CN107785567A - Nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping and preparation method thereof - Google Patents
Nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping and preparation method thereof Download PDFInfo
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- CN107785567A CN107785567A CN201710891925.3A CN201710891925A CN107785567A CN 107785567 A CN107785567 A CN 107785567A CN 201710891925 A CN201710891925 A CN 201710891925A CN 107785567 A CN107785567 A CN 107785567A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping and preparation method thereof, the molecular formula of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping is LiaNixCoyMnzCebO2, wherein, b is 4/3 a/3 x y z, 1≤a≤1.2,0.3≤x≤0.98,0.01≤y≤0.6,0.001≤z≤0.6,0.00001≤b≤0.02；The present invention by the compound of nickel cobalt manganese monocrystalline composite precursor and nano-scale cerium by carrying out ultrahigh speed premixing, again by the compound of nickel cobalt manganese monocrystalline presoma and cerium compound and common nickel cobalt manganese presoma mixed at high speed, improve mixed effect, because monocrystalline composite precursor high mechanical strength, ultra-high-speed mixing can be used, and it is unlikely to broken, monocrystalline composite precursor can play a part of collision medium simultaneously, the compound of nano-scale cerium is fully broken up, is sufficiently mixed doped chemical and host element.
Description
Technical field
The invention belongs to cell positive material preparation method technical field, and in particular to the nickel cobalt manganese lithium-ion electric of cerium dopping
Pond positive electrode and preparation method thereof.
Background technology
Nickel-cobalt-manganese ternary anode material for lithium-ion batteries is due to higher energy density and relatively simple system
Standby technique is widely used in IT product and new-energy automobile field.But simple nickle cobalt lithium manganate is owed due to structural stability
It is good, it is easy in charge and discharge process because the deintercalation of Li ions and the change of Ni, Co, Mn ionic valence condition cause material structure
Collapse, the cycle life and security to material cause greatly to endanger.In order to solve the above problems, using the appropriate Ce of incorporation
The mode of ion improves to it, due to Ce3+With Ni3+Valence state it is identical, the Ce of incorporation3+Occupy Ni3+Position；Charging
Ni can occur for Cheng Zhong, Ni ion3+To Ni4+Transformation, and with volume contraction, if charging voltage is too high, depth of charge mistake
Greatly, the volume contraction of material will be irreversible, and finally loses electro-chemical activity, and Ce3+Do not appraise at the current rate, be electrochemicaUy inert
, the change of valence state does not occur in discharge and recharge, thus the change of volume does not occur yet, skeleton can be played a part of, it is stable
Crystal structure, improve the cycle life and security performance of material.
The incorporation of Ce ions has significant improvement result to the structural stability of material, but simultaneously because incorporation is all
The material of non-electroactive, the specific discharge capacity for mutually tackling material affects, if incorporation is too high, electric discharge is held
Amount will significantly reduce, if incorporation is insufficient, the electrical conductivity of material cannot effectively improve, therefore, doped chemical and
The uniform mixing of host element is to realize an important factor for specific discharge capacity reaches balance with electrical conductivity.
The content of the invention
It is an object of the invention to provide a kind of nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping.
It is a further object to provide the preparation side of the nickel cobalt manganese anode material for lithium-ion batteries of above-mentioned cerium dopping
Method, by by the doped chemical of Nano grade first with the advance ultra-high-speed mixing of nickel cobalt manganese monocrystalline composite precursor, then with it is other
Common nickel cobalt manganese composite precursor mixed at high speed, it is uneven to solve the problems, such as that doped chemical mixes with host element.
The technical solution adopted in the present invention is：
A kind of nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping, molecular formula LiaNixCoyMnzCebO2, wherein, b is
4/3-a/3-x-y-z, 1≤a≤1.2,0.3≤x≤0.98,0.01≤y≤0.6,0.001≤z≤0.6,0.00001≤b≤
0.02。
The preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of above-mentioned cerium dopping, specifically implements according to following steps：
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source；
Step 2, nickel cobalt manganese monocrystalline composite precursor and the compound of cerium that the step 1 weighs are carried out into ultrahigh speed to mix
Close, obtain the first mixture；
Step 3, the first mixture of the step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are carried out high
Speed mixing, obtains the second mixture；
Step 4, the second mixture of the step 3 is calcined, is obtaining the nickel cobalt manganese lithium ion battery of cerium dopping just
Pole material.
The features of the present invention also resides in,
The compound of the cerium is Nano grade, and its incorporation is nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline
The 0.001-2% of composite precursor Ni, Co, Mn integral molar quantity.
The compound of the cerium of the Nano grade is Ce2O3Or Ce (OH)3。
The nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor are the compound hydrogen-oxygen of nickel, cobalt, manganese
One or several kinds in compound or composite oxides or compound oxyhydroxide.
Nickel, cobalt, the mol ratio of manganese are in the nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor
0.3-0.98:0.001-0.6:0.001-0.6。
The mass ratio of the nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 2-20:1.
The lithium source is lithium carbonate or lithium hydroxide, and the mole of its incorporation and the ratio of nickel cobalt manganese mole sum are 0.9-
1.2:1。
The ultrahigh speed and mixed at high speed use ternary material high speed blender, and ultra-high-speed mixing rotating speed is 5500-
20000r/min, mixed at high speed rotating speed are 500-10000r/min.
Second mixture is calcined in porcelain boat, and sintering temperature is 600-1200 DEG C, time 6-36h.
Compared with prior art, the present invention is first surpassed the compound of nickel cobalt manganese monocrystalline composite precursor and nano-scale cerium
Mixed at high speed, then by the compound of nickel cobalt manganese monocrystalline presoma and cerium compound and common nickel cobalt manganese presoma mixed at high speed, carry
High mixed effect, do not broken up because monocrystalline composite precursor high mechanical strength, during ultra-high-speed mixing, while monocrystalline compound precursor
Body can play a part of collision medium, and the compound of nano-scale cerium is fully broken up, and make doped chemical and host element fully mixed
Close.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The embodiment of the present invention provides a kind of nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping, and its molecular formula is
LiaNixCoyMnzCebO2, wherein, b 4/3-a/3-x-y-z, 1≤a≤1.2,0.3≤x≤0.98,0.01≤y≤0.6,
0.001≤z≤0.6,0.00001≤b≤0.02.
It is a further object to provide the preparation side of the nickel cobalt manganese anode material for lithium-ion batteries of above-mentioned cerium dopping
Method, specifically implement according to following steps：
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source；Step 2, the nickel cobalt manganese monocrystalline composite precursor and the compound of cerium step 1 weighed carries out ultra-high-speed mixing, obtains
First mixture；Step 3, the first mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are carried out high
Speed mixing, obtains the second mixture；Step 4, the second mixture of step 3 is subjected to roasting 6-36h, the temperature of roasting in porcelain boat
Spend the nickel cobalt manganese anode material for lithium-ion batteries for for 600-1200 DEG C, obtaining cerium dopping, nickel cobalt manganese polycrystalline composite precursor and nickel
The mass ratio of cobalt manganese monocrystalline composite precursor is 2-20:1, so, the compound of nickel cobalt manganese monocrystalline composite precursor and cerium is entered
Row mixed at high speed, do not broken up because monocrystalline composite precursor rugged construction, during ultra-high-speed mixing, while monocrystalline composite precursor
Collision medium can be played a part of, the compound of cerium is fully broken up, be sufficiently mixed doped chemical and host element.
The compound of cerium is Nano grade, and its incorporation is that nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are compound
The 0.001-2% of Ni, Co, Mn integral molar quantity in presoma, the compound of the cerium of Nano grade is Ce2O3Or Ce (OH)3, this
Sample, the compound of Nano grade are easier to be well mixed.
Nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor are the complex hydroxide of nickel, cobalt, manganese
It is or one or more than one kinds of in composite oxides or compound oxyhydroxide.
Nickel, cobalt, the mol ratio of manganese are 0.3- in nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor
0.98:0.001-0.6:0.001-0.6, so, the nickel cobalt manganese presoma of the mol ratio have better performance.
Lithium source is lithium carbonate or lithium hydroxide, and the mole of its incorporation and the ratio of nickel cobalt manganese mole sum are 0.9-1.2:
1, so, appropriate lithium carbonate or lithium hydroxide can make cell positive material have more preferable chemical property and cyclicity.
Ultrahigh speed and mixed at high speed use ternary material high speed blender, and ultra-high-speed mixing rotating speed is 5500-
20000r/min, mixed at high speed rotating speed are 500-10000r/min, so, doped chemical and host element mixing can be made more equal
It is even.
Embodiment 1
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 2:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.5 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.2:0.3, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 0.9:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor and
The 0.001% of Ni, Co, Mn integral molar quantity in nickel cobalt manganese monocrystalline composite precursor；Step 2, nickel cobalt manganese monocrystalline step 1 weighed
The compound of composite precursor and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed are adopted
With ternary material high speed blender, ultra-high-speed mixing rotating speed is 5500r/min, and mixed at high speed rotating speed is 500r/min；Step 3,
First mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are subjected to mixed at high speed, it is mixed to obtain second
Compound；Step 4, the second mixture of step 3 is subjected to roasting 6h in porcelain boat, the temperature of roasting is 700 DEG C, obtains cerium and mixes
Miscellaneous nickel cobalt manganese anode material for lithium-ion batteries；
Wherein, the compound of cerium is the Ce of Nano grade2O3, nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are compound
Presoma is the complex hydroxide of nickel, cobalt, manganese, and lithium source is lithium carbonate.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 148.5mAh/ under 0.5C multiplying powers
G, 100 charge and discharges circulation after capability retention 96.9%, and undoped with positive electrode first discharge specific capacity be 149mAh/g,
Capability retention 96.9% after 100 charge and discharges circulation.
Embodiment 2
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 10:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.5 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.2:0.3, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 1.2:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor and
The 0.8% of Ni, Co, Mn integral molar quantity in nickel cobalt manganese monocrystalline composite precursor；Step 2, the nickel cobalt manganese monocrystalline that step 1 weighs is answered
The compound for closing presoma and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed use
Ternary material high speed blender, ultra-high-speed mixing rotating speed are 20000r/min, and mixed at high speed rotating speed is 10000r/min；Step 3,
First mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are subjected to mixed at high speed, it is mixed to obtain second
Compound；Step 4, the second mixture of step 3 is subjected to roasting 26h in porcelain boat, the temperature of roasting is 760 DEG C, obtains cerium and mixes
Miscellaneous nickel cobalt manganese anode material for lithium-ion batteries；
Wherein, the compound of cerium is the Ce (OH) of Nano grade3, nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are answered
The composite oxides that presoma is nickel, cobalt, manganese are closed, lithium source is lithium hydroxide.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 158mAh/g under 0.5C multiplying powers,
100 charge and discharges circulation after capability retention 97.6%, and undoped with positive electrode first discharge specific capacity be 159mAh/g,
Capability retention 95.6% after 100 charge and discharges circulation.
Embodiment 3
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 20:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.8 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.1:0.1, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 1.2:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor and
The 2% of Ni, Co, Mn integral molar quantity in nickel cobalt manganese monocrystalline composite precursor；Step 2, nickel cobalt manganese monocrystalline step 1 weighed is compound
The compound of presoma and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed use three
First material high speed blender, ultra-high-speed mixing rotating speed are 10000r/min, and mixed at high speed rotating speed is 1000r/min；Step 3, will
First mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source carry out mixed at high speed, obtain the second mixing
Thing；Step 4, the second mixture of step 3 is subjected to roasting 36h in porcelain boat, the temperature of roasting is 800 DEG C, obtains cerium dopping
Nickel cobalt manganese anode material for lithium-ion batteries, the mass ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor
For 20:1；
Wherein, the compound of cerium is the Ce of Nano grade2O3, nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are compound
Presoma it is non-not Wei nickel, cobalt, the complex hydroxide of manganese and compound oxyhydroxide, lithium source be lithium carbonate.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 185mAh/g under 0.5C multiplying powers,
100 charge and discharges circulation after capability retention 97.8%, and undoped with positive electrode first discharge specific capacity be 193mAh/g,
Capability retention 93.2% after 100 charge and discharges circulation.
Embodiment 4
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 8:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.6 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.2:0.2, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 0.96:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor with
And in nickel cobalt manganese monocrystalline composite precursor Ni, Co, Mn integral molar quantity 0.3%；Step 2, nickel cobalt manganese monocrystalline step 1 weighed
The compound of composite precursor and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed are adopted
With ternary material high speed blender, ultra-high-speed mixing rotating speed is 12000r/min, and mixed at high speed rotating speed is 9000r/min；Step
3, the first mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are subjected to mixed at high speed, obtain second
Mixture；Step 4, the second mixture of step 3 is subjected to roasting 10h in porcelain boat, the temperature of roasting is 750 DEG C, obtains cerium
The nickel cobalt manganese anode material for lithium-ion batteries of doping；
Wherein, the compound of cerium is the Ce (OH) of Nano grade3, nickel cobalt manganese polycrystalline composite precursor is that nickel, cobalt, manganese are answered
The combination of oxyhydroxide and composite oxides is closed, nickel cobalt manganese monocrystalline composite precursor is nickel, cobalt, the complex hydroxide of manganese,
Lithium source is lithium carbonate or lithium hydroxide.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 164mAh/g under 0.5C multiplying powers,
100 charge and discharges circulation after capability retention 97.8%, and undoped with positive electrode first discharge specific capacity be 165mAh/g,
Capability retention 95.1% after 100 charge and discharges circulation.
Embodiment 5
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 18:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.6 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.2:0.2, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 1.1:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor and
The 1.5% of Ni, Co, Mn integral molar quantity in nickel cobalt manganese monocrystalline composite precursor；Step 2, the nickel cobalt manganese monocrystalline that step 1 weighs is answered
The compound for closing presoma and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed use
Ternary material high speed blender, ultra-high-speed mixing rotating speed are 6000r/min, and mixed at high speed rotating speed is 700r/min；Step 3, will
First mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source carry out mixed at high speed, obtain the second mixing
Thing；Step 4, the second mixture of step 3 is subjected to roasting 32h in porcelain boat, the temperature of roasting is 840 DEG C, obtains cerium dopping
Nickel cobalt manganese anode material for lithium-ion batteries；
Wherein, the compound of cerium is the Ce of Nano grade2O3, nickel cobalt manganese polycrystalline composite precursor be nickel, cobalt, manganese it is compound
Oxide, nickel cobalt manganese monocrystalline composite precursor are that nickel, cobalt, the complex hydroxide of manganese and compound oxyhydroxide combine, lithium
Source is lithium carbonate.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 160mAh/g under 0.5C multiplying powers,
100 charge and discharges circulation after capability retention 97.3%, and undoped with positive electrode first discharge specific capacity be 162mAh/g,
Capability retention 94.6% after 100 charge and discharges circulation.
Embodiment 6
Step 1, weigh respectively nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, cerium compound with
And lithium source, wherein, the ratio of nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 11:1, nickel cobalt manganese polycrystalline
Nickel, cobalt, the mol ratio of manganese are 0.7 in composite precursor and nickel cobalt manganese monocrystalline composite precursor:0.1:0.2, mole of lithium source
The ratio of amount and nickel cobalt manganese mole sum is 1.05:1, the incorporation of the compound of cerium for nickel cobalt manganese polycrystalline composite precursor with
And in nickel cobalt manganese monocrystalline composite precursor Ni, Co, Mn integral molar quantity 0.001%；Step 2, nickel cobalt manganese list step 1 weighed
The compound of brilliant composite precursor and cerium carries out ultra-high-speed mixing, obtains the first mixture, wherein, ultrahigh speed and mixed at high speed are equal
Using ternary material high speed blender, ultra-high-speed mixing rotating speed is 19000r/min, and mixed at high speed rotating speed is 9000r/min；Step
Rapid 3, the first mixture of step 2 and the nickel cobalt manganese polycrystalline composite precursor that weighs and lithium source are subjected to mixed at high speed, obtain the
Two mixtures；Step 4, the second mixture of step 3 is subjected to roasting 36h in porcelain boat, the temperature of roasting is 900 DEG C, is obtained
The nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping；
Wherein, the compound of cerium is the Ce of Nano grade2O3, nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are compound
Presoma is the combination of nickel, cobalt, the complex hydroxide of manganese and compound oxyhydroxide, and lithium source is lithium hydroxide.
Using the positive electrode that the inventive method obtains, first discharge specific capacity reaches 173mAh/g under 0.5C multiplying powers,
100 charge and discharges circulation after capability retention 96.8%, and undoped with positive electrode first discharge specific capacity be 173mAh/g,
Capability retention 95.6% after 100 charge and discharges circulation.
Using such scheme, compared with prior art, the present invention is first by nickel cobalt manganese monocrystalline composite precursor and nano-scale cerium
Compound carry out ultra-high-speed mixing, then by the compound of nickel cobalt manganese monocrystalline presoma and cerium compound and common nickel cobalt manganese forerunner
Body mixed at high speed, mixed effect is improved, do not broken up because monocrystalline composite precursor high mechanical strength, during ultra-high-speed mixing, together
Shi Danjing composite precursors can play a part of collision medium, and the compound of nano-scale cerium is fully broken up, and make doped chemical
It is sufficiently mixed with host element.
More than, it is only the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and it is any
Those familiar with the art the invention discloses technical scope in, the change or replacement that can readily occur in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (10)
1. the nickel cobalt manganese anode material for lithium-ion batteries of a kind of cerium dopping, it is characterised in that its molecular formula is
LiaNixCoyMnzCebO2, wherein, b 4/3-a/3-x-y-z, 1≤a≤1.2,0.3≤x≤0.98,0.01≤y≤0.6,
0.001≤z≤0.6,0.00001≤b≤0.02.
It is 2. a kind of such as the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping in claim 1, it is characterised in that
Specifically implement according to following steps：
Step 1, nickel cobalt manganese polycrystalline composite precursor, nickel cobalt manganese monocrystalline composite precursor, the compound and lithium of cerium are weighed respectively
Source；
Step 2, the nickel cobalt manganese monocrystalline composite precursor and the compound of the cerium step 1 weighed carries out ultra-high-speed mixing, obtains
Obtain the first mixture；
Step 3, the first mixture of the step 2 and the nickel cobalt manganese polycrystalline composite precursor weighed and lithium source are carried out mixed at a high speed
Close, obtain the second mixture；
Step 4, the second mixture of the step 3 is calcined, obtains the nickel cobalt manganese lithium ion cell positive material of cerium dopping
Material.
3. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 2, its feature exist
In the compound of the cerium is Nano grade, and its incorporation is that nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline are compound
The 0.001-2% of presoma Ni, Co, Mn integral molar quantity.
4. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 3, its feature exist
In the compound of the cerium of the Nano grade is Ce2O3Or Ce (OH)3。
5. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 4, its feature exist
In, the nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor be nickel, cobalt, manganese complex hydroxide or
It is one or more than one kinds of in composite oxides or compound oxyhydroxide.
6. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 5, its feature exist
In nickel, cobalt, the mol ratio of manganese are 0.3- in the nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor
0.98:0.001-0.6:0.001-0.6。
7. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 6, its feature exist
In the mass ratio of the nickel cobalt manganese polycrystalline composite precursor and nickel cobalt manganese monocrystalline composite precursor is 2-20:1.
8. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 7, its feature exist
In the lithium source is lithium carbonate or lithium hydroxide, and the mole of its incorporation and the ratio of nickel cobalt manganese mole sum are 0.9-1.2:
1。
9. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 8, its feature exist
In the ultrahigh speed and mixed at high speed use ternary material high speed blender, and ultra-high-speed mixing rotating speed is 5500-20000r/
Min, mixed at high speed rotating speed are 500-10000r/min.
10. the preparation method of the nickel cobalt manganese anode material for lithium-ion batteries of cerium dopping according to claim 9, its feature exist
In second mixture is calcined in porcelain boat, and sintering temperature is 600-1200 DEG C, time 6-36h.
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