CN103956476B - Rich lithium manganese material, preparation method and the application in lithium ion battery of a kind of surface modification - Google Patents
Rich lithium manganese material, preparation method and the application in lithium ion battery of a kind of surface modification Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides rich lithium manganese material, preparation method and the application in lithium ion battery of a kind of surface modification, belongs to lithium battery applications technical field.Solve the existing rich lithium manganese material first charge-discharge coulombic efficiency problem less than 100%.The compound of rich lithium manganese material and molybdenum is ground by the method, obtain compound powder, compound powder is heated with 1 10 DEG C/min heating rate in atmosphere, 0.5 5h is calcined under the conditions of 100 500 DEG C, it is cooled to room temperature with 1 10 DEG C/min rate of temperature fall, i.e. obtains the rich lithium manganese material of surface modification.Test result indicate that: by the rich lithium manganese material of this surface modification as lithium ion secondary battery anode material in discharge capacity first up to 250mAh/g, coulombic efficiency is 100%, is greatly improved rich lithium manganese material as anode material for lithium-ion batteries safety in full battery applications.
Description
Technical field
The invention belongs to lithium battery applications technical field, be specifically related to a kind of surface modification rich lithium manganese material,
Preparation method and the application in lithium ion battery.
Background technology
Rich lithium manganese, English entitled Li-richlayeredmaterials, molecular formula is
xLi2MnO3-(1-x)LiMO2(M=Mn,Ni,Co).Rich lithium manganese material is important lithium ion cell positive material
Material.
Traditional rich lithium manganese anode material its initial coulomb efficiency when first charge-discharge is 70%-80%, first
Coulombic efficiency is less than 100%, can have safety the biggest with the releasing of oxygen in the application of full battery
Threat, this is the rich lithium manganese material of restriction as anode material for lithium-ion batteries key in Commercialization application
Factor.U.S. Argonne high-energy laboratory professor M.M.Thackeray proposes to utilize acid treatment richness lithium manganese positive pole
The method of material improves its initial coulomb efficiency, but the method had both changed the structure of rich lithium manganese, dropped simultaneously
Its initial charge capacity low；Korea S Han Yang University professor Yang-KookSun is by entering rich lithium manganese material
Row surface A lF3The initial coulomb efficiency of rich lithium manganese material is effectively improved to more than 90% by cladding, but still
Not up to 100%, in charge and discharge process, the precipitation of oxygen still exists；University Of Tianjin Zhao Naiqin teaches problem
Group is by rich lithium manganese material Surface coating FePO4Effectively its initial coulomb efficiency is improved to more than 80%,
But the most fundamentally solve its initial coulomb efficiency problem less than 100%.
Summary of the invention
The invention aims to solve existing rich lithium manganese material first charge-discharge coulombic efficiency less than 100%
Problem, and provide the rich lithium manganese material of a kind of surface modification, preparation method and in lithium ion battery should
With.
Present invention firstly provides the preparation method of the rich lithium manganese material of a kind of surface modification, comprise the steps:
Step one: the compound of rich lithium manganese material and molybdenum is ground, obtains compound powder, described molybdenum
The mass ratio of the molybdenum element in compound and rich lithium manganese material is 1:(10～1000)；
Step 2: compound powder step one obtained heats with 1-10 DEG C/min heating rate in atmosphere,
Calcine 0.5-5h under the conditions of 100-500 DEG C, be cooled to room temperature with 1-10 DEG C/min rate of temperature fall, i.e. obtain surface
Modified rich lithium manganese material.
Preferably, the structural formula of described rich manganese lithium material is
(xLi2MnO3-(1-x)Li(MnaNibCoc)O2, wherein, 0.3 < < x < < 0.7,0 < < a < < 1,0 < <b < < 0.5,0 < < c < < 0.5,
a+b+c=1。
Preferably, the structural formula of described rich manganese lithium material is 0.5Li2MnO3-0.5Li(MnNiCo)1/3O2。
Preferably, the structural formula of described rich manganese lithium material is 0.5Li2MnO3-0.5Li(MnNi)1/2O2。
Preferably, the compound of described molybdenum is selected from one or both in molybdenum trioxide or ammonium molybdate.
Preferably, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:150.
Preferably, described milling time is 20～60min.
Preferably, the calcining heat of described step 2 is 300 DEG C, and calcination time is 5h.
The present invention also provides for the rich lithium manganese material of the surface modification that above-mentioned preparation method obtains.
The present invention also provides for the application in lithium ion battery of the rich lithium manganese material of above-mentioned surface modification.
Beneficial effects of the present invention
The present invention provides the preparation method of the rich lithium manganese material of a kind of surface modification, and the method is by richness lithium manganese material
Grind with the compound of molybdenum, obtain compound powder, the molybdenum element in the compound of described molybdenum and rich lithium manganese
Presoma mass ratio is 1:(10～1000)；By compound powder in atmosphere with 1-10 DEG C/min heating rate
Heating, calcines 0.5-5h under the conditions of 100-500 DEG C, is cooled to room temperature with 1-10 DEG C/min rate of temperature fall,
I.e. obtain surface modification rich lithium manganese material.The method technique is simple, by controlling reaction temperature, due to
The Monolayer Dispersion effect of molybdenum compound, makes molybdenum compound be coated on rich lithium manganese presoma surface completely.
The present invention also provides for the rich lithium manganese material of a kind of surface modification and the application in lithium ion battery, this table
Anode material for lithium-ion batteries prepared by the rich lithium manganese material of face modification has good chemical property, due to
The cladding completely of molybdenum compound makes rich lithium manganese completely cut off completely with electrolyte, the initial coulomb efficiency of rich lithium manganese is carried
High.Test result indicate that: the initial coulomb efficiency ining contrast to rich lithium manganese presoma is 70%-80%, the present invention
The initial coulomb efficiency of the rich lithium manganese material of the surface modification of preparation improves to 100%, meanwhile, is maintaining rich lithium
On the premise of manganese presoma specific discharge capacity, greatly improve the safety of full battery.
Accompanying drawing explanation
Fig. 1 is rich lithium manganese (b) that in presoma richness lithium manganese (a) and the embodiment of the present invention 1, Mo modifies
XRD figure is composed；
Fig. 2 is sweeping of rich lithium manganese (b) that in presoma richness lithium manganese (a) and the embodiment of the present invention 1, Mo modifies
Retouch electron microscopic picture；
Fig. 3 is prepared by rich lithium manganese (b) that in presoma richness lithium manganese (a) and the embodiment of the present invention 1, Mo modifies
Lithium ion battery first charge-discharge curve under 0.1C multiplying power；
Fig. 4 is prepared by rich lithium manganese (b) that in presoma richness lithium manganese (a) and the embodiment of the present invention 1, Mo modifies
Lithium ion battery first charge-discharge curve under different multiplying；
Fig. 5 is prepared by rich lithium manganese (b) that in presoma richness lithium manganese (a) and the embodiment of the present invention 1, Mo modifies
Lithium ion battery charge and discharge circulation life under 0.1C multiplying power.
Detailed description of the invention
Present invention firstly provides the preparation method of the rich lithium manganese material of a kind of surface modification, comprise the steps:
Step one: the compound of rich lithium manganese material and molybdenum is ground, obtains compound powder, described molybdenum
The mass ratio of the molybdenum element in compound and rich lithium manganese material is 1:(10～1000)；
Step 2: compound powder step one obtained heats with 1-10 DEG C/min heating rate in atmosphere,
Calcine 0.5-5h under the conditions of 100-500 DEG C, be cooled to room temperature with 1-10 DEG C/min rate of temperature fall, i.e. obtain surface
Modified rich lithium manganese material.
According to the present invention, the most first being ground by the compound of rich lithium manganese material and molybdenum, described milling time does not has
There is particular restriction, be fully ground into powder, preferably more than 20min, more preferably 20～60min.
The structural formula of described rich manganese lithium material is preferably (xLi2MnO3-(1-x)Li(MnaNibCoc)O2, its
In, 0.3 < < x < < 0.7,0 < < a < < 1,0 < <b < < 0.5,0 < < c < < 0.5, a+b+c=1.More preferably structural formula is
0.5Li2MnO3-0.5Li(MnNiCo)1/3O2Or 0.5Li2MnO3-0.5Li(MnNi)1/2O2。
The compound of described molybdenum is preferably selected from one or both in molybdenum trioxide or ammonium molybdate.Described molybdenum
Compound in molybdenum element and the mass ratio of rich lithium manganese material be preferably 1:150.
According to the present invention, compound powder step one obtained is in atmosphere with 1-10 DEG C/min heating rate
Heating, preferably 5 DEG C/min, under the conditions of 100-500 DEG C, calcine 0.5-5h, reaction temperature is preferably
250-450 DEG C, most preferably 300 DEG C, calcination time is preferably 5h, then lowers the temperature speed with 1-10 DEG C/min
Rate is cooled to room temperature, preferably 5 DEG C/min, i.e. obtain surface modification rich lithium manganese material.Step of the present invention
The rich lithium manganese material that reaction temperature in two controls its surface obtained is modified is the most crucial, when temperature is low
In 100 DEG C time, described ammonium molybdate will not decompose at such a temperature, if the raw material secondly used is MoO3,
MoO can not be made at such a temperature3Monolayer Dispersion, cannot reach the effect being coated with completely, to coulomb first
The raising impact of efficiency is little；When temperature is higher than 500 DEG C, calcining the most for a long time, Mo can
In the rich lithium manganese material of entrance of adulterating, change rich lithium manganese material structure, generate unnecessary by-product.
The present invention also provides for the rich lithium manganese material of the surface modification that above-mentioned preparation method obtains.
The present invention also provides for the application in lithium ion battery of the rich lithium manganese material of above-mentioned surface modification, by gained
The rich lithium manganese anode material of the surface modification method of preparing lithium ion battery be method commonly used in the art, tool
Body method is: by prepared positive electrode by rich lithium manganese: acetylene black: PVDF(Kynoar)=80:
The quality of 10:10, than precise, is subsequently adding a certain amount of NMP(N-methyl ketopyrrolidine) grind all
Even, then uniformly it is coated onto on aluminium foil with scraper, 120 DEG C of vacuum dry 12h, the most sliced, tabletting,
In the glove box of full argon, it is assembled into button cell after the techniques such as weighing.Electrolyte used is 1mol/L
LiPF6Ethylene carbonate+dimethyl carbonate (mass ratio is 1:1) solution, barrier film is celgard2400
Both positive and negative polarity battery case needed for film, and assembled battery, lithium sheet, pad.
The rich lithium manganese anode material of surface modification of the present invention, due to the Monolayer Dispersion effect of molybdenum compound, makes molybdenum
Compound is coated on rich lithium manganese presoma surface completely, owing to the cladding completely of molybdenum compound makes rich lithium manganese and electrolysis
Liquid completely cuts off completely, improves the initial coulomb efficiency of rich lithium manganese to 100%.
For making those skilled in the art be better understood from technical scheme, below in conjunction with specific embodiment
And the present invention is described in further detail by accompanying drawing.
Embodiment 1
By 50g0.5Li2MnO3-0.5Li(MnNiCo)1/3O2 and 0.97g ammonium molybdate mixed grinding 20min, extremely
Mix homogeneously, obtains compound powder, with 5 DEG C/min, compound powder is warming up to 300 DEG C in atmosphere and forges
Burn 5h, 5 DEG C/min and be down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, be designated as
(0.5Li2MnO3-0.5Li(MnNiCo)1/3O2@1.5%Mo).
The rich lithium manganese material that prepared surface is modified is pressed
(0.5Li2MnO3-0.5Li(MnNiCo)1/3O2@1.5%Mo): acetylene black: PVDF(Kynoar)
The quality of=80:10:10, than precise, is subsequently adding a certain amount of NMP(N-methyl ketopyrrolidine)
Grind uniformly, be then uniformly coated onto on aluminium foil with scraper, 120 DEG C of vacuum baking 12h, the most sliced,
In the glove box of full argon, button cell it is assembled into, electrolysis used in battery after tabletting, weighing technique
Liquid is 1mol/LLiPF6Ethylene carbonate+dimethyl carbonate (mass ratio is 1:1) solution, barrier film is
Celgard2400 film, and the both positive and negative polarity battery case needed for assembled battery, lithium sheet, pad.
Fig. 1 is the XRD figure spectrum of the rich lithium manganese that in embodiment 1, presoma richness lithium manganese and Mo modify, Qi Zhongtu
A is the XRD figure spectrum of presoma richness lithium manganese, and figure b is that Mo modifies rich lithium manganese XRD figure spectrum, test result table
Bright Mo modifies rich lithium manganese material can keep the basic feature peak of rich lithium manganese material, and peak type is sharp-pointed, and back end is smooth,
There is small change in the peak type of 65 °, illustrates that rich lithium manganese presoma is played certain modification by molybdenum trioxide
The characteristic peak of rich lithium manganese presoma can be kept simultaneously.Figure b does not find the characteristic peak of molybdenum trioxide,
Illustrate that molybdenum trioxide is dispersed in the surface of rich lithium manganese presoma, richness lithium manganese material is coated with completely.
Fig. 2 is the scanning electron microscopic picture of the rich lithium manganese that rich lithium manganese presoma and Mo modify in embodiment 1, schemes a
For the scanning electron microscopic picture of rich lithium manganese presoma that amplification is 5000 times, figure b be amplification be 5000
Mo again modifies the scanning electron microscopic picture of rich lithium manganese, and as can be seen from the figure Mo modifies rich lithium manganese at 300 DEG C
In air, after calcining, also particle diameter does not become big, and uniform particle sizes, narrowly distributing.
Fig. 3 is that rich lithium manganese that in the embodiment of the present invention 1, rich lithium manganese presoma and Mo modify is under the conditions of 0.1C
First charge-discharge curve, figure a is the first charge-discharge curve of presoma richness lithium manganese, and figure b is that Mo modifies richness
The first charge-discharge curve of lithium manganese.From figure 3, it can be seen that after the button cell being assembled into stands 4-5h,
With the rate charge-discharge of 0.1C, in figure a, discharge capacity is 280mAhg first-1, initial coulomb efficiency is
80.9%, in figure b, discharge capacity is 280mAhg first-1, initial coulomb efficiency is 100%.Fig. 3 shows
Rich lithium manganese presoma chemical property is good, and Mo modifies the not decay of rich lithium manganese discharge capacity first, and first
Secondary coulombic efficiency.
Fig. 4 is the head of the rich lithium manganese different multiplying that rich lithium manganese presoma and Mo modify in the embodiment of the present invention 1
Secondary charging and discharging curve, figure a is presoma richness lithium manganese first charge-discharge curve under different multiplying, and figure b is
Mo modifies rich lithium manganese first charge-discharge curve under different multiplying.Figure 4, it is seen that be assembled into
After button cell stands 4-5h, with different multiplying (0.1C, 0.2C, 0.5C) first charge-discharge, in figure a
Initial coulomb efficiency is respectively 80.9%, and 80.7%, 71.6%；In figure b, initial coulomb efficiency is 100%.
Fig. 4 shows that Mo modifies rich lithium manganese material during first charge-discharge, and initial coulomb efficiency all can bring up to
100%。
Fig. 5 is that rich lithium manganese that in the embodiment of the present invention 1, rich lithium manganese presoma and Mo modify is under 0.5C multiplying power
Charge and discharge cycles curve, figure a be presoma richness lithium manganese charge and discharge cycles curve under 0.5C multiplying power, figure
B is that Mo modifies rich lithium manganese charging and discharging curve under 0.1C multiplying power.From figure 5 it can be seen that be assembled into
After button cell stands 4-5h, carrying out charge and discharge cycles under 0.1C multiplying power, in figure a, initial coulomb efficiency is
80%, the most all close to 100%, after 40 circle circulations, specific discharge capacity is by 280mAhg-1Drop to 181.5mAh
g-1, capability retention is 64.8%；And in figure b, initial coulomb efficiency is 100%, the most all close to 100%,
After 40 circle circulations, specific discharge capacity is by 268mAhg-1Drop to 152.5mAhg-1, capability retention is
56.9%。
Embodiment 2
By 50g0.5Li2MnO3-0.5Li(MnNi)1/2O2With 0.97g ammonium molybdate mixed grinding 20min, extremely mixing
Uniformly, obtain compound powder, compound powder be warming up to 300 DEG C of calcining 5h with 5 DEG C/min in atmosphere,
5 DEG C/min is down to room temperature, i.e. obtains the rich lithium manganese material of surface modification, is designated as
(0.5Li2MnO3-0.5Li(MnNi)1/2O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese presoma positive electrode and is assembled into button electricity as described in Example 1
Pond, discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electricity
Chemical property is good.
Embodiment 3
By 50g0.5Li2MnO3-0.5Li(MnNiCo)1/3O2With 0.11g molybdenum trioxide mixed grinding 30min,
To mix homogeneously, obtain compound powder, compound powder is warming up to 250 DEG C with 10 DEG C/min in atmosphere
Calcining 3h, 10 DEG C/min are down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, are designated as
(0.5Li2MnO3-0.5Li(MnNiCo)1/3O2@1.5%MoO3).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 4
By 50g0.5Li2MnO3-0.5Li(MnNiCo)1/3O2With 0.065g ammonium molybdate mixed grinding 60min, extremely
Mix homogeneously, obtains compound powder, with 1 DEG C/min, compound powder is warming up to 450 DEG C in atmosphere and forges
Burn 0.5h, 1 DEG C/min and be down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, be designated as
(0.5Li2MnO3-0.5Li(MnNiCo)1/3O2@0.1%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 90%, shows its electrochemistry
Can be good.
Embodiment 5
By 50g0.5Li2MnO3-0.5Li(MnNiCo)1/3O2With 6.47g ammonium molybdate mixed grinding 20min, extremely
Mix homogeneously, obtains compound powder, with 5 DEG C/min, compound powder is warming up to 300 DEG C in atmosphere and forges
Burn 5h, 5 DEG C/min and be down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, be designated as
(0.5Li2MnO3-0.5Li(MnNiCo)1/3O2@10%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 6
By 50g0.3Li2MnO3-0.7Li(Mn0.3Ni0.7)O2With 0.97g ammonium molybdate mixed grinding 20min, extremely mix
Close uniformly, obtain compound powder, compound powder is warming up to 300 DEG C of calcinings with 5 DEG C/min in atmosphere
5h, 5 DEG C/min are down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, are designated as
(0.3Li2MnO3-0.7Li(Mn0.3Ni0.7)O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 7
By 50g0.7Li2MnO3-0.3Li(Mn0.3Ni0.7)O2With 0.97g ammonium molybdate mixed grinding 20min, extremely mix
Close uniformly, obtain compound powder, compound powder is warming up to 300 DEG C of calcinings with 5 DEG C/min in atmosphere
5h, 5 DEG C/min are down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, are designated as
(0.7Li2MnO3-0.3Li(Mn0.3Ni0.7)O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 8
By 50g0.3Li2MnO3-0.7Li(Mn0.7Ni0.3)O2With 0.97g ammonium molybdate mixed grinding 20min, extremely mix
Close uniformly, obtain compound powder, compound powder is warming up to 300 DEG C of calcinings with 5 DEG C/min in atmosphere
5h, 5 DEG C/min are down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, are designated as
(0.3Li2MnO3-0.7Li(Mn0.7Ni0.3)O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 9
By 50g0.7Li2MnO3-0.3Li(Mn0.7Ni0.3)O2With 0.97g ammonium molybdate mixed grinding 20min, extremely mix
Close uniformly, obtain compound powder, compound powder is warming up to 300 DEG C of calcinings with 5 DEG C/min in atmosphere
5h, 5 DEG C/min are down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, are designated as
(0.7Li2MnO3-0.3Li(Mn0.7Ni0.3)O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 10
By 50g0.3Li2MnO3-0.7Li(MnNiCo)1/3O2With 0.97g ammonium molybdate mixed grinding 20min, extremely
Mix homogeneously, obtains compound powder, with 5 DEG C/min, compound powder is warming up to 300 DEG C in atmosphere and forges
Burn 5h, 5 DEG C/min and be down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, be designated as
(0.3Li2MnO3-0.7Li(MnNiCo)1/3O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
Embodiment 11
By 50g0.7Li2MnO3-0.3Li(MnNiCo)1/3O2With 0.97g ammonium molybdate mixed grinding 20min, extremely
Mix homogeneously, obtains compound powder, with 5 DEG C/min, compound powder is warming up to 300 DEG C in atmosphere and forges
Burn 5h, 5 DEG C/min and be down to room temperature, i.e. obtain the rich lithium manganese material of surface modification, be designated as
0.7Li2MnO3-0.3Li(MnNiCo)1/3O2@1.5%Mo).
Prepared Mo is modified rich lithium manganese anode material and is assembled into button cell as described in Example 1,
Discharge and recharge under 0.1C, 0.2C, 0.5C multiplying power, its initial coulomb efficiency is 100%, shows its electrochemistry
Can be good.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.Should refer to
Go out, for those skilled in the art, under the premise without departing from the principles of the invention, also
The present invention can be carried out some improvement and modification, these improve and modify and also fall into the claims in the present invention
In protection domain.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses this
Invention.Multiple amendment to these embodiments will be apparent from for those skilled in the art,
Generic principles defined herein can without departing from the spirit or scope of the present invention, at other
Embodiment realizes.Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is intended to
Meet the widest scope consistent with principles disclosed herein and features of novelty.
Claims (9)
1. the preparation method of the rich lithium manganese material of a surface modification, it is characterised in that comprise the steps:
Step one: the compound of rich lithium manganese material and molybdenum is ground, obtains compound powder, described molybdenum
The mass ratio of the molybdenum element in compound and rich lithium manganese material is 1:(10～1000)；
Step 2: compound powder step one obtained heats with 1-10 DEG C/min heating rate in atmosphere,
Calcine 0.5-5h under the conditions of 100-500 DEG C, be cooled to room temperature with 1-10 DEG C/min rate of temperature fall, i.e. obtain surface
Modified rich lithium manganese material；
The compound of described molybdenum is selected from one or both in molybdenum trioxide or ammonium molybdate.
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 1, its feature
Being, the structural formula of described rich lithium manganese material is (xLi2MnO3-(1-x)Li(MnaNibCoc)O2, wherein,
0.3 < x < 0.7,0 < a < 1,0 <b < 0.5,0 < c < 0.5, a+b+c=1.
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 2, its feature
Being, the structural formula of described rich lithium manganese material is 0.5Li2MnO3-0.5Li(MnNiCo)1/3O2。
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 2, its feature
Being, the structural formula of described rich lithium manganese material is 0.5Li2MnO3-0.5Li(MnNi)1/2O2。
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 1, its feature
Being, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:150.
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 1, its feature
Being, described milling time is 20～60min.
The preparation method of the rich lithium manganese material of a kind of surface modification the most according to claim 1, its feature
Being, the calcining heat of described step 2 is 300 DEG C, and calcination time is 5h.
8. the rich lithium manganese material of the surface modification that the preparation method described in claim 1-7 any one obtains.
9. the rich lithium manganese material of the surface modification described in claim 8 application in lithium ion battery.
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| CN108091852B (en) * | 2017-12-12 | 2020-09-11 | 中国科学院过程工程研究所 | Molybdenum trioxide coated lithium ion battery positive electrode material and preparation method thereof |
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| CN102244259A (en) * | 2011-06-17 | 2011-11-16 | 中国科学院化学研究所 | Composite lithium-rich anode material, its preparation method and its application |
| CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
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| CN102244259A (en) * | 2011-06-17 | 2011-11-16 | 中国科学院化学研究所 | Composite lithium-rich anode material, its preparation method and its application |
| CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
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