CN103956476A - Surface-modified lithium-rich manganese material and its preparation method and use in lithium ion battery - Google Patents
Surface-modified lithium-rich manganese material and its preparation method and use in lithium ion battery Download PDFInfo
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- CN103956476A CN103956476A CN201410106775.7A CN201410106775A CN103956476A CN 103956476 A CN103956476 A CN 103956476A CN 201410106775 A CN201410106775 A CN 201410106775A CN 103956476 A CN103956476 A CN 103956476A
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention provides a surface-modified lithium-rich manganese material and its preparation method and use in a lithium ion battery, and belongs to the technical field of lithium ion battery application. The surface-modified lithium-rich manganese material solves the problem that the existing lithium-rich manganese material has first charge-discharge coulombic efficiency less than 100%. The preparation method comprises the following steps of grinding a lithium-rich manganese material and a compound of molybdenum to obtain compound powder, heating the compound powder in air at a heating rate of 1-10 DEG C/min, carrying out calcination at a temperature of 100-500 DEG C for 0.5-5h, and carrying out cooling to a room temperature at a cooling rate of 1-10 DEG C/min to obtain the surface-modified lithium-rich manganese material. An experiment result shows that the surface-modified lithium-rich manganese material as a lithium ion secondary cell positive pole material has a first discharge capacity of 250mAh/g and coulombic efficiency of 100%, and greatly improves the safety of the surface-modified lithium-rich manganese material as the lithium ion secondary cell positive pole material in total battery application.
Description
Technical field
The invention belongs to lithium battery applications technical field, be specifically related to a kind of rich lithium manganese material, preparation method and application in lithium ion battery of surface modification.
Background technology
Rich lithium manganese, English Li-richlayeredmaterials by name, molecular formula is xLi
2mnO
3-(1-x) LiMO
2(M=Mn, Ni, Co).Rich lithium manganese material is important anode material for lithium-ion batteries.
Traditional rich lithium manganese anode material when first charge-discharge its first coulombic efficiency be 70%-80%, coulombic efficiency is less than 100% first, can follow emitting of oxygen, in the application of full battery, fail safe is had to very large threat, this be the rich lithium manganese material of restriction as anode material for lithium-ion batteries the key factor in Commercialization application.U.S. Argonne high-energy laboratory professor M.M.Thackeray proposes to utilize the method for the rich lithium manganese anode material of acid treatment to improve its coulombic efficiency first, but the method had both changed the structure of rich lithium manganese, had reduced its initial charge capacity simultaneously; Korea S Han Yang University professor Yang-KookSun is by carrying out surface A lF to rich lithium manganese material
3be coated and effectively the coulombic efficiency first of rich lithium manganese material be increased to more than 90%, but do not reach yet 100%, in charge and discharge process, separating out still of oxygen exists; Zhao of University Of Tianjin is that diligent teach problem group is by being coated FePO to rich lithium manganese material surface
4effectively by its first coulombic efficiency be increased to more than 80%, but equally fundamentally do not solve its problem of coulombic efficiency less than 100% first yet.
Summary of the invention
The object of the invention is the problem that is less than 100% in order to solve existing rich lithium manganese material first charge-discharge coulombic efficiency, and a kind of rich lithium manganese material, preparation method and the application in lithium ion battery of surface modification are provided.
First the present invention provides a kind of preparation method of rich lithium manganese material of surface modification, comprises the steps:
Step 1: the compound of rich lithium manganese material and molybdenum is ground, obtain compound powder, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:(10～1000);
Step 2: the compound powder that step 1 is obtained with 1-10 ℃/min heating rate heating, is calcined 0.5-5h under 100-500 ℃ of condition in air, is cooled to room temperature with 1-10 ℃/min rate of temperature fall, obtain surface modification rich lithium manganese material.
Preferably, the structural formula of described rich manganese lithium material is (xLi
2mnO
3-(1-x) Li (Mn
ani
bco
c) O
2wherein, 0.3<<x<LEssT.LTss T.LT0.7,0<<a<LEssT.LTssT. LT1,0<<b<LEssT.LTssT. LT0.5,0<<c<LEssT.LTssT. LT0.5, a+b+c=1.
Preferably, the structural formula of described rich manganese lithium material is 0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2.
Preferably, the structural formula of described rich manganese lithium material is 0.5Li
2mnO
3-0.5Li (MnNi)
1/2o
2.
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 ℃, and calcination time is 5h.
The present invention also provides the rich lithium manganese material of the surface modification that above-mentioned preparation method obtains.
The application of the rich lithium manganese material that the present invention also provides above-mentioned surface modification in lithium ion battery.
Beneficial effect of the present invention
The invention provides a kind of preparation method of rich lithium manganese material of surface modification, the method is ground the compound of rich lithium manganese material and molybdenum, obtain compound powder, the molybdenum element in the compound of described molybdenum and rich lithium manganese presoma mass ratio are 1:(10～1000); By compound powder in air with 1-10 ℃/min heating rate heating, under 100-500 ℃ of condition, calcine 0.5-5h, with 1-10 ℃/min rate of temperature fall, be cooled to room temperature, 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 a kind of rich lithium manganese material and application in lithium ion battery of surface modification, anode material for lithium-ion batteries prepared by the rich lithium manganese material of this surface modification has good chemical property, because completely coated rich lithium manganese and the electrolyte of making of molybdenum compound is completely isolated, by the raising of coulombic efficiency first of rich lithium manganese.Experimental result shows: the coulombic efficiency first that in contrast to rich lithium manganese presoma is 70%-80%, the coulombic efficiency first of the rich lithium manganese material of surface modification prepared by the present invention is increased to 100%, simultaneously, maintaining under the prerequisite of rich lithium manganese presoma specific discharge capacity the fail safe that has improved greatly full battery.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the rich lithium manganese (b) that in the rich lithium manganese (a) of presoma and the embodiment of the present invention 1, Mo modifies;
Fig. 2 is the ESEM picture of the rich lithium manganese (b) that in the rich lithium manganese (a) of presoma and the embodiment of the present invention 1, Mo modifies;
Fig. 3 is the first charge-discharge curve of the lithium ion battery prepared of the rich lithium manganese (b) of Mo modification in the rich lithium manganese (a) of presoma and the embodiment of the present invention 1 under 0.1C multiplying power;
Fig. 4 is lithium ion battery first charge-discharge curve under different multiplying prepared by the rich lithium manganese (b) of Mo modification in the rich lithium manganese (a) of presoma and the embodiment of the present invention 1;
Fig. 5 is the charge and discharge circulation life of the lithium ion battery prepared of the rich lithium manganese (b) of Mo modification in the rich lithium manganese (a) of presoma and the embodiment of the present invention 1 under 0.1C multiplying power.
Embodiment
First the present invention provides a kind of preparation method of rich lithium manganese material of surface modification, comprises the steps:
Step 1: the compound of rich lithium manganese material and molybdenum is ground, obtain compound powder, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:(10～1000);
Step 2: the compound powder that step 1 is obtained with 1-10 ℃/min heating rate heating, is calcined 0.5-5h under 100-500 ℃ of condition in air, is cooled to room temperature with 1-10 ℃/min rate of temperature fall, obtain surface modification rich lithium manganese material.
According to the present invention, first first the compound of rich lithium manganese material and molybdenum to be ground, described milling time is not particularly limited, abundant grind into powder, more than being preferably 20min, 20～60min more preferably.
The structural formula of described rich manganese lithium material is preferably (xLi
2mnO
3-(1-x) Li (Mn
ani
bco
c) O
2wherein, 0.3<<x<LEssT.LTss T.LT0.7,0<<a<LEssT.LTssT. LT1,0<<b<LEssT.LTssT. LT0.5,0<<c<LEssT.LTssT. LT0.5, a+b+c=1.More preferably structural formula is 0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2or 0.5Li
2mnO
3-0.5Li (MnNi)
1/2o
2.
The compound of described molybdenum is preferably selected from one or both in molybdenum trioxide or ammonium molybdate.The mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is preferably 1:150.
According to the present invention, the compound powder that step 1 is obtained heats with 1-10 ℃/min heating rate in air, be preferably 5 ℃/min, under 100-500 ℃ of condition, calcine 0.5-5h, reaction temperature is preferably 250-450 ℃, most preferably is 300 ℃, calcination time is preferably 5h, then with 1-10 ℃/min rate of temperature fall, be cooled to room temperature, be preferably 5 ℃/min, obtain surface modification rich lithium manganese material.Reaction temperature in step 2 of the present invention is controlled very crucial to the rich lithium manganese material of the product surface modification obtaining, and when temperature is during lower than 100 ℃, described ammonium molybdate can not decompose at this temperature, if the raw material secondly using is MoO
3, at this temperature, can not make MoO
3monolayer Dispersion, just can not reach completely coated effect, on the raising of coulombic efficiency first, affects little; When temperature is during higher than 500 ℃, calcining for a long time under hot conditions, Mo may adulterate and enter in rich lithium manganese material, changes rich lithium manganese material structure, generates unnecessary accessory substance.
The present invention also provides the rich lithium manganese material of the surface modification that above-mentioned preparation method obtains.
The application of the rich lithium manganese material that the present invention also provides above-mentioned surface modification in lithium ion battery, the method that the rich lithium manganese anode material of the surface modification of gained is prepared to lithium ion battery is the conventional method in this area, concrete grammar is: by the positive electrode making by rich lithium manganese: acetylene black: the mass ratio of PVDF(Kynoar)=80:10:10 accurately weighs, then add a certain amount of NMP(nitrogen methyl pyrrolidone) grind evenly, then with scraper, be evenly coated on aluminium foil, 120 ℃ of vacuum are dried 12h, then through section, compressing tablet, after the techniques such as weighing, in being full of the glove box of argon gas, be assembled into button cell.Electrolyte used is 1mol/LLiPF
6ethylene carbonate+dimethyl carbonate (mass ratio is 1:1) solution, barrier film is celgard2400 film, and the required both positive and negative polarity battery case of assembled battery, lithium sheet, pad.
The rich lithium manganese anode material of surface modification of the present invention is due to the Monolayer Dispersion effect of molybdenum compound, make molybdenum compound be coated on rich lithium manganese presoma surface completely, due to molybdenum compound completely coated make rich lithium manganese and electrolyte completely isolated, the coulombic efficiency first of rich lithium manganese is increased to 100%.
For making those skilled in the art better understand technical scheme of the present invention, below in conjunction with specific embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
By 50g0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o2 and 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, and compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, and 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2@1.5%Mo).
By the rich lithium manganese material of the finishing making by (0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2@1.5%Mo): acetylene black: the mass ratio of PVDF(Kynoar)=80:10:10 accurately weighs, then add a certain amount of NMP(nitrogen methyl pyrrolidone) grind evenly, then with scraper, be evenly coated on aluminium foil, 120 ℃ of vacuum are dried 12h, then after section, compressing tablet, weighing technique, be full of in the glove box of argon gas and be assembled into button cell, in battery, electrolyte used is 1mol/LLiPF
6ethylene carbonate+dimethyl carbonate (mass ratio is 1:1) solution, barrier film is celgard2400 film, and the required both positive and negative polarity battery case of assembled battery, lithium sheet, pad.
Fig. 1 is the XRD collection of illustrative plates of the rich lithium manganese that in embodiment 1, the rich lithium manganese of presoma and Mo modify, wherein scheming a is the XRD collection of illustrative plates of the rich lithium manganese of presoma, figure b is that Mo modifies rich lithium manganese XRD collection of illustrative plates, test result shows that Mo modifies the essential characteristic peak that rich lithium manganese material can keep rich lithium manganese material, peak type is sharp-pointed, back end is smooth, and small change occurs the peak type of 65 °, illustrates that molybdenum trioxide plays to rich lithium manganese presoma the characteristic peak that certain modification can keep rich lithium manganese presoma simultaneously.The characteristic peak of not finding molybdenum trioxide in figure b, illustrates that molybdenum trioxide is dispersed in the surface of rich lithium manganese presoma, and rich lithium manganese material is completely coated.
Fig. 2 is the ESEM picture of the rich lithium manganese that in embodiment 1, rich lithium manganese presoma and Mo modify, figure a is that multiplication factor is the ESEM picture of the rich lithium manganese presoma of 5000 times, figure b is that multiplication factor is the ESEM picture that the Mo of 5000 times modifies rich lithium manganese, as can be seen from the figure after Mo modifies rich lithium manganese and calcines in 300 ℃ of air and particle diameter do not become large, and particle diameter is even, narrowly distributing.
Fig. 3 is rich lithium manganese that in the embodiment of the present invention 1, rich lithium manganese presoma and Mo the modify first charge-discharge curve under 0.1C condition, and figure a is the first charge-discharge curve of the rich lithium manganese of presoma, and figure b is the first charge-discharge curve that Mo modifies rich lithium manganese.As can be seen from Figure 3,, after the standing 4-5h of button cell being assembled into, with the rate charge-discharge of 0.1C, in figure a, discharge capacity is 280mAhg first
-1, coulombic efficiency is 80.9% first, in figure b, discharge capacity is 280mAhg first
-1, coulombic efficiency is 100% first.Fig. 3 shows that rich lithium manganese presoma chemical property is good, and Mo modifies the not decay of discharge capacity first of rich lithium manganese, and coulombic efficiency first.
Fig. 4 is the first charge-discharge curve of the rich lithium manganese different multiplying that in the embodiment of the present invention 1, rich lithium manganese presoma and Mo modify, figure a is the first charge-discharge curve of the rich lithium manganese of presoma under different multiplying, and figure b is that Mo modifies the first charge-discharge curve of rich lithium manganese under different multiplying.As can be seen from Figure 4,, after the standing 4-5h of button cell being assembled into, with different multiplying (0.1C, 0.2C, 0.5C) first charge-discharge, in figure a, coulombic efficiency is respectively 80.9%, 80.7%, 71.6% first; In figure b, coulombic efficiency is 100% first.Fig. 4 shows that Mo modifies rich lithium manganese material in first charge-discharge process, and coulombic efficiency all can bring up to 100% first.
Fig. 5 is rich lithium manganese that in the embodiment of the present invention 1, rich lithium manganese presoma and Mo the modify charge and discharge cycles curve under 0.5C multiplying power, figure a is the charge and discharge cycles curve of the rich lithium manganese of presoma under 0.5C multiplying power, and figure b is that Mo modifies the charging and discharging curve of rich lithium manganese under 0.1C multiplying power.As can be seen from Figure 5, be assembled into after the standing 4-5h of button cell, carry out charge and discharge cycles under 0.1C multiplying power, in figure a, coulombic efficiency is 80% first, all approaches after 100%, 40 circle circulation later, and specific discharge capacity is by 280mAhg
-1drop to 181.5mAhg
-1, capability retention is 64.8%; And in figure b, coulombic efficiency is 100% first, all approach after 100%, 40 circle circulation later, specific discharge capacity is by 268mAhg
-1drop to 152.5mAhg
-1, capability retention is 56.9%.
Embodiment 2
By 50g0.5Li
2mnO
3-0.5Li (MnNi)
1/2o
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.5Li
2mnO
3-0.5Li (MnNi)
1/2o
2@1.5%Mo).
The Mo making is modified to rich lithium manganese presoma positive electrode and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 3
By 50g0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2with 0.11g molybdenum trioxide mixed grinding 30min, to mixing, obtain compound powder, compound powder is warming up to 250 ℃ of calcining 3h with 10 ℃/min in air, 10 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2@1.5%MoO
3).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 4
By 50g0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2with 0.065g ammonium molybdate mixed grinding 60min, to mixing, obtain compound powder, compound powder is warming up to 450 ℃ of calcining 0.5h with 1 ℃/min in air, 1 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2@0.1%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 90%, show that its chemical property is good.
Embodiment 5
By 50g0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2with 6.47g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2@10%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 6
By 50g0.3Li
2mnO
3-0.7Li (Mn
0.3ni
0.7) O
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.3Li
2mnO
3-0.7Li (Mn
0.3ni
0.7) O
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 7
By 50g0.7Li
2mnO
3-0.3Li (Mn
0.3ni
0.7) O
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.7Li
2mnO
3-0.3Li (Mn
0.3ni
0.7) O
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 8
By 50g0.3Li
2mnO
3-0.7Li (Mn
0.7ni
0.3) O
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.3Li
2mnO
3-0.7Li (Mn
0.7ni
0.3) O
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 9
By 50g0.7Li
2mnO
3-0.3Li (Mn
0.7ni
0.3) O
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.7Li
2mnO
3-0.3Li (Mn
0.7ni
0.3) O
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 10
By 50g0.3Li
2mnO
3-0.7Li (MnNiCo)
1/3o
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as (0.3Li
2mnO
3-0.7Li (MnNiCo)
1/3o
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
Embodiment 11
By 50g0.7Li
2mnO
3-0.3Li (MnNiCo)
1/3o
2with 0.97g ammonium molybdate mixed grinding 20min, to mixing, obtain compound powder, compound powder is warming up to 300 ℃ of calcining 5h with 5 ℃/min in air, 5 ℃/min is down to room temperature, obtains the rich lithium manganese material of surface modification, is designated as 0.7Li
2mnO
3-0.3Li (MnNiCo)
1/3o
2@1.5%Mo).
The Mo making is modified to rich lithium manganese anode material and by the method for embodiment 1, be assembled into button cell, at 0.1C, 0.2C, discharges and recharges under 0.5C multiplying power, its first coulombic efficiency be 100%, show that its chemical property is good.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for the rich lithium manganese material of surface modification, is characterized in that, comprises the steps:
Step 1: the compound of rich lithium manganese material and molybdenum is ground, obtain compound powder, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:(10～1000);
Step 2: the compound powder that step 1 is obtained with 1-10 ℃/min heating rate heating, is calcined 0.5-5h under 100-500 ℃ of condition in air, is cooled to room temperature with 1-10 ℃/min rate of temperature fall, obtain surface modification rich lithium manganese material.
2. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 1, is characterized in that, the structural formula of described rich manganese lithium material is (xLi
2mnO
3-(1-x) Li (Mn
ani
bco
c) O
2wherein, 0.3<<x<LEssT.LTss T.LT0.7,0<<a<LEssT.LTssT. LT1,0<<b<LEssT.LTssT. LT0.5,0<<c<LEssT.LTssT. LT0.5, a+b+c=1.
3. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 2, is characterized in that, the structural formula of described rich manganese lithium material is 0.5Li
2mnO
3-0.5Li (MnNiCo)
1/3o
2.
4. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 2, is characterized in that, the structural formula of described rich manganese lithium material is 0.5Li
2mnO
3-0.5Li (MnNi)
1/2o
2.
5. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 1, is characterized in that, the compound of described molybdenum is selected from one or both in molybdenum trioxide or ammonium molybdate.
6. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 1, is characterized in that, the mass ratio of the molybdenum element in the compound of described molybdenum and rich lithium manganese material is 1:150.
7. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 1, is characterized in that, described milling time is 20～60min.
8. the preparation method of the rich lithium manganese material of a kind of surface modification according to claim 1, is characterized in that, the calcining heat of described step 2 is 300 ℃, and calcination time is 5h.
9. the rich lithium manganese material of the surface modification that the preparation method of claim 1-8 described in any one obtains.
10. the application of the rich lithium manganese material of surface modification claimed in claim 9 in lithium ion battery.
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| CN105932233A (en) * | 2016-05-04 | 2016-09-07 | 合肥国轩高科动力能源有限公司 | Preparation method for lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN108091852A (en) * | 2017-12-12 | 2018-05-29 | 中国科学院过程工程研究所 | A kind of molybdenum trioxide coated lithium ion battery positive electrode and preparation method thereof |
| CN108511710A (en) * | 2018-03-22 | 2018-09-07 | 中南大学 | Lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof |
| CN108923032A (en) * | 2018-07-16 | 2018-11-30 | 力信（江苏）能源科技有限责任公司 | With the ternary cathode material of lithium ion battery and preparation method of modified metal oxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105932233A (en) * | 2016-05-04 | 2016-09-07 | 合肥国轩高科动力能源有限公司 | Preparation method for lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN105932233B (en) * | 2016-05-04 | 2019-01-22 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery lithium-rich manganese base |
| CN108091852A (en) * | 2017-12-12 | 2018-05-29 | 中国科学院过程工程研究所 | A kind of molybdenum trioxide coated lithium ion battery positive electrode and preparation method thereof |
| 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 |
| CN108511710A (en) * | 2018-03-22 | 2018-09-07 | 中南大学 | Lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof |
| CN108511710B (en) * | 2018-03-22 | 2020-09-11 | 中南大学 | Lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof |
| CN108923032A (en) * | 2018-07-16 | 2018-11-30 | 力信（江苏）能源科技有限责任公司 | With the ternary cathode material of lithium ion battery and preparation method of modified metal oxide |
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