voltage lithium cobalt oxide anode, includes the following steps:
(1) by cobaltosic oxide, lithium carbonate, aluminium oxide, lanthana, grain refiner TiO2With fluxing agent Mg (OH)2It carries out
Ingredient is mixed using coulter type mixer, obtains mixed once material；Wherein, the elemental lithium in lithium carbonate and four oxidations three
The molar ratio of cobalt element is n (Li): n (Co)=1.07:1 in cobalt, and the doping of Al is double sintering products weight
The doping of 0.50wt%, La are the 0.1wt%, grain refiner TiO of lithium cobaltate cathode material weight2Additional amount is cobalt acid lithium
The 0.1wt% of positive electrode weight, fluxing agent Mg (OH)2Additional amount is the 0.2wt% of lithium cobaltate cathode material weight.
(2) the mixed once material that step (1) obtains is placed in air and is sintered: by mixed material from room temperature to
700 DEG C, and 2 hours are kept the temperature, 990 DEG C are then heated to, keeps the temperature 10 hours, with furnace natural cooling, resulting bulk is once sintered
Material, after jaw crusher and twin rollers coarse crushing, crushes to obtain the once sintered powder of powdery using airslide disintegrating mill,
D50 is 17.31 μm.
(3) the once sintered powder of powdery for obtaining step (2) and Co (OH)2、TiO2It is put into coulter type mixer and carries out
Mixing, obtains secondary mixed material；Wherein, Co (OH)2For the 3wt% of lithium cobaltate cathode material weight, TiO2For lithium cobaltate cathode material
Expect the 0.05wt% of weight.
(4) secondary mixed material that step (3) obtains air is placed in be sintered: by secondary mixed material from room temperature to
920 DEG C, and 10 hours are kept the temperature, then with furnace natural cooling, then by resulting blocky double sintering material, by jaw crusher
After twin rollers coarse crushing, crushed using airslide disintegrating mill to get high voltage lithium cobalt oxide anode product is arrived.
The SEM photograph for the high voltage lithium cobalt oxide anode that this comparative example is prepared is as shown in Fig. 2, can from figure
Out, which is mainly class monocrystalline pattern, and compacted density is only 3.9g/cm when making battery3, the D50 of the positive electrode is
17.21 μm, specific surface area 0.22m2/g。
Embodiment 2:
A kind of preparation method of high voltage lithium cobalt oxide anode of the invention, comprising the following steps:
(1) by the cobaltosic oxide adulterated comprising Zr uniform ion, lithium carbonate, aluminum oxide, grain refiner TiO2
With fluxing agent Mg (OH)2Ingredient is carried out, is mixed using coulter type mixer, obtains mixed once material；Wherein, four oxidation three
The amount of the Zr metallic element adulterated in cobalt is the 0.50wt% of lithium cobaltate cathode material weight, elemental lithium and four oxygen in lithium carbonate
The molar ratio for changing cobalt element in three cobalts is n (Li): n (Co)=1.06:1, and the doping of Al is lithium cobaltate cathode material weight
0.1wt%, grain refiner TiO2Additional amount is the 0.1wt%, fluxing agent Mg (OH) of lithium cobaltate cathode material weight2Additional amount
For the 0.1wt% of lithium cobaltate cathode material weight；The preparation method of the cobaltosic oxide of the doping of uniform ion containing Zr used, packet
Include following steps:
(S1) cobalt chloride is added in aqueous solution and is tuned into pulpous state, zirconium nitrate is then added, stirs to get mixed slurry；
(S2) in the mixed slurry after sodium hydroxide and ammonium hydroxide to be sequentially added to step (S1), control reaction process stirring turns
Speed is 600rmp, and temperature is 45 DEG C, time 18h, pH value 9.5, solid-liquid mass ratio 1:4, and reaction obtains the element containing Zr
Cobalt hydroxide slurry；Wherein, the concentration of ammonium hydroxide is 0.8mol/L, additive amount and Co, Zr total amount of precipitating reagent sodium hydroxide
Molar ratio n (precipitating reagent): n (Co2++Zr4+)=2.3:1；
(S3) it in the cobalt hydroxide slurry after oxidant oxygen to be added to step (S2), is stirred, reaction obtains
Mix the cobaltosic oxide slurry of zirconium；Wherein, the cobaltosic oxide for mixing zirconium by every kilogram calculates, and oxidant additive amount is 300g/kg；
Speed of agitator is 1200rmp, and reaction temperature is 70 DEG C, reaction time 5h；
(S4) by the cobaltosic oxide slurry filtration after step (S3) to filter cake aqueous 55%, the item for being 300 DEG C in temperature
10h is dried under part, obtains the cobaltosic oxide of the doping of uniform ion containing Zr.
(2) the mixed once material that step (1) is prepared is placed in oxygen and is sintered: by mixed material from room temperature liter
Temperature keeps the temperature 2 hours to 750 DEG C, then heats to 1040 DEG C, 8 hours is kept the temperature, with furnace natural cooling, then by acquired block
The primary sintered material of shape crushes to obtain powdery using airslide disintegrating mill after jaw crusher and twin rollers coarse crushing
Once sintered powder, D50 are 18.34 μm.
(3) the once sintered powder of powdery for obtaining step (2) and Co (OH)2、TiO2It is added in coulter type mixer and carries out
Mixing, obtains secondary mixed material；Wherein, Co (OH)2For the 2wt% of lithium cobaltate cathode material weight, TiO2For lithium cobaltate cathode material
Expect the 0.08wt% of weight.
(4) secondary mixed material that step (3) obtains is placed in oxygen to be sintered: from room temperature to 930 DEG C, and is kept the temperature
It is 8 hours, thick by jaw crusher and twin rollers then by acquired block-like double sintering material then with furnace natural cooling
After broken, crushed using airslide disintegrating mill to get high voltage lithium cobalt oxide anode product is arrived.
The SEM photograph for the high voltage lithium cobalt oxide anode that the present embodiment is prepared is as shown in figure 3, can from figure
Out, which is the mixing of monocrystalline pattern and class monocrystalline pattern, and compacted density can arrive 4.15g/cm when making battery3, the anode
The D50 of material is 18.21 μm, specific surface area 0.20m2/g。
Comparative example 2:
The preparation method of the high voltage lithium cobalt oxide anode of this comparative example, comprising the following steps:
(1) cobaltosic oxide, the lithium carbonate that will be adulterated comprising Zr uniform ion, is mixed using coulter type mixer,
Obtain mixed once material；Wherein, the amount of the Zr metallic element adulterated in cobaltosic oxide is lithium cobaltate cathode material weight
0.50wt%, the molar ratio of cobalt element is n (Li): n (Co)=1.06:1 in the elemental lithium and cobaltosic oxide in lithium carbonate；Institute
The preparation method of the cobaltosic oxide of the doping of uniform ion containing Zr, comprising the following steps:
(S1) cobalt chloride is added in aqueous solution and is tuned into pulpous state, zirconium nitrate is then added, stirs to get mixed slurry；
(S2) in the mixed slurry after sodium hydroxide and ammonium hydroxide to be sequentially added to step (S1), control reaction process stirring turns
Speed is 600rmp, and temperature is 45 DEG C, time 18h, pH value 9.5, solid-liquid mass ratio 1:4, and reaction obtains the element containing Zr
Cobalt hydroxide slurry；Wherein, the concentration of ammonium hydroxide is 0.8mol/L, additive amount and Co, Zr total amount of precipitating reagent sodium hydroxide
Molar ratio n (precipitating reagent): n (Co2++Zr4+)=2.3:1；
(S3) it in the cobalt hydroxide slurry after oxidant oxygen to be added to step (S2), is stirred, reaction obtains
Mix the cobaltosic oxide slurry of zirconium；Wherein, the cobaltosic oxide for mixing zirconium by every kilogram calculates, and oxidant additive amount is 300g/kg；
Speed of agitator is 1200rmp, and reaction temperature is 70 DEG C, reaction time 5h；
(S4) by the cobaltosic oxide slurry filtration after step (S3) to filter cake aqueous 55%, the item for being 300 DEG C in temperature
10h is dried under part, obtains the cobaltosic oxide of the doping of uniform ion containing Zr.
(2) the mixed once material that step (1) is prepared is placed in oxygen and is sintered: by mixed material from room temperature liter
Temperature keeps the temperature 2 hours to 750 DEG C, then heats to 1040 DEG C, 8 hours is kept the temperature, with furnace natural cooling, then by acquired block
The primary sintered material of shape crushes to obtain powdery using airslide disintegrating mill after jaw crusher and twin rollers coarse crushing
Once sintered powder, D50 are 18.29 μm.
(3) the once sintered powder of powdery for obtaining step (2) and Co (OH)2、TiO2It is added in coulter type mixer and carries out
Mixing, obtains secondary mixed material；Wherein, Co (OH)2For the 2wt% of lithium cobaltate cathode material weight, TiO2For lithium cobaltate cathode material
Expect the 0.08wt% of weight.
(4) secondary mixed material that step (3) obtains is placed in oxygen to be sintered: from room temperature to 930 DEG C, and is kept the temperature
It is 8 hours, thick by jaw crusher and twin rollers then by acquired block-like double sintering material then with furnace natural cooling
After broken, crushed using airslide disintegrating mill to get high voltage lithium cobalt oxide anode product is arrived.
The SEM photograph for the high voltage lithium cobalt oxide anode that this comparative example is prepared is as shown in figure 4, can from figure
Out, which is the mixing of monocrystalline pattern and class monocrystalline pattern, and compacted density can arrive 4.15g/cm when making battery3, the anode
The D50 of material is 18.14 μm, specific surface area 0.20m2/g。
The high voltage lithium cobaltate cathode that the embodiment of the present invention 1, embodiment 2, comparative example 1 and comparative example 2 are prepared
Material carries out electrochemical property test (3.0~4.45V of actual effect cell voltage test scope), specific discharge capacity, high rate performance
The results are shown in Table 1, and the results are shown in Table 2 for cycle performance.
The result of table 1 high voltage lithium cobalt oxide anode specific discharge capacity and high rate performance
The result of 2 high voltage lithium cobalt oxide anode cycle performance of table
Note: 1C-1 represents the discharge capacity of 1C multiplying power lower first time；1C-200 indicates to recycle 200 capacity under 1C multiplying power
Conservation rate.
From above experimental result it is found that the result of Examples 1 and 2 is superior to comparative example, embodiment 1 and comparative example 1 are
Stablize the structure of cobalt acid lithium under high voltages, is all made of the Al element of equal higher-doped amount.And the maximum difference of the two
It is that embodiment 1 prepares cobaltosic oxide using wet process, the Al for making cobalt element by the method for co-precipitation and mixing in advance exists
It is able to achieve the uniform mixing of atomic level in product, is segregated on a microscopic scale to solve these distributions of metallic elements in product
The problem of, be conducive to the promotion of product electrical property；And in comparative example 1, the Al element of higher-doped amount dry method in a mixing
It is mixed into, since Al doping is larger, it is more difficult to evenly into cobalt acid lithium lattice, to deteriorate the performance of material.
In addition, embodiment 2 and comparative example 2 are to stablize the structure of cobalt acid lithium under high voltages, it is all made of cobaltosic oxide
In mix equal Zr element in advance.The maximum difference of the two is in the preparation process of comparative example 2, without adding the oxygen of doped chemical M ' again
Compound, grain refiner and fluxing agent.And dopant is added in two portions, while also adding grain refiner and fluxing agent, this
The combination of kind multiple form, is notable feature of the invention, while also having relatively good result.It can be with from the result of Tables 1 and 2
Find out, the capacity and cycle performance of embodiment 2 are all significantly better than comparative example 2.
Claims (10)
1. a kind of preparation method of high voltage lithium cobalt oxide anode, which comprises the following steps:
(1) mixing: by cobaltosic oxide, lithium source, the M containing doped chemical of the M containing doped chemical ' oxide, crystal grain refinement
Agent and fluxing agent are mixed, and mixed once material is obtained；
(2) once sintered: the mixed once material being sintered, is crushed, once sintered powder is obtained；
(3) rerolling: the once sintered powder is mixed with coating, obtains secondary mixed material；
(4) double sintering: the secondary mixed material is sintered, is crushed to get high voltage lithium cobalt oxide anode is arrived.
2. preparation method as described in claim 1, which is characterized in that in the step (3), coating is Co (OH)2With
TiO2；The weight of coating accounts for 0.005~5wt% of high voltage lithium cobalt oxide anode weight.
3. preparation method according to claim 1, which is characterized in that the cobaltosic oxide of the M containing doped chemical is main
It is prepared by following preparation method:
(S1) soluble ingredient containing cobalt is added in aqueous solution and is tuned into pulpous state, the solubility comprising doped chemical M is then added
Raw material stirs to get mixed slurry；
(S2) it is reacted in the mixed slurry after precipitating reagent and complexing agent to be sequentially added to step (S1), control reaction process stirring turns
Speed be 100~900rmp, temperature be 20 DEG C~90 DEG C, the time be 5~40h, pH value be 6~11, solid-liquid mass ratio be 1:(3~
7), reaction obtains the cobalt hydroxide slurry of the M containing doped chemical；
(S3) it is reacted in the cobalt hydroxide slurry after oxidant to be added to step (S2), controls the speed of agitator of reaction process
For 300~1300rmp, temperature is 30 DEG C~90 DEG C, and the time is 2~15h, and reaction obtains the cobaltosic oxide of the M containing doped chemical
Slurry；
(S4) by the cobaltosic oxide slurry filtration after step (S3), drying, drying temperature is 80 DEG C~400 DEG C, drying time
For 1~30h, the cobaltosic oxide of the M containing doped chemical is obtained.
4. preparation method according to claim 3, which is characterized in that in the step (S1), the soluble ingredient containing cobalt
For one or more of cobalt chloride, cobalt nitrate, cobaltous sulfate；Soluble ingredient comprising doped chemical M is sulfate, nitric acid
One or more of salt, acetate, chlorate；
In the step (S2), precipitating reagent is sodium hydroxide；The molar ratio of precipitating reagent additive amount and Co, M total amount is n (precipitating
Agent): n (Co+M)=(2~3): 1；The complexing agent is ammonium hydroxide, and the complexing agent concentration is 0.05~1mol/L；
In the step (S3), oxidant is one or more of air, oxygen, hydrogen peroxide；By every kilogram of member containing doping
Plain cobaltosic oxide calculates, and the oxidant additive amount is 80~350g/kg.
5. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that the gold adulterated in the cobaltosic oxide
Belonging to element M is one of Ga, Mo, Al, Ni, Mn, Zn, Zr or a variety of；The weight of doped metallic elements M is high voltage cobalt acid lithium
0.01~5wt% of positive electrode weight.
6. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that the lithium source is lithium hydroxide, carbonic acid
One or more of lithium, lithium nitrate and lithium acetate；Mole of cobalt element in elemental lithium and cobaltosic oxide in the lithium source
Than for n (Li): n (Co)=(1.1~0.9): 1；Doped metallic elements M ' be Al, La, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One of Yb, Lu, Y, Nb, Tc, Ru, Rh, Pd, Ag, Cd or a variety of, the doping of M ' are high voltage lithium cobalt oxide anode weight
0.005~5wt% of amount.
7. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that the grain refiner is Ti, Nb, V,
One or more of the oxide of Al and Zr；The grain refiner additional amount is high voltage lithium cobalt oxide anode weight
0.01~5wt%；The fluxing agent is one or more of the oxide of B, Ba, Bi, Pb, Mo, W, Li, K, Na, Ca and Mg；
The fluxing agent additional amount is 0.01~5wt% of high voltage lithium cobalt oxide anode weight.
8. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that in the step (2), it is once sintered
Carried out under air or oxygen-enriched atmosphere, once sintered detailed process are as follows: by mixed once material from room temperature to 500 DEG C~
900 DEG C, 2~10 hours are kept the temperature, after then heating to 900 DEG C~1150 DEG C, heat preservation 5~20 hours, with furnace natural cooling.
9. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that in the step (4), double sintering exists
Under air or oxygen-enriched atmosphere, the detailed process of double sintering are as follows: by secondary mixed material from room temperature to 800 DEG C~1100 DEG C,
Heat preservation 5~20 hours, then with furnace natural cooling.
10. such as the described in any item preparation methods of Claims 1 to 4, which is characterized in that in the step (2) and (4), crush
Refer to first by sintering feed after jaw crusher and twin rollers coarse crushing, is crushed using airslide disintegrating mill；
In the step (1) and (3), mixing is carried out using coulter type mixer.
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