CN105552322B - Composite modified anode material for lithium-ion batteries of quaternary ion and preparation method thereof - Google Patents
Composite modified anode material for lithium-ion batteries of quaternary ion and preparation method thereof Download PDFInfo
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- CN105552322B CN105552322B CN201510924007.7A CN201510924007A CN105552322B CN 105552322 B CN105552322 B CN 105552322B CN 201510924007 A CN201510924007 A CN 201510924007A CN 105552322 B CN105552322 B CN 105552322B
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- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 150000002500 ions Chemical group 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000011219 quaternary composite Substances 0.000 claims abstract description 14
- 229910002549 Fe–Cu Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910011017 Li2CoO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 ion Ion Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of composite modified anode material for lithium-ion batteries of quaternary ion, including：Positive active material；And conductive material, it is coated on the positive active material surface；The conductive material is Mn Ni Fe Cu quaternary Composite Oxides Nanometric Powder bodies, wherein, the molecular formula of the Mn Ni Fe Cu quaternary composite oxides is MnzNiFexCuyO4.The invention further relates to a kind of preparation methods of the composite modified anode material for lithium-ion batteries of above-mentioned quaternary ion.The composite modified anode material for lithium-ion batteries of quaternary ion provided by the invention, since Mn Ni Fe Cu quaternary Composite Oxides Nanometric Powders body has good electric conductivity, the high rate performance and cycle performance of positive electrode can be greatly improved by improving the electronic conductivity of material.
Description
Technical field
The present invention relates to composite modified anode material for lithium-ion batteries of a kind of quaternary ion and preparation method thereof, especially relate to
And a kind of modifies positive electrode of Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder and preparation method thereof.
Background technology
Lithium ion battery as a new generation environmentally protective power supply, with energy density is big, voltage is high, self discharge is small,
The advantages that memory-less effect, is widely used in mobile phone, camera, laptop, electric tool, electric bicycle and electric vehicle
Wait products.It is higher and higher to the energy and power requirement of lithium ion battery with the fast development of electronic product, and lithium-ion electric
The positive electrode in pond is the important component of lithium ion battery, is the major influence factors of performance of lithium ion battery.
Mainly there are cobalt acid lithium, lithium nickelate, LiMn2O4 and nickle cobalt lithium manganate three using most lithium ion anode materials at present
First material.These positive electrodes have the advantages of respective, but also have the shortcomings that respective simultaneously, can not meet electronic product pair
The requirements of lithium ion battery.At present, common method of modifying is mutually coated including bulk phase-doped with table.It is bulk phase-doped to have
Effect stablizes the internal structure of positive electrode, inhibits the mixing of cation；And table mutually coats can effectively inhibit positive electrode surface
Corroded by hydrofluoric acid in electrolyte.But doping does not mutually have good electric conductivity and electro-chemical activity with clad, because
This carries out positive electrode the bulk phase-doped specific capacity that can influence positive electrode and forthright again of mutually coating with table.
Invention content
The present invention provides composite modified anode material for lithium-ion batteries of a kind of quaternary ion and preparation method thereof, Ke Yiyou
Effect solves the above problems.
The present invention provides a kind of quaternary ion composite modified anode material for lithium-ion batteries, including：Positive active material；
And conductive material, it is coated on the positive active material surface；The conductive material is Mn-Ni-Fe-Cu quaternary combined oxidations
Object nano-powder, wherein, the molecular formula of the Mn-Ni-Fe-Cu quaternarys composite oxides is MnzNiFexCuyO4。
Further, z is more than or equal to 0.3 and is more than or equal to 0.2 less than or equal to 1, x and is more than or equal to less than or equal to 1, y
0.17 and less than or equal to 1.
Further, z be more than or equal to 0.4 and less than or equal to 0.9, x be more than or equal to 0.5 and less than or equal to 0.7, y be more than etc.
In 0.3 and less than or equal to 0.9.
Further, the mass ratio of the conductive material and the positive active material is 0.001~0.1:1.
Further, the mass ratio of the conductive material and the positive active material is 0.01~0.05:1.
Further, the positive active material is nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, cobalt acid lithium, ferric phosphate
At least one of lithium, lithium ferric manganese phosphate, lithium nickel cobalt dioxide or nickel ion doped.
A kind of preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion, including：
Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders body is added in, high-speed stirred and ultrasound are carried out in easy volatile solvent
Dispersion forms a mixed solution；
Positive active material is added under conditions of high-speed stirred in the mixed solution, mixed solution is made uniformly to coat
On positive active material surface, a mixture is obtained；And
By the mixture by drying, calcining is cooled down, is crushed and is sieved to obtain the composite modified lithium of the quaternary ion
Ion battery positive electrode.
Further, the preparation method of the Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder body includes：It will oxidation
Stoichiometrically dispensing carries out wet-mixing for manganese, nickel oxide, copper oxide and iron oxide, obtains a mixture；By the mixing
Object is dry, is sintered, obtains Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders after grinding.
Further, the sintering temperature is 800~900 DEG C, and the time of sintering is 2~6h, and the atmosphere of sintering is sky
Gas atmosphere.
Further, 400~700 DEG C of calcination temperature, time are 3~8h, and calcination atmosphere is air or oxygen atmosphere.
Composite modified anode material for lithium-ion batteries of quaternary ion provided by the invention and preparation method thereof has following
Advantage：
(1) there is the Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders of electro-chemical activity in active material surface cladding,
So that clad is completely cutting off electrolyte with passing freely through lithium ion while positive electrode, so as to while charge and discharge are completed
The decomposition of electrolyte is avoided, the cycle performance and stability of lithium ion battery are improved in the case where not influencing specific capacity.
(2) Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder has good electric conductivity, can be by improving material
Electronic conductivity greatly increases the high rate performance of positive electrode.
(3) Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder has special layer structure, can be the migration of lithium ion
Channel is provided, so as to improve the first charge discharge efficiency of material.
Description of the drawings
Fig. 1 is the preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion provided in an embodiment of the present invention
Flow chart.
Fig. 2 is that the cycle of the composite modified anode material for lithium-ion batteries of the quaternary ion that provides of the embodiment of the present invention 1 is put
Electric curve graph.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is only used for explaining the present invention rather than limitation of the invention.It also should be noted that for the ease of
It describes, part related to the present invention rather than entire infrastructure is illustrated only in attached drawing.
The present invention provides a kind of quaternary ion composite modified anode material for lithium-ion batteries, including：Positive active material；
And conductive material, it is coated on the positive active material surface；The conductive material is Mn-Ni-Fe-Cu quaternary combined oxidations
Object nano-powder, wherein, the molecular formula of the Mn-Ni-Fe-Cu quaternarys composite oxides is MnzNiFexCuyO4.Wherein, Mn is
Positive tetravalence, positive trivalent and positive divalent hybrid ionic, Ni are positive divalent, and Fe is positive trivalent and positive divalent hybrid ionic, and Cu is positive one
Valency and positive divalent hybrid ionic.Since manganese has a positive trivalent and positive quadrivalent ion pair, while also there are positive divalent ion, exactly these
The ion pair of different valence state constitutes the core of Spectrametry of Electron Exchange conduction so that the resistivity of material reduces.Similarly for iron and copper,
The ion pair of different valence state constitutes the core of Spectrametry of Electron Exchange conduction, but also the resistivity of material further reduces, so as to
To form positive monovalence to the core of the Spectrametry of Electron Exchange conduction of positive tetravalence.
It is appreciated that when the content of conductive material is higher, although preferable electric conductivity can be obtained, can influence
The energy density of anode material for lithium-ion batteries.When the content of conductive material is less, and cannot clad anode active matter completely
Matter surface.Since the conductive material is nano-powder, therefore, the anode work can just be coated completely by leading to too small amount of conductive material
The surface of property substance.Therefore the mass ratio of the conductive material and the positive active material is 0.001~0.1:1.Preferably,
The mass ratio of the conductive material and the positive active material is 0.01~0.05:1.It is furthermore preferred that conductive material with it is described
The mass ratio of positive active material is 0.03~0.05:Between 1.
The positive active material can be common positive electrode, as nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4,
Cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, lithium nickel cobalt dioxide, nickel ion doped and its mixture etc..
Experiment proves to pass through, and by adjusting the content of component each in quad arrangement, can significantly improve nano-powder
Electric conductivity.Preferably, z is more than or equal to 0.3 and is more than or equal to 0.2 less than or equal to 1, x and is more than or equal to 0.17 less than or equal to 1, y
And less than or equal to 1.It is furthermore preferred that z is more than or equal to 0.4 and more than or equal to 0.5 and big less than or equal to 0.7, y less than or equal to 0.9, x
In equal to 0.3 and less than or equal to 0.9.Most preferably, make in quad arrangement, positive monovalence, positive divalent, positive trivalent and positive tetravalence from
The content of son is identical.On the one hand electric conductivity can be improved by the mutual doping of quad arrangement, on the other hand can also be formed
Defect is conducive to passing freely through for lithium ion.The grain size of the Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder body is received for 10
Rice~100 nanometers, it is preferred that its grain size is 30 nanometers~40 nanometers.
Fig. 1 is please referred to, the present invention also provides a kind of preparations of the composite modified anode material for lithium-ion batteries of quaternary ion
Method, including：
S1, will Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders body add in easy volatile solvent in carry out high-speed stirred and
Ultrasonic disperse forms a mixed solution；
Positive active material is added under conditions of high-speed stirred in the mixed solution, makes mixed solution uniform by S2
Positive active material surface is coated on, obtains a mixture；And
S3, by the mixture by drying, calcining is cooled down, is crushed and is sieved to obtain the quaternary ion composite modified
Anode material for lithium-ion batteries.
In step sl, the Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder body can be prepared by the following：
S11, by manganese oxide, nickel oxide, copper oxide and iron oxide, stoichiometrically dispensing carries out wet-mixing, obtains one
Mixture；
S12 will obtain Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders after mixture drying, sintering, grinding.
In step s 11, the temperature of sintering is 800~900 DEG C, and the time of sintering is 2~6h, and the atmosphere of sintering is air
Atmosphere.Preferably, sintering temperature is 840~850 DEG C, so as to obtain more good crystallization.
In step S2, the time of the high-speed stirred is 20~40 minutes, and the time of the ultrasonic disperse is 5~15 points
Clock.Preferably, high-speed stirred, ultrasonic dispersion cycle 3~5 times successively.The frequency of the ultrasonic disperse is 20kHz~40kHz.It is excellent
Choosing, the side that can be combined by the ultrasonic wave of high-frequency (small range strenuous vibration) and low frequency (a wide range of common vibrations)
Formula carries out, if 20kHz disperses 5 dispersion of 40kHz dispersions again in 5 minutes, it is hereby achieved that preferably dispersion.The easy volatile solvent
For deionized water, ethyl alcohol, methanol, acetone and its mixture.
Further, in step s3, it is dried after directly can drying or filter, so as to obtain the mixture.It is described
The temperature of calcining is 400~700 DEG C, and the time is 3~8h, and calcination atmosphere is air or oxygen atmosphere.It is demonstrated experimentally that when it is described just
Pole active material is LiNi0.5Co0.2Mn0.3O2When, the temperature of the calcining is preferably 500~520 DEG C；When the positive-active
Substance is Li2CoO2When, the temperature of the calcining is preferably 600 DEG C~610 DEG C.
Embodiment 1：
Manganese dioxide, nickel oxide, copper oxide and iron oxide are pressed into Mn0.9NiCu0.3Fe0.6O4Stoichiometric ratio dispensing into
Row wet-mixing, is dried after mixing, and Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders are obtained after oversintering, grinding.
Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder is added in deionized water and carries out high-speed stirred, is uniformly mixed and is formed uniformly
Solution.By active material LiNi0.8Co0.15Al0.05O2It is added under conditions of high-speed stirred in above-mentioned mixed solution, makes cladding
Material is evenly coated at active material LiNi0.8Co0.15Al0.05O2Then mixture is dried 6h by surface, by dried solid
After material calcines 8h at 500 DEG C, cooling, crushing, sieving obtain positive electrode.
The electrochemical property test of material is tested using blue electric battery test system at 25 DEG C, test voltage range
For 3V~4.3V；High rate performance test condition：0.2C charge and discharge are primary, and respectively electric discharge is primary by 0.2C chargings 1C/5C/10C；；Cycle
Performance test conditions：Charge and discharge are carried out with 1C multiplying powers, are recycled 500 weeks, investigate capacity retention ratio.Material putting under 0.2C multiplying powers
Electric specific capacity is 196.1mAh/g, and the specific discharge capacity under 1C multiplying powers is 185.8mAh/g, and the specific discharge capacity under 5C multiplying powers is
Specific discharge capacity under 176.2mAh/g, 10C multiplying power is 168.3mAh/g, and 10C/0.2C electric discharge ratios are 85.8%, forthright again
It can be preferably.500 weeks capacity retention ratios of 1C charge and discharge cycles are more than 94%, and cycle performance is preferable.
Embodiment 2：
Manganese dioxide, nickel oxide, copper oxide and iron oxide are pressed into Mn0.43NiCu0.9Fe0.67O4Stoichiometric ratio dispensing into
Row wet-mixing, is dried after mixing, and Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders are obtained after oversintering, grinding.
Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder is added in deionized water and carries out high-speed stirred, is uniformly mixed and is formed uniformly
Solution.By active material LiNi0.5Co0.2Mn0.3O2It is added under conditions of high-speed stirred in above-mentioned mixed solution, makes cladding
Material is evenly coated at active material LiNi0.5Co0.2Mn0.3O2Then mixture is dried 6h by surface, by dried solid
After material calcines 6h at 600 DEG C, cooling, crushing, sieving obtain positive electrode.
It is demonstrated experimentally that the material identical that above-mentioned material is obtained with embodiment 1, it may have good high rate performance and cycle
Performance.
Note that it above are only presently preferred embodiments of the present invention and institute's application technology principle.It will be appreciated by those skilled in the art that
The present invention is not limited to specific embodiment described here, can carry out for a person skilled in the art various apparent variations,
It readjusts and substitutes without departing from protection scope of the present invention.Therefore, although being carried out by above example to the present invention
It is described in further detail, but the present invention is not limited only to above example, without departing from the inventive concept, also
It can include other more equivalent embodiments, and the scope of the present invention is determined by scope of the appended claims.
Claims (9)
1. a kind of composite modified anode material for lithium-ion batteries of quaternary ion, including：
Positive active material；And
Conductive material is coated on the positive active material surface；
It is characterized in that, the conductive material is Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powder bodies, wherein, the Mn-
The molecular formula of Ni-Fe-Cu quaternary composite oxides is MnzNiFexCuyO4, Mn for positive tetravalence, positive trivalent and positive divalent mix from
Son, Ni are positive divalent, and Fe is positive trivalent and positive divalent hybrid ionic, and Cu is more than or equal to for positive monovalence and positive divalent hybrid ionic, z
0.3 and it is more than or equal to 0.2 less than or equal to 1, x and is more than or equal to 0.17 and less than or equal to 1 less than or equal to 1, y.
2. the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 1, which is characterized in that z is big
In being more than or equal to 0.5 equal to 0.4 and less than or equal to 0.9, x and be more than or equal to 0.3 and less than or equal to 0.9 less than or equal to 0.7, y.
3. the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 1, which is characterized in that described
The mass ratio of conductive material and the positive active material is 0.001~0.1:1.
4. the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 3, which is characterized in that described
The mass ratio of conductive material and the positive active material is 0.01~0.05:1.
5. the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 1, which is characterized in that described
Positive active material is nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, nickel cobalt acid
At least one of lithium or nickel ion doped.
6. a kind of preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion, which is characterized in that including：
Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders body is added in, high-speed stirred and ultrasound point are carried out in easy volatile solvent
It dissipates, forms a mixed solution；
Positive active material is added under conditions of high-speed stirred in the mixed solution, mixed solution is made to be evenly coated at just
Pole active material surface obtains a mixture；And
By the mixture by drying, calcining is cooled down, is crushed and is sieved to obtain the composite modified lithium ion of the quaternary ion
Cell positive material.
7. the preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 6, special
Sign is that the preparation method of the Mn-Ni-Fe-Cu quaternarys Composite Oxides Nanometric Powder body includes：
By manganese oxide, nickel oxide, copper oxide and iron oxide, stoichiometrically dispensing carries out wet-mixing, obtains a mixture；
Mn-Ni-Fe-Cu quaternary Composite Oxides Nanometric Powders will be obtained after mixture drying, sintering, grinding.
8. the preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 7, special
Sign is that the sintering temperature is 800~900 DEG C, and the time of sintering is 2~6h, and the atmosphere of sintering is air atmosphere.
9. the preparation method of the composite modified anode material for lithium-ion batteries of quaternary ion according to claim 6, special
Sign is that 400~700 DEG C of calcination temperature, the time is 3~8h, and calcination atmosphere is air or oxygen atmosphere.
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| Low-Temperature Synthesis by Autocombustion and Investigation of Structural and Magnetic Properties of Mn0.5Cu0.5-xNixFe2O4 Nanocrystallites;Shahid M. Ramay，et al.;《IEEE Transactions on Magnetics》;20140831;第50卷(第8期);2200204 * |
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