CN104332617A - Lithium-rich manganese-based mixed conductor positive electrode material and preparation method thereof - Google Patents
Lithium-rich manganese-based mixed conductor positive electrode material and preparation method thereof Download PDFInfo
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- CN104332617A CN104332617A CN201410483295.2A CN201410483295A CN104332617A CN 104332617 A CN104332617 A CN 104332617A CN 201410483295 A CN201410483295 A CN 201410483295A CN 104332617 A CN104332617 A CN 104332617A
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- lithium
- positive electrode
- mixed conductor
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- rich manganese
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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
- 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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- 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
- H01M4/364—Composites as mixtures
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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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- 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 discloses a lithium-rich manganese-based mixed conductor positive electrode material and a preparation method thereof, the lithium-rich manganese-based mixed conductor positive electrode material comprises xLi2MnO3. (1-x) LiMn1 / 3Ni1 / 3Co1 / 3O2, FeF3 and CNTs, wherein x = 0.05 ~ 0.08; and the mass ratio of xLi2MnO3. (1-x) LiMn1 / 3Ni1 / 3Co1 / 3O2 to FeF3 to CNTs is (60 ~ 65%): (10 ~ 25%): (5 ~ 10%); x = 0.05 ~ 0.06, the lithium-rich manganese-based mixed conductor positive electrode material is a very good lithium ion conductor, can greatly improve the ion conductivity of materials, and the CNTs in the three component is an excellent electronic conductor, can obviously increase material electronic conductivity, reduces electrode and battery internal resistance, and significantly improves the cyclic stability of the electrode material.
Description
Technical field
The present invention relates to field of lithium ion battery anode, particularly, the present invention relates to a kind of lithium-rich manganese-based mixed conductor positive electrode and preparation method thereof.
Background technology
High-energy-density and high-specific-power are the necessity of future market to lithium ion battery, and the anode material for lithium-ion batteries developing high power capacity and high rate capability is key wherein.The specific discharge capacity of business-like anode material for lithium-ion batteries LiCoO2, LiMn2O4, LiFePO4 etc. is all at below 200mAh/g, and its energy density is limited.And lithium-rich anode material particularly lithium-rich manganese-based anode material pay close attention to widely because the specific capacity of superelevation and cheaper price cause.Lithium-rich manganese-based anode material mainly stratified material Li2MnO3 and the LiMO2 (M=Ni of current report, Co, Mn) solid solution formed, this solid solution specific discharge capacity is up to 250mAh/g (theoretical discharge specific capacity is at more than 300mAh/g), can meet the demand of following electric automobile power battery to high-energy-density, be one of the most potential current anode material for lithium-ion batteries.Although rich lithium manganese base solid solution material has significant advantage, but consider from practical angle, still there is many difficult problems urgently to be resolved hurrily: (1) initial coulomb efficiency low (generally only 60 ~ 70%), cause the negative material demand matched to increase, be difficult to the target realizing reducing battery weight and cost of manufacture; (2) native electronic conductivity and ionic conductance are not good, cause the high rate performance of material poor; (3) cyclical stability is not good, is difficult to the requirement meeting electrokinetic cell.
Fluoride is the lithium ion battery positive electrode received much concern at present, and because having, theoretical specific capacity is high, structural stability good, cost is low, safety and be environmentally friendlyly considered to one of the most potential anode material for lithium-ion batteries of a new generation.Wherein, especially typical with FeF3.FeF3 is as lithium ion cell positive host material, there is special open structure (openstructures), it can not only carry out reversible embedding with Li+ and deviate to react, whole oxidation state of Fe element can also be utilized fully, there is chemical conversioning reaction with Li+ and carry out stored energy, reaction, with 3e-transfer, has high theoretical specific capacity 237mAh/g (2.0 ~ 4.5V) and 712mAh/g (1.0 ~ 4.5V).On cost and environmental effect, FeF3 has the unrivaled advantage of layered cathode material LiCoO2 and LiNiO2, is a kind of rising anode material for lithium-ion batteries.But lithium ion battery electrode material must have unique mixed conducting, shows reasonable ion and electronic conductivity.The open structure (open structures) of FeF3 uniqueness makes it can provide extraordinary ionic conductivity, but the electronic conductivity of itself is poor, and this have impact on the performance of its chemical property to a certain extent
For the problems referred to above, the invention provides lithium-rich manganese-based mixed conductor positive electrode of a kind of lithium ion battery and preparation method thereof.Innovation is high power capacity rich lithium manganese base solid solution, Lithium Ionic Conducting Materials FeF3 and electronic conductive material CNTs (carbon nano-tube) conduction liquid mixing high-energy ball milling, the obtained lithium-rich manganese-based mixed conductor positive electrode of annealing, wherein, rich lithium manganese base solid solution is combined with FeF3, the effective compensation to rich lithium material specific discharge capacity can be realized, in initial charge process, the a large amount of irreversible lithium ion that rich lithium manganese base solid solution is deviate from because recurring structure changes, can reversiblely in discharge process be embedded in FeF3, significantly improve the first charge-discharge coulombic efficiency of material, and the mixed conductor of rich lithium manganese base solid solution, FeF3 and CNTs triplicity formation significantly can improve ionic conductivity and the electronic conductivity of material, reduce electrode, the internal resistance of cell, significantly improve cyclical stability and the high rate performance of electrode material.
Summary of the invention
The present invention proposes a kind of lithium-rich manganese-based mixed conductor positive electrode, not only prevent electrolyte reducing side reaction under the catalysis of rich lithium manganese base solid solution nano particle, FeF3 simultaneously in three components is owing to having unique open structure, it is extraordinary lithium ion conductor, significantly can improve the ionic conductivity of material, and the CNTs in three components is excellent electronic conductor, obviously can increase the electronic conductivity of material, reduce electrode, the internal resistance of cell, significantly improve the stable circulation of electrode material.
Lithium-rich manganese-based mixed conductor positive electrode of the present invention, it comprises xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, wherein x=0.05 ~ 0.08.
Described lithium-rich manganese-based mixed conductor positive electrode is made up of xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, and its each constituent mass percentage is (60 ~ 65%): (10 ~ 25%): (5 ~ 10%); X=0.05 ~ 0.06.
The present invention also comprises the lithium ion battery using above-mentioned lithium-rich manganese-based mixed conductor positive electrode.
The present invention also comprises the preparation method making described lithium-rich manganese-based mixed conductor positive electrode, comprising: mixed by rich lithium manganese base solid solution xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs (adding with CNTs conduction liquid form) high-energy ball milling, annealing obtains the lithium-rich manganese-based mixed conductor positive electrode of described lithium ion battery.
The present invention has following beneficial effect:
(1) the present invention is by having prepared a kind of novel mixed conductor positive electrode by rich lithium manganese base solid solution and FeF3 and CNTs (adding with CNTs conduction liquid form) high-energy ball milling.This mixed conductor positive electrode not only prevents electrolyte reducing side reaction under the catalysis of rich lithium manganese base solid solution nano particle, FeF3 simultaneously in three components is owing to having unique open structure, it is extraordinary lithium ion conductor, significantly can improve the ionic conductivity of material, and the CNTs in three components is excellent electronic conductor, obviously can increase the electronic conductivity of material, reduce electrode, the internal resistance of cell, significantly improve cyclical stability and the high rate performance of electrode material.
(2) in mixed conductor positive electrode, rich lithium manganese base solid solution and FeF3 combine, and can realize the effective compensation to rich lithium material specific discharge capacity; In initial charge process, a large amount of irreversible lithium ion that rich lithium manganese base solid solution is deviate from because recurring structure changes, can reversiblely in discharge process be embedded in FeF3, significantly improve the first charge-discharge coulombic efficiency of material.
(3) to have initial coulomb efficiency high for lithium-rich manganese-based mixed conductor positive electrode of the present invention, good with negative material matching, good cycling stability and the advantage such as high rate performance is superior, specific discharge capacity is up to 270mAh/g, higher by 55% than the capacity of cobalt acid lithium and LiFePO4, first charge-discharge efficiency reaches 90%, and have good matching with hard carbon and silicon-carbon class high-capacity cathode material, under 0.5C multiplying power, the 100 weeks capability retentions that circulate reach more than 95%, under 2C multiplying power, specific discharge capacity still can reach more than 210mAh/g, and high rate performance significantly improves.
Embodiment
Lithium-rich manganese-based mixed conductor positive electrode of the present invention, it comprises xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, wherein x=0.05 ~ 0.08.
Described lithium-rich manganese-based mixed conductor positive electrode is made up of xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, and its each constituent mass percentage is (60 ~ 65%): (10 ~ 25%): (5 ~ 10%); X=0.05 ~ 0.06.
The present invention also comprises the lithium ion battery using above-mentioned lithium-rich manganese-based mixed conductor positive electrode.
The present invention also comprises the preparation method making described lithium-rich manganese-based mixed conductor positive electrode, comprising: mixed by rich lithium manganese base solid solution xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs (adding with CNTs conduction liquid form) high-energy ball milling, annealing obtains the lithium-rich manganese-based mixed conductor positive electrode of described lithium ion battery.
The present invention is by having prepared a kind of novel mixed conductor positive electrode by rich lithium manganese base solid solution and FeF3 and CNTs (adding with CNTs conduction liquid form) high-energy ball milling.This mixed conductor positive electrode not only prevents electrolyte reducing side reaction under the catalysis of rich lithium manganese base solid solution nano particle, FeF3 simultaneously in three components is owing to having unique open structure, it is extraordinary lithium ion conductor, significantly can improve the ionic conductivity of material, and the CNTs in three components is excellent electronic conductor, obviously can increase the electronic conductivity of material, reduce electrode, the internal resistance of cell, significantly improve cyclical stability and the high rate performance of electrode material.
In mixed conductor positive electrode, rich lithium manganese base solid solution and FeF3 combine, and can realize the effective compensation to rich lithium material specific discharge capacity; In initial charge process, a large amount of irreversible lithium ion that rich lithium manganese base solid solution is deviate from because recurring structure changes, can reversiblely in discharge process be embedded in FeF3, significantly improve the first charge-discharge coulombic efficiency of material.
It is high that lithium-rich manganese-based mixed conductor positive electrode of the present invention has initial coulomb efficiency, good with negative material matching, good cycling stability and the advantage such as high rate performance is superior, specific discharge capacity is up to 270mAh/g, higher by 55% than the capacity of cobalt acid lithium and LiFePO4, first charge-discharge efficiency reaches 90%, and have good matching with hard carbon and silicon-carbon class high-capacity cathode material, under 0.5C multiplying power, the 100 weeks capability retentions that circulate reach more than 95%, under 2C multiplying power, specific discharge capacity still can reach more than 210mAh/g, and high rate performance significantly improves.
Claims (4)
1. a lithium-rich manganese-based mixed conductor positive electrode, it comprises xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, wherein x=0.05 ~ 0.08.
2. lithium-rich manganese-based mixed conductor positive electrode as claimed in claim 1, it is characterized in that, described lithium-rich manganese-based mixed conductor positive electrode is made up of xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs, and its each constituent mass percentage is (60 ~ 65%): (10 ~ 25%): (5 ~ 10%); X=0.05 ~ 0.06.
3. a lithium ion battery, is characterized in that, described lithium ion battery comprises lithium-rich manganese-based mixed conductor positive electrode described in claim 1 or 2.
4. a preparation method for lithium-rich manganese-based mixed conductor positive electrode as claimed in claim 1 or 2, comprising: mixed by rich lithium manganese base solid solution xLi2MnO3 (1-x) LiMn1/3Ni1/3Co1/3O2, FeF3 and CNTs (adding with CNTs conduction liquid form) high-energy ball milling, annealing obtains the lithium-rich manganese-based mixed conductor positive electrode of described lithium ion battery.
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| CN201410483295.2A CN104332617A (en) | 2014-09-19 | 2014-09-19 | Lithium-rich manganese-based mixed conductor positive electrode material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713235A (en) * | 2017-10-25 | 2019-05-03 | 华为技术有限公司 | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713235A (en) * | 2017-10-25 | 2019-05-03 | 华为技术有限公司 | A kind of sub- composite material and preparation method of conduction diversion, modified electrode material and energy storage device |
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Application publication date: 20150204 |