CN109755524A - Modified LiNi0.6Co0.2Mn0.2O2The preparation method and product and battery of tertiary cathode material - Google Patents
Modified LiNi0.6Co0.2Mn0.2O2The preparation method and product and battery of tertiary cathode material Download PDFInfo
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Abstract
The invention discloses a kind of modified LiNi0.6Co0.2Mn0.2O2The preparation method and product and battery of tertiary cathode material.The preparation method of the tertiary cathode material includes: first to introduce magnesium elements when preparing nickel cobalt manganese hydroxide precursor, then ammonium metatungstate aqueous solution is used instead as complexing agent in the coprecipitation reaction later period, occur after being hydrolyzed in water using ammonium metatungstate with ammonium ion and tungstate ion, ammonium ion is served as complexing agent to be used to compensate coprecipitation reaction, and it is partially deposited on the nickel cobalt manganese hydroxide precursor surface that tungstate ion is formed in precipitation reaction, realize that the in situ of wolfram element introduces, it is handled again through lithiumation later to obtain the tertiary cathode powder of surface tungsten element.The present invention adulterates wolfram element by addition magnesium elements and surface element in situ, is effectively improved charge-discharge performance, the cycle performance etc. of the modified tertiary cathode powder of gained.
Description
Technical field
The present invention relates to a kind of nickel-cobalt-manganternary ternary anode materials of high nickel content, and in particular to modified
LiNi0.6Co0.2Mn0.2O2The preparation method and product and battery of tertiary cathode material.
Background technique
Lithium ion battery is able to carry out positive electrode and cathode material of the reversible embedding de- material as battery using lithium ion
Material, constitutes lithium ion secondary battery system in conjunction with electrolyte appropriate or solid electrolyte powder film.Because of the energy of battery
Amount depends on the product of its voltage and capacity, so the means for improving the energy density of battery are using high voltage and high capacity
Positive and negative pole material.For same negative electrode material, the capacity and current potential of positive electrode are higher, then the energy density of battery is higher.
The energy density of lithium ion battery is promoted, the high nickel content tertiary cathode powder of exploitation more height ratio capacity is the main of battery research and development
Direction.
LiFePO4 (the theoretical specific capacity of the spinel structure LiMn2O4 and olivine-type structure low compared to theoretical specific capacity
For 170mAh/g), theoretical specific capacity is the layer structure ternary composite cathode material (LiNi of 280mAh/gxCoyMnzO2) have
Apparent advantage, and actual capacity of the layer structure tertiary cathode in lithium ion battery can rise with the raising of Ni content
Height, thus ternary composite cathode material of the nickel ratio in three kinds of elements of nickel cobalt manganese higher than 60% be current high-energy density lithium from
The first choice anode of sub- battery.
High nickel content tertiary cathode powder is usually to be synthesized by co-precipitation-high temperature solid state reaction, that is, is first passed through coprecipitated
Shallow lake method prepares nickel cobalt manganese hydroxide precursor, adds the mixed sinterings such as lithium source such as lithium hydroxide or lithium carbonate and nickel cobalt is made
Lithium manganate cathode powder.It is well known that the precursor powder pattern and granularity etc. in co-precipitation-high temperature solid state reaction technique influence
Many performances of the positive pole powder in lithium ion battery, high nickel content nickel-cobalt-manganese ternary positive pole powder surface doping and be overmolding to
For the effective ways for improving positive pole powder performance.Existing research shows that clad can alleviate electrolyte to high nickel content nickel
The corrosion on cobalt-manganese ternary positive pole powder surface, doped chemical can also inhibit the crystal structure of tertiary cathode powder surface portion to become
Change, improves the cyclical stability and thermal stability of ternary material.
The research of its electrochemical stability is improved using metal oxide cladding nickle cobalt lithium manganate tertiary cathode powder expectation
There are many, such as the patent of invention of Publication No. CN104393277A, disclose the lithium of surface clad oxide a kind of from
The preparation method of sub- battery tertiary cathode material, this method includes: high polymer polyacrylamide 1. is added in soluble metal salt and is made
Be it is evenly dispersed in the solution of dispersing agent, 2. tertiary cathode material powder is added in above-mentioned solution and is stirred；3. mixed
The aqueous solution that alkali metal hydroxide is added in solution is closed, the pH value of solution is adjusted to 9-12, is filtered after precipitating, dry, obtain table
Bread covers the positive electrode of hydroxide；4. hot at 400-700 DEG C again by the positive electrode of above-mentioned surface cladding hydroxide
Processing, obtains the tertiary cathode material of surface clad oxide.The for another example patent of invention of Publication No. CN108777296A,
A kind of nickelic tertiary cathode material surface reforming layer forming method is disclosed, coats two on the kernel of nickelic tertiary cathode material
Kind of surface modifying species, one of which are yttria-stabilized zirconia, another be selected from metal oxide, metal fluoride,
Metal phosphate or C, surface modifying species are coated on bulk material surface, reduce nickelic tertiary cathode material and electrolyte
Side reaction, it is suppressed that the irreversible capacity loss of tertiary cathode material.For another example the invention of Publication No. CN105576233A is special
Benefit discloses a kind of Ni-based tertiary cathode material surface modifying method, mixed in nickel cobalt manganese hydroxide precursor powder and lithium salts
The Ni-based tertiary cathode material surface obtained after calcining is closed, using titanate coupling agent, aluminate coupling agent and silane coupling agent
It is one or more react in organic solvent it is compound, through calcining heat treatment obtained titanium, aluminium or Si oxide coating modification
Ni-based tertiary cathode material.Although similar metal oxide coating modification processing can improve positive powder to a certain extent
The cycle performance and thermal stability at end, but counter productive is also brought along, because the metal oxide of cladding is inert material, inhibit
The transmission of lithium ion and electronics.
On the other hand, also there are the method for improving tertiary cathode material powdered conductive performance using carbon coating, such as Publication No.
The patent of invention of CN103474628A, it includes: 1. with nickel salt, cobalt salt that disclosed carbon coating, which improves tertiary cathode material powder method,
It is raw material with manganese salt, prepares ternary anode material precursor；2. dispersing preparation in the water containing organic carbon source for conductive carbon to lead
Electrical carbon dispersion liquid；3. ternary anode material precursor and lithium compound are added in conductive carbon dispersion liquid, uniformly mixing is obtained
Object；4. mixture is dried under vacuum conditions；5. in confined conditions or inert gas shielding by the mixture of drying
Atmosphere high temperature processing, obtain carbon coating tertiary cathode material.The invention is pointed out conductive carbon powder and tertiary cathode material is same
When be coated on in network-like conductive media amorphous carbon, the high rate performance of tertiary cathode material can be improved.Publication number
For CN104733721A patent of invention then disclose liquid phase sugar coat spray drying prepare nickle cobalt lithium manganate tertiary cathode material
Method, specifically will Ni, Co, Mn sulfate liquor mix after under alkaline condition be co-precipitated be made tri compound presoma
(NixCoyMnz)(OH)2, after filtration, washing and drying, it is added to jointly with soluble metal lithium compound, rare earth compound
It has dissolved in the solvent of sugar and has been uniformly mixed, then the spray-dried ternary precursor for obtaining sugar and coating and being doped with rare earth element,
The ternary material LiNi of carbon-containing bed and rare earth doped element is most obtained through high-temperature calcination afterwardsxCoyMnzRnO2Powder.
In addition, the patent of invention of Publication No. CN107895793A discloses a kind of lithium of surface cladding witch culture boride
Tungsten source is specifically dissolved in water by the preparation method of cell positive material, is sprayed onto ternary precursor and lithium in spraying mode
Dried material is stirred to get in the mixed raw material of source, then roasting obtains the tertiary cathode material of witch culture；Again by metal boride
It is added in above-mentioned witch culture tertiary cathode material and stirs evenly, then sintering at a certain temperature obtains witch culture boride cladding
Anode material of lithium battery.
In spite of a variety of tertiary cathode powder surface cladding as described above or doping treatment method, but they are all in ternary
The clad of positive pole powder surface superposition is not based on the crystal structure that doping wolfram element replaces tertiary cathode powder surface portion
In nickel, cobalt, manganese atom, that is to say, that using wolfram element high chemical valence reduce layered crystal structure in nickel, cobalt, manganese
Valence mumber variation of the element in charge and discharge process, while also not accounting for and adulterating high chemical valence tungsten member in layered crystal structure
Element causes vacancy concentration to increase, and is conducive to the diffusion of lithium ion to reach the mesh for improving tertiary cathode powder property by doping
's.On the other hand, well known to those skilled in the art, high nickel content tertiary cathode powder surface is in alkalinity, if directly answered
During subsequent size mixing, it will lead to slurry when (- 30 DEG C of dew point) progress slurrying under normal conditions and become gel (jelly
Shape colloid) the problem of；If removing tertiary cathode powder surface alkalinty, although can be using the operation of washing, this can make
The lithium ion on surface loses and the discharge capacity of tertiary cathode material is caused to reduce.Therefore, it is necessary to provide it is a kind of both had compared with
High charge/discharge capacity, and be not in that slurry becomes solidifying when by its (- 30 DEG C of dew point) progress slurrying under normal condition
The LiNi of glue problem0.6Co0.2Mn0.2O2Tertiary cathode material and preparation method thereof.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of modified LiNi0.6Co0.2Mn0.2O2The system of tertiary cathode material
Preparation Method and product and battery, LiNi obtained by this method0.6Co0.2Mn0.2O2Tertiary cathode material is not only with higher to be filled
Discharge capacity, and be not in that slurry becomes asking for gel when by its (- 30 DEG C of dew point) progress slurrying under normal condition
Topic.
In order to solve the above technical problems, modified LiNi of the present invention0.6Co0.2Mn0.2O2The preparation of tertiary cathode material
Method, comprising the following steps:
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) take nickel salt, cobalt salt and manganese salt soluble in water, obtain the first mixed liquor, control in the first mixed liquor total metal from
The concentration of son is 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion is 6: 2: 2；
1.2) magnesium sulfate is added into mixed liquor, dissolves, obtains the second mixed liquor；Wherein the additional amount of magnesium sulfate be nickel from
The 0.05-0.25% of son, cobalt ions and manganese ion integral molar quantity；
1.3) precipitating reagent is added into the second mixed liquor and complexing agent carries out coprecipitation reaction, in which:
The coprecipitation reaction process includes two stages, respectively first stage of reaction and second stage of reaction, wherein
The reaction time of second stage of reaction accounts for the 12-20% of coprecipitation reaction total reaction time；
The complexing agent includes the first complexing agent and the second complexing agent, wherein the first complexing agent is ammonium hydroxide, the second complexing agent
For ammonium metatungstate aqueous solution；
What is be added in first stage of reaction of coprecipitation reaction is the first complexing agent, and the first complexing agent reacts rank first
Duan Quancheng is uniformly added into；It is 25% (NH when the first complexing agent is concentration3Mass fraction be 25%, similarly hereinafter) ammonium hydroxide when,
Additional amount is added the first complexing agent of 10-50mL by every liter of first mixed liquor and calculates；
What second stage of reaction was added is the second complexing agent, and the second complexing agent uniformly adds in second stage of reaction whole process
Enter；When the concentration of the second complexing agent is 0.2-0.5mol/L, 40-60mL second is added by every liter of first mixed liquor in additional amount
Complexing agent calculates；
During entire coprecipitation reaction, the dosage of precipitating reagent is the pH=10-13 of control system, after the reaction was completed, institute
Reaction mass filtering is obtained, precipitating is collected and is dried, obtain the nickel cobalt manganese hydroxide precursor of surface tungsten；
2) the nickel cobalt manganese hydroxide precursor and lithium source of surface tungsten are uniformly mixed, hot place is carried out in oxidizing atmosphere
Reason, obtains the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder；
3) polyamic acid solution is obtained；
4) by the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder is placed in polyamic acid solution, is stirred a timing
Between, it takes out, it is dry, obtain the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2Powder；
5) LiNi of gained polyamic acid cladding0.6Co0.2Mn0.2O2Powder, which is placed under vacuum condition, carries out Low Temperature Heat Treatment,
Medium temperature heat treatment is carried out in oxidizing atmosphere later to get the modification LiNi is arrived0.6Co0.2Mn0.2O2Tertiary cathode material
Material.
In the step 1.1) of above-mentioned preparation method, the selection of the nickel salt, cobalt salt and manganese salt is same as the prior art, specifically
, nickel salt can be the combination of one or more of nickel sulfate, nickel nitrate and nickel chloride, cobalt salt can be cobaltous sulfate,
The combination of one or more of cobalt nitrate and cobalt chloride, manganese salt can be one in manganese sulfate, manganese nitrate and manganese chloride
Kind or two or more combinations.
In the step 1.2) of above-mentioned preparation method, the additional amount of magnesium sulfate is preferably that nickel ion, cobalt ions and manganese ion are total
The 0.1-0.2% of mole.
In the step 1.3) of above-mentioned preparation method, during entire coprecipitation reaction, the dosage of precipitating reagent is control volume
The pH=10.5-11.5 of system；The selection of the precipitating reagent is same as the prior art, specifically can be the hydrogen that concentration is 1-5mol/L
Sodium hydroxide solution or potassium hydroxide solution etc..In the step, the total time of coprecipitation reaction can be designed as needed, and applicant exists
It is found in test, more appropriate when the total time of coprecipitation reaction being designed as 6h, with this condition, further preferred second is anti-
The reaction time in stage is answered to account for 15-18% (the i.e. 0.9-1.08h, and remaining 4.92-5.1h of coprecipitation reaction total reaction time
It is then the reaction time of first stage of reaction).
In the step 2) of above-mentioned preparation method, the lithium source is conventional selection in the prior art, specifically can be hydrogen
Lithia and/or lithium carbonate etc., the amount of lithium source are by LiNi to be prepared0.6Co0.2Mn0.2O2Required theory dosage,
1.01-1.1 times of theoretical amount is usually weighed in the actual operation process.Realize that surface contains using existing conventional mechanical hybrid mode
The nickel cobalt manganese hydroxide precursor of tungsten and being uniformly mixed for lithium source, such as carried out using drum type high-speed blender or ball mill
Mixing.Heat treatment after mixing is to complete lithiation, and technique is identical as existing conventional techniques, is usually existed
6-8h is kept the temperature under the conditions of 720-800 DEG C to complete lithiation.
In the step 3) of above-mentioned preparation method, the polyamic acid solution that can be obtained by existing conventional method, such as by two
It is molten that amine (such as 4,4 ' ,-diaminodiphenyl ether (ODA) etc.) and dianhydride (such as pyromellitic acid dianhydride (PMDA)) are placed in aprotic, polar
Polycondensation reaction is carried out in agent (such as n-methyl-2-pyrrolidone (NMP)) and is obtained.In the application, preferably use solid content for
The polyamic acid solution of 0.001-0.005% (quality, similarly hereinafter).It can for the polyamic acid solution of solid content not in this range
Required solid content is diluted to using polar non-solute.
In the step 4) of above-mentioned preparation method, under the conditions of low moisture (such as -30 DEG C of dew point) by surface tungsten
LiNi0.6Co0.2Mn0.2O2Powder, which is placed in polyamic acid solution, is stirred certain time so that the two comes into full contact with, due to poly-
Amide acid solution itself has certain viscosity, on the one hand being stirred makes weakly acidic polyamic acid solution and surface in alkalinity
The LiNi of tungstenic0.6Co0.2Mn0.2O2Powder reacts to each other, and on the other hand also realizes that polyamic acid solution contains surface in alkalinity
The LiNi of tungsten0.6Co0.2Mn0.2O2The cladding of powder.The LiNi of the surface tungsten0.6Co0.2Mn0.2O2Powder and polyamic acid are molten
The solid-liquid ratio of liquid can be designed as needed, when polyamic acid solution is the polyamic acid that solid content is 0.001-0.005%
When solution, the LiNi of the surface tungsten0.6Co0.2Mn0.2O2The solid-liquid ratio of powder and polyamic acid solution can be 1: 1-10,
More preferably 1: 1-3.The time being stirred preferably >=0.1h, usually 0.5-3h.In the step, the drying is logical
Often carried out at 120-200 DEG C.
In the step 5) of above-mentioned preparation method, the Low Temperature Heat Treatment is to solidify polyamic acid, and concrete operations are
1-4h is kept the temperature under the conditions of 300-400 DEG C.The medium temperature heat treatment is then to keep the temperature 2-6h under the conditions of 600-680 DEG C.
The invention also includes modified LiNi prepared by the above method0.6Co0.2Mn0.2O2Tertiary cathode material.
The present invention also provides a kind of lithium ion battery, including positive plate, the positive electrode used on the positive plate is by upper
The modification LiNi that the method for stating is prepared0.6Co0.2Mn0.2O2Tertiary cathode material.
Compared with prior art, present invention is characterized in that
1, ammonium metatungstate aqueous solution is used instead as complexing agent, metatungstic acid in the coprecipitation reaction later period (i.e. second stage of reaction)
Ammonium occurs after hydrolyzing in water with ammonium ion and tungstate ion, wherein ammonium ion serve as complexing agent for compensate co-precipitation instead
It answers, and tungstate ion partially deposits on established nickel cobalt manganese hydroxide precursor early period surface, realizes wolfram element
It is in situ to introduce, it is handled again through lithiumation later to obtain the LiNi of surface tungsten element0.6Co0.2Mn0.2O2Tertiary cathode powder.This
Invention adulterates wolfram element by addition magnesium elements and surface element in situ, can increase while stablizing nickel cobalt manganese layered crystal construction
Add the vacancy for being conducive to lithium ion diffusion, makes the modified LiNi of gained0.6Co0.2Mn0.2O2The charge-discharge performance of tertiary cathode powder follows
Ring performance etc. is effectively improved.
2, using polyamic acid solution to the LiNi of surface tungsten0.6Co0.2Mn0.2O2Tertiary cathode powder is coated, and is led to
The alkali compounds that surface reaction removes high nickel content tertiary cathode material surface is crossed, to eliminate high nickel content tertiary cathode material
Material carries out the problem of slurry becomes gel occur when slurrying under normal conditions.
3, further to the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2After tertiary cathode powder progress low-temperature setting again
Medium temperature carbonization is carried out, to obtain the LiNi of surface carbon (indefinite form carbon) layer cladding0.6Co0.2Mn0.2O2Tertiary cathode material.
4, using the modified LiNi in surface made from the method for the invention0.6Co0.2Mn0.2O2Tertiary cathode material keeps three
First original layered crystal structure of positive electrode, the not generation of impurity phase.The electricity of the positive electrode is tested using button cell
Chemical property, not occurring being similar to after the processing of metal oxide cladding leads to anode since the diffusional resistance of lithium ion rises
The problem of capacity declines, charge/discharge capacity is high and stablizes, under conditions of 0.2C, first discharge specific capacity > 190mAh/g, and
Good cycle；Also there is not the problem of slurry becomes gel and fails in subsequent size mixing technology.
Detailed description of the invention
Fig. 1 is modified LiNi made from the embodiment of the present invention 10.6Co0.2Mn0.2O2The XRD spectrum of tertiary cathode material；
Fig. 2 is modified LiNi made from the embodiment of the present invention 10.6Co0.2Mn0.2O2The SEM of tertiary cathode material schemes；
Fig. 3 is modified LiNi made from the embodiment of the present invention 10.6Co0.2Mn0.2O2Tertiary cathode material is under the conditions of 0.2C
Charging and discharging curve figure；
Fig. 4 is modified LiNi made from the embodiment of the present invention 10.6Co0.2Mn0.2O2Tertiary cathode material is the 1C under the conditions of
Charging and discharging curve figure；
Fig. 5 is LiNi made from comparative example 1 of the present invention0.6Co0.2Mn0.2O2The XRD spectrum of tertiary cathode material；
Fig. 6 is LiNi made from comparative example 1 of the present invention0.6Co0.2Mn0.2O2The SEM of tertiary cathode material schemes；
Fig. 7 is using LiNi made from comparative example 10.6Co0.2Mn0.2O2What tertiary cathode material was formed during sizing mixing
The picture of gel.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
Embodiment 1
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) it takes nickel sulfate, cobaltous sulfate and manganese sulfate soluble in water, obtains the first mixed liquor, control total in the first mixed liquor
The concentration of metal ion is 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion is 6: 2: 2；
1.2) magnesium sulfate is added into mixed liquor, dissolves, obtains the second mixed liquor；Wherein the additional amount of magnesium sulfate be nickel from
The 0.1% of sub, cobalt ions and manganese ion integral molar quantity；
1.3) precipitating reagent is added into the second mixed liquor and complexing agent carries out coprecipitation reaction, in which:
Design coprecipitation reaction total time is 6h, and institute's coprecipitation reaction process includes two stages, the respectively first reaction
Stage and second stage of reaction, wherein the reaction time of first stage of reaction is 5h, the reaction time of second stage of reaction is 1h
(account for coprecipitation reaction total reaction time 16.7%)；
The precipitating reagent is the sodium hydroxide solution that concentration is 2mol/L, and dosage is to control entire coprecipitation reaction process
The pH=11.0-11.5 of middle system is added dropwise and runs through entire coprecipitation reaction process；The complexing agent includes the first complexing agent
With the second complexing agent, wherein the first complexing agent is the ammonium hydroxide that concentration is 25%, the second complexing agent is that concentration is the inclined of 0.3mol/L
Ammonium tungstate aqueous solution；
What is be added in first stage of reaction of coprecipitation reaction is the first complexing agent, and additional amount presses every liter of first mixed liquor
The first complexing agent of 20mL is added to calculate；The first complexing agent control has dropped evenly in 5h；
What is be added in second stage of reaction of coprecipitation reaction is the second complexing agent, and additional amount presses every liter of first mixed liquor
The second complexing agent of 50mL is added to calculate, the second complexing agent control has dropped evenly in 1h；
After the completion of coprecipitation reaction, precipitating is collected in the filtering of gained reactant material, dry under the conditions of 80 DEG C after washing, is obtained
To the nickel cobalt manganese hydroxide precursor of surface tungsten；
2) the nickel cobalt manganese hydroxide precursor and lithium hydroxide of surface tungsten are placed in drum type high-speed blender and are mixed
It closes uniformly, wherein the dosage of lithium hydroxide is according to LiNi0.6Co0.2Mn0.2O21.03 times of theoretical lithium content, gained mixing
Object, which is placed in oxidizing atmosphere, keeps the temperature 6h under the conditions of 760 DEG C, obtains the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder；
3) polyamic acid solution that solid content is 0.002% is obtained；
4) LiNi of surface tungsten is weighed by 1: 1 mass ratio0.6Co0.2Mn0.2O2Powder and solid content are 0.002%
Polyamic acid solution, later by the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder is placed in the polyamide that solid content is 0.002%
In acid solution, it is stirred 3h, is taken out, it is dry under the conditions of 150 DEG C, obtain the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2
Powder；
5) LiNi of gained polyamic acid cladding0.6Co0.2Mn0.2O2Powder is placed under vacuum condition, is warming up to 350 DEG C and (is risen
Warm rate is 5 DEG C/min) heat preservation 1h, it is passed through oxidizing atmosphere later, and be warming up to 650 DEG C of (heating rate is 5 DEG C/min) heat preservations
5h is to get the LiNi for arriving modification0.6Co0.2Mn0.2O2(i.e. through the carbonization of surface doping cladding, treated for tertiary cathode material
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material).
To modified LiNi made from the present embodiment0.6Co0.2Mn0.2O2Tertiary cathode material carries out X-ray diffraction analysis and electricity
Scarnning mirror, gained XRD spectrum and SEM figure are as depicted in figs. 1 and 2 respectively.
(- 30 DEG C of dew point) is prepared under environment in traditional lithium-ion battery slurry, it will be modified made from the present embodiment
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material, superconduction carbon black (SP) and PVDF binder are mixed by 94: 3: 3 weight ratio, with
NMP breaks into slurry by existing common process for solvent, the case where slurry becomes gel (g., jelly-like colloid) does not occur.
Slurry obtained above is coated on aluminium foil and obtains positive plate after drying.It is surveyed using 2032 type button half-cells
The chemical property of positive plate is tried, the cathode of 2032 type button half-cells is metal lithium sheet, and electrolyte uses LiPF6Concentration is
EC/DMC (volume ratio 1: 1) solution of 1.0M, diaphragm use business polyolefin.Positive electric discharge for the first time is held under the conditions of 0.2C
Amount is 193.7mAh/g, and capacity is 184.6mAh/g after 50 circle of circulation, and capacity retention ratio 95.3%, charging and discharging curve is as schemed
Shown in 3；Capacity is 176.8mAh/g after 50 circle of circulation under the conditions of 1C, and capacity retention ratio 98.2%, charging and discharging curve is such as
Shown in Fig. 4.As it can be seen that the LiNi of preparation of the present invention0.6Co0.2Mn0.2O2High discharge capacity that tertiary cathode material has, height
The characteristics of electrochemical stability.
Comparative example 1
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) it takes nickel sulfate, cobaltous sulfate and manganese sulfate soluble in water, obtains mixed liquor, control total metal ion in mixed liquor
Concentration be 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion be 6: 2: 2；
1.2) precipitating reagent is added into mixed liquor and complexing agent carries out coprecipitation reaction, in which:
Design coprecipitation reaction total time is 6h；
The precipitating reagent is the sodium hydroxide solution that concentration is 2mol/L, and dosage is to control entire coprecipitation reaction process
The pH=11.0-11.5 of middle system is added dropwise and runs through entire coprecipitation reaction process；The complexing agent is that concentration is 25%
Ammonium hydroxide；
The complexing agent control has dropped evenly in 6h；
After the completion of coprecipitation reaction, precipitating is collected in the filtering of gained reactant material, dry under the conditions of 80 DEG C after washing, is obtained
To nickel cobalt manganese hydroxide precursor；
2) that nickel cobalt manganese hydroxide precursor and lithium hydroxide are placed in drum type high-speed stirrer for mixing is uniform, wherein
The dosage of lithium hydroxide is according to LiNi0.6Co0.2Mn0.2O21.03 times of theoretical lithium content, gained mixture is placed in oxic gas
6h is kept the temperature under the conditions of 760 DEG C in atmosphere, obtains LiNi0.6Co0.2Mn0.2O2Tertiary cathode material.
To LiNi made from this comparative example0.6Co0.2Mn0.2O2Tertiary cathode material carries out X-ray diffraction analysis and Electronic Speculum is swept
It retouches, gained XRD spectrum and SEM figure are as shown in Figure 5 and Figure 6 respectively.
It, will be made from this comparative example in the case where pulp of lithium ion battery in the same manner as in Example 1 prepares environment
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material, SP and PVDF binder are mixed by 94: 3: 3 weight ratio, are pressed by solvent of NMP
The identical technique of embodiment 1 prepares slurry, and slurry fails because forming gel (g., jelly-like colloid) during sizing mixing, such as Fig. 7 institute
Show.
By LiNi made from this comparative example0.6Co0.2Mn0.2O2Tertiary cathode material washed, dried after by 1 phase of embodiment
Slurrying is carried out with Pulping conditions, anode sizing agent can be made.Press the identical pole piece preparation condition of embodiment 1 and battery pack again later
Condition test is filled, positive discharge capacity for the first time only has 142.8mAh/g under the conditions of 0.2C.
Comparative example 1 and comparative example 1, modified LiNi made from the method for the invention0.6Co0.2Mn0.2O2Tertiary cathode
The crystal structure of material does not change, and also generates without impurity phase；And its specific discharge capacity is high, is keeping stablizing chemical property
While, it eliminates during high nickel content tertiary cathode powder prepares cell size under normal conditions and is also easy to produce g., jelly-like glue
Body and the problem of fail.
Embodiment 2
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) it takes nickel sulfate, cobaltous sulfate and manganese sulfate soluble in water, obtains the first mixed liquor, control total in the first mixed liquor
The concentration of metal ion is 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion is 6: 2: 2；
1.2) magnesium sulfate is added into mixed liquor, dissolves, obtains the second mixed liquor；Wherein the additional amount of magnesium sulfate be nickel from
The 0.2% of sub, cobalt ions and manganese ion integral molar quantity；
1.3) precipitating reagent is added into the second mixed liquor and complexing agent carries out coprecipitation reaction, in which:
Design coprecipitation reaction total time is 6h, and institute's coprecipitation reaction process includes two stages, the respectively first reaction
Stage and second stage of reaction, wherein the reaction time of first stage of reaction is 4.8h, the reaction time of second stage of reaction is
1.2h (account for coprecipitation reaction total reaction time 20%)；
The precipitating reagent is the sodium hydroxide solution that concentration is 1mol/L, and dosage is to control entire coprecipitation reaction process
The pH=10-11 of middle system is added dropwise and runs through entire coprecipitation reaction process；The complexing agent includes the first complexing agent and the
Two complexing agents, wherein the first complexing agent is the ammonium hydroxide that concentration is 25%, the second complexing agent is the metatungstic acid that concentration is 0.2mol/L
Aqueous ammonium；
What is be added in first stage of reaction of coprecipitation reaction is the first complexing agent, and additional amount presses every liter of first mixed liquor
The first complexing agent of 10mL is added to calculate；The first complexing agent control has dropped evenly in 4.8h；
What is be added in second stage of reaction of coprecipitation reaction is the second complexing agent, and additional amount presses every liter of first mixed liquor
The second complexing agent of 60mL is added to calculate, the second complexing agent control has dropped evenly in 1.2h；
After the completion of coprecipitation reaction, precipitating is collected in the filtering of gained reactant material, dry under the conditions of 60 DEG C after washing, is obtained
To the nickel cobalt manganese hydroxide precursor of surface tungsten；
2) the nickel cobalt manganese hydroxide precursor and lithium hydroxide of surface tungsten are placed in drum type high-speed blender and are mixed
It closes uniformly, wherein the dosage of lithium hydroxide is according to LiNi0.6Co0.2Mn0.2O21.01 times of theoretical lithium content, gained mixing
Object, which is placed in oxidizing atmosphere, keeps the temperature 7h under the conditions of 720 DEG C, obtains the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder；
3) polyamic acid solution that solid content is 0.005% is obtained；
4) LiNi of surface tungsten is weighed by 1: 1 mass ratio0.6Co0.2Mn0.2O2Powder and solid content are 0.005%
Polyamic acid solution, later by the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder is placed in the polyamide that solid content is 0.005%
In acid solution, it is stirred 2h, is taken out, it is dry under the conditions of 120 DEG C, obtain the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2
Powder；
5) LiNi of gained polyamic acid cladding0.6Co0.2Mn0.2O2Powder is placed under vacuum condition, is warming up to 400 DEG C and (is risen
Warm rate is 5 DEG C/min) heat preservation 3h, it is passed through oxidizing atmosphere later, and be warming up to 680 DEG C of (heating rate is 5 DEG C/min) heat preservations
1h is to get to modified LiNi0.6Co0.2Mn0.2O2Tertiary cathode material.
(- 30 DEG C of dew point) is prepared under environment in traditional lithium-ion battery slurry, it will be modified made from the present embodiment
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material, superconduction carbon black (SP) and PVDF binder are mixed by 94: 3: 3 weight ratio, with
NMP breaks into slurry by existing common process for solvent, the case where slurry becomes gel (g., jelly-like colloid) does not occur.
Embodiment 3
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) it takes nickel sulfate, cobaltous sulfate and manganese sulfate soluble in water, obtains the first mixed liquor, control total in the first mixed liquor
The concentration of metal ion is 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion is 6: 2: 2；
1.2) magnesium sulfate is added into mixed liquor, dissolves, obtains the second mixed liquor；Wherein the additional amount of magnesium sulfate be nickel from
The 0.08% of sub, cobalt ions and manganese ion integral molar quantity；
1.3) precipitating reagent is added into the second mixed liquor and complexing agent carries out coprecipitation reaction, in which:
Design coprecipitation reaction total time is 6h, and institute's coprecipitation reaction process includes two stages, the respectively first reaction
Stage and second stage of reaction, wherein the reaction time of first stage of reaction is 5.28h, the reaction time of second stage of reaction is
0.72h (account for coprecipitation reaction total reaction time 12%)；
The precipitating reagent is the sodium hydroxide solution that concentration is 5mol/L, and dosage is to control entire coprecipitation reaction process
The pH=12-13 of middle system is added dropwise and runs through entire coprecipitation reaction process；The complexing agent includes the first complexing agent and the
Two complexing agents, wherein the first complexing agent is the ammonium hydroxide that concentration is 25%, the second complexing agent is the metatungstic acid that concentration is 0.5mol/L
Aqueous ammonium；
What is be added in first stage of reaction of coprecipitation reaction is the first complexing agent, and additional amount presses every liter of first mixed liquor
The first complexing agent of 25mL is added to calculate；The first complexing agent control has dropped evenly in 5.28h；
What is be added in second stage of reaction of coprecipitation reaction is the second complexing agent, and additional amount presses every liter of first mixed liquor
The second complexing agent of 40mL is added to calculate, the second complexing agent control has dropped evenly in 0.72h；
After the completion of coprecipitation reaction, precipitating is collected in the filtering of gained reactant material, dry under the conditions of 80 DEG C after washing, is obtained
To the nickel cobalt manganese hydroxide precursor of surface tungsten；
2) the nickel cobalt manganese hydroxide precursor and lithium hydroxide of surface tungsten are placed in drum type high-speed blender and are mixed
It closes uniformly, wherein the dosage of lithium hydroxide is according to LiNi0.6Co0.2Mn0.2O21.05 times of theoretical lithium content, gained mixing
Object, which is placed in oxidizing atmosphere, keeps the temperature 6h under the conditions of 780 DEG C, obtains the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder；
3) polyamic acid solution that solid content is 0.001% is obtained；
4) LiNi of surface tungsten is weighed by 1: 1 mass ratio0.6Co0.2Mn0.2O2Powder and solid content are 0.001%
Polyamic acid solution, later by the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder is placed in the polyamide that solid content is 0.001%
In acid solution, it is stirred 1h, is taken out, it is dry under the conditions of 200 DEG C, obtain the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2
Powder；
5) LiNi of gained polyamic acid cladding0.6Co0.2Mn0.2O2Powder is placed under vacuum condition, is warming up to 300 DEG C and (is risen
Warm rate is 5 DEG C/min) heat preservation 2h, it is passed through oxidizing atmosphere later, and be warming up to 600 DEG C of (heating rate is 5 DEG C/min) heat preservations
3h is to get to modified LiNi0.6Co0.2Mn0.2O2Tertiary cathode material.
(- 30 DEG C of dew point) is prepared under environment in traditional lithium-ion battery slurry, it will be modified made from the present embodiment
LiNi0.6Co0.2Mn0.2O2Tertiary cathode material, superconduction carbon black (SP) and PVDF binder are mixed by 94: 3: 3 weight ratio, with
NMP breaks into slurry by existing common process for solvent, the case where slurry becomes gel (g., jelly-like colloid) does not occur.
Claims (9)
1. a kind of modified LiNi0.6Co0.2Mn0.2O2The preparation method of tertiary cathode material, comprising the following steps:
1) nickel cobalt manganese hydroxide precursor is prepared:
1.1) it takes nickel salt, cobalt salt and manganese salt soluble in water, obtains the first mixed liquor, control total metal ion in the first mixed liquor
Concentration is 2mol/L, and the molar ratio of nickel ion, cobalt ions and manganese ion is 6: 2: 2；
1.2) magnesium sulfate is added into mixed liquor, dissolves, obtains the second mixed liquor；Wherein the additional amount of magnesium sulfate be nickel ion,
The 0.05-0.25% of cobalt ions and manganese ion integral molar quantity；
1.3) precipitating reagent is added into the second mixed liquor and complexing agent carries out coprecipitation reaction, in which: the coprecipitation reaction mistake
Journey includes two stages, respectively first stage of reaction and second stage of reaction, wherein the reaction time of second stage of reaction accounts for
The 12-20% of coprecipitation reaction total reaction time；
The complexing agent includes the first complexing agent and the second complexing agent, wherein the first complexing agent is ammonium hydroxide, the second complexing agent is inclined
Ammonium tungstate aqueous solution；
What is be added in first stage of reaction of coprecipitation reaction is the first complexing agent, and the first complexing agent is complete in first stage of reaction
Journey is uniformly added into；When the first complexing agent is the ammonium hydroxide that concentration is 25%, 10- is added by every liter of first mixed liquor in additional amount
The first complexing agent of 50mL calculates；
What second stage of reaction was added is the second complexing agent, and the second complexing agent is uniformly added into the second stage of reaction whole process；When
When the concentration of second complexing agent is 0.2-0.5mol/L, additional amount is added 40-60mL second by every liter of first mixed liquor and is complexed
Agent calculates；
During entire coprecipitation reaction, the dosage of precipitating reagent is the pH=10-13 of control system, and after the reaction was completed, gained is anti-
Material filtering is answered, precipitating is collected and is dried, obtain the nickel cobalt manganese hydroxide precursor of surface tungsten；
2) the nickel cobalt manganese hydroxide precursor and lithium source of surface tungsten are uniformly mixed, are heat-treated in oxidizing atmosphere,
Obtain the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder；
3) polyamic acid solution is obtained；
4) by the LiNi of surface tungsten0.6Co0.2Mn0.2O2Powder is placed in polyamic acid solution, is stirred certain time, is taken
Out, dry, obtain the LiNi of polyamic acid cladding0.6Co0.2Mn0.2O2Powder；
5) LiNi of gained polyamic acid cladding0.6Co0.2Mn0.2O2Powder, which is placed under vacuum condition, carries out Low Temperature Heat Treatment, later
Medium temperature heat treatment is carried out in oxidizing atmosphere to get the modification LiNi is arrived0.6Co0.2Mn0.2O2Tertiary cathode material.
2. preparation method according to claim 1, it is characterised in that: in step 1.3), in entire coprecipitation reaction process
In, the dosage of precipitating reagent is the pH=10.5-11.5 of control system.
3. preparation method according to claim 1, it is characterised in that: in step 1.3), the precipitating reagent is that concentration is
The sodium hydroxide solution or potassium hydroxide solution of 1-5mol/L.
4. preparation method according to claim 1, it is characterised in that: in step 3), the polyamic acid solution is solid
Content is the polyamic acid solution of 0.001-0.005%.
5. preparation method according to claim 1, it is characterised in that: in step 4), time >=0.1h for being stirred.
6. preparation method according to claim 1, it is characterised in that: in step 5), the Low Temperature Heat Treatment be
1-4h is kept the temperature under the conditions of 300-400 DEG C.
7. preparation method according to claim 1, it is characterised in that: in step 5), the described medium temperature heat treatment be
2-6h is kept the temperature under the conditions of 600-680 DEG C.
8. the modification LiNi that any one of claim 1-7 the method is prepared0.6Co0.2Mn0.2O2Tertiary cathode material.
9. a kind of lithium ion battery, including positive plate, it is characterised in that: the positive electrode used on the positive plate is wanted for right
Modification LiNi described in asking 80.6Co0.2Mn0.2O2Tertiary cathode material.
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