CN107069013A - A kind of modified lithium-rich manganese-based anode material and preparation method thereof - Google Patents

A kind of modified lithium-rich manganese-based anode material and preparation method thereof Download PDF

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CN107069013A
CN107069013A CN201710428327.2A CN201710428327A CN107069013A CN 107069013 A CN107069013 A CN 107069013A CN 201710428327 A CN201710428327 A CN 201710428327A CN 107069013 A CN107069013 A CN 107069013A
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lithium
anode material
based anode
rich manganese
rich
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CN107069013B (en
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张国华
夏永高
刘兆平
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Ningbo Fuli Battery Material Technology Co Ltd
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Ningbo Fuli Battery Material Technology Co Ltd
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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
    • 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
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a kind of modified lithium-rich manganese-based anode material, it is made up of rich lithium material and composite oxide of metal；The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.Compared with prior art, composite oxide of metal has stable spinel structure in the modification lithium-rich manganese-based anode material that the present invention is provided, not only can be with the surface texture of stabilizing lithium rich material, and the three-dimensional channel of its spinel structure is conducive to the insertion and abjection of lithium ion, so as to make obtained modification lithium-rich manganese-based anode material that also there is good high rate performance.Test result indicates that, coulombic efficiency, 91% or so, has more excellent cycle performance and more preferable high rate performance to the modification lithium-rich manganese-based anode material that the present invention is provided compared to pure lithium-rich manganese-based anode material first.

Description

A kind of modified lithium-rich manganese-based anode material and preparation method thereof
Technical field
It is to be related to a kind of modified lithium-rich manganese-based anode material more specifically the present invention relates to technical field of lithium ion Material and preparation method thereof.
Background technology
Lithium ion battery has the low advantage of memory-less effect, high security, high-energy-density, self-discharge rate, extensive use In fields such as mobile device, notebook computer, mobile communication and electrokinetic cells.At present, electrokinetic cell face course continuation mileage it is short, The problems such as cycle performance difference and not enough security, seriously constrain its fast-developing and application.In recent years, lithium-rich manganese-based anode material Material specific discharge capacity is up to 300mAh/g, and its energy density can break through 300Wh/Kg, be considered as the reason of dynamic lithium battery of new generation Think selection.However, lithium-rich manganese-based anode material is present, initial coulomb efficiency is low, high rate performance is not good and cyclical stability is poor etc. Shortcoming, seriously hinders its commercialization process.
For the disadvantages mentioned above of lithium-rich manganese-based anode material, people have done substantial amounts of study on the modification, main to include doping, table The method of modifying such as face modification, surface construction Lacking oxygen, particle nanosizing and rich lithium and other positive electrodes are compound.At present, state It is inside and outside to have many documents and patent report Al2O3、MnO2、AlPO4、ZrO2、TiO2Rich lithium material, energy are coated Deng metal oxide The irreversible capacity loss first of enough rich lithium materials of reduction, improves the cycle performance of material, still, its high rate performance fails always It is effectively improved.Such as A.Manthiram (US7678503B2) reports a kind of changing for oxide cladding lithium-rich anode material Property method, the oxide include Al2O3、ZrO2、CeO2、SiO2With the one or more in ZnO, after coating modification, though The discharge capacity first and coulombic efficiency of material are so improved, but cladding is not obviously improved to the high rate performance of rich lithium material； Publication No. JP 2002-260659 Japan Patent uses spinelle LiMn2O4Clad anode material improves it at high temperature In cycle performance, but charge and discharge process, Mn variation of valence is also easy to produce Jahn-Teller effects, causes collapsing for spinel structure Collapse, structure destruction is more obvious especially among high temperature, high voltage system, accelerates the decay of capacity.
Therefore, in order to break through the commercialization bottleneck of rich lithium material, improve the coulombic efficiency first of material, cycle performance and High rate performance, researchs and develops a kind of effective method of modifying most important.
The content of the invention
In view of this, it is an object of the invention to provide a kind of modified lithium-rich manganese-based anode material and preparation method thereof, this Invent the modification lithium-rich manganese-based anode material provided has higher coulombic efficiency first, excellent cycle performance and good simultaneously High rate performance.
The invention provides a kind of modified lithium-rich manganese-based anode material, it is made up of rich lithium material and composite oxide of metal；
The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.
It is preferred that, the rich lithium material has the formula shown in formula (I)：
xLi2MnO3·(1-x)LiMO2Formula (I)；
In formula (I), M is transition metal, 0.3 ＜ x ＜ 0.7；
The M is the one or more in Ni, Co, Mn, Cr, Fe, Ru and Sn.
It is preferred that, the composite oxide of metal has the formula shown in formula (II)：
M’2+ (1-y)M”3+ yO(1+y/2)Formula (II)；
Layered dihydroxy composite metal hydroxide has the formula shown in formula (III)：
[M’2+ (1-y)M”3+ y(OH)2]y+(An-)y/n·mH2O formulas (III)；
In formula (II) and formula (III), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+ For Al3+、Mn3+、Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、 Cl-、OH-、SO4 2-And PO4 3-In one or more.
It is preferred that, the mass ratio of the rich lithium material and composite oxide of metal is (90~99.9)：(0.1~10).
Present invention also offers a kind of preparation method of the modification lithium-rich manganese-based anode material described in above-mentioned technical proposal, bag Include following steps：
A) by M '2+Metal salt and M "3+Dissolving metal salts add interlayer anion agent in the dispersion liquid of rich lithium material And precipitating reagent, adjust pH value of reaction system and reacted, obtain lithium-rich manganese-based anode material presoma；
B) the lithium-rich manganese-based anode material presoma that step a) is obtained is calcined, obtains being modified lithium-rich manganese-based anode material Material.
It is preferred that, interlayer anion agent described in step a) is sodium carbonate, potassium carbonate, urea, ammonium hydrogen carbonate and ammonium carbonate In one or more.
It is preferred that, precipitating reagent described in step a) is one kind or many in sodium hydroxide, potassium hydroxide, urea and ammoniacal liquor Kind.
It is preferred that, the pH value reacted described in step a) is 7~13.
It is preferred that, reaction temperature described in step a) is 25 DEG C~180 DEG C, and the time is 6h~24h.
It is preferred that, the temperature calcined described in step b) is 300 DEG C~700 DEG C, and the time is 2h~10h.
The invention provides a kind of modified lithium-rich manganese-based anode material, it is made up of rich lithium material and composite oxide of metal； The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.Compared with prior art, the present invention is provided Modification lithium-rich manganese-based anode material in composite oxide of metal there is stable spinel structure, not only can be with stabilizing lithium rich material The surface texture of material, and the three-dimensional channel of its spinel structure is conducive to the insertion and abjection of lithium ion, so as to make what is obtained Modified lithium-rich manganese-based anode material also has good high rate performance.Test result indicates that, the modified rich lithium manganese that the present invention is provided Base anode material first coulombic efficiency 91% or so, compared to pure lithium-rich manganese-based anode material have more excellent cycle performance and More preferable high rate performance.
In addition, the preparation method for the modification lithium-rich manganese-based anode material that the present invention is provided is simple and easy to control, cost is low, is adapted to production Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is the head of the modification lithium-rich manganese-based anode material that the embodiment of the present invention 1 is provided and pure lithium-rich manganese-based anode material Secondary charging and discharging curve comparison diagram；
Fig. 2 is the modification lithium-rich manganese-based anode material of the offer of the embodiment of the present invention 1 and following for pure lithium-rich manganese-based anode material Ring performance curve comparison diagram；
Fig. 3 is times of the modification lithium-rich manganese-based anode material that the embodiment of the present invention 1 is provided and pure lithium-rich manganese-based anode material Rate performance curve comparison figure.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair The scope of bright protection.
The invention provides a kind of modified lithium-rich manganese-based anode material, it is made up of rich lithium material and composite oxide of metal；
The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.
In the present invention, the modified lithium-rich manganese-based anode material is made up of rich lithium material and composite oxide of metal. In the present invention, the composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide, not only with modified rich lithium The advantage of material, so as to get modification lithium-rich manganese-based anode material have higher coulombic efficiency first and excellent cyclicity Can, and its stable spinel structure is conducive to the insertion and abjection of lithium ion, so as to make obtained modification lithium-rich manganese-based just Pole material also has good high rate performance.
In the present invention, the rich lithium material preferably has the formula shown in formula (I)：
xLi2MnO3·(1-x)LiMO2Formula (I)；
In formula (I), M is transition metal, 0.3 ＜ x ＜ 0.7.
In the present invention, the M is preferably the one or more in Ni, Co, Mn, Cr, Fe, Ru and Sn, more preferably Ni, One or more in Co and Mn, most preferably Ni-Co-Mn.In a preferred embodiment of the invention, the M is Ni- Co-Mn, wherein, described Ni, Co and Mn mol ratio are preferably 1：(0.5~1.5)：(3~5), more preferably 1：(0.8~ 1.2)：(3.5~4.5), most preferably 1：1：4.
In the present invention, the composite oxide of metal preferably has the formula shown in formula (II)：
M’2+ (1-y)M”3+ yO(1+y/2)Formula (II)；
In formula (II), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+For Al3+、Mn3+、 Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、Cl-、OH-、SO4 2- And PO4 3-In one or more.
In the present invention, the M '2+Represent divalent metal；The M '2+Preferably Mg2+、Co2+、Ni2+、Zn2+、 Fe2+And Cu2+In one or more, more preferably Mg2+、Co2+、Ni2+And Zn2+In one or more, most preferably Mg2+Or Co2+.In the present invention, the M "3+Represent trivalent metal cation；The M "3+Preferably Al3+、Mn3+、Co3+、Cr3+、Fe3+、 V3+、In3+And Ga3+In one or more, more preferably Al3+、Mn3+And Cr3+In one or more, most preferably Al3+. In a preferred embodiment of the invention, M '2+For Mg2+、M”3+For Al3+, the M '2+With M "3+Mol ratio be preferably 2：1, i.e., Y=1/3.
In the present invention, layered dihydroxy composite metal hydroxide preferably has the formula shown in formula (III)：
[M’2+ (1-y)M”3+ y(OH)2]y+(An-)y/n·mH2O formulas (III)；
In formula (III), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+For Al3+、Mn3 +、Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、Cl-、OH-、 SO4 2-And PO4 3-In one or more.
In the present invention, the M '2+Represent divalent metal；The M '2+Preferably Mg2+、Co2+、Ni2+、Zn2+、 Fe2+And Cu2+In one or more, more preferably Mg2+、Co2+、Ni2+And Zn2+In one or more, most preferably Mg2+Or Co2+.In the present invention, the M "3+Represent trivalent metal cation；The M "3+Preferably Al3+、Mn3+、Co3+、Cr3+、Fe3+、 V3+、In3+And Ga3+In one or more, more preferably Al3+、Mn3+And Cr3+In one or more, most preferably Al3+. In a preferred embodiment of the invention, M '2+For Mg2+、M”3+For Al3+, the M '2+With M "3+Mol ratio be preferably 2：1, i.e., Y=1/3.
In the present invention, the An-Represent interlayer anion；The An-Preferably CO3 2-、NO3 -、Cl-、OH-、SO4 2-With PO4 3-In one or more, more preferably CO3 2-And NO3 -One or both of.In the present invention, the mH2O expression layers The crystallization water and free water between layers of shape dihydroxy composite metal hydroxide, it is not specifically limited to this by the present invention.
In the present invention, the mass ratio of the rich lithium material and composite oxide of metal is preferably (90~99.9)：(0.1 ~10), more preferably (98~99.5)：(0.5~2).In a preferred embodiment of the invention, the rich lithium material and gold The mass ratio for belonging to composite oxides is 99：1；In presently preferred embodiment, the rich lithium material and metal are answered The mass ratio for closing oxide is 99.5：0.5；In presently preferred embodiment, the rich lithium material and metal are answered The mass ratio for closing oxide is 98：2.
Present invention also offers a kind of preparation method of the modification lithium-rich manganese-based anode material described in above-mentioned technical proposal, bag Include following steps：
A) by M '2+Metal salt and M "3+Dissolving metal salts add interlayer anion agent in the dispersion liquid of rich lithium material And precipitating reagent, adjust pH value of reaction system and reacted, obtain lithium-rich manganese-based anode material presoma；
B) the lithium-rich manganese-based anode material presoma that step a) is obtained is calcined, obtains being modified lithium-rich manganese-based anode material Material.
The present invention is first by M '2+Metal salt and M "3+Dissolving metal salts add interlayer in the dispersion liquid of rich lithium material Anionics and precipitating reagent, regulation pH value of reaction system are reacted, and obtain lithium-rich manganese-based anode material presoma.
In the present invention, the M '2+Metal salt is divalent metal salt；Wherein, the M '2+Preferably Mg2+、Co2+、Ni2+、 Zn2+、Fe2+And Cu2+In one or more, more preferably Mg2+、Co2+、Ni2+And Zn2+In one or more, be most preferably Mg2+Or Co2+；The M '2+Metal salt is preferably M '2+Nitrate, M '2+Sulfate, M '2+Acetate, M '2+Chloride And M '2+Phosphate in one or more, more preferably M '2+Nitrate.In a preferred embodiment of the invention, The M '2+Metal salt is Co (NO3)2·6H2O；In presently preferred embodiment, the M '2+Metal salt is Mg (NO3)2·6H2O.The present invention is to the M '2+The source of metal salt is not particularly limited, using well known to those skilled in the art Commercial goods.
In the present invention, the M "3+Metal salt is trivalent metal salt；Wherein, the M "3+Preferably Al3+、Mn3+、Co3+、 Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, more preferably Al3+、Mn3+And Cr3+In one or more, it is optimal Elect Al as3+；The M "3+Metal salt is preferably M "3+Nitrate, M "3+Sulfate, M "3+Acetate, M "3+Chloride And M "3+Phosphate in one or more, more preferably M "3+Nitrate.In a preferred embodiment of the invention, The M "3+Metal salt is Al (NO3)3·9H2O.The present invention is not particularly limited to the source of the trivalent metal salt, using this Commercial goods known to art personnel.
In the present invention, the dispersion liquid of the rich lithium material is preferred to use well known to those skilled in the art by rich lithium material It is dispersed in water the dispersion liquid of obtained rich lithium material.In the present invention, the rich lithium material preferably has logical shown in formula (I) Formula：
xLi2MnO3·(1-x)LiMO2Formula (I)；
In formula (I), M is transition metal, 0.3 ＜ x ＜ 0.7.
In the present invention, the M is preferably the one or more in Ni, Co, Mn, Cr, Fe, Ru and Sn, more preferably Ni, One or more in Co and Mn, most preferably Ni-Co-Mn.In a preferred embodiment of the invention, the M is Ni- Co-Mn, wherein, described Ni, Co and Mn mol ratio are preferably 1：(0.5~1.5)：(3~5), more preferably 1：(0.8~ 1.2)：(3.5~4.5), most preferably 1：1：4.The present invention is not particularly limited to the species of the rich lithium material and source, is adopted With the lithium-rich manganese-based anode material well known to those skilled in the art with above-mentioned formula.
In the present invention, the interlayer anion agent is preferably sodium carbonate, potassium carbonate, urea, ammonium hydrogen carbonate and ammonium carbonate In one or more, more preferably sodium carbonate.The present invention is not particularly limited to the source of the interlayer anion agent, is used Commercial goods well known to those skilled in the art.
In the present invention, the precipitating reagent is preferably one kind or many in sodium hydroxide, potassium hydroxide, urea and ammoniacal liquor Plant, more preferably sodium hydroxide.The present invention is not particularly limited to the source of the precipitating reagent, ripe using those skilled in the art The commercial goods known.
In the present invention, the concentration of the dispersion liquid of the rich lithium material is preferably 90g/L~110g/L, more preferably 100g/L.In the present invention, the M '2+Metal salt and M "3+The mol ratio of metal salt is preferably (1~4)：1, more preferably 2： 1.In the present invention, the mol ratio of the interlayer anion agent and precipitating reagent is preferably 1：(4~20), more preferably 1：12.
In the present invention, the pH value of the reaction is preferably 7~13, and more preferably 9~11.In the present invention, it is described anti- The temperature answered is preferably 25 DEG C~180 DEG C, more preferably 60 DEG C~150 DEG C, most preferably 90 DEG C~120 DEG C；The reaction Time is preferably 6h~24h, more preferably 10h~16h.
Complete after the course of reaction, the present invention preferably also includes：
Reaction product is centrifuged successively, dried, lithium-rich manganese-based anode material presoma is obtained.In the present invention, institute State in lithium-rich manganese-based anode material presoma and contain laminated dihydroxy composite metal hydroxide；The compound gold of layered pair of hydroxyl Belong to hydroxide preferably with the formula shown in formula (III)：
[M’2+ (1-y)M”3+ y(OH)2]y+(An-)y/n·mH2O formulas (III)；
In formula (III), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+For Al3+、Mn3 +、Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、Cl-、OH-、 SO4 2-And PO4 3-In one or more.
In the present invention, the M '2+Represent divalent metal；The M '2+Preferably Mg2+、Co2+、Ni2+、Zn2+、 Fe2+And Cu2+In one or more, more preferably Mg2+、Co2+、Ni2+And Zn2+In one or more, most preferably Mg2+Or Co2+.In the present invention, the M "3+Represent trivalent metal cation；The M "3+Preferably Al3+、Mn3+、Co3+、Cr3+、Fe3+、 V3+、In3+And Ga3+In one or more, more preferably Al3+、Mn3+And Cr3+In one or more, most preferably Al3+. In a preferred embodiment of the invention, M '2+For Mg2+、M”3+For Al3+, the M '2+With M "3+Mol ratio be preferably 2：1, i.e., Y=1/3.
In the present invention, the An-Represent interlayer anion；The An-Preferably CO3 2-、NO3 -、Cl-、OH-、SO4 2-With PO4 3-In one or more, more preferably CO3 2-And NO3 -One or both of.In the present invention, the mH2O expression layers The crystallization water and free water between layers of shape dihydroxy composite metal hydroxide, it is not specifically limited to this by the present invention.
Obtain after the lithium-rich manganese-based anode material presoma, it is of the invention by obtained lithium-rich manganese-based anode material presoma Calcined, obtain being modified lithium-rich manganese-based anode material.In the present invention, the temperature of the calcining is preferably 300 DEG C~700 DEG C, more preferably 400 DEG C~600 DEG C；The time of the calcining is preferably 2h~10h, more preferably 3h~6h.In the present invention In, the lithium-rich manganese-based anode material presoma is through calcining, wherein the laminated dihydroxy composite metal hydroxide included turns into The composite oxide of metal being combined with rich lithium material, so as to realize the modification to rich lithium material.
In the present invention, the composite oxide of metal preferably has the formula shown in formula (II)：
M’2+ (1-y)M”3+ yO(1+y/2)Formula (II)；
In formula (II), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+For Al3+、Mn3+、 Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、Cl-、OH-、SO4 2- And PO4 3-In one or more.
In the present invention, the M '2+Represent divalent metal；The M '2+Preferably Mg2+、Co2+、Ni2+、Zn2+、 Fe2+And Cu2+In one or more, more preferably Mg2+、Co2+、Ni2+And Zn2+In one or more, most preferably Mg2+Or Co2+.In the present invention, the M "3+Represent trivalent metal cation；The M "3+Preferably Al3+、Mn3+、Co3+、Cr3+、Fe3+、 V3+、In3+And Ga3+In one or more, more preferably Al3+、Mn3+And Cr3+In one or more, most preferably Al3+. In a preferred embodiment of the invention, M '2+For Mg2+、M”3+For Al3+, the M '2+With M "3+Mol ratio be preferably 2：1, i.e., Y=1/3.
The invention provides a kind of modified lithium-rich manganese-based anode material, it is made up of rich lithium material and composite oxide of metal； The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.Compared with prior art, the present invention is provided Modification lithium-rich manganese-based anode material in composite oxide of metal there is stable spinel structure, not only can be with stabilizing lithium rich material The surface texture of material, and the three-dimensional channel of its spinel structure is conducive to the insertion and abjection of lithium ion, so as to make what is obtained Modified lithium-rich manganese-based anode material also has good high rate performance.Test result indicates that, the modified rich lithium manganese that the present invention is provided Base anode material first coulombic efficiency 91% or so, compared to pure lithium-rich manganese-based anode material have more excellent cycle performance and More preferable high rate performance.
In addition, the preparation method for the modification lithium-rich manganese-based anode material that the present invention is provided is simple and easy to control, cost is low, is adapted to production Industry metaplasia is produced.
In order to further illustrate the present invention, it is described in detail below by following examples.Following examples of the present invention In used pharmaceutical raw material be commercial goods.
Embodiment 1
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
Temperature be 25 DEG C, voltage range be that 2.0~4.8V, charging and discharging currents density are 0.1C (1C is 250mAh/g) Under test condition, the charge-discharge property of the modification lithium-rich manganese-based anode material prepared to the embodiment of the present invention 1 is carried out Test, and with pure lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2For control.Test result such as Fig. 1 institutes Show, Fig. 1 is the charge and discharge first of modification lithium-rich manganese-based anode material and pure lithium-rich manganese-based anode material that the embodiment of the present invention 1 is provided Electric curve comparison figure, as shown in Figure 1, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 1 is provided For 319.2mAh/g, discharge capacity is 293.2mAh/g, and coulombic efficiency is 91.9% first, and pure lithium-rich manganese-based anode material Initial charge capacity is 324.2mAh/g, and discharge capacity is 275.3mAh/g, and coulombic efficiency is 84.9% first.
The cycle performance of the modification lithium-rich manganese-based anode material prepared to the embodiment of the present invention 1 is tested, and with Pure lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2For control.Test result is as shown in Fig. 2 Fig. 2 is this Modification lithium-rich manganese-based anode material and the cycle performance curve comparison of pure lithium-rich manganese-based anode material that inventive embodiments 1 are provided Figure, as shown in Figure 2, the lithium-rich manganese-based positive material of modification that the embodiment of the present invention 1 is provided show excellent cyclical stability, compare Pure lithium-rich manganese-based anode material has more excellent cycle performance.
The high rate performance of the modification lithium-rich manganese-based anode material prepared to the embodiment of the present invention 1 is tested, and with Pure lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2For control.Test result is as shown in figure 3, Fig. 3 is this Modification lithium-rich manganese-based anode material and the high rate performance curve comparison of pure lithium-rich manganese-based anode material that inventive embodiments 1 are provided Figure, from the figure 3, it may be seen that the modification lithium-rich manganese-based anode material that the embodiment of the present invention 1 is provided has compared to pure lithium-rich manganese-based anode material There is more preferable high rate performance.
Embodiment 2
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 10, be subsequently placed in 100 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 2 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 2 is provided is 321.2mAh/g, and discharge capacity is 285.6mAh/g, coulombic efficiency is 88.9% first.
Embodiment 3
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 98:The 2 compound raw material dosages that prepare medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 3 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 3 is provided is 320.1mAh/g, and discharge capacity is 281.4mAh/g, coulombic efficiency is 87.9% first.
Embodiment 4
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 11, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 4 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 4 is provided is 319.6mAh/g, and discharge capacity is 290.2mAh/g, coulombic efficiency is 90.8% first.
Embodiment 5
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 9, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 5 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 5 is provided is 319.8mAh/g, and discharge capacity is 283.7mAh/g, coulombic efficiency is 88.7% first.
Embodiment 6
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 90 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 6 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 6 is provided is 319.0mAh/g, and discharge capacity is 288.7mAh/g, coulombic efficiency is 90.5% first.
Embodiment 7
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 120 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 7 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 7 is provided is 322.6mAh/g, and discharge capacity is 280.4mAh/g, coulombic efficiency is 86.9% first.
Embodiment 8
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 400 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 8 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 8 is provided is 320.3mAh/g, and discharge capacity is 280.0mAh/g, coulombic efficiency is 87.4% first.
Embodiment 9
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 9 is prepared is tested, and is as a result shown, The initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 9 is provided is 323.1mAh/g, and discharge capacity is 289.9mAh/g, coulombic efficiency is 89.7% first.
Embodiment 10
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 11, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 10 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 10 is provided is 320.8mAh/g, and electric discharge is held Measure as 291.6mAh/g, coulombic efficiency is 90.9% first.
Embodiment 11
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.8:The 0.2 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 11, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 11 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 11 is provided is 321.2mAh/g, and electric discharge is held Measure as 283.7mAh/g, coulombic efficiency is 88.3% first.
Embodiment 12
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 9, it is subsequently placed in 110 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 12 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 12 is provided is 321.1mAh/g, and electric discharge is held Measure as 287.9mAh/g, coulombic efficiency is 89.6% first.
Embodiment 13
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 12, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 13 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 13 is provided is 319.9mAh/g, and electric discharge is held Measure as 285.5mAh/g, coulombic efficiency is 89.2% first.
Embodiment 14
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 12, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 14 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 14 is provided is 323.6mAh/g, and electric discharge is held Measure as 283.9mAh/g, coulombic efficiency is 87.7% first.
Embodiment 15
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 13, be subsequently placed in 100 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 15 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 15 is provided is 321.8mAh/g, and electric discharge is held Measure as 282.7mAh/g, coulombic efficiency is 87.8% first.
Embodiment 16
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 8, be subsequently placed in 120 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 16 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 16 is provided is 318.9mAh/g, and electric discharge is held Measure as 286.1mAh/g, coulombic efficiency is 89.7% first.
Embodiment 17
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 7, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 400 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 17 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 17 is provided is 320.6mAh/g, and electric discharge is held Measure as 279.6mAh/g, coulombic efficiency is 87.2% first.
Embodiment 18
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 11, be subsequently placed in 110 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 5h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 18 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 18 is provided is 321.6mAh/g, and electric discharge is held Measure as 289.3mAh/g, coulombic efficiency is 90.0% first.
Embodiment 19
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by NiC4H6O4·4H2O and MnC4H6O4·4H2O is according to mol ratio 2:1 ratio It is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reaction system is adjusted PH is subsequently placed in 90 DEG C of water-baths to 11 and reacts 12h, through centrifugation, dries, obtains lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 3h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 19 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 19 is provided is 321.8mAh/g, and electric discharge is held Measure as 285.1mAh/g, coulombic efficiency is 88.6% first.
Embodiment 20
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Zn (NO3)2·6H2O and Cr (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 9, it is subsequently placed in 100 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 3h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 20 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 20 is provided is 317.9mAh/g, and electric discharge is held Measure as 278.2mAh/g, coulombic efficiency is 87.5% first.
Embodiment 21
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Zn (NO3)2·6H2O and Al (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 9, be subsequently placed in 60 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 21 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 21 is provided is 320.8mAh/g, and electric discharge is held Measure as 281.7mAh/g, coulombic efficiency is 87.8% first.
Embodiment 22
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Zn (NO3)2·6H2O and Fe (NO3)2·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 10, it is subsequently placed in 90 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 22 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 22 is provided is 320.1mAh/g, and electric discharge is held Measure as 285.8mAh/g, coulombic efficiency is 89.3% first.
Embodiment 23
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Zn (NO3)2·6H2O and Ga (NO3)3·xH2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 11, be subsequently placed in 100 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 23 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 23 is provided is 321.6mAh/g, and electric discharge is held Measure as 282.7mAh/g, coulombic efficiency is 87.9% first.
Embodiment 24
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 12, it is subsequently placed in 110 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 24 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 24 is provided is 322.5mAh/g, and electric discharge is held Measure as 290.5mAh/g, coulombic efficiency is 90.1% first.
Embodiment 25
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99.5:The 0.5 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Fe (NO3)3·9H2O is according to mol ratio 2:1 ratio Example is added in above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, reactant is adjusted Be pH to 13, be subsequently placed in 120 DEG C of water-baths and react 12h, through centrifugation, dry, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 500 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 25 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 25 is provided is 320.8mAh/g, and electric discharge is held Measure as 283.3mAh/g, coulombic efficiency is 88.3% first.
Embodiment 26
(1) by lithium-rich manganese-based anode material Li [Li0.144Ni0.136Co0.136Mn0.544]O2It is scattered in deionized water, prepares Into 100g/L lithium-rich manganese-based anode material dispersion liquid, according to lithium-rich manganese-based anode material and composite oxide of metal mass ratio 99:The 1 compound raw material dosage for preparing medicines, by Mg (NO3)2·6H2O and Cr (NO3)3·9H2O is according to mol ratio 2:1 ratio adds Enter into above-mentioned dispersion liquid, then it is 1 to be gradually added into mol ratio:12 Na2CO3With NaOH mixed solution, regulation reaction system pH To 8, it is subsequently placed in 150 DEG C of water-baths and reacts 12h, through centrifugation, dries, obtain lithium-rich manganese-based anode material presoma；
(2) the lithium-rich manganese-based anode material presoma for obtaining step (1) calcines 4h at 600 DEG C, obtains modified rich lithium Manganese-based anode material.
It is 25 DEG C, under voltage range is the test condition that 2.0~4.8V, charging and discharging currents density are 0.1C in temperature, it is right The charge-discharge property for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 26 is prepared is tested, as a result table Bright, the initial charge capacity for the modification lithium-rich manganese-based anode material that the embodiment of the present invention 26 is provided is 322.8mAh/g, and electric discharge is held Measure as 282.9mAh/g, coulombic efficiency is 87.6% first.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.It is right A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty Most wide scope.

Claims (10)

1. a kind of modified lithium-rich manganese-based anode material, is made up of rich lithium material and composite oxide of metal；
The composite oxide of metal is made up of laminated dihydroxy composite metal hydroxide.
2. modified lithium-rich manganese-based anode material according to claim 1, it is characterised in that the rich lithium material has formula (I) formula shown in：
xLi2MnO3·(1-x)LiMO2Formula (I)；
In formula (I), M is transition metal, 0.3 ＜ x ＜ 0.7；
The M is the one or more in Ni, Co, Mn, Cr, Fe, Ru and Sn.
3. modified lithium-rich manganese-based anode material according to claim 1, it is characterised in that the composite oxide of metal tool There is the formula shown in formula (II)：
M’2+ (1-y)M”3+ yO(1+y/2)Formula (II)；
Layered dihydroxy composite metal hydroxide has the formula shown in formula (III)：
[M’2+ (1-y)M”3+ y(OH)2]y+(An-)y/n·mH2O formulas (III)；
In formula (II) and formula (III), M '2+For Mg2+、Co2+、Ni2+、Zn2+、Fe2+And Cu2+In one or more, M "3+For Al3 +、Mn3+、Co3+、Cr3+、Fe3+、V3+、In3+And Ga3+In one or more, 0.2≤y≤0.5, An-For CO3 2-、NO3 -、Cl-、 OH-、SO4 2-And PO4 3-In one or more.
4. modified lithium-rich manganese-based anode material according to claim 1, it is characterised in that the rich lithium material and metal are answered The mass ratio for closing oxide is (90~99.9)：(0.1~10).
5. a kind of preparation method of the modification lithium-rich manganese-based anode material described in any one of Claims 1 to 4, including following step Suddenly：
A) by M '2+Metal salt and M "3+Dissolving metal salts add interlayer anion agent and precipitation in the dispersion liquid of rich lithium material Agent, regulation pH value of reaction system is reacted, and obtains lithium-rich manganese-based anode material presoma；
B) the lithium-rich manganese-based anode material presoma that step a) is obtained is calcined, obtains being modified lithium-rich manganese-based anode material.
6. preparation method according to claim 5, it is characterised in that interlayer anion agent described in step a) is carbonic acid One or more in sodium, potassium carbonate, urea, ammonium hydrogen carbonate and ammonium carbonate.
7. preparation method according to claim 5, it is characterised in that precipitating reagent described in step a) is sodium hydroxide, hydrogen One or more in potassium oxide, urea and ammoniacal liquor.
8. preparation method according to claim 5, it is characterised in that the pH value reacted described in step a) is 7~13.
9. preparation method according to claim 5, it is characterised in that reaction temperature described in step a) is 25 DEG C~180 DEG C, the time is 6h~24h.
10. preparation method according to claim 5, it is characterised in that the temperature calcined described in step b) is 300 DEG C~ 700 DEG C, the time is 2h~10h.
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