CN108899535A - Lithium ion battery tertiary cathode modified material and preparation method thereof - Google Patents
Lithium ion battery tertiary cathode modified material and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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 present invention provides a kind of lithium ion battery tertiary cathode modified materials and preparation method thereof, including：Pure phase ternary anode material for lithium-ion batteries and the clad that the pure phase ternary anode material for lithium-ion batteries surface is arranged in, clad is manganese dioxide.The present invention passes through surface depositing homogeneous and complete manganese dioxide clad of the precipitation method in pure phase ternary anode material for lithium-ion batteries, the contact probability between active material and electrolyte can be reduced, it can effectively inhibit electrolyte to the corrosiveness of active material, simultaneously, it is suppressed that side reaction between the two；And, improve the structural stability of positive electrode, the volume change of positive electrode in charge and discharge process can also be alleviated, it is more conducive to the deintercalation of lithium ion, the phenomenon that alleviate active material capacity attenuation, so that modified ternary cathode material of lithium ion battery has preferable stability and cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, modified in particular to a kind of lithium ion battery tertiary cathode
Material and preparation method thereof.
Background technique
Today's society economic development is very rapid, and people's lives level is continuously improved, need of the human society for the energy
It asks and also increasingly rises therewith.However the non-renewable fossil energy such as coal, petroleum, natural gas has been far from satisfying people
Growing energy demand, and problem of environmental pollution caused by combustion of fossil fuels is also got worse, wherein PM2.5
Most noticeable, many city hazes are serious, therefore the main task of today's society is that searching and development high-efficiency environment friendly are sustainable
The new energy of development.The device that chemical energy can be converted to electric energy is known as electrochmical power source, has been subjected to many researchers
Extensive concern.Wherein, secondary cell first entered the public visual field in 1899, is a kind of novel electrochmical power source, realizes
The reversible transformation of electric energy and chemical energy, secondary cell have that at low cost, specific energy is high, high-efficient environmentally friendly and follow
The advantages that ring is functional is therefore widely used in social life every field, pushes the fast development of social economy.
Representative secondary cell has lead-acid accumulator, ickel-cadmium cell, nickel-metal hydride battery and lithium ion battery, relatively
In other secondary cells, lithium ion battery because operating voltage is high, energy density is big, good rate capability, long service life and
Environmentally friendly equal many merits, are current comprehensive performance secondary chemical sources of electric energy the most excellent.In recent years, lithium ion battery
Application field it is more and more extensive, with the development of electric vehicle (EV) and hybrid electric vehicle (HEV), high specific energy and high power are
Important directions as Study on Li-ion batteries from now on and development.Key component of the positive electrode as lithium ion battery, grinds
Studying carefully seems especially urgent with exploitation.
Lithium ion battery LiNi1/3Co1/3Mn1/3O2Tertiary cathode material specific discharge capacity is high, but in the process of circulation
In its capacity attenuation it is serious.
Summary of the invention
In consideration of it, the invention proposes a kind of lithium ion battery tertiary cathode modified materials and preparation method thereof, it is intended to solve
Certainly existing lithium ion battery LiNi1/3Co1/3Mn1/3O2The serious problem of tertiary cathode material capacity attenuation.
Specifically, first aspect present invention proposes a kind of lithium ion battery tertiary cathode modified material, the lithium ion
Battery tertiary cathode modified material includes pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2With setting in institute
State pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2The clad on surface, wherein the material of the clad
Material is manganese dioxide, and cheap, from a wealth of sources, the preparation process of complex compound is relatively simple and complex reaction can
Adequately generate；Simultaneously as MnO2Active force between molecule is larger, it is difficult to mix positive electrode LiNi1/3Co1/3Mn1/ 3O2Internal structure in, therefore will not having an impact to the crystal structure of positive electrode itself.It is pure in the embodiment of the present invention
Phase LiNi1/3Co1/3Mn1/3O2For commercial product, without limitation to its source.
Further, in above-mentioned lithium ion battery tertiary cathode modified material, the material of the clad and the pure phase
Ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2Mass ratio be (0.01-0.05)：1；Preferably (0.02-
0.04):1；Further preferably 0.03:1.The coating layer material and pure phase ternary lithium ion cell positive material of appropriate mass ratio
Expect LiNi1/3Co1/3Mn1/3O2, the clad type positive electrode of stable structure can be formed, and it is preferable steady to have the positive electrode
Qualitative and preferable chemical property, in addition, also the capacity of positive electrode can be adjusted by adjusting the mass ratio.
Correspondingly, the molecular formula of the lithium ion battery tertiary cathode modified material can be expressed as in the present embodiment：x
MnO2/LiNi1/3Co1/3Mn1/3O2, x=0.01,0.02,0.03,0.04 or 0.05.
The lithium ion battery tertiary cathode modified material that first aspect present invention provides, by the precipitation method in pure phase ternary
Anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2Surface depositing homogeneous and complete manganese dioxide clad, energy
Reduce active material LiNi1/3Co1/3Mn1/3O2Contact probability between electrolyte effectively can inhibit electrolyte to activity
Substance LiNi1/3Co1/3Mn1/3O2Corrosiveness, simultaneously, it is suppressed that side reaction between the two；Also, improve positive material
The structural stability of material can also alleviate the volume change of positive electrode in charge and discharge process, be more conducive to the de- of lithium ion
It is embedding, thus the phenomenon that alleviating active material capacity attenuation so that modified ternary cathode material of lithium ion battery have compared with
Good stability and cycle performance.
Second aspect of the present invention provides a kind of preparation method of lithium ion battery tertiary cathode modified material, including with
Lower step：
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to solvent
In, it is uniformly dispersed, then appropriate manganese salt is added thereto, it is fully dispersed, obtain the first mixed liquor.
Specifically, manganese salt can be manganese acetate, four hydration chloric acid manganese (MnCl2·4H2O), seven hydrated manganese sulfate
(MnSO4·7H2) and manganese nitrate hexahydrate ((Mn (NO O3)2·6H2At least one of O), it is preferred that manganese salt is manganese acetate,
Its is cheap, is easily obtained, and with the complex reaction of complexing agent can be carried out more thoroughly, the by-product of reaction is less.
When it is implemented, each raw material can be enabled adequately to disperse in deionized water by the way of ultrasonic vibration, stirring.It is logical
Cross the step manganese salt is fully dispersed to positive electrode LiNi1/3Co1/3Mn1/3O2Aqueous solution in, convenient for post precipitation react
Middle manganese salt can uniformly be deposited in positive electrode surface.
(2) appropriate complexing agent is added into first mixed liquor, keeps it abundant with the manganese salt in first mixed liquor
Mixing, obtains the second mixed liquor.
Specifically, complexing agent is ethylenediamine tetra-acetic acid (EDTA), hydroxyl ethylenediamine tetra-acetic acid (HEDTA) or diethylenetriamine
Manganese acetate, is deposited in positive electrode table by EDTA by pentaacetic acid (DTPA), preferably ethylenediamine tetra-acetic acid (EDTA) completely
Face.When it is implemented, select the sodium salt of EDTA so that EDTA sufficiently in water, and participates in subsequent complex reaction, it is specific anti-
Answer formula as follows：
Mn(CH3COO)2+(NaOOCCH2)2NCH2CH2N(CH2COOH)2=
Mn(OOCCH2)2NCH2CH2N(CH2COONa)2+2CH3COOH
In the step, the mass ratio of manganese salt and complexing agent is (49~245)：447；Preferably 49：149, matched with appropriate
Than being reacted, is conducive to the complete precipitating of manganese salt, reduces the generation of impurity.
(3) appropriate anionic surfactant is added into second mixed liquor, it is fully dispersed, obtain third mixing
Liquid, and the third mixed liquor is stirred under conditions of temperature is (25-40) DEG C.
Specifically, anionic surfactant can be lauryl sodium sulfate, neopelex and alpha-olefin
At least one of sulfonate, such as can be preferably lauryl sodium sulfate.It can be by the way of ultrasonic vibration, stirring
Reinforce the mixability of solution.Since the temperature of reaction is lower, it can guarantee the temperature of reaction by the way of heating water bath.
When it is implemented, the temperature of reaction can be kept by the way that thermocouple is added.It, can be by the complex precipitate of Mn by the step
More uniform is dispersed in positive electrode surface.
(4) it is dissolved after weighing appropriate PH regulator and oxidant respectively；The solution that the two is formed successively is added dropwise to
It in the third mixed liquor, quickly stirs, starts timing to completion of dropwise addition, isothermal reaction (10-16) is small at (25-40) DEG C
When, obtain the 4th mixed liquor.Preferably, the temperature of isothermal reaction is (30-35) DEG C, and the reaction time is (12-14) hour.
PH regulator is at least one of sodium hydroxide and potassium hydroxide, such as sodium hydroxide can be selected to carry out PH
Adjusting, the pH value of solution is adjusted to PH=7 by sodium hydroxide, with provide Mn salt generate precipitating environment,
In, the acid-base neutralization reaction formula of PH regulator is as follows：
NaOH+CH3COOH=CH3COONa+H2O
2NaOH+(NaOOCCH2)2NCH2CH2N(CH2COOH)2
=(NaOOCCH2)2NCH2CH2N(CH2COONa)2+2H2O
2NaOH+H2SO4=Na2SO4+2H2O
Due to Mn2+Unstable, oxide is easy to decompose, therefore divalent manganesetion is oxidized to four by oxidant
Valence manganese ion, so that the oxide structure containing Mn for being coated on positive electrode surface is more stable.When it is implemented, oxidant can
Think at least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.The reaction equation of oxidation process is as follows：
Na2S2O8+Mn(OOCCH2)2NCH2CH2N(CH2COONa)2+2H2O=MnO2+2H2SO4+ (NaOOCCH2)2NCH2CH2N(CH2COONa)2
(5) the 4th mixed liquor is filtered and is precipitated, washed, collect the precipitating and it is dried
Processing, can be obtained lithium ion battery tertiary cathode modified material xMnO2/LiNi1/3Co1/3Mn1/3O2。
Specifically, the product in above-mentioned steps (4) is filtered, x MnO can be obtained2/LiNi1/3Co1/3Mn1/3O2It is heavy
It forms sediment, first the precipitating can be cleaned multiple times with deionized water to remove other generated in complex reaction and neutralization reaction
Then impurity component is quickly taken away deionized water remaining in precipitating by ethyl alcohol, drying conventional under room temperature finally can be used
It is dried in operation, ensure that the degree of purity and aridity of product.
The preparation method for the lithium ion battery tertiary cathode modified material that second aspect of the present invention provides, by pure phase ternary
After positive electrode is mixed with manganese salt, the Mn that is formed under the action of complexing agent2+Complex precipitate is dispersed in tertiary cathode material
Expect surface, then will be by Mn by oxidant2+It is oxidized to Mn4+, so that be coated on pure phase ternary material surface is stable structure
MnO2, the preparation method is at low cost and can guarantee MnO2It uniformly is deposited in pure phase ternary material surface, can effectively inhibit electricity
Liquid is solved to active material LiNi1/3Co1/3Mn1/3O2Corrosiveness so that modified ternary cathode material of lithium ion battery
With preferable stability and cycle performance.
Detailed description of the invention
Fig. 1 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The SEM figure of the ternary modified material after manganese dioxide is coated in 1-5；
Fig. 2 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The TEM figure of the ternary modified material after manganese dioxide is coated in 1-5；
Fig. 3 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The XED figure of the ternary modified material after manganese dioxide is coated in 1-5；
Fig. 4 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
In 1-5 coat manganese dioxide after ternary modified material voltage range be 2.5V-4.5V, current density be 200mA/g item
Cycle performance curve graph under part；
Fig. 5 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
In 1-5 coat manganese dioxide after ternary modified material voltage range be 2.5V-4.5V, current density be 200mA/g item
First charge-discharge curve graph under part；
Fig. 6 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
Ternary modified material after coating manganese dioxide in 3 is 2.5V-4.5V in voltage range, when current density is 200mA/g,
Cycle performance curve graph under different multiplying；
Fig. 7 be 3 in the embodiment of the present invention in coat the ternary modified material after manganese dioxide in voltage range be 2.5V-
4.5V, current density are the cycle performance curve graph under 200mA/g.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification also regard
For protection scope of the present invention.
Embodiment 1
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to deionization
In water, ultrasonic vibration is until the pure phase ternary material is uniformly dispersed；0.49g manganese acetate, ultrasound shake are added into the dispersion liquid
Swing until manganese acetate be completely dissolved, obtain the first mixed liquor；
(2) 4.47g hydroxyl ethylenediamine tetra-acetic acid is added into first mixed liquor, ultrasonic vibration is until the complexing agent
It is completely dissolved, obtains the second mixed liquor；
(3) appropriate dodecyl sodium sulfate is added into second mixed liquor, ultrasonic vibration is obtained up to being completely dissolved
The third mixed liquor is stirred to third mixed liquor, and under conditions of bath temperature is 25 DEG C；
(4) appropriate potassium hydroxide and potassium peroxydisulfate are weighed respectively, is add to deionized water, and are dissolved；By the two successively by
It is added dropwise in the third mixed liquor, quickly stirs, to both add beginning timing, isothermal reaction 10 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material 0.01MnO can be obtained2/
LiNi1/3Co1/3Mn1/3O2。
Embodiment 2
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to deionization
In water, ultrasonic vibration is until the pure phase ternary material is uniformly dispersed；0.98g manganese acetate, ultrasound shake are added into the dispersion liquid
Swing until manganese acetate be completely dissolved, obtain the first mixed liquor；
(2) 4.47g diethylene triamine pentacetic acid (DTPA) is added into first mixed liquor, ultrasonic vibration is until the complexing
Agent is completely dissolved, and obtains the second mixed liquor；
(3) appropriate alpha-alkene sulfonate is added into second mixed liquor, ultrasonic vibration is obtained up to being completely dissolved
Third mixed liquor, and the third mixed liquor is stirred under conditions of bath temperature is 35 DEG C；
(4) appropriate sodium hydroxide and sodium peroxydisulfate are weighed respectively, is add to deionized water, and are dissolved；By the two successively by
It is added dropwise in the third mixed liquor, quickly stirs, to both add beginning timing, isothermal reaction 13 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material 0.02MnO can be obtained2/
LiNi1/3Co1/3Mn1/3O2。
Embodiment 3
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to deionization
In water, ultrasonic vibration is until the pure phase ternary material is uniformly dispersed；0.49g manganese acetate, ultrasound shake are added into the dispersion liquid
Swing until manganese acetate be completely dissolved, obtain the first mixed liquor；
(2) 1.49g ethylenediamine tetra-acetic acid (EDTA) is added into first mixed liquor, ultrasonic vibration is until the network
Mixture is completely dissolved, and obtains the second mixed liquor；
(3) appropriate lauryl sodium sulfate is added into second mixed liquor, ultrasonic vibration is obtained up to being completely dissolved
The third mixed liquor is stirred to third mixed liquor, and under conditions of bath temperature is 30 DEG C；
(4) appropriate sodium hydroxide and potassium peroxydisulfate are weighed respectively, is add to deionized water, and are dissolved；By the two successively by
It is added dropwise in the third mixed liquor, quickly stirs, to both add beginning timing, isothermal reaction 12 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material 0.03MnO can be obtained2/
LiNi1/3Co1/3Mn1/3O2。
Embodiment 4
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to deionization
In water, ultrasonic vibration is until the pure phase ternary material is uniformly dispersed；1.96g manganese acetate, ultrasound shake are added into the dispersion liquid
Swing until manganese acetate be completely dissolved, obtain the first mixed liquor；
(2) 4.47g ethylenediamine tetra-acetic acid (EDTA) is added into first mixed liquor, ultrasonic vibration is until the network
Mixture is completely dissolved, and obtains the second mixed liquor；
(3) be added appropriate neopelex into second mixed liquor, ultrasonic vibration until be completely dissolved,
Third mixed liquor is obtained, and the third mixed liquor is stirred under conditions of bath temperature is 40 DEG C；
(4) appropriate sodium hydroxide and potassium peroxydisulfate are weighed respectively, is add to deionized water, and are dissolved；By the two successively by
It is added dropwise in the third mixed liquor, quickly stirs, to both add beginning timing, isothermal reaction 14 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material 0.04MnO can be obtained2/
LiNi1/3Co1/3Mn1/3O2。
Embodiment 5
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added to deionization
In water, ultrasonic vibration is until the pure phase ternary material is uniformly dispersed；2.45g manganese acetate, ultrasound shake are added into the dispersion liquid
Swing until manganese acetate be completely dissolved, obtain the first mixed liquor；
(2) 4.47g ethylenediamine tetra-acetic acid (EDTA) is added into first mixed liquor, ultrasonic vibration is until the network
Mixture is completely dissolved, and obtains the second mixed liquor；
(3) it is added into second mixed liquor appropriate lauryl sodium sulfate (SDS), ultrasonic vibration is until completely molten
Solution obtains third mixed liquor, and is stirred under conditions of bath temperature is 30 DEG C to the third mixed liquor；
(4) appropriate sodium hydroxide and potassium peroxydisulfate are weighed respectively, is add to deionized water, and are dissolved；By the two successively by
It is added dropwise in the third mixed liquor, quickly stirs, to both add beginning timing, isothermal reaction 16 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material 0.05MnO can be obtained2/
LiNi1/3Co1/3Mn1/3O2。
Comparative example
To the pure phase ternary anode material for lithium-ion batteries LiNi of purchase1/3Co1/3Mn1/3O2It is without any processing.
Experimental example
In order to verify MnO2Whether positive electrode LiNi is successfully coated on1/3Co1/3Mn1/3O2Surface and MnO2Cladding
Influence of the layer to tertiary cathode material crystal structure, the positive electrode in embodiment 1-5 and comparative example has been carried out respectively SEM,
TEM and XRD test.As a result as shown in Figs. 1-3：
Fig. 1 a is LiNi in comparative example1/3Co1/3Mn1/3O2Scanning electron microscope (SEM) photograph, Fig. 1 b-f be respectively embodiment 1-5 be made
Different coating contents xMnO2/LiNi1/3Co1/3Mn1/3O2Scanning electron microscope (SEM) photograph, it can be seen that it is uncoated in comparative example
LiNi1/3Co1/3Mn1/3O2Material be stacked with by rod-shpaed particle composed by, the surface of particle is smooth, between particle
Mutually there is gap in not dense packing.Sample surfaces after caning be found that cladding in Fig. 1 b-f are due to laminated structure dioxy
The presence for changing manganese becomes coarse rough. MnO2When coating content is lower, clad is imperfect, some ternary material
Grain exposure；As the increase clad of coating content is complete, but when too high levels, manganese dioxide nano-plates are constantly grown, and are formed
Very thick and very loose clad.
In order to further appreciate that the variation of cladding front and back material surface, to xMnO made from embodiment 1-52/LiNi1/ 3Co1/3Mn1/3O2The phenogram of transmission electron microscope is carried out, Fig. 2 a-1,2a-2 are LiNi uncoated in comparative example1/3Co1/ 3Mn1/3O2Material.As can be seen that uncoated LiNi1/3Co1/3Mn1/3O2Surface is smooth.Fig. 2 b-1 to 2f-2 is respectively to implement
The transmission electron microscope picture of positive electrode obtained in example 1-5, it can be seen that when coating content is lower, the clad of material surface compared with
Thin imperfect, with the increase of coating content, clad becomes complete uniform, but when too high levels, clad becomes very
Thickness, and the manganese dioxide nano-plates on surface become very loose.The characterization result and above-mentioned scanning electron microscope characterization gained
To result be consistent.
Fig. 3 is positive electrode and xMnO made from embodiment 1-5 in comparative example2/LiNi1/3Co1/3Mn1/3O2XRD characterization
Figure.It can be seen from the figure that the material of cladding front and back all has α-NaFeO2Layered rock salt structure, belong to hexagonal crystal
System, R-3m space group.The diffraction maximum of each sample is sharp in figure, occurs without impurity peaks, it was demonstrated that the crystallinity of each sample is good
It is good.For ternary material, (006) and (102) and (108) and (110) two groups of peaks split point degree and can be used to characterize material
Whether there is good layer structure.It is generally believed that (006) and (102) and (108) and (110) two groups of peaks split a point journey
It spends bigger, splits and point be more obvious, it was demonstrated that the layer structure feature of ternary material is more obvious, not vice versa.It can be sent out from figure
Existing, (006) and (102) and (108) and (110) two groups of peak homolysis for coating the sample of front and back are shown clearly, it was demonstrated that sample has
There is good layer structure.For stratified material, it can also be characterized according to the ratio of the relative intensity of certain characteristic peaks
The degree of crystallization of mixing degree and material.It is generally believed that the intensity ratio of characteristic peak I003 and I104 can be used for measuring material
Expect Li+And Ni2+The ratio of mixing degree, I003 and I104 are bigger, it was demonstrated that the Li of the material+And Ni2+The degree of mixing is smaller,
Degree of crystallization is higher.Li+And Ni2+The spacing that mixing will lead to lithium layer becomes smaller, and the diffusion admittance of lithium ion becomes smaller, thus right
The diffusion of lithium ion causes to hinder, therefore should reduce mixing degree as far as possible by calculating it is found that coating preceding LiNi1/3Co1/ 3Mn1/3O2I003/I104 peak value ratio be 1.138, manganese dioxide coating content be 1wt%, 2wt%, 3wt%, 4wt%,
The sample I003/I104 peak value of 5wt% is than being respectively 1.240,1.414,1.526,1.335,1.277.By coating titanium dioxide
Manganese can reduce Li+And Ni2+The degree of mixing, wherein embodiment 3, i.e. coating content are the sample I003 and I104 of 3wt%
Ratio it is maximum, it was demonstrated that its Li+And Ni2+The degree of mixing is small, and degree of crystallization is high, can preferably maintain the stratiform knot of crystal
Structure is also more conducive to the diffusion of lithium ion.
Meanwhile in order to detect every electrochemistry of the cell positive material in embodiment 1- embodiment 5 and comparative example
Can, charge and discharge cycles test is carried out respectively to above-mentioned specific example, Fig. 4-Fig. 7 shows experimental result.
Fig. 4 shows the cycle performance curve of positive electrode in each specific example, as can be seen from the figure uncoated
LiNi1/3Co1/3Mn1/3O2First discharge specific capacity be 181.6mAh/g, manganese dioxide coating content be 1wt%, 2wt%,
The sample first discharge specific capacity of 3wt%, 4wt%, 5wt% be respectively 175.1 mAh/g, 177.7mAh/g, 183mAh/g,
176.4mAh/g and 181.4mAh/g.By 100 circle circulation after, the specific discharge capacity of above-mentioned sample be respectively 70.2mAh/g,
132.6mAh/g, 151.1mAh/g, 165mAh/g, 134.3mAh/g and 140.1mAh/g.Its capacity retention ratio is respectively
38.6%, 75.72%, 85.03%, 90.16%, 76.13%, 77.23%.Material capacity after manganese dioxide cladding is kept
Rate obviously rises, this is primarily due to the Ni that ternary material generates under high pressure4+It is easy to react with electrolyte, make
The quality of Viability substance declines, can be with however, form protective layer on the surface of ternary material by cladding manganese dioxide
Electrolyte is reduced to the corrosiveness of active material, to improve its cyclical stability.It is very easy to find in from the above,
The content of manganese dioxide is that the cycles samples stability of 3wt% is the most excellent.This mainly due to manganese dioxide coating content compared with
When low, the clad of formation is sufficiently complete, and the still particle exposure of some ternary material in the electrolytic solution, is easy to happen
Side reaction；When coating content is higher, the manganese dioxide nano-plates on ternary material surface are constantly grown, and form thicker cladding
Layer, is unfavorable for the diffusion of lithium ion, meanwhile, clad becomes loose, structure collapses are be easy to cause during charge and discharge,
So as to cause the decline of its cyclical stability.Embodiment 3, i.e. coating content be 3wt% sample be formed by clad it is thin and
Uniformly, complete protective layer is formed on the surface of material, contains the side reaction between ternary material and electrolyte；Meanwhile the material
The lithium nickel mixing degree of material is minimum, and structure is more stable, is more favorable to the diffusion of lithium ion, thus the material show it is good
Good cyclical stability.
Fig. 5-Fig. 7 shows LiNi uncoated in comparative example1/3Co1/3Mn1/3O2And MnO2Covering amount is the sample of 3 wt%
The chemical property figure of product.From fig. 5, it is seen that the first discharge specific capacity of cladding front and back material is not much different, but coat
3wt%MnO2Sample specific discharge capacity slightly increase.From the figure, it can be seen that two charging and discharging curves are all very smooth,
There are a charging platforms by 3.8V or so, this is mainly Ni2+Redox reaction.Material after cladding has in 3.0V or so
The charging platform of very little, in 2.8V or so, there are the discharge platforms of very little, this may be since the material surface after cladding exists
The deintercalation of lithium ion has occurred in a certain amount of LixMnO2, the compound during charge and discharge, in cyclic voltammetric later
Available confirmation in test.Therefore the material first discharge specific capacity after coating can be increased slightly.From fig. 6, it can be seen that packet
Specific discharge capacity of the sample under 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, 5.0C multiplying power before covering be respectively 189mAh/g,
172.2mAh/g, 158.4mAh/g, 140.3mAh/g, 115.8mAh/g, 86.9mAh/g coat 3wt%MnO2Sample
Specific discharge capacity is respectively 199 mAh/g, 197.5mAh/g, 186mAh/g, 166.8mAh/g, 150.4mAh/g, 121.5mAh/
g.It can be seen that the high rate performance of the sample after cladding all has biggish raising, and big under each current density
Under current density, increase it is more obvious.It can be seen from figure 7 that the sample after cladding has fabulous cyclical stability,
Its capacity retention ratio is 90.16% after 100 circle of circulation, and its coulombic efficiency is almost close to 100%.Material after cladding
The raising of high rate performance and cycle performance, this is primarily due to manganese dioxide clad and hinders electrolyte and active material
Side reaction, and there are gaps between manganese dioxide nano-plates, can alleviate the volume of the ternary material in charge and discharge process
Variation, improves the structural stability of positive electrode.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to of the invention
Protection scope.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of lithium ion battery tertiary cathode modified material, which is characterized in that the modified material of the lithium ion battery tertiary cathode
Material includes pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2With setting in the pure phase ternary lithium-ion electric
Pond positive electrode LiNi1/3Co1/3Mn1/3O2The clad on surface, wherein the material of the clad is manganese dioxide.
2. lithium ion battery tertiary cathode modified material according to claim 1, which is characterized in that the material of the clad
Material and the pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2Mass ratio be (0.01-0.05)：1；Institute
The molecular formula for stating lithium ion battery tertiary cathode modified material is xMnO2/LiNi1/3Co1/3Mn1/3O2, wherein x=0.01,
0.02,0.03,0.04 or 0.05.
3. a kind of preparation method of lithium ion battery tertiary cathode modified material, which is characterized in that include the following steps：
(1) suitable pure phase ternary anode material for lithium-ion batteries LiNi is weighed1/3Co1/3Mn1/3O2, it is added in solvent, disperses
Uniformly, then thereto appropriate manganese salt is added, it is fully dispersed, obtain the first mixed liquor；
(2) appropriate complexing agent is added into first mixed liquor, is sufficiently mixed it with the manganese salt in first mixed liquor,
Obtain the second mixed liquor；
(3) appropriate anionic surfactant is added into second mixed liquor, it is fully dispersed, third mixed liquor is obtained, and
The third mixed liquor is stirred under conditions of temperature is (25-40) DEG C；
(4) it is dissolved after weighing appropriate PH regulator and oxidant respectively；The solution that the two is formed successively is added dropwise to described
It in third mixed liquor, quickly stirs, starts timing to completion of dropwise addition, isothermal reaction (10-16) hour at (25-40) DEG C, obtain
To the 4th mixed liquor；
(5) the 4th mixed liquor is filtered and is precipitated, washed, collect the precipitating and it is dried,
Lithium ion battery tertiary cathode modified material xMnO can be obtained2/LiNi1/3Co1/3Mn1/3O2。
4. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that described
Manganese salt is at least one of manganese acetate, four hydration chloric acid manganese, seven hydrated manganese sulfates and manganese nitrate hexahydrate.
5. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that described
Complexing agent is ethylenediamine tetra-acetic acid, hydroxyl ethylenediamine tetra-acetic acid or diethylene triamine pentacetic acid (DTPA).
6. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that described
Anionic surfactant is at least one of lauryl sodium sulfate, neopelex and alpha-alkene sulfonate.
7. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that described
PH regulator is at least one of sodium hydroxide and potassium hydroxide；The oxidant is potassium peroxydisulfate, sodium peroxydisulfate and over cure
At least one of sour ammonium.
8. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that described
The mass ratio of manganese salt and the complexing agent is (49~245)：447.
9. the preparation method of lithium ion battery tertiary cathode modified material according to claim 8, which is characterized in that described
The mass ratio of manganese salt and the complexing agent is 49：149.
10. the preparation method of lithium ion battery tertiary cathode modified material according to claim 3, which is characterized in that institute
Stating the reaction temperature in step (3) is (30-35) DEG C；Reaction time in the step (4) is (12-14) hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2708481B2 (en) * | 1987-08-03 | 1998-02-04 | ヴアルタ・バツテリー・アクチエンゲゼルシヤフト | Battery and manufacturing method thereof |
| US20110219607A1 (en) * | 2010-03-12 | 2011-09-15 | Nanjundaswamy Kirakodu S | Cathode active materials and method of making thereof |
| CN103943854A (en) * | 2014-03-26 | 2014-07-23 | 长沙矿冶研究院有限责任公司 | Surface-coated modified lithium ion battery cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2708481B2 (en) * | 1987-08-03 | 1998-02-04 | ヴアルタ・バツテリー・アクチエンゲゼルシヤフト | Battery and manufacturing method thereof |
| US20110219607A1 (en) * | 2010-03-12 | 2011-09-15 | Nanjundaswamy Kirakodu S | Cathode active materials and method of making thereof |
| CN103943854A (en) * | 2014-03-26 | 2014-07-23 | 长沙矿冶研究院有限责任公司 | Surface-coated modified lithium ion battery cathode material and preparation method thereof |
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