CN108862394A - The preparation method of manganese dioxide and the anode modified material formed is coated by manganese dioxide - Google Patents
The preparation method of manganese dioxide and the anode modified material formed is coated by manganese dioxide Download PDFInfo
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Abstract
Coat the present invention provides a kind of preparation method of manganese dioxide and by manganese dioxide the anode modified material formed.The preparation method of manganese dioxide provided by the invention passes through the Mn for forming manganous salt under the action of complexing agent2+Complex precipitate, then will be by Mn by oxidant2+It is oxidized to Mn4+, so that the MnO of stable structure be made2, and to obtained MnO2It is heat-treated to remove absorption water therein and combine water, to guarantee its chemical property, the preparation method simple process, low in cost, the manganese dioxide of preparation is flaky nanometer structure, can not only shorten the diffusion admittance of lithium ion, the contact area of itself and electrolyte can also be increased, to advantageously reduce the contact probability in positive electrode between active material and electrolyte, it can effectively inhibit electrolyte to the corrosiveness of active material, improve the stability of positive modified material.
Description
Technical field
The present invention relates to technical field of lithium ion, a kind of preparation method in particular to manganese dioxide and by
Manganese dioxide coats the anode modified material to be formed.
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 day
The energy demand that benefit increases, and problem of environmental pollution caused by combustion of fossil fuels is also got worse, and wherein PM2.5 most draws
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
Can be with the reversible transformation of chemical energy, secondary cell is at low cost, specific energy is high, high-efficient environmentally friendly and cycle performance
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, nickel-metal hydride 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, long service life 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 especially urgent.
Lithium ion battery LiNi1/3Co1/3Mn1/3O2Tertiary cathode material specific discharge capacity is high, but during circulation
Its capacity attenuation is serious, in the prior art by oxide coated to alleviate capacity attenuation phenomenon on it, but often occurs
The problem of structural instability.
Summary of the invention
In consideration of it, coating the invention proposes a kind of preparation method of manganese dioxide and by manganese dioxide the battery formed just
Pole modified material, it is intended to solve the problems, such as existing lithium ion cell positive modified material structural instability.
Specifically, first aspect present invention proposes a kind of preparation method of manganese dioxide, includes the following steps：
(1) appropriate manganese salt is weighed, sufficiently dissolves, obtains the first solution.Specifically, manganese salt can be manganese acetate, four hydrations
Chloric acid manganese (MnCl2·4H2O), seven hydrated manganese sulfate (MnSO4·7H2) and manganese nitrate hexahydrate ((Mn (NO O3)2·6H2O in)
At least one, it is preferred that manganese salt is manganese acetate, cheap, is easily obtained, and can be into the complex reaction of complexing agent
Capable is more thorough, and the by-product of reaction is less.When it is implemented, deionized water can be selected to dissolve manganese salt, nothing as solvent
Poison and advantageously reduce reaction after organic waste materials；Manganese salt can be adequately dissolved in by the way of ultrasonic vibration, stirring
In deionized water.
(2) appropriate complexing agent is added into first solution, keeps it sufficiently mixed with the manganese salt in first mixed liquor
It closes, obtains the second mixed liquor, and be stirred under conditions of temperature is (25-40) DEG C to 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 surface by EDTA by pentaacetic acid (DTPA), preferably ethylenediamine tetra-acetic acid (EDTA) completely.
Preferably, reaction temperature be (30-35) DEG C, can with heating water bath and be added thermocouple keep reaction temperature.
When it is implemented, selecting the sodium salt of EDTA so that EDTA sufficiently 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 precipitating of manganous salt, reduces the generation of impurity.
(3) 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 second mixed liquor, quickly stirs, starts timing to completion of dropwise addition, isothermal reaction (10-16) is small at (25-40) DEG C
When, obtain third mixed liquor.Preferably, 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's
It adjusts, is adjusted the pH value of solution to PH=7 by sodium hydroxide, to provide the environment that divalent Mn salt generates precipitating,
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 can be oxidized to divalent manganesetion by oxidant
Tetravalence 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
(4) the 4th mixed liquor is filtered and is precipitated, washed, collect the precipitating and it is dried place
Reason, can be obtained MnO2。
Specifically, the product in above-mentioned steps (3) is filtered, MnO can be obtained2Precipitating, can use deionized water
First the precipitating is cleaned multiple times to remove the other impurities ingredient generated in complex reaction and neutralization reaction, then passes through second
Alcohol quickly takes away deionized water remaining in precipitating, ensure that the degree of purity of product, the MnO obtained by the step2For nanometer sheet
Shape structure, morphology characterization see below continuous experimental example.
Can also include in the embodiment of the present invention：Step (5) weighs MnO made from appropriate step (4)2It is put into crucible,
Then crucible is placed in tube furnace, is heat-treated at 300-600 DEG C.
Specifically, due to MnO obtained2It is interior containing absorption water and combine water, will affect MnO2Application in some aspects
(such as by MnO obtained above2In the preparation of anode modified material, adsorbs water and the presence of water is combined to will affect
MnO2Conductivity, to will affect the chemical property of positive electrode), it is therefore desirable to remove absorption water therein and combination
Water.Preferably, treatment temperature is 400 DEG C.When it is implemented, weighing 0.5g manganese dioxide, it is put into ceramic crucible, then by earthenware
Crucible is placed in tube furnace, is heat-treated at 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C respectively, heat treatment time 2h, is risen
Warm rate and rate of temperature fall are 2 DEG C/min.
First aspect present invention provide manganese dioxide preparation method, by by manganous salt under the action of complexing agent
The Mn of formation2+Complex precipitate, then will be by Mn by oxidant2+It is oxidized to Mn4+, so that the MnO of stable structure be made2, and it is right
Obtained MnO2It is heat-treated to remove absorption water therein and combine water, to guarantee its chemical property, the preparation method
The manganese dioxide of simple process and low cost, preparation is flaky nanometer structure, can not only shorten the diffusion admittance of lithium ion,
The contact area of itself and electrolyte can also be increased, to advantageously reduce in positive electrode between active material and electrolyte
Contact probability can effectively inhibit electrolyte to the corrosiveness of active material, improve the stability of positive modified material.
Second aspect of the present invention provides a kind of MnO prepared according to above-mentioned preparation method2Purposes, MnO obtained2With
In preparing lithium ion cell positive modified material.The positive electrode includes 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 cladding on surface
Layer, wherein the material of the clad is above-mentioned manganese dioxide, cheap, from a wealth of sources, the preparation of complex compound
Journey is relatively simple and complex reaction can be generated adequately；Simultaneously as MnO2Active force between molecule is larger, it is difficult to mix
Enter positive electrode LiNi1/3Co1/3Mn1/3O2Internal structure in, therefore will not be to the production of the crystal structure of positive electrode itself
It is raw to influence.Pure phase LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2For commercial product, without limitation to its source.
Further, in above-mentioned anode modified material, the material of the clad and the pure phase ternary lithium ion
Cell positive material LiNi1/3Co1/3Mn1/3O2Mass ratio be (0.01-0.05)：1；Preferably (0.02-0.04):1；Into one
Step preferably 0.03:1.The coating layer material and pure phase ternary anode material for lithium-ion batteries LiNi of appropriate mass ratio1/3Co1/ 3Mn1/3O2, the clad type positive electrode of stable structure can be formed, and make the positive electrode that there is preferable stability 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.
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 circulation
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 to deionization
It in water, 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 O
(NO3)2·6H2At least one of O), it is preferred that manganese salt is manganese acetate, cheap, is easily obtained, and and complexing agent
Complex reaction can be carried out more thoroughly, the by-product of reaction is less.When it is implemented, can be using ultrasonic vibration, stirring
Mode each raw material is adequately dispersed in deionized water.It is by the step that manganese salt is fully dispersed to 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, and complexing agent is ethylenediamine tetra-acetic acid (EDTA), hydroxyl ethylenediamine tetra-acetic acid (HEDTA) or divinyl
Pentaacetic acid (DTPA), preferably ethylenediamine tetra-acetic acid (EDTA), are deposited in positive electrode for manganese acetate by EDTA completely
Surface.When it is implemented, selecting the sodium salt of EDTA so that EDTA sufficiently in water, and participates in subsequent complex reaction, specifically
Reaction equation 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 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 bath temperature is (25-40) DEG C.Specifically, anionic surface
Activating agent can be at least one of for lauryl sodium sulfate, neopelex and alpha-alkene sulfonate, such as can
To be preferably lauryl sodium sulfate.It can reinforce the mixability of solution by the way of ultrasonic vibration, stirring；Preferably,
Reaction temperature is (30-35) DEG C.By the step, can by the complex precipitate of Mn it is more uniform be dispersed in positive electrode table
Face.
(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) hour, it is mixed to obtain the 4th
Close liquid.
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's
It adjusts, is adjusted the pH value of solution to PH=7 by sodium hydroxide, to provide the environment that Mn salt generates precipitating, wherein
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 tetravalence by oxidant
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 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, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects the precipitating and is dried at room temperature for, lithium ion battery tertiary cathode modified material xMnO can be obtained2/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 miscellaneous to remove other that generate in complex reaction and neutralization reaction
Then matter ingredient is quickly taken away deionized water remaining in precipitating by ethyl alcohol, ensure that the degree of purity 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.
Detailed description of the invention
Fig. 1 a-b is MnO under the different amplification provided in the embodiment of the present invention2SEM figure；
Fig. 2 a-c is MnO under the different multiplying provided in the embodiment of the present invention2TEM figure；
Fig. 3 is the MnO provided in the embodiment of the present invention 32Thermal multigraph at a temperature of different disposal；
Fig. 4 is the MnO provided in the embodiment of the present invention 32XRD diagram at a temperature of different disposal；
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 SEM figure of the ternary modified material after manganese dioxide is 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 TEM figure of the ternary modified material after manganese dioxide is 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
The XED figure of the ternary modified material after manganese dioxide is coated in 1-5；
Fig. 8 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. 9 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；
Figure 10 is pure phase ternary anode material for lithium-ion batteries LiNi in the embodiment of the present invention1/3Co1/3Mn1/3O2And implement
Ternary modified material after coating manganese dioxide in example 3 is 2.5V-4.5V in voltage range, when current density is 200mA/g,
Cycle performance curve graph under different multiplying；
Figure 11 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 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 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 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, to both add beginning timing, isothermal reaction 10 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects 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
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, to both add beginning timing, isothermal reaction 13 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects 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 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, to both add beginning timing, isothermal reaction 12 hours, obtain the
Four mixed liquors；
(5) the 4th mixed liquor is filtered and is precipitated, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects 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 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
The third mixed liquor is stirred to third mixed liquor, and 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, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects 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 complexing
Agent 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, wash the precipitating respectively with deionized water and ethyl alcohol,
It collects 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
Fig. 1 and Fig. 2 is the MnO prepared to above-described embodiment 1-52The spectrogram that is characterized of pattern, Fig. 1 puts for difference
The scanning figure of manganese dioxide, should be apparent that manganese dioxide was made of ultra-thin nanometer sheet from Fig. 1 under big multiple, and
And be stacked between nanometer sheet, being formed has very lacunose duct, and this structure can not only shorten the diffusion of lithium ion
Channel can also increase the contact area with electrolyte, to be more conducive to the diffusion of lithium ion.
Fig. 2 is the transmission plot under manganese dioxide different multiplying, as can be seen from Figure 2 it can be seen that the manganese dioxide of preparation
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 investigate heat treatment temperature to MnO2Influence, to MnO2Thermogravimetric test and XRD test, test result are carried out
As Figure 3-Figure 4.
Fig. 3 is the MnO prepared to embodiment 32The curve graph of thermogravimetric test is carried out, the sample after Overheating Treatment is ordered respectively
Entitled MnO2- 300 DEG C, MnO2- 400 DEG C, MnO2- 500 DEG C, MnO2- 600 DEG C, not the material designation Jing Guo high-temperature heat treatment be
MnO2-25℃.It can be seen from the figure that manganese dioxide within 150 DEG C, there is biggish mass loss, this mainly removes two
The process of the absorption water on manganese oxide surface, mass loss is still had from 150 DEG C to 350 DEG C, this mainly removes manganese dioxide
The middle stronger millipore water of binding force.Continue to increase with temperature, the quality of manganese dioxide continues to decline, and this is mainly due to two
Manganese oxide gradually changes to manganese sesquioxide managnic oxide, since the conductivity of manganese sesquioxide managnic oxide is low, so this transformation is for improving material
Electric conductivity be unfavorable.Absorption water and the combination in manganese dioxide are completely removed in view of the positive electrode as battery
Water, therefore select at 400 DEG C to MnO2It is heat-treated.
Fig. 4 is the MnO prepared to embodiment 32Heat treatment progress is carried out at 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C respectively
The XRD diagram of crystal phase analysis, the sample after Overheating Treatment are respectively designated as MnO2- 300 DEG C, MnO2- 400 DEG C, MnO2- 500 DEG C,
MnO2- 600 DEG C, the material designation Jing Guo high-temperature heat treatment is not MnO2-25℃.As seen from Figure 4 from 25 DEG C of room temperature to
The diffraction maximum and δ-MnO of 400 DEG C of XRD spectra2Diffraction maximum fit like a glove, comparison PDF card can be found that and meets
JCPDS:NO.43-1456.When heat treatment temperature increases once again, sample is no longer single-phase manganese dioxide, become manganese dioxide and
The mixed phase of manganese sesquioxide managnic oxide, this is corresponding with the thermogravimetric curve of Fig. 3.
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, carries out the positive modified material in embodiment 1-5 and comparative example respectively
SEM, TEM and XRD test.As a result as illustrated in figs. 5-7：
B-f is respectively the xMnO of difference coating content made from embodiment 1-5 in Fig. 52/LiNi1/3Co1/3Mn1/3O2Sweep
Retouch electron microscope, it can be seen that uncoated LiNi in comparative example1/3Co1/3Mn1/3O2Material is that institute is stacked with by rod-shpaed particle
Composition, the surface of particle is smooth, is not dense packing between particle, mutually there is gap.It can be sent out from Fig. 5 b-f
Sample surfaces after now coating become coarse rough due to the presence of laminated structure manganese dioxide.MnO2Coating content is lower
When, clad is imperfect, the exposure of some ternary material particle；As the increase clad of coating content is complete, but content
When excessively high, manganese dioxide nano-plates are constantly grown, and form 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. 6 a-1,6a-2 are LiNi uncoated in comparative example1/3Co1/ 3Mn1/3O2Material.As can be seen that uncoated LiNi1/3Co1/3Mn1/3O2Surface is smooth.Fig. 6 b-1 to 6f-2 is respectively embodiment
The transmission electron microscope picture of positive electrode obtained in 1-5, it can be seen that when coating content is lower, 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 and above-mentioned scanning electron microscope characterize obtained knot
Fruit is consistent.
Fig. 7 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.
For ternary material, (006) and (102) and (108) and (110) two groups of peaks split point degree and can be used to characterize material and be
It is no that there is good layer structure.It is generally believed that point degree of splitting at (006) and (102) and (108) and (110) two groups of peaks is got over
Greatly, it splits and point is more obvious, it was demonstrated that the layer structure feature of ternary material is more obvious, not vice versa.It can be found that cladding from figure
(006) and (102) and (108) of the sample of front and back and (110) two groups of peak homolysis are shown clearly, it was demonstrated that sample all has well
Layer structure.For stratified material, mixing degree can also be characterized according to the ratio of the relative intensity of certain characteristic peaks
And the degree of crystallization of material.It is generally believed that the intensity ratio of characteristic peak I003 and I104 can be used for measuring material 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
It 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 the diffusion to lithium ion
It causes to hinder, therefore mixing degree should be reduced as far as possible by calculating it is found that coating preceding LiNi1/3Co1/3Mn1/3O2I003/
I104 peak value ratio is 1.138, and manganese dioxide coating content is 1wt%, 2wt%, 3wt%, the sample I003/ of 4wt%, 5wt%
I104 peak value is than being respectively 1.240,1.414,1.526,1.335,1.277.By coating manganese dioxide, Li can be reduced+With
Ni2+The degree of mixing, wherein embodiment 3, i.e. coating content are maximum for the ratio of the sample I003 and I104 of 3wt%, 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
The diffusion of ion.
Meanwhile in order to detect every chemical property of the cell positive material in embodiment 1- embodiment 5 and comparative example,
Charge and discharge cycles test is carried out respectively to above-mentioned specific example, Fig. 8-Figure 11 shows experimental result.
Fig. 8 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, cause
The quality of active material declines, however, foring protective layer by cladding manganese dioxide on the surface of ternary material, can dropping
Low electrolyte is to the corrosiveness of active material, to improve its cyclical stability.It is very easy to find in from the above, dioxy
The cycles samples stability that the content for changing manganese is 3wt% is the most excellent.When this is lower mainly due to the coating content of manganese dioxide,
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 are formed thicker clad, are unfavorable for
The diffusion of lithium ion, meanwhile, clad becomes loose, structure collapses is be easy to cause during charge and discharge, so as to cause it
Cyclical stability decline.Embodiment 3, i.e. coating content are that the sample of 3wt% is formed by that clad is uniform and thin, in material
Surface forms complete protective layer, contains the side reaction between ternary material and electrolyte；Meanwhile the lithium nickel mixing journey of the material
Degree is minimum, and structure is more stable, is more favorable to the diffusion of lithium ion, therefore the material shows good stable circulation
Property.
Fig. 9-Figure 11 shows LiNi uncoated in comparative example1/3Co1/3Mn1/3O2And MnO2Covering amount is the sample of 3wt%
The chemical property figure of product.As it can be seen in figure 9 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 very in 3.0V or so
Small charging platform, in 2.8V or so, there are the discharge platforms of very little, this may be since there are one for the material surface after cladding
The deintercalation of lithium ion has occurred in quantitative LixMnO2, the compound during charge and discharge, surveys in cyclic voltammetric later
Available confirmation in examination.Therefore the material first discharge specific capacity after coating can be increased slightly.From fig. 10 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 in big electricity under each current density
Under current density, increase it is more obvious.It can be seen from fig. 11 that the sample after cladding has fabulous cyclical stability, follow
Its capacity retention ratio is 90.16% after ring 100 encloses, and its coulombic efficiency is almost close to 100%.The multiplying power of material after cladding
The raising of performance 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, mention
The high 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 guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (12)
1. a kind of preparation method of manganese dioxide, which is characterized in that include the following steps：
(1) suitable manganese salt is weighed, sufficiently dissolves, obtains the first solution；
(2) appropriate complexing agent is added into first solution, is sufficiently mixed it with the manganese salt in first mixed liquor, obtains
Second mixed liquor is stirred to the second mixed liquor, and under conditions of temperature is (25-40) DEG C；
(3) it takes appropriate oxidizing agent solution to be added dropwise in second mixed liquor, quickly stirs, start to count to completion of dropwise addition
When, isothermal reaction (10-16) hour at (25-40) DEG C, obtain third mixed liquor；
(4) the third mixed liquor is filtered and is precipitated, washed, collect the precipitating and it is dried
Obtain MnO2。
2. the preparation method of manganese dioxide according to claim 1, which is characterized in that in the step (3), oxygen is being added dropwise
Before agent, appropriate PH regulator is weighed, is added dropwise in second mixed liquor.
3. the preparation method of manganese dioxide according to claim 1, which is characterized in that further include：Step (5), weighs suitable
Measure MnO made from step (4)2It is put into crucible, then crucible is placed in tube furnace, be heat-treated at 300-600 DEG C.
4. the preparation method of manganese dioxide according to any one of claim 1 to 3, 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.
5. the preparation method of manganese dioxide according to any one of claim 1 to 3, which is characterized in that the complexing agent
For ethylenediamine tetra-acetic acid, hydroxyl ethylenediamine tetra-acetic acid or diethylene triamine pentacetic acid (DTPA).
6. the preparation method of manganese dioxide according to claim 2, which is characterized in that the PH regulator is sodium hydroxide
At least one of with potassium hydroxide.
7. the preparation method of manganese dioxide according to any one of claim 1 to 3, which is characterized in that the oxidant
For at least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate.
8. the preparation method of manganese dioxide according to any one of claim 1 to 3, which is characterized in that the manganese salt with
The mass ratio of the complexing agent is (49~245)：447.
9. the preparation method of manganese dioxide according to claim 8, which is characterized in that the manganese salt and the complexing agent
Mass ratio is 49：149.
10. the preparation method of manganese dioxide according to any one of claim 1 to 3, which is characterized in that the step
(2) reaction temperature in is (30-35) DEG C；Reaction time in the step (3) is (12-14) hour.
11. the preparation method of manganese dioxide according to any one of claim 1 to 3, which is characterized in that the step
(4) MnO obtained in2For flaky nanometer structure.
12. a kind of anode of the manganese dioxide cladding of the preparation of the method as described in any one of the claims 1 to 11
Modified material, which is characterized in that including 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 MnO on surface2Clad, wherein the MnO2Cladding
Layer 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.
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| CN111268736A (en) * | 2020-02-14 | 2020-06-12 | 广东工业大学 | Three-dimensional flower-ball-shaped β -manganese dioxide and preparation method and application thereof |
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