CN107204426A - A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property - Google Patents
A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property.The cobalt nickel oxide manganses lithium anode material that the positive electrode is adulterated with Co deposited synthesis zirconium first, is then coated using lithium titanate active electrode material to ternary material.On the one hand electronic conductivity and ionic conductivity can be improved, the output power density of battery is improved, but also the structural stability of ternary material can be improved.On the other hand, by cladding can integrate the advantage of two kinds of materials so that obtain cyclicity preferably, the composite positive pole that capacity is higher, energy density is larger.
Description
Technical field
The invention belongs to field of lithium ion battery anode, more particularly to a kind of cobalt nickel oxide manganses lithium of zirconium doping vario-property/
Titanate composite anode material for lithium.
Background technology
Lithium ion battery is the secondary cell of new generation developed rapidly 1990s, is widely used in miniature portable
Formula electronic communication product and electric vehicle.The anode material for lithium-ion batteries of current industrialization mainly have cobalt acid lithium,
Modified lithium manganate, ternary material, LiFePO4 etc..Cobalt acid lithium is mainly used in small-sized lithium ion battery with high energy density field,
But cobalt toxicity is larger, scarcity of resources is expensive, and its overcharge safety can be poor.Lithium manganate having spinel structure specific capacity is low, and
High temperature circulation and storage performance are poor.The disposable poor, poor performance at low temperatures of LiFePO4 poorly conductive, product batches, and exist micro
The problem of dissolving of iron may cause battery short circuit.Therefore, research is found, with LiNixMnyCo1-x-yO2 For the stratiform oxygen of representative
Change nickel cobalt manganese series material（Abbreviation ternary material）Preferably the advantage of above-mentioned material has been had both, and make up it to a certain extent
Deficiency, the features such as with height ratio capacity, stable cycle performance, advantage of lower cost, preferable security performance, it is considered to be for mixing
The ideal chose of mould assembly electrical source of power.But simultaneously it there is also relatively low electrical conductivity and capacity attenuation are fast, high rate performance is not good etc.
Shortcoming.
Current LiNixMnyCo1-x-yO2Preparation method mainly have high temperature solid-state method, coprecipitation, sol-gel process etc..
This problem prepares the thinner nickel-cobalt lithium manganate material of particle using coprecipitation, shortens the diffusion path of lithium ion, improves it
Chemical property.Material prepared by coprecipitation can reach the mixing of molecule or atomic level, solve conventional solid-state method and mix
Material is uneven and the problem of excessive particle diameter, and the material purity prepared is high, particle diameter is small, narrow distribution and sintering character is good.
LiNixMnyCo1-x-yO2Positive electrode set LiNiO2、LiCoO2、LiMnO2Three kinds of positive electrode advantages, possess
Excellent cost performance and chemical property, are used widely in electronic product, are expected to replace LiCoO2Positive electrode, is recognized
To be one of most potential wide variety of positive electrode.LiNixMnyCo1-x-yO2Material is in cobalt nickel lithium manganate ternary material system
Middle excellent performance, obtains the concern of domestic and international many research institutions, is not only widely used in small-sized electronic product, large-scale
Also there is preferable development trend on automobile power cell, with good application prospect.But simultaneously it there is also relatively low conductance
The shortcomings of rate and capacity attenuation are fast, high rate performance is not good, in order to obtain more excellent tertiary cathode material, to nickle cobalt lithium manganate
It is doped and coats.Lattice is occurred certain distortion by ion doping, produce certain defect, improve electronic conductivity
And ion diffusion rates, to improve high rate performance and cycle performance.
Lithium titanate is " zero strain " material, during Lithium-ion embeding is deviate from, the structure of energy stabilizing material；Its
Secondary, in Li-Ti-O, the bond energy of Ti-O keys is more than the bond energy of M-O (M=Mn, Ni, Go) key, i.e. Ti4+Ion ratio Mx+Ion pair oxygen
With stronger binding force, the layer structure of energy stabilizing material；Furthermore, in Li-Ti-O, lithium is a fast lithium ion conductor.
The material is introduced into the lithium ion diffusion coefficient high-transmission passage that can expand in ternary material；Finally, in nickel cobalt manganese stratiform knot
Lithium titanate spinel component is implanted into structure, coulombic efficiency first can be improved, suppresses irreversible capacity loss, this is primarily due to
Lithium titanate can receive the unnecessary lithium ion of the deintercalation from nickel cobalt manganese material.So, the nickel that zirconium adulterates is coated by lithium titanate
Cobalt-manganese ternary material, can not only improve the security of material, can also improve the cycle performance of material, improve active material profit
With rate.
The content of the invention
The present invention is intended to provide a kind of use zirconium Y-oxides doping cobalt manganese lithium anode material, and lithium titanate is used on its basis
Cladding, technical problem to be solved is ternary layered positive pole material cobalt nickel oxide manganses lithium poor repeatability and high rate performance, simultaneously
A kind of nickel cobalt manganese lithium anode material of the zirconium doping for the lithium titanate cladding that technical process is simple, safe, stability is good is provided.
The present invention solves technical problem and adopted the following technical scheme that：
A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property, it is characterised in that：Preparing includes following step
Suddenly：
(1) lithium source, part cobalt source, manganese source, zirconium source are dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol,
Labeled as solution A, nickel source, remaining cobalt source are dissolved according to certain mol proportion in the solution of water and ethanol, labeled as solution
B, two oxalic acid hydrates is dissolved in water and ethanol solution, labeled as solution C；Solution A is poured into solution C first, reaction 10 ~
After 12min, then B solution poured into A and C mixed solution, react 5 ~ 6h, be allowed to precipitation completely；Reacted material is put
After being dried in drying box, powder is obtained, then is ground, is then placed in crucible, after calcining, obtains black powder；By powder
End is ground, and crosses 400 ~ 500 mesh sieves, you can obtain the cobalt nickel oxide manganses lithium LiNi of zirconium dopingxCoyMnl-x-y-zZrzO2Positive pole
Material, wherein 0<x<0.6,0<y<0.6,0<z<0.1；
(2) by lithium titanate and above-mentioned（1）The LiNi of preparationxCoyMn1-x-y-zZrzO2Positive electrode is placed in absolute ethyl alcohol/isopropanol
In solution, concentration is 0.01 ~ 0.02mol/L, then heating stirring is evaporated at 75 ~ 85 DEG C, and grinds sieving, obtains presoma,
The presoma is placed in Muffle furnace, heated up with 3 ~ 5 DEG C/min speed, 2 ~ 5h is calcined at 600 ~ 800 DEG C, is subsequently cooled to
Room temperature, obtains LiNixCoyMn1-x-y-zZrzO2/ LTO positive electrodes.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that described nickel
Source is the one or more in nickelous carbonate, nickel acetate, nickel nitrate；
Described cobalt source is the one or more in cobalt carbonate, cobalt acetate, cobalt nitrate；
Described manganese source is the one or more in manganese carbonate, manganese acetate, manganese nitrate；
Described zirconium source is the one or more in zirconium nitrate, basic zirconium phosphate, zirconium chloride；
Described lithium salts is the one or more in lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide；
Described water and the mixed solution reclaimed water of absolute ethyl alcohol and the volume ratio of absolute ethyl alcohol are 1：0~10.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that by lithium source,
Part cobalt source, manganese source, zirconium source are dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol, concentration be 0.1 ~
0.15mol/L, labeled as solution A；Nickel source, remaining cobalt source are dissolved according to certain mol proportion in the solution of water and ethanol,
Concentration be 0.03 ~ 0.04mol/L, labeled as solution B, two oxalic acid hydrates are dissolved in water and ethanol solution, concentration be 0.15 ~
0.2mol/L, labeled as solution C.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that：Step（1）
Described drying is referred in 70 ~ 90 DEG C of dry 8 ~ 12h；The calcination process is first to be warming up to 300 ~ 600 DEG C of 4 ~ 10h of calcining,
700 ~ 950 DEG C of 10 ~ 24h of calcining are warming up to again.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that：Step（2）
It is middle that the presoma is placed in Muffle furnace, heated up with 4 DEG C/min speed.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that the metatitanic acid
The consumption of lithium accounts for the 0.5% ~ 15% of cobalt nickel oxide manganses lithium quality.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that described titanium
The preparation method of sour lithium comprises the following steps：
(1) titanium source compound is dissolved in absolute ethyl alcohol, both volume ratios are 1:1 ~ 1.2 forms solution A；Li source compound is dissolved in
In deionized water, it is configured to certain density containing Li+Solution；
(2) the certain density of above-mentioned preparation is added dropwise into solution A under magnetic stirring and contains Li+Solution, formed white
Suspension B, continues to stir 1 ~ 1.5 h energetically；
(3) the white suspension B is transferred in stainless steel autoclave, be put into air blast electrically heated drying cabinet 120 ~
Room temperature is naturally cooled to after 12 ~ 24h of successive reaction at 200 DEG C, gains are centrifuged, wash, are dried to obtain precursor powder；
(4) white powder for obtaining the presoma after 2 ~ 12h of calcining in Muffle furnace, under air atmosphere, at 500 ~ 800 DEG C
As obtained lithium titanate.
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of described zirconium doping vario-property, it is characterised in that the titanium source
Compound is the one or more in butyl titanate, tetraisopropyl titanate, titanium tetrachloride, Nano titanium dioxide；
The Li source compound is the one or more in lithium hydroxide, lithium acetate, lithium carbonate, lithia；
The mol ratio between the Ti in Li and titanium source in the lithium source is 0.8 ~ 1；
What the Li source compound was configured to contains Li+Solution concentration be 1 ~ 5mol/L；
Heating rate when being calcined described in the preparation method of lithium titanate is 4 DEG C/min.
Compared with prior art, the present invention has the beneficial effect that：
1st, composite positive pole of the present invention is a kind of more height ratio capacity, the LiNi of more preferable high rate performancexCoyMn1-x-y-zZrzO2/
LTO composite positive poles.
2nd, the present invention is simple and easy to apply, and production efficiency is high, reduces production process, saves production cost, proper scale
Production, compared with the material not being modified, has obtained very big carry on battery capacity, high rate performance and cycle performance
It is high.
3rd, the present invention is implanted into lithium titanate spinel component in the cobalt nickel oxide manganses lithium structure that zirconium adulterates, energy stabilizing material
Layer structure, improves security；Lithium titanate can receive the unnecessary lithium ion deviate from from nickel cobalt manganese material, can improve first
Coulombic efficiency, suppresses irreversible capacity loss.
Brief description of the drawings
Fig. 1 is LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2XRD spectrum.
Fig. 2 is LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2And LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/ LTO XRD spectrum.
Fig. 3 is LiNi1/3Co1/3Mn1/3O2、LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2And LiNi1/3Co1/3Mn1/3- 0.02Zr0.02O2/ LTO first charge-discharge curves under 0.2C.
Fig. 4 is LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2The cycle performance of composite positive pole
Figure.
Fig. 5 is LiNi prepared by embodiment 21/3Co1/3Mn1/3-0.02Zr0.02O2FE-SEM figure.
Embodiment
In order to further appreciate that present disclosure feature and beneficial effect, below by specific example with reference
The present invention is described in further detail.
Embodiment 1：
Lithium ion battery cobalt nickel oxide manganses lithium anode material is prepared according to following steps in the present embodiment：
0.536g lithium acetates, 0.409g manganese acetates, 0.276g cobalt acetates are weighed, the mixing for being dissolved in 10ml water and 50ml ethanol is molten
In liquid, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；Weigh 0.415g nickel acetates,
0.138g cobalt acetates are dissolved in the mixed solution of 10ml water and 50ml ethanol, are designated as B solution；Weigh 1.1649g bis- and be hydrated grass
In acid, the mixed solution for being dissolved in 10ml water and 50ml ethanol, C solution is designated as.Solution A is added drop-wise in C solution, is allowed to heavy
Form sediment, after 10min, B solution is poured into C, 5h is reacted at room temperature.Then 12h is dried at 80 DEG C in an oven, grinding obtains forerunner
Body powder.Presoma is placed on into crucible to be built in Muffle furnace, is warming up in air atmosphere with 4 DEG C/min heating rate
500 DEG C, 6h is calcined, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, sample is taken out and regrinds
To LiNi1/3Co1/3Mn1/3O2Powder.
By obtained LiNi1/3Co1/3Mn1/3O2With acetylene black and Kynoar（PVDF）By 8:1:1 mass ratio is mixed
Close uniform, be rolled into thick 120 μm film, after 120 DEG C are dried in vacuo 10h, be used as the positive pole of experiment half-cell；Using l
mol/L LiPF6/ ethylene carbonate（EC）- dimethyl carbonate（DMC）(EC and DMC volume ratio 1:1）Electrolyte, dry
In the dry glove box full of argon gas, using metal lithium sheet as negative pole, battery is assembled into.With the LiNi prepared by the present embodiment1/ 3Co1/3Mn1/3O2For positive pole, using lithium piece as the button cell of negative pole, in 2.5 ~ 4.3V voltage ranges, with constant current under 0.1C multiplying powers-
First discharge specific capacity is 166.3mAh/g during constant-current discharge under constant-voltage charge, 0.2C multiplying powers, but the capacity after 50 times circulate
Only 125.32mAh/g.
Embodiment 2：
Lithium ion battery with the cobalt nickel oxide manganses lithium anode material of zirconium doping vario-property is prepared according to following steps in the present embodiment
Obtain：
A, 0.536g lithium acetates, 0.409g manganese acetates, 0.276g cobalt acetates are weighed, be dissolved in the mixing of 10ml water and 50ml ethanol
In solution, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；Weigh 0.415g nickel acetates,
0.138g cobalt acetates are dissolved in the mixed solution of 10ml water and 50ml ethanol, are designated as B solution；Weigh 1.1649g bis- and be hydrated grass
In acid, the mixed solution for being dissolved in 10ml water and 50ml ethanol, C solution is designated as.Solution A is added drop-wise in C solution, is allowed to heavy
Form sediment, after 10min, B solution is poured into C, 5h is reacted at room temperature.Then 12h is dried at 80 DEG C in an oven, grinding obtains forerunner
Body powder.Presoma is placed on into crucible to be built in Muffle furnace, is warming up in air atmosphere with 4 DEG C/min heating rate
500 DEG C, 6h is calcined, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, sample is taken out and regrinds
To LiNi1/3Co1/3Mn1/3O2Powder.
B, 0.536g lithium acetates, 0.407g manganese acetates, 0.276g cobalt acetates, 0.045g zirconium nitrates are weighed, be dissolved in 10ml
In the mixed solution of water and 50ml ethanol, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；
Weigh 0.415g nickel acetates, 0.138g cobalt acetates to be dissolved in the mixed solution of 10ml water and 50ml ethanol, be designated as B solution；Claim
Take in the oxalic acid hydrates of 1.1649g bis-, the mixed solution for being dissolved in 10ml water and 50ml ethanol, be designated as C solution.Solution A is added dropwise
Into C solution, it is allowed to precipitate, after 10min, B solution is poured into C, 5h is reacted at room temperature.Then dry in an oven at 80 DEG C
12h, grinding obtains precursor powder.Presoma is placed on into crucible to be built in Muffle furnace, with 4 DEG C/min's in air atmosphere
Heating rate is warming up to 500 DEG C, calcines 6h, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, takes out
Sample regrinding obtains LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2Powder.
The LiNi prepared will be tested1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2X-ray diffraction
Spectrogram is shown in Fig. 1.From figure 1 it appears that the LiNi prepared1/3Co1/3Mn1/3-0.02Zr0.02O2Positive electrode with undoped with
LiNi1/3Co1/3Mn1/3O2The XRD peak shape of material is identical, miscellaneous peak does not occur, and this is probably that Zr enters LiNi1/3Col/3Mnl/ 3O2In lattice, the Mn on substitution portion4+, this illustrates that doping has no effect on main body layer structure.
By obtained LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2With acetylene black and Kynoar（PVDF）By 8:1:1
Mass ratio is well mixed, and is rolled into thick 120 μm film, after 120 DEG C are dried in vacuo 10h, is used as the positive pole of experiment half-cell；
Using l mol/L LiPF6/ ethylene carbonate（EC）- dimethyl carbonate（DMC）(EC and DMC volume ratio 1:1）Electrolysis
Liquid, in the dry glove box full of argon gas, using metal lithium sheet as negative pole, is assembled into battery.With prepared by the present embodiment
LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2For positive pole, using lithium piece as the button cell of negative pole, in 2.5 ~ 4.3V voltage ranges, with
First discharge specific capacity is 180.5mAh/g during constant-current discharge under constant current-constant-voltage charge under 0.1C multiplying powers, 0.2C multiplying powers, but is passed through
Capacity is only 137.54mAh/g after 50 circulations.
Embodiment 3：
Lithium ion battery with the cobalt nickel oxide manganses lithium anode material of zirconium doping vario-property is prepared according to following steps in the present embodiment
Obtain：
Weigh 0.536g lithium acetates, 0.381g manganese acetates, 0.276g cobalt acetates, 0.091g zirconium nitrates, be dissolved in 10ml water and
In the mixed solution of 50ml ethanol, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；Weigh
0.415g nickel acetates, 0.138g cobalt acetates are dissolved in the mixed solution of 10ml water and 50ml ethanol, are designated as B solution；Weigh
In the oxalic acid hydrates of 1.1649g bis-, the mixed solution for being dissolved in 10ml water and 50ml ethanol, C solution is designated as.Solution A is added drop-wise to C
In solution, be allowed to precipitate, in 10min after, B solution is poured into C, 5h is reacted at room temperature.Then dry in an oven at 80 DEG C
12h, grinding obtains precursor powder.Presoma is placed on into crucible to be built in Muffle furnace, with 4 DEG C/min's in air atmosphere
Heating rate is warming up to 500 DEG C, calcines 6h, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, takes out
Sample regrinding obtains LiNi1/3Co1/3Mn1/3-0.04Zr0.04O2Powder.
Composite positive pole manufactured in the present embodiment is assembled into battery, specific method be the same as Example 1, in 2.5 ~ 4.3V electricity
Scope is pressed, with constant current-constant-voltage charge under 0.1C multiplying powers, first discharge specific capacity is during constant-current discharge under 0.2C multiplying powers
177.3mAh/g, and capacity is maintained at 135.24mAh/g after 50 circulations.
Embodiment 4：
Lithium ion battery with the cobalt nickel oxide manganses lithium anode material of zirconium doping vario-property is prepared according to following steps in the present embodiment
Obtain：
Weigh 0.536g lithium acetates, 0.343g manganese acetates, 0.276g cobalt acetates, 0.1314g zirconium nitrates, be dissolved in 10ml water and
In the mixed solution of 50ml ethanol, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；Weigh
0.415g nickel acetates, 0.138g cobalt acetates are dissolved in the mixed solution of 10ml water and 50ml ethanol, are designated as B solution；Weigh
In the oxalic acid hydrates of 1.1649g bis-, the mixed solution for being dissolved in 10ml water and 50ml ethanol, C solution is designated as.Solution A is added drop-wise to C
In solution, be allowed to precipitate, in 10min after, B solution is poured into C, 5h is reacted at room temperature.Then dry in an oven at 80 DEG C
12h, grinding obtains precursor powder.Presoma is placed on into crucible to be built in Muffle furnace, with 4 DEG C/min's in air atmosphere
Heating rate is warming up to 500 DEG C, calcines 6h, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, takes out
Sample regrinding obtains LiNi1/3Co1/3Mn1/3-0.06Zr0.06O2Powder.
Composite positive pole manufactured in the present embodiment is assembled into battery, specific method be the same as Example 1, in 2.5 ~ 4.3V electricity
Scope is pressed, with constant current-constant-voltage charge under 0.1C multiplying powers, first discharge specific capacity is during constant-current discharge under 0.2C multiplying powers
168.7mAh/g, and capacity is maintained at 133.26mAh/g after 50 circulations.
Embodiment 5：
Cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property is prepared into according to following steps in the present embodiment
Arrive：
A, weigh 0.536g lithium acetates, 0.407g manganese acetates, 0.276g cobalt acetates, 0.045g zirconium nitrates, be dissolved in 10ml water and
In the mixed solution of 50ml ethanol, solution A is designated as, in order to make up the loss of lithium source in calcination process, lithium acetate excessive 5%；Weigh
0.415g nickel acetates, 0.138g cobalt acetates are dissolved in the mixed solution of 10ml water and 50ml ethanol, are designated as B solution；Weigh
In the oxalic acid hydrates of 1.1649g bis-, the mixed solution for being dissolved in 10ml water and 50ml ethanol, C solution is designated as.Solution A is added drop-wise to C
In solution, it is allowed to precipitate, after 10min, B solution is poured into C, 5h is reacted at room temperature.Then dry in an oven at 80 DEG C
12h, grinding obtains precursor powder.Presoma is placed on into crucible to be built in Muffle furnace, with 4 DEG C/min's in air atmosphere
Heating rate is warming up to 500 DEG C, calcines 6h, is further continued for being warming up to 850 DEG C, calcines 24h, then cool to room temperature with the furnace, takes out
Sample regrinding obtains LiNi1/3Co1/3Mn1/3O2Powder.
B, by LiNi obtained above1/3Co1/3Mn1/3-0.02Zr0.02O21.00g is weighed, magnetic in 20ml absolute ethyl alcohols is dissolved in
Power is stirred, and adds the lithium titanate powder 0.01g that mass ratio is 1%, is mixed solution and is stirred to be evaporated at 80 DEG C and obtains powder.
Gained powder is calcined into 3h at 500 DEG C again, you can obtain LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/ LTO powder.
The LiNi prepared will be tested1/3Co1/3Mn1/3-0.02Zr0.02O2And LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2/LTO
X-ray diffraction spectrogram see in Fig. 1.From figure 1 it appears that the LiNi prepared1/3Co1/3Mn1/3-0.02Zr0.02O2/ LTO is multiple
Close positive electrode and LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2The XRD peak shape of material is identical, miscellaneous peak does not occur, and this is probably
Zr enters LiNi1/3Col/3Mnl/3O2In lattice, the Mn on substitution portion4+, and the addition of lithium titanate has no effect on body layer
Shape structure.
With LiNi prepared by the present embodiment1/3Co1/3Mn1/3-0.02Zr0.02O2/ LTO is positive pole, using lithium piece as the button of negative pole
Battery, in 2.5 ~ 4.3V voltage ranges, with constant current-constant-voltage charge under 0.1C multiplying powers, puts first under 0.2C multiplying powers during constant-current discharge
Electric specific capacity is 182.7mAh/g, but capacity is 138.8mAh/g after 50 times circulate.
Do not have an impact the crystal structure of material, different dopings by the embodiment 1-4 doping that can be seen that zr element
Zr element can improve LiNi1/3Col/3Mnl/3O2The charge-discharge performance and cycle performance of ternary material.Also, doping is
2% LiNi1/3Co1/3Mn1/3-0.02Zr0.02O2Performance is best.The optimal doping of performance is obtained by doping, and on its basis
Upper progress lithium titanate cladding.Pass through XRD, it can be seen that cladding does not also change the crystal structure of material, and charge and discharge electrical measurement
Examination display, the charge-discharge performance and cycle performance of material have obtained further raising.As can be seen here, not only doping is improved
The performance of ternary material, and coated can also improve its performance on its basis.
Claims (6)
1. a kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property, it is characterised in that：Prepare including as follows
Step：
(1) lithium source, part cobalt source, manganese source, zirconium source are dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol,
Labeled as solution A, nickel source, remaining cobalt source are dissolved according to certain mol proportion in the solution of water and ethanol, labeled as solution
B, two oxalic acid hydrates is dissolved in water and ethanol solution, labeled as solution C；Solution A is poured into solution C first, reaction 10 ~
After 12min, then B solution poured into A and C mixed solution, react 5 ~ 6h, be allowed to precipitation completely；Reacted material is put
After being dried in drying box, powder is obtained, then is ground, is then placed in crucible, after calcining, obtains black powder；By powder
End is ground, and crosses 400 ~ 500 mesh sieves, you can obtain the cobalt nickel oxide manganses lithium LiNi of zirconium dopingxCoyMnl-x-y-zZrzO2Positive pole
Material, wherein 0<x<0.6,0<y<0.6,0<z<0.1；
(2) by lithium titanate and above-mentioned（1）The LiNi of preparationxCoyMn1-x-y-zZrzO2It is molten that positive electrode is placed in absolute ethyl alcohol/isopropanol
In liquid, concentration is 0.01 ~ 0.02mol/L, then heating stirring is evaporated at 75 ~ 85 DEG C, and grinds sieving, obtains presoma, will
The presoma is placed in Muffle furnace, is heated up with 3 ~ 5 DEG C/min speed, and 2 ~ 5h is calcined at 600 ~ 800 DEG C, room is subsequently cooled to
Temperature, obtains LiNixCoyMn1-x-y-zZrzO2/ LTO positive electrodes.
2. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists
In described nickel source is the one or more in nickelous carbonate, nickel acetate, nickel nitrate；
Described cobalt source is the one or more in cobalt carbonate, cobalt acetate, cobalt nitrate；
Described manganese source is the one or more in manganese carbonate, manganese acetate, manganese nitrate；
Described zirconium source is the one or more in zirconium nitrate, basic zirconium phosphate, zirconium chloride；
Described lithium salts is the one or more in lithium carbonate, lithium acetate, lithium nitrate, lithium hydroxide；
Described water and the mixed solution reclaimed water of absolute ethyl alcohol and the volume ratio of absolute ethyl alcohol are 1：0~10.
3. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists
In lithium source, part cobalt source, manganese source, zirconium source being dissolved according to certain mol proportion in the mixed solution of water and absolute ethyl alcohol, concentration
For 0.1 ~ 0.15mol/L, labeled as solution A；Nickel source, remaining cobalt source are dissolved in the molten of water and ethanol according to certain mol proportion
In liquid, concentration is 0.03 ~ 0.04mol/L, labeled as solution B, two oxalic acid hydrates is dissolved in water and ethanol solution, concentration is
0.15 ~ 0.2mol/L, labeled as solution C.
4. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists
In：Step（1）Described drying is referred in 70 ~ 90 DEG C of dry 8 ~ 12h；The calcination process is first to be warming up to 300 ~ 600 DEG C
4 ~ 10h is calcined, then is warming up to 700 ~ 950 DEG C of 10 ~ 24h of calcining.
5. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists
In：Step（2）It is middle that the presoma is placed in Muffle furnace, heated up with 4 DEG C/min speed.
6. cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property according to claim 1, its feature exists
In the consumption of the lithium titanate accounts for the 0.5% ~ 15% of cobalt nickel oxide manganses lithium quality.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037609A (en) * | 2018-07-03 | 2018-12-18 | 江苏乐能电池股份有限公司 | A kind of porous triple composite positive pole and preparation method thereof |
| CN109873140A (en) * | 2019-02-18 | 2019-06-11 | 合肥工业大学 | A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof |
| CN111446433A (en) * | 2020-04-23 | 2020-07-24 | 华鼎国联四川电池材料有限公司 | Positive electrode composite material for lithium battery and preparation method thereof |
| CN112928253A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-manganese-titanium composite material and preparation method and application thereof |
| CN113651373A (en) * | 2021-10-19 | 2021-11-16 | 河南科隆新能源股份有限公司 | Anode material with uniform porous structure and preparation method thereof |
| CN113809329A (en) * | 2020-06-11 | 2021-12-17 | 中国科学院上海硅酸盐研究所 | Modified positive electrode for high-voltage lithium ion battery and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161713A (en) * | 2015-09-10 | 2015-12-16 | 朱振业 | Positive electrode material of lithium ion battery and preparation method of positive electrode material |
| CN105958052A (en) * | 2016-05-29 | 2016-09-21 | 合肥国轩高科动力能源有限公司 | Preparation method for metal-element-doped manganese-based positive electrode material for lithium ion battery |
-
2017
- 2017-06-09 CN CN201710432855.5A patent/CN107204426A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161713A (en) * | 2015-09-10 | 2015-12-16 | 朱振业 | Positive electrode material of lithium ion battery and preparation method of positive electrode material |
| CN105958052A (en) * | 2016-05-29 | 2016-09-21 | 合肥国轩高科动力能源有限公司 | Preparation method for metal-element-doped manganese-based positive electrode material for lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| LI-NA CONG ET AL: ""Enhancement of electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 by surface modification with Li4Ti5O12"", 《ELECTROCHIMICA ACTA》 * |
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| CN109037609A (en) * | 2018-07-03 | 2018-12-18 | 江苏乐能电池股份有限公司 | A kind of porous triple composite positive pole and preparation method thereof |
| CN109873140A (en) * | 2019-02-18 | 2019-06-11 | 合肥工业大学 | A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof |
| CN109873140B (en) * | 2019-02-18 | 2021-09-17 | 合肥工业大学 | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material |
| CN111446433A (en) * | 2020-04-23 | 2020-07-24 | 华鼎国联四川电池材料有限公司 | Positive electrode composite material for lithium battery and preparation method thereof |
| CN113809329A (en) * | 2020-06-11 | 2021-12-17 | 中国科学院上海硅酸盐研究所 | Modified positive electrode for high-voltage lithium ion battery and preparation method thereof |
| CN113809329B (en) * | 2020-06-11 | 2023-07-11 | 中国科学院上海硅酸盐研究所 | Modified positive electrode for high-voltage lithium ion battery and preparation method thereof |
| CN112928253A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-manganese-titanium composite material and preparation method and application thereof |
| CN113651373A (en) * | 2021-10-19 | 2021-11-16 | 河南科隆新能源股份有限公司 | Anode material with uniform porous structure and preparation method thereof |
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Application publication date: 20170926 |