CN103996844A - Composite lithium nickel manganese oxide positive electrode material and preparation method thereof - Google Patents
Composite lithium nickel manganese oxide positive electrode material and preparation method thereof Download PDFInfo
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- CN103996844A CN103996844A CN201410224928.8A CN201410224928A CN103996844A CN 103996844 A CN103996844 A CN 103996844A CN 201410224928 A CN201410224928 A CN 201410224928A CN 103996844 A CN103996844 A CN 103996844A
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- lithium
- cathode material
- manganate cathode
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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
- 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
- H01M4/48—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a composite lithium nickel manganese oxide positive electrode material and a preparation method thereof; comprises a lithium nickel manganese oxide positive electrode material and a conductive polymer coated on the surface of the lithium nickel manganese oxide positive electrode material, wherein the chemical formula of the lithium nickel manganese oxide positive electrode material isLiNi0.5Mn1.5O4(ii) a Compared with the existing lithium nickel manganese oxide cathode material, the lithium nickel manganese oxide cathode material has the advantages of good cycling stability, excellent rate capability and stable voltage in the cycling process.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of compound nickel manganate cathode material for lithium and preparation method thereof.
Background technology
The progress in modern epoch, the continuous miniaturization of consuming device, multifunction, also improving constantly for the requirement of battery accordingly.Lithium ion battery has many advantages: voltage platform is high, and specific capacity is high, has extended cycle life, and self discharge is low, and memory-less effect etc. have huge application prospect on electric automobile and energy storage device.
At present, high-energy-density, durable, high magnification (fast charging and discharging ability), cheapness, safety have become the target that lithium ion battery development is pursued.Nickel manganate cathode material for lithium is subject to people compared with high specific energy and more and more payes attention to owing to having in existing lithium ion anode material system.But its cyclical stability and high rate performance (conductivity is low) also need further raising, to meet its practical application.
Summary of the invention
In order to address the above problem, one of object of the present invention is, the problem such as poor for nickel manganate cathode material for lithium cyclical stability, electronic conductivity is low, propose a kind of coated nickel manganate cathode material for lithium of conducting polymer original position that uses and make NEW TYPE OF COMPOSITE nickel manganate cathode material for lithium, this compound nickel manganate cathode material for lithium not only good cycling stability, conductivity is high, and high rate performance is good.
Two of object of the present invention is, provide a kind of simple, be easy to that large-scale industrialization produces, the preparation method of described compound nickel manganate cathode material for lithium.
The present invention is achieved through the following technical solutions:
A kind of compound nickel manganate cathode material for lithium, comprise nickel manganate cathode material for lithium and the conducting polymer that is coated on described nickel manganate cathode material for lithium surface, the quality ratio of described conducting polymer and nickel manganate cathode material for lithium is 0.02~1, and the chemical formula of described nickel manganate cathode material for lithium is LiNi
0.5mn
1.5o
4.Wherein, through experiment, the amount ratio between conducting polymer and nickel manganate cathode material for lithium, is coated on positive electrode surface because conducting polymer forms coating layer, so consumption can not very few (2%); Conducting polymer has the characteristic of embedding/de-lithium simultaneously, also can be used as positive electrode and uses, and its maximum can reach 100%.
Preferably, described conducting polymer is acetylene, thiophene, pyrroles, aniline, penylene, phenylene ethylene or two alkynes.Wherein, conducting polymer monomer, mainly as clad material main body, can improve the performance of coating layer, as improved electronic conductivity etc.Penylene described in literary composition, its molecular formula is C
6h
6, but structure is different from benzene, and it is conjugation not, and one of them C is connected with two H, and four carbon are double key carbons.Such structure is more conducive to coated nickel lithium manganate material, and improves simultaneously and improve its conductivity.
Wherein, in described compound nickel manganate cathode material for lithium, also include dopant, calculate according to mol ratio, the value of described dopant/conducting polymer is 0.5%~100%.Preferably hydrochloric acid, sulfuric acid, phosphoric acid or DBSA.Its concentration is not had to particular/special requirement, and variable concentrations all can be realized it and act in the present invention.
Described compound nickel manganate cathode material for lithium: first described nickel manganate cathode material for lithium is dispersed in solvent, mix and obtain mixing material I, again conducting polymer and dopant are joined in above-mentioned mixing material I, mix, obtain mixing material II; Finally oxidant is added in above-mentioned mixing material II, reaction 2~48h, filters, washs and obtain described compound nickel manganate cathode material for lithium.
Preferably, the mass ratio of described nickel manganate cathode material for lithium and solvent is 1 ︰ 1~100; The mixture of one or more in described solvent preferred water, ethanol, ethylene glycol, nitrogen methyl pyrrolidone solvent.
Wherein, calculate according to mol ratio, the value of described oxidant/conducting polymer is 0.5~3; Described oxidant is (NH preferably
4)
2s
2o
8, K
2cr
2o
7, H
2o
2, FeCl
3in one or more mixtures.Preferably, finally oxidant is added in above-mentioned mixing material II, at 0~5 DEG C, temperature constant magnetic stirring 2~48h.Temperature is lower, and polymerization reaction occurs slower, is conducive to be coated on uniformly positive electrode surface.The effect of this oxidant is the polymerization reaction of initiated polymerization thing monomer, polymer monomer is aggregated into be coated on the high molecular polymer on positive electrode surface.
The present invention uses the coated nickel manganate cathode material for lithium of conducting polymer original position to make NEW TYPE OF COMPOSITE nickel manganate cathode material for lithium, and wherein nickel manganate cathode material for lithium conductivity is low, and conducting polymer conductivity is high.By at nickel manganate cathode material for lithium surface coated with conductive polymer, improve material monolithic conductivity.Conducting polymer (as polyaniline etc.) in order to improve its conductivity, can be selected dopant in polymerization process.For example HF is also the one in dopant, and the HF that battery produces in cyclic process can, for conducting polymer absorption, reduce the harm of HF to battery system on the one hand, has improved on the other hand the conductivity of coating layer.The present invention uses situ aggregation method to make described compound nickel manganate cathode material for lithium, this in-situ polymerization is that one all adds polymer monomer (reactive monomer) and oxidant (catalyst) in solvent (decentralized photo), and positive electrode (core material) is decentralized photo.Because monomer is soluble in single-phase, and its polymer is insoluble in whole system, so polymerization reaction occurs on decentralized photo core.Reaction beginning, monomer pre-polymerization, performed polymer polymerization, after performed polymer polymerization size progressively increases, be deposited on the surface of core material.
In a word, the invention has the beneficial effects as follows:
(1), the present invention uses situ aggregation method at nickel manganate cathode material for lithium surface in situ coated with conductive polymer, can greatly improve the conductivity of nickel manganate cathode material for lithium, thereby improve its high rate performance.
(2), the surface coated conducting polymer of nickel manganate cathode material for lithium, not only can form coating layer on nickel manganate cathode material for lithium surface, effectively stop damage to nickel manganate cathode material for lithium of harmful substance in electrolyte (as HF etc.), can also absorb the harmful substances such as the HF that produces in circulating battery process, thereby improve the cyclical stability of nickel lithium manganate material.
(3), the conducting polymer of nickel lithium manganate material in situ Polymerization has the characteristic of de-/embedding lithium ion, can improve the specific capacity of compound nickel lithium manganate material.
Brief description of the drawings
Fig. 1 is the specific capacity contrast of the positive material of nickel LiMn2O4 in the present invention and prior art.
concrete execution mode
Below in conjunction with embodiment, the present invention is described in further detail, understands the present invention to help those skilled in the art.
Embodiment 1
A kind of polyaniline-coated nickel manganate cathode material for lithium, is first scattered in 10g nickel manganate cathode material for lithium in 500mL deionized water ultrasonic dispersion 10 minutes under 300w.The aniline monomer of 1g, 1mL hydrochloric acid solution are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 2.94g (NH
4)
2s
2o
8, K
2cr
2o
7, H
2o
2, FeCl
3be dissolved in 0.5L deionized water and make (NH
4)
2s
2o
8, K
2cr
2o
7, H
2o
2, FeCl
3the aqueous solution, by (NH
4)
2s
2o
8, K
2cr
2o
7, H
2o
2, FeCl
3the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 4 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain polyaniline-coated nickel manganate cathode material for lithium.
Embodiment 2
A kind of polymer overmold nickel manganate cathode material for lithium, is first scattered in 50g nickel manganate cathode material for lithium in 1000mL deionized water ultrasonic dispersion 10 minutes under 300w.(0.5g acetylene and 0.5g phenylene ethylene) monomer, the 2mL hydrochloric acid solution of 1g are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 0.5gK
2cr
2o
7be dissolved in 0.5L deionized water and make K
2cr
2o
7the aqueous solution, by K
2cr
2o
7the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 48 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain the coated nickel manganate cathode material for lithium of polymer (acetylene, phenylene ethylene).
Embodiment 3
The coated nickel manganate cathode material for lithium of a kind of polythiophene, is first scattered in 10g nickel manganate cathode material for lithium in 1000mL deionized water ultrasonic dispersion 10 minutes under 300w.The thiophene monomer of 1g, 3mL sulfuric acid solution are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 2.5g FeCl
3be dissolved in 0.5L deionized water and make H
2o
2the aqueous solution, by FeCl
3the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 12 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain the coated nickel manganate cathode material for lithium of polythiophene.
Embodiment 4
The coated nickel manganate cathode material for lithium of a kind of polypyrrole, is first scattered in 4g nickel manganate cathode material for lithium in 500mL deionized water ultrasonic dispersion 10 minutes under 300w.The pyrrole monomer of 1g, 5mL dodecylbenzenesulfonic acid solution are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 0.05L H
2o
2be dissolved in 0.5L deionized water and make H
2o
2the aqueous solution, by H
2o
2the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 8 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain the coated nickel manganate cathode material for lithium of polypyrrole.
Embodiment 5
The coated nickel manganate cathode material for lithium of a kind of polyhenylene, is first scattered in 15g nickel manganate cathode material for lithium in 500mL deionized water ultrasonic dispersion 10 minutes under 300w.The penylene monomer of 1g, 1mL hydrochloric acid solution are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 1.2g (NH
4)
2s
2o
8be dissolved in 0.5L deionized water and make (NH
4)
2s
2o
8the aqueous solution, by (NH
4)
2s
2o
8the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 4 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain the coated nickel manganate cathode material for lithium of polyhenylene.
Embodiment 6
The coated nickel manganate cathode material for lithium of a kind of poly-two alkynes, is first scattered in 5g nickel manganate cathode material for lithium in 500mL deionized water ultrasonic dispersion 10 minutes under 300w.Two alkynes monomers, the 2mL sulfuric acid solution of 1g are added in scattered nickel manganate cathode material for lithium system, temperature constant magnetic stirring, stirs 0.5 hour again, and temperature is controlled at 0~5 DEG C.Finally, by 3.2gK
2cr
2o
7be dissolved in 0.5L deionized water and make K
2cr
2o
7the aqueous solution, by K
2cr
2o
7the aqueous solution adds above-mentioned mixed system, temperature constant magnetic stirring 4 hours, and temperature is controlled at 0~5 DEG C; Filter, wash, obtain the coated nickel manganate cathode material for lithium of poly-two alkynes.
Above-described embodiment, is preferred embodiment of the present invention, is not used for limiting the scope of the present invention, and the equivalence of being done with the feature described in the claims in the present invention and principle therefore all changes or modifies, within all should being included in the claims in the present invention scope.
By finding out in Fig. 1, use the coated nickel manganate cathode material for lithium of conducting polymer original position to make NEW TYPE OF COMPOSITE nickel manganate cathode material for lithium, along with the increase of cycle-index, do not have the capacitance of the nickel manganate cathode material for lithium of coated with conductive polymer to reduce gradually, when after circulation 60 times, from 120mAhg
-1almost be reduced to 90mAhg
-1, and substantially also maintain 115mAhg after being coated the nickel manganate cathode material for lithium circulation 60 times of conducting polymer
-1left back.Illustrate that good cycling stability of the present invention, conductivity are high, long service life.
Claims (8)
1. a compound nickel manganate cathode material for lithium, it is characterized in that, comprise nickel manganate cathode material for lithium and the conducting polymer that is coated on described nickel manganate cathode material for lithium surface, the quality ratio of described conducting polymer and nickel manganate cathode material for lithium is 0.02~1, and the chemical formula of described nickel manganate cathode material for lithium is LiNi
0.5mn
1.5o
4.
2. compound nickel manganate cathode material for lithium as claimed in claim 1, is characterized in that, described conducting polymer is acetylene, thiophene, pyrroles, aniline, penylene, phenylene ethylene or two alkynes.
3. compound nickel manganate cathode material for lithium as claimed in claim 1, is characterized in that, in described compound nickel manganate cathode material for lithium, also includes dopant, calculates according to mol ratio, and the value of described dopant/conducting polymer is 0.5%~100%.
4. compound nickel manganate cathode material for lithium as claimed in claim 3, is characterized in that, described dopant is hydrochloric acid, sulfuric acid, phosphoric acid or DBSA.
5. compound nickel manganate cathode material for lithium described in any one in preparation claim 1-4, is characterized in that, is specially:
First described nickel manganate cathode material for lithium is dispersed in solvent, mixes and obtain mixing material I, then conducting polymer and dopant are joined in above-mentioned mixing material I, mix and obtain mixing material II; Finally oxidant is added in above-mentioned mixing material II, reaction 2~48h, filters, washs and obtain described compound nickel manganate cathode material for lithium.
6. compound nickel manganate cathode material for lithium as claimed in claim 5, is characterized in that, the mass ratio of described nickel manganate cathode material for lithium and solvent is 1 ︰ 1~100; Described solvent is one or more the mixture in water, ethanol, ethylene glycol, nitrogen methyl pyrrolidone solvent.
7. compound nickel manganate cathode material for lithium as claimed in claim 5, is characterized in that, calculates according to mol ratio, and the value of described oxidant/conducting polymer is 0.5~3; Described oxidant is (NH
4)
2s
2o
8, K
2cr
2o
7, H
2o
2, FeCl
3in one or more mixtures.
8. compound nickel manganate cathode material for lithium as claimed in claim 5, is characterized in that, finally oxidant added in above-mentioned mixing material II, and at 0~5 DEG C, temperature constant magnetic stirring 2~48h.
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Cited By (14)
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CN105932243A (en) * | 2016-05-16 | 2016-09-07 | 绵阳师范学院 | Nickel-cobalt-aluminum ternary material modification technology |
CN106058240A (en) * | 2016-07-26 | 2016-10-26 | 常熟理工学院 | Preparation method of high-voltage lithium battery composite with core-shell structure |
CN106299264A (en) * | 2015-06-05 | 2017-01-04 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN106299263A (en) * | 2015-06-05 | 2017-01-04 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN106469813A (en) * | 2015-08-17 | 2017-03-01 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN106469806A (en) * | 2015-08-17 | 2017-03-01 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN107611358A (en) * | 2017-07-24 | 2018-01-19 | 中南大学 | A kind of method of liquid phase in-situ polymerization coating spinelle manganate cathode material for lithium |
CN109119607A (en) * | 2018-08-04 | 2019-01-01 | 浙江瓦力新能源科技有限公司 | A kind of polypyrrole nanotube cladding nickel lithium manganate cathode material and preparation method thereof |
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CN106469813B (en) * | 2015-08-17 | 2019-02-12 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN106469806B (en) * | 2015-08-17 | 2019-02-12 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
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CN106469806A (en) * | 2015-08-17 | 2017-03-01 | 惠州市豪鹏科技有限公司 | A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery |
CN105932243A (en) * | 2016-05-16 | 2016-09-07 | 绵阳师范学院 | Nickel-cobalt-aluminum ternary material modification technology |
CN106058240A (en) * | 2016-07-26 | 2016-10-26 | 常熟理工学院 | Preparation method of high-voltage lithium battery composite with core-shell structure |
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