CN108695503A - In the anode modified material that material surface coats the method for manganese dioxide and prepared with this method - Google Patents
In the anode modified material that material surface coats the method for manganese dioxide and prepared with this method Download PDFInfo
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- CN108695503A CN108695503A CN201810507368.5A CN201810507368A CN108695503A CN 108695503 A CN108695503 A CN 108695503A CN 201810507368 A CN201810507368 A CN 201810507368A CN 108695503 A CN108695503 A CN 108695503A
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- manganese dioxide
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- 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 present invention provides a kind of anode modified material for coating the method for manganese dioxide in material surface and being prepared with this method, method for coating includes:Material to be covered and manganese salt are distributed in solvent successively, obtain the first mixed solution;Complexing agent is added into the first solution of the mixing and forms the second mixed liquor, after the heated stirring of the second mixed liquor, suction filtration is precipitated, and is cleaned to the precipitation, and dry, you can obtains the material of cladding manganese dioxide.Method for coating provided by the invention, it is simple for process, it is of low cost, it is flaky nanometer structure in the manganese dioxide of material surface cladding, the diffusion admittance that lithium ion can not only be shortened, can also increase the contact area of itself and electrolyte, to advantageously reduce the contact probability in positive electrode between active material and electrolyte, corrosiveness of the electrolyte to active material can effectively be inhibited, improve the stability of positive modified material.
Description
Technical field
The present invention relates to technical field of lithium ion, and manganese dioxide is coated in material surface in particular to one kind
Method and with this method prepare anode modified material.
Background technology
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, oil, natural gas far can not meet people day
The energy demand that benefit increases, and also getting worse, wherein PM2.5 most draw the problem of environmental pollution caused by combustion of fossil fuels
People gazes at, and many city hazes are serious, therefore the main task of today's society is to find and develop high-efficiency environment friendly sustainable development
New energy.The device that chemical energy can be converted to electric energy is known as electrochmical power source, has been subjected to the wide of many researchers
General concern.Wherein, secondary cell first entered the public visual field in 1899, is a kind of novel electrochmical power source, realizes electricity
There can be at low cost, higher than energy, efficient environmentally friendly and cycle performance with the reversible transformation of chemical energy, secondary cell
The advantages that good, 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, Ni-MH battery and lithium ion battery, relative to
Other secondary cells, lithium ion battery is because operating voltage is high, energy density is big, good rate capability, service life are long and right
Environmental-friendly equal many merits, are current comprehensive performance secondary chemical sources of electric energy the most excellent.In recent years, lithium ion battery is answered
More and more extensive with field, with the development of electric vehicle (EV) and hybrid electric vehicle (HEV), high specific energy and high power have become the present
The important directions of Study on Li-ion batteries and development afterwards.Key component of the positive electrode as lithium ion battery is studied and is opened
Hair seems particularly urgent.
Lithium ion battery LiNi1/3Co1/3Mn1/3O2Tertiary cathode material specific discharge capacity is high, but during cycle
Its capacity attenuation is serious, in the prior art by oxide coated to alleviate capacity attenuation phenomenon on it, but often occurs
Structural unstable adverse consequences.
Invention content
In consideration of it, the present invention proposes a kind of electricity for coating the method for manganese dioxide in material surface and being prepared with this method
Pond anode modified material, it is intended to solve existing lithium ion battery LiNi1/3Co1/3Mn1/3O2Tertiary cathode modified material electrochemistry
The poor problem of energy.
Specifically, first aspect present invention proposes a kind of method coating manganese dioxide in material surface, including following
Step:
(1) material to be covered and manganese salt are distributed in solvent successively, obtain the first solution.
Specifically, material to be covered is anode material for lithium-ion batteries, inorganic oxide or organic compound.The present invention
Embodiment is with anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2For (pure phase LiNi1/3Co1/3Mn1/3O2For commercial product,
Its source is not limited), coat manganese dioxide on its surface.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), preferably
, manganese salt is manganese acetate, cheap, is easily obtained, and with the complex reaction of complexing agent can carry out more thoroughly, instead
The by-product answered is less.When it is implemented, ultrasonic vibration may be used, the mode of stirring enables each raw material to be adequately dispersed in
In deionized water.It is by the step that manganese salt is fully dispersed to positive electrode LiNi1/3Co1/3Mn1/3O2Aqueous solution in, be convenient for
Manganese salt can uniformly be deposited in positive electrode surface in post precipitation reaction.
(2) complexing agent is added into first solution and forms the second mixed liquor, stir second mixed liquor is heated
After mixing, suction filtration is precipitated, and is cleaned, is collected the precipitation and it is dried processing, you can obtains cladding manganese dioxide
Material.
Specifically, complexing agent is ethylenediamine tetra-acetic acid (EDTA), hydroxyl ethylenediamine tetra-acetic acid (HEDTA) or diethylenetriamine five
Manganese acetate, positive electrode surface is deposited in by EDTA by acetic acid (DTPA), preferably ethylenediamine tetra-acetic acid (EDTA) completely.
When it is implemented, selecting the sodium salt of EDTA so that EDTA fully in water, and participates in subsequent complex reaction, specifically
Reaction equation it is 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 precipitation of manganese salt, reduces the generation of impurity.
Before heating stirring, appropriate anion surfactant is added into second mixed liquor, it is fully dispersed, it obtains
Third mixed liquor;And the third mixed liquor is stirred under conditions of temperature is (25-40) DEG C.
Specifically, anion surfactant can be lauryl sodium sulfate, neopelex and alpha-olefin
At least one of sulfonate, such as can be preferably lauryl sodium sulfate.Ultrasonic vibration may be used, the mode of stirring adds
The mixability of strong solution;Preferably, reaction temperature is (30-35) DEG C.When it is implemented, can be kept by the way that thermocouple is added
The temperature of reaction.By the step, the complex precipitate of Mn can be more uniformly dispersed in positive electrode surface.
After to the third mixed liquor heating stirring with before suction filtration, weigh respectively it is molten after appropriate PH conditioning agents and oxidant
Solution, and the solution that the two is formed is added dropwise to successively in the third mixed liquor, it quickly stirs, waits for that completion of dropwise addition starts to count
When, in (25-40) DEG C isothermal reaction (10-16) hour, obtain the 4th mixed liquor.
Since the temperature of reaction is relatively low, the mode that heating water bath may be used ensures the temperature of reaction, it is preferred that constant temperature is anti-
The temperature answered is (30-35) DEG C, and the reaction time is (12-14) hour.
PH conditioning agents are at least one of sodium hydroxide and potassium hydroxide, such as sodium hydroxide can be selected to carry out PH's
It adjusts, is adjusted the pH value of solution to PH=7 by sodium hydroxide, to provide the environment that Mn salt generates precipitation, wherein PH
The acid-base neutralization reaction formula of conditioning agent 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 tetravalence by oxidant
Manganese ion so that the oxide structure containing Mn for being coated on positive electrode surface is more stablized.When it is implemented, oxidant can be
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
4th mixed liquor obtained above is filtered and is precipitated, it is described heavy to be washed respectively with deionized water and ethyl alcohol
It forms sediment, collect the precipitation and is dried at room temperature for, you can obtain the material of cladding manganese dioxide.
Specifically, product obtained in above-mentioned steps is filtered, you can the material of cladding manganese dioxide is obtained, such as
x MnO2/LiNi1/3Co1/3Mn1/3O2Precipitation, first can be cleaned multiple times to remove complex reaction the precipitation with deionized water
With the other impurities ingredient generated in neutralization reaction, deionized water remaining in precipitation is then quickly taken away by ethyl alcohol, finally
Drying process conventional under room temperature can be used it is dried, ensure that the degree of purity and aridity of product.
The method for coating manganese dioxide in material surface that first aspect present invention provides, by lithium ion cell positive material
After material, inorganic oxide or organic compound material wait for covering material to be mixed with manganese salt, formed under the action of complexing agent
Mn2+Complex precipitate is dispersed in the surface of material to be covered, then will be by Mn by oxidant2+It is oxidized to Mn4+So that packet
That overlay on material surface to be covered is the MnO of stable structure2, the preparation method is at low cost and can guarantee MnO2Uniformly it is deposited in
Material surface to be covered.
Second aspect of the present invention provides a kind of anode modified material, which includes pure phase ternary lithium ion
Cell positive material LiNi1/3Co1/3Mn1/3O2With setting in the pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/ 3Mn1/3O2The manganese dioxide clad on surface, wherein, the preparation process of manganese salt 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 LiNi1/3Co1/3Mn1/3O2
Internal structure in, therefore will not having an impact to the crystal structure of positive electrode itself.Pure phase in the embodiment of the present invention
LiNi1/3Co1/3Mn1/3O2For commercial product, its source is not limited.
Further, in above-mentioned anode modified material, material and the pure phase three of the manganese dioxide clad
First 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.Appropriate mass than coating layer material and pure phase ternary anode material for lithium-ion batteries
LiNi1/3Co1/3Mn1/3O2, the clad type positive electrode of stable structure can be formed, and make the positive electrode that there is preferable stablize
Property and preferable chemical property, in addition, also the capacity of positive electrode can be adjusted by adjusting the mass ratio.
Correspondingly, in the present embodiment, the molecular formula of the anode modified material can be expressed as:x MnO2/
LiNi1/3Co1/3Mn1/3O2, x=0.01,0.02,0.03,0.04 or 0.05.
Second aspect of the present invention provide anode modified material, by the precipitation method pure phase ternary lithium ion battery just
Pole material LiNi1/3Co1/3Mn1/3O2Surface depositing homogeneous and complete manganese dioxide clad, active material can be reduced
LiNi1/3Co1/3Mn1/3O2Contact probability between electrolyte can effectively inhibit electrolyte to active material LiNi1/3Co1/ 3Mn1/3O2Corrosiveness, simultaneously, it is suppressed that side reaction between the two;Also, the structural stability of positive electrode is improved,
The volume change that positive electrode in charge and discharge process can also be alleviated is more conducive to the deintercalation of lithium ion, to alleviate work
Property matter content decaying the phenomenon that so that modified ternary cathode material of lithium ion battery have preferable stability and cycle
Performance.
Third aspect present invention provides a kind of preparation method of cell positive material, includes 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,
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, and price is low
It is honest and clean, be easily obtained, and with the complex reaction of complexing agent can carry out more thoroughly, the by-product of reaction is less.Specific implementation
When, ultrasonic vibration may be used, the mode of stirring enables each raw material adequately to disperse in deionized water.It will by the step
Manganese salt is fully dispersed to arrive positive electrode LiNi1/3Co1/3Mn1/3O2Aqueous solution in, convenient for post precipitation reaction in 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 five
Manganese acetate, positive electrode surface is deposited in by EDTA by acetic acid (DTPA), preferably ethylenediamine tetra-acetic acid (EDTA) completely.Tool
When body is implemented, the sodium salt of EDTA is selected so that EDTA fully in water, and participates in subsequent complex reaction, specific reaction equation is such as
Under:
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 precipitation of manganese salt, reduces the generation of impurity.
(3) appropriate anion 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, anion surfactant can be lauryl sodium sulfate, neopelex and alpha-olefin
At least one of sulfonate, such as can be preferably lauryl sodium sulfate.Ultrasonic vibration may be used, the mode of stirring adds
The mixability of strong solution;Preferably, reaction temperature is (30-35) DEG C.When it is implemented, can be kept by the way that thermocouple is added
The temperature of reaction.By the step, the complex precipitate of Mn can be more uniformly dispersed in positive electrode surface.
(4) it is dissolved after weighing appropriate PH conditioning agents and oxidant respectively;The solution that the two is formed is added dropwise to successively
It in the third mixed liquor, quickly stirs, waits for that completion of dropwise addition starts timing, isothermal reaction (10-16) is small at (25-40) DEG C
When, obtain the 4th mixed liquor.
Since the temperature of reaction is relatively low, the mode that heating water bath may be used ensures the temperature of reaction, it is preferred that constant temperature is anti-
The temperature answered is (30-35) DEG C, and the reaction time is (12-14) hour.
PH conditioning agents are at least one of sodium hydroxide and potassium hydroxide, such as sodium hydroxide can be selected to carry out PH's
It adjusts, is adjusted the pH value of solution to PH=7 by sodium hydroxide, to provide the environment that Mn salt generates precipitation, wherein PH
The acid-base neutralization reaction formula of conditioning agent 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 tetravalence by oxidant
Manganese ion so that the oxide structure containing Mn for being coated on positive electrode surface is more stablized.When it is implemented, oxidant can be
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 precipitation and it is dried place
Reason, you can obtain lithium ion battery tertiary cathode modified material xMnO2/LiNi1/3Co1/3Mn1/3O2。
Specifically, the product in above-mentioned steps (4) is filtered, you can obtain x MnO2/LiNi1/3Co1/3Mn1/3O2It is heavy
It forms sediment, first the precipitation can be cleaned multiple times with deionized water miscellaneous to remove other that generated in complex reaction and neutralization reaction
Then matter ingredient quickly takes away deionized water remaining in precipitation by ethyl alcohol, dry behaviour conventional under room temperature finally can be used
Opposing, it is dried, and ensure that the degree of purity and aridity of product.
The preparation method for the anode modified material that third aspect present invention provides, by pure phase tertiary cathode material and manganese
After salt mixing, the Mn that is formed under the action of complexing agent2+Complex precipitate is dispersed in tertiary cathode material surface, then passes through
Oxidant will be by Mn2+It is oxidized to Mn4+So that be coated on pure phase ternary material surface is the MnO of stable structure2, the preparation side
Method is at low cost and can guarantee MnO2It uniformly is deposited in pure phase ternary material surface, effectively electrolyte can be inhibited to active material
LiNi1/3Co1/3Mn1/3O2Corrosiveness so that modified ternary cathode material of lithium ion battery have preferable stability
And cycle performance.
Description of the drawings
Fig. 1 is the method flow diagram in material surface cladding manganese dioxide provided in the embodiment of the present invention;
Fig. 2 a-b are MnO under the different amplification provided in the embodiment of the present invention2SEM figure;
Fig. 3 a-c are MnO under the different multiplying provided in the embodiment of the present invention2TEM figure;
Fig. 4 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The SEM figures of the ternary modified material after manganese dioxide are coated in 1-5;
Fig. 5 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The TEM figures of the ternary modified material after manganese dioxide are coated in 1-5;
Fig. 6 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The XED figures of the ternary modified material after manganese dioxide are coated in 1-5;
Fig. 7 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
It is 2.5V-4.5V that the ternary modified material after manganese dioxide is coated in 1-5 in voltage range, and current density is the item of 200mA/g
Cycle performance curve graph under part;
Fig. 8 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
It is 2.5V-4.5V that the ternary modified material after manganese dioxide is coated in 1-5 in voltage range, and current density is the item of 200mA/g
First charge-discharge curve graph under part;
Fig. 9 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And embodiment
The ternary modified material after manganese dioxide is coated in 3 and is 2.5V-4.5V in voltage range, when current density is 200mA/g, not
Cycle performance curve graph under same multiplying;
Figure 10 be 3 in the embodiment of the present invention in ternary modified material after cladding manganese dioxide in voltage range be 2.5V-
4.5V, current density are the cycle performance curve graph under 200mA/g.
Specific implementation mode
As described below is the 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 are also considered as
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 acetates, 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 acids are added into first mixed liquor, ultrasonic vibration is until the complexing agent is complete
Fully 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
Third mixed liquor, and the third mixed liquor is stirred 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, wait for both adding beginning timing, isothermal reaction 10 hours, obtain the
Four mixed liquors;
(5) the 4th mixed liquor is filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol,
It collects the precipitation and is dried at room temperature for, you can obtain lithium ion battery tertiary cathode modified material 0.01MnO2/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 acetates, 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)s are added into first mixed liquor, ultrasonic vibration is until the complexing agent
It is completely dissolved, obtains the second mixed liquor;
(3) it is added appropriate alpha-alkene sulfonate into second mixed liquor, ultrasonic vibration obtains the until be completely dissolved
Three mixed liquors, 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, wait for both adding beginning timing, isothermal reaction 13 hours, obtain the
Four mixed liquors;
(5) the 4th mixed liquor is filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol,
It collects the precipitation and is dried at room temperature for, you can obtain lithium ion battery tertiary cathode modified material 0.02MnO2/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 acetates, 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 acids (EDTA) are added into first mixed liquor, ultrasonic vibration is until the complexing
Agent 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
Third mixed liquor, and the third mixed liquor is stirred 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, wait for both adding beginning timing, isothermal reaction 12 hours, obtain the
Four mixed liquors;
(5) the 4th mixed liquor is filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol,
It collects the precipitation and is dried at room temperature for, you can obtain lithium ion battery tertiary cathode modified material 0.03MnO2/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 acetates, 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 acids (EDTA) are added into first mixed liquor, ultrasonic vibration is until the complexing
Agent is completely dissolved, and obtains the second mixed liquor;
(3) appropriate neopelex is added into second mixed liquor, ultrasonic vibration is obtained up to being completely dissolved
To third mixed liquor, 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, wait for both adding beginning timing, isothermal reaction 14 hours, obtain the
Four mixed liquors;
(5) the 4th mixed liquor is filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol,
It collects the precipitation and is dried at room temperature for, you can obtain lithium ion battery tertiary cathode modified material 0.04MnO2/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 acetates, 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 acids (EDTA) are added into first mixed liquor, ultrasonic vibration is until the complexing
Agent is completely dissolved, and obtains the second mixed liquor;
(3) appropriate lauryl sodium sulfate (SDS) is added into second mixed liquor, ultrasonic vibration is until completely molten
Solution obtains third mixed liquor, and is stirred to the third mixed liquor 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, wait for both adding beginning timing, isothermal reaction 16 hours, obtain the
Four mixed liquors;
(5) the 4th mixed liquor is filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol,
It collects the precipitation and is dried at room temperature for, you can obtain lithium ion battery tertiary cathode modified material 0.05MnO2/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
Fig. 2 and Fig. 3 is the MnO prepared to above-described embodiment 1-52The spectrogram that is characterized of pattern:
Fig. 2 is the scanning figure of manganese dioxide under different amplification, should be apparent that manganese dioxide is by surpassing from Fig. 1
Thin nanometer sheet composition, and be stacked between nanometer sheet, being formed, there is very lacunose duct, this structure not only may be used
To shorten the diffusion admittance of lithium ion, the contact area with electrolyte can also be increased, to be more conducive to the expansion of lithium ion
It dissipates.
Fig. 3 is the transmission plot under manganese dioxide different multiplying, as can be seen from Figure 3 it can be seen that the manganese dioxide prepared
It is nano-sheet, and these manganese dioxide nano-plates are superthin structures, this structure is conducive to the lithium in charge and discharge process
The diffusion of ion.
In order to verify MnO2Whether positive electrode LiNi is successfully coated on1/3Co1/3Mn1/3O2Surface and MnO2Clad
Influence to tertiary cathode material crystal structure carries out the positive modified material in embodiment 1-5 and comparative example respectively
SEM, TEM and XRD are tested.As a result as in Figure 3-5:
Fig. 4 a are LiNi in comparative example1/3Co1/3Mn1/3O2Scanning electron microscope (SEM) photograph, Fig. 4 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 is stacked with by rod-shpaed particle and is formed, and 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. 4 b-f are due to laminated structure dioxy
Changing the presence of manganese becomes coarse rough.MnO2When coating content is relatively low, clad is imperfect, some ternary material particle
Exposure;It is complete with the increase clad of coating content, 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 the front and back material surface of cladding, to xMnO made from embodiment 1-52/LiNi1/ 3Co1/3Mn1/3O2The phenogram of transmission electron microscope is carried out, Fig. 5 a-1,5a-2 are LiNi uncoated in comparative example1/3Co1/ 3Mn1/3O2Material.As can be seen that uncoated LiNi1/3Co1/3Mn1/3O2Surface is smooth.Fig. 5 b-1 to 5f-2 are respectively embodiment
The transmission electron microscope picture of positive electrode obtained in 1-5, it can be seen that when coating content is relatively low, the clad of material surface is relatively thin
Imperfect, with the increase of coating content, clad becomes complete uniform, but when too high levels, clad becomes very thick, and
And the manganese dioxide nano-plates on surface become very loose.The characterization result characterizes obtained knot with above-mentioned scanning electron microscope
Fruit is consistent.
Fig. 6 is positive electrode and xMnO made from embodiment 1-5 in comparative example2/LiNi1/3Co1/3Mn1/3O2XRD characterization
Figure.As can be seen that the material before and after cladding 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.For three
First material, (006) and (102) and (108) and (110) two groups of peaks split point degree can be used for characterizing material whether have it is good
Good layer structure.It is generally believed that (006) and (102) and (108) and (110) two groups of peaks to split point degree bigger, split point more
Obviously, it was demonstrated that the layer structure feature of ternary material is more apparent, not vice versa.It can be found that coating front and back sample from figure
(006) and (102) and (108) of product and (110) two groups of peak homolysis are shown clearly, it was demonstrated that sample all has good stratiform knot
Structure.For stratified material, mixing degree and material can also be characterized according to the ratio of the relative intensity of certain characteristic peaks
The degree of crystallization of material.It is generally believed that the intensity ratio of characteristic peak I003 and I104 can be used for weighing material Li+And Ni2+Mixing
The ratio of degree, I003 and I104 are bigger, it was demonstrated that the Li of the material+And Ni2+The degree of mixing is smaller, and degree of crystallization is higher.
Li+And Ni2+Mixing can cause the spacing of lithium layer to become smaller, and the diffusion admittance of lithium ion becomes smaller, to be caused to the diffusion of lithium ion
It hinders, therefore mixing degree should be reduced as possible by calculating it is found that the preceding LiNi of cladding1/3Co1/3Mn1/3O2The peaks I003/I104
For value than being 1.138, manganese dioxide coating content is 1wt%, 2wt%, 3wt%, the peaks sample I003/I104 of 4wt%, 5wt%
Value is than being respectively 1.240,1.414,1.526,1.335,1.277.By coating manganese dioxide, Li can be reduced+And Ni2+Mixing
Degree, the ratio that wherein embodiment 3, i.e. coating content are the sample I003 and I104 of 3wt% 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 layer structure of crystal, also be more conducive to lithium ion
Diffusion.
Meanwhile in order to detect every chemical property of embodiment 1- embodiments 5 and the cell positive material in comparative example,
Charge and discharge cycles test is carried out respectively to above-mentioned specific example, Fig. 7-Figure 10 shows experimental result.
Fig. 7 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 175.1mAh/g, 177.7mAh/g, 183mAh/g,
176.4mAh/g and 181.4mAh/g.After 100 circle cycles, 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 conservation rate after manganese dioxide cladding
Apparent to rise, this is primarily due to the Ni that ternary material generates under high pressure4+It is easy to react with electrolyte, causes to live
Property substance quality decline, however, by coat manganese dioxide, form protective layer on the surface of ternary material, can reduce
Electrolyte is to the corrosiveness of active material, to improve its cyclical stability.It is very easy to find in from the above, titanium dioxide
The content of manganese is that the cycles samples stability of 3wt% is the most excellent.When this is relatively low mainly due to the coating content of manganese dioxide, shape
At clad it is sufficiently complete, still some ternary material particle exposure in the electrolytic solution, be easy to happen side reaction;When
When coating content is higher, the manganese dioxide nano-plates on ternary material surface are constantly grown, and are formed thicker clad, are unfavorable for lithium
The diffusion of ion, meanwhile, clad becomes loose, be easy to cause structure collapses during charge and discharge, is followed so as to cause it
Ring stability declines.Embodiment 3, i.e. coating content are that the sample of 3wt% is formed by that clad is uniform and thin, in the table of material
Face forms complete protective layer, contains the side reaction between ternary material and electrolyte;Meanwhile the lithium nickel mixing degree of the material
Minimum, structure are more stablized, and are more favorable to the diffusion of lithium ion, therefore the material shows good cyclical stability.
Fig. 8-Figure 10 shows LiNi uncoated in comparative example1/3Co1/3Mn1/3O2And MnO2Covering amount is the sample of 3wt%
The chemical property figure of product.As can see from Figure 7, the first discharge specific capacity for coating front and back material is not much different, but coats
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 very in 3.0V or so
Small charging platform, in 2.8V or so there are the discharge platform of very little, this may be due to cladding after material surface there are one
Quantitative LixMnO2, which has occurred the deintercalation of lithium ion during charge and discharge, in cyclic voltammetry later
In can be confirmed.Therefore the material first discharge specific capacity after coating can be increased slightly.From fig. 9, it can be seen that before cladding
Specific discharge capacity of the sample under 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, 5.0C multiplying power be respectively 189mAh/g,
172.2mAh/g, 158.4mAh/g, 140.3mAh/g, 115.8mAh/g, 86.9mAh/g coat 3wt%MnO2Sample put
Electric specific capacity is respectively 199mAh/g, 197.5mAh/g, 186mAh/g, 166.8mAh/g, 150.4mAh/g, 121.5mAh/g.
It can be seen that under each current density, the high rate performance of the sample after cladding all has larger raising, and in high current
It is increased more obvious under density.It can be seen from fig. 10 that the sample after cladding has fabulous cyclical stability, cycle
Its capacity retention ratio is 90.16% after 100 circles, and its coulombic efficiency is almost close to 100%.Material after cladding it is forthright again
The raising of energy and cycle performance, this is primarily due to, and manganese dioxide clad hinders electrolyte and the pair of active material is anti-
It answers, and there are gaps between manganese dioxide nano-plates, can alleviate the volume change of the ternary material in charge and discharge process, carry
The high structural stability of positive electrode.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore 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 the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (15)
1. a kind of method coating manganese dioxide in material surface, which is characterized in that include the following steps:
(1) material to be covered and manganese salt are distributed in solvent successively, obtain the first mixed liquor;
(2) complexing agent is added into first mixed liquor and forms the second mixed liquor, by the heated stirring of the second mixed liquor
Afterwards, it filters and is precipitated, clean, collect the precipitation and it is dried processing, you can obtain the material of cladding manganese dioxide
Material.
2. the method according to claim 1 for coating manganese dioxide in material surface, which is characterized in that the material to be covered
Material is anode material for lithium-ion batteries, inorganic oxide or organic compound.
3. method for coating according to claim 1, which is characterized in that in the step (2), before heating stirring, to institute
It states and appropriate anion surfactant is added in the second mixed liquor, it is fully dispersed, obtain third mixed liquor.
4. it is according to claim 3 material surface coat manganese dioxide method, which is characterized in that temperature be (25-
DEG C 40) the third mixed liquor is stirred under conditions of.
5. the method according to claim 4 for coating manganese dioxide in material surface, which is characterized in that the step (2)
In, it is dissolved with after before suction filtration, weighing appropriate PH conditioning agents and oxidant respectively after to the third mixed liquor heating stirring, and
The solution that the two is formed is added dropwise to successively in the third mixed liquor, quickly stirs, waits for that completion of dropwise addition starts timing,
(25-40) DEG C isothermal reaction (10-16) hour, obtain the 4th mixed liquor.
6. the method according to claim 5 for coating manganese dioxide in material surface, which is characterized in that mixed to the described 4th
It closes liquid to be filtered and is precipitated, the precipitation is washed respectively with deionized water and ethyl alcohol, collect the precipitation and at room temperature
It is dry, you can to obtain the material of cladding manganese dioxide.
7. the method according to any one of claim 1 to 6 for coating manganese dioxide in material surface, which is characterized in that
The manganese salt is at least one of manganese acetate, four hydration chloric acid manganese, seven hydrated manganese sulfates and manganese nitrate hexahydrate.
8. the method according to any one of claim 1 to 6 for coating manganese dioxide in material surface, which is characterized in that
The complexing agent is ethylenediamine tetra-acetic acid, hydroxyl ethylenediamine tetra-acetic acid or diethylene triamine pentacetic acid (DTPA).
9. the method according to any one of claim 3 to 6 for coating manganese dioxide in material surface, which is characterized in that
The anion surfactant is at least one in lauryl sodium sulfate, neopelex and alpha-alkene sulfonate
Kind.
10. the method according to claim 5 or 6 for coating manganese dioxide in material surface, which is characterized in that the PH tune
It is at least one of sodium hydroxide and potassium hydroxide to save agent.
11. the method according to claim 5 or 6 for coating manganese dioxide in material surface, which is characterized in that the oxidation
Agent is at least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
12. the method according to any one of claim 1 to 6 for coating manganese dioxide in material surface, which is characterized in that
The mass ratio of the manganese salt and the complexing agent is (49~245):447.
13. it is according to claim 12 material surface coat manganese dioxide method, which is characterized in that the manganese salt with
The mass ratio of the complexing agent is 49:149.
14. the anode modified material that a kind of method by described in any one of the claims 1 to 13 is prepared,
It is characterized in that, including:Pure phase ternary anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2With setting in the pure phase ternary
Anode material for lithium-ion batteries LiNi1/3Co1/3Mn1/3O2The manganese dioxide clad on surface.
15. anode modified material according to claim 14, which is characterized in that the material of the manganese dioxide 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 anode modified material is xMnO2/LiNi1/3Co1/3Mn1/3O2, wherein x=0.01,0.02,0.03,0.04
Or 0.05.
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