CN109192972A - Mixture of multi-elements is mixed with modified tertiary cathode material and preparation method thereof - Google Patents
Mixture of multi-elements is mixed with modified tertiary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of mixture of multi-elements to be mixed with modified tertiary cathode material and preparation method thereof.For tertiary cathode material lattice structure characteristic, the method adulterated using mixture of multi-elements, the selectively metal ion of two class different ions radiuses of doping, carries out the doping of different location: the one type metal ion suitable or close with lithium ion radius, it is possible to reduce cationic mixing；Another kind of and transition metal ions (Mn4+、Co3+) the suitable or close metal ion of radius, it is possible to reduce polarization enhances chemical property.Meanwhile by double sintering technique, a protective layer is coated on the surface of the material, prevents the dissolution of tertiary cathode material surface transition metal ion, to prepare the tertiary cathode material with excellent high rate performance and cycle performance.This method simple process, easy to operate, favorable reproducibility, are adapted to scale industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion battery electrode, and in particular to a kind of mixture of multi-elements, which is mixed with, to be changed
Property tertiary cathode material and preparation method thereof.
Background technique
Layered Lithium nickel, cobalt, manganese and oxygen tertiary cathode material (hereinafter referred to as " tertiary cathode material " or " NCM ") preferably has both
The advantages of cobalt acid lithium, lithium nickelate, LiMn2O4, trielement synergistic effect make its comprehensive performance be better than any one-component compound, thus
It has many advantages, such as that height ratio capacity, stable cycle performance, advantage of lower cost, security performance are preferable, is widely used to all kinds of
The fields such as electronic product and new-energy automobile.
In tertiary cathode material, there are five types of the cations of different valence state and radius altogether: Li+(radius:)、Ni2+
(radius:)、Ni3+(radius:)、Mn4+(radius:)、Co3+(radius:).Above-mentioned five
In kind cation, can be divided into two classes by ionic radius size: one kind is the larger and close Li of cation radius+And Ni2+, separately
One kind is the smaller and close transition metal ions Ni of ionic radius3+、Mn4+、Co3+。
Due to Ni2+Radius and Li+Radius is close, so Ni2+It is easy to occupy Li+Position, it is mixed so as to cause cation
Arrange the generation of phenomenon, Ni2+In Li+Layer not only reduces specific discharge capacity, and hinders Li+Diffusion, the nothing of this structure
The chemical property that sequence state directly results in material is deteriorated.In addition, tertiary cathode material surface texture is unstable, due to LiPF6
The HF contained in electrolyte can corroding electrode material cause metal ion to dissolve so that the cycle life of material is greatly reduced.
In view of the above-mentioned problems, researcher often improves the performance of tertiary cathode material using element doping and cladding.Sun from
Son doping is a kind of common method for improving tertiary cathode material chemical property, and common foreign cation has Zn2+、Zr2 +、La3+、Al3+、Ti4+、V5+、Mo6+Deng lattice defect will be caused in the lattice of these ion dopings to material, or increase interlayer
Away from or stabilizing material crystal structure, so that the chemical property of material be made to get a promotion.For example, application No. is
After the patent of CN201410110848.X is by rare earth oxide and ternary anode material precursor ball milling, by being sintered three times
To rear-earth-doped tertiary cathode material；Application No. is the patent of CN201710979691.8 disclose a kind of Er, Zr metal from
Sub- mixing and doping improves tertiary cathode material chemical property method.Application No. is the patents of CN201710121639.9 to disclose
It is a kind of to prepare Al using sol-gel method3+、Zr2+、Ti4+The method of the tertiary cathode material of equal doping.It is single in the above method
Introduce a kind of ion, or introduce ion similar in different kinds of ions radius, cause the cell parameter of tertiary cathode material not at
The variation of ratio causes lattice lopsided, it is difficult to ensure that the performance of tertiary cathode material is made to be greatly improved or improve.
Summary of the invention
The technical problem to be solved in the present invention is that overcome the deficiencies in the prior art, for tertiary cathode material lattice structure
Feature, the method adulterated using mixture of multi-elements selectively adulterate the metal ion of two class different ions radiuses, so that ternary
Positive electrode keeps good lattice structure.Meanwhile by double sintering technique, a protective layer is coated on the surface of the material, is prevented
The only dissolution of tertiary cathode material surface transition metal ion, to prepare three with excellent high rate performance and cycle performance
First positive electrode.
To achieve the goals above, the present invention adopts the following technical scheme:
The chemical formula that a kind of mixture of multi-elements is mixed with modified tertiary cathode material is Li (NixCoyMnz)1-a-bMaM’bNcO2+c；Wherein, the radius Yu lithium ion of metal ions M are close, are selected from Mg2+、Sc3+、、Y3+、Nb5+、In3+、Sn4+、Ce4+、Eu3 +、Gd3+、Er3+、Ta4+One of or it is a variety of；Metal ions M ' radius and tertiary cathode material in transition metal ions
(Ni3+、Mn4+、Co3+) radius it is close, be selected from Al3+、Ti4+、Ge4+、W6+、V5+It is one or more；N is tertiary cathode material
Surface coated element, selection contain Al3+、Zr4+、B3+、Ti4+、Ge4+、W6+、V5+Compound it is one or more.Wherein 0.6≤
X≤0.9,0 < y≤0.4,0 < z≤0.4, x+y+z=1,0.0001≤a≤0.01,0.0001≤b≤0.01 and a/2≤b≤
2a, 0.0001≤c≤0.01.
A kind of mixture of multi-elements is mixed with modified tertiary cathode material and preparation method, and it is rapid that Bao includes Ru Xia Walk:
(1) according to chemical formula Li (NixCoyMnz)1-a-bMaM’bNcO2+cEach element molar ratio, weigh respectively it is suitable containing
The presoma of nickel-cobalt-manganese ternary element, lithium source, the ionic compound for containing M and M ', wherein lithium source is measured according to chemical formula than excessive 1-
10%；It is sufficiently mixed, obtains mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, is once burnt under oxidizing atmosphere
Knot obtains once sintered product B after natural cooling, broken.
(3) according to chemical Li (NixCoyMnz)1-a-bMaM’bNcO2+cElemental mole ratios weigh a certain amount of compound containing N,
Step (2) is added to obtain uniformly being sufficiently mixed in once sintered product B, after drying, obtaining mixture C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, secondary burning is carried out under oxidizing atmosphere
Knot, then after natural cooling, broken, screening, obtain metal cation M and M ' codope, N oxide cladding ternary just
Pole material Li (NixCoyMnz)1-a-bMaM’bNcO2+c。
A kind of mixture of multi-elements is mixed with the preparation method of modified tertiary cathode material, and step contains described in (1)
There is the presoma of three elements of nickel cobalt manganese, can be one of the hydroxide of three elements for including nickel cobalt manganese, carbonate
Or it is a variety of；The lithium source is one of the lithium carbonate containing elemental lithium, lithium hydroxide, lithium acetate or a variety of；The M ionization
Closing object can be comprising Mg2+、Sc3+、Y3+、Nb5+、In3+、Sn4+、Ce4+、Eu3+、Gd3+、Er3+、Ta4+Oxide, hydroxide
Object, nitrate, acetate, oxalates, carbonate, sulfate, alkoxide it is one or more；M ' the ionic compound is metal
Ion A l3+、Ti4+、Ge4+、W6+、V5+Oxide, hydroxide, oxalates, carbonate, nitrate, acetate, sulfate,
Alkoxide it is one or more.
The mixture of multi-elements is mixed with the preparation method of modified tertiary cathode material, and step (2) is described once sintered
It is to be carried out under air or oxygen atmosphere, 700-1100 DEG C of sintering temperature, 1-10 DEG C of heating rate/min, sintering time 5-
30h。
The mixture of multi-elements is mixed with the preparation method of modified tertiary cathode material, chemical combination containing N described in step (3)
Object can be comprising Al3+、B3+、Zr4+、Ti4+、Ge4+、W6+、V5+Oxide, hydroxide, nitrate, acetate, oxalates,
Carbonate, sulfate, organic salt it is one or more.The solvent can be one of pure water, ethyl alcohol, acetone or a variety of；
The additional amount of solvent is no less than the 10% of solid matter mass, not higher than the 20% of solid matter mass.
The mixture of multi-elements is mixed with the preparation method of modified tertiary cathode material, and step (4) is described once sintered
It is to be carried out under air or oxygen atmosphere, 400-900 DEG C of sintering temperature, 1-10 DEG C of heating rate/min, sintering time 3-
10h。
Compared with prior art, the invention has the following beneficial effects:
(1) mixture of multi-elements prepared by the present invention is mixed with modified tertiary cathode material, selectively injects two classes not
With radius metal ion, wherein the metal ion suitable or close with lithium ion radius, it is possible to reduce cationic mixing；It is another kind of
The suitable or close metal ion with transition metal ions radius, it is possible to reduce polarization enhances chemical property.In high temperature sintering
In the process, under the synergistic effect of two class different metal ions, involvement tertiary cathode material that doped chemical can faster more evenly
In the lattice of material, the doping of different location is carried out, cell parameter collaborative variation can expand the channel of lithium ion transport, again
Tertiary cathode material can be made to keep good lattice structure.
(2) mixture of multi-elements prepared by the present invention is mixed with modified tertiary cathode material, in mixture of multi-elements doping
On the basis of, by double sintering technique, protective oxide film is introduced on positive electrode surface, to reduce and inhibit electrolyte to just
The erosion of pole material.Under the collective effect that mixture of multi-elements is mixed with, prepare with excellent cycling performance and forthright again
The tertiary cathode material of energy.
Detailed description of the invention
Fig. 1: the scanning electron microscope (SEM) photograph of 1 sample of embodiment.
Fig. 2: the XRD diagram of 1 sample of embodiment.
Fig. 3: the first charge-discharge curve graph of 1 sample of embodiment.
Fig. 4: the circulation curve graph of 1 sample of embodiment.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the invention.Externally it should be understood that after reading the contents of the present invention, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1:
The present embodiment prepares Nb5+With Al3+Codope, ZrO2The tertiary cathode material of coating modification, includes the following steps:
(1) Ni of 9.9mol is weighed0.8Co0.1Mn0.1(OH)2, the lithium hydroxide of 10.4mol, 0.05mol six water plants acid
Niobium, 0.025mol Patent alum, are placed in high speed mixer, are sufficiently mixed, obtain a homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 3 DEG C/min's
It under the rate of heat addition, is warming up to 760 DEG C and keeps 20h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) 1 liter of ethyl alcohol is added in the zirconium acetate for weighing 0.05mol, and after being thoroughly mixed, mixture is added to step
(2) in the once sintered product B prepared, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent is evaporated；
It is then transferred in baking oven, dry 10h, obtains mixture C under the conditions of 90 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 700 DEG C and keeps 6h, stops heating.Then after natural cooling, broken, screening, Nb is obtained5+With Al3+Codope,
ZrO2The tertiary cathode material of cladding.
Table morphology characterization is carried out to tertiary cathode material in embodiment 1 using scanning electron microscope (SEM), such as Fig. 1 institute
Show.From figure 1 it appears that tertiary cathode material still maintains preferable spherical after being mixed with high temperature sintering
Grain, the size of spheric granules is at 6-8 μm；It is observed that, the surface of micron ball can uniformly coat one layer of oxidation from picture
Zirconium.Micron ball is accumulated by micron flakes close structure, and 0.5 μm of thickness or so of most of micron chips, size is at 1-2 μm
Between.
Structural characterization is carried out to tertiary cathode material prepared by embodiment 1 using x-ray powder diffraction instrument, as a result such as Fig. 2
It is shown.It can be seen that diffraction maximum and α-NaFeO2Kissing is right higher, and without dephasign peak, peak shape is more sharp, illustrates have very
Good layer structure.
The present embodiment prepares Nb5+With Al3+The chemical property of the modified tertiary cathode material of codope, alumina-coated
Test method it is as follows:
CR2025 button cell will be assembled into for positive electrode active materials with the tertiary cathode material sample of this example preparation: first
First, N-Methyl pyrrolidone is dispersed by tertiary cathode material, acetylene black and PVDF prepared by this example for 8:1:1 in mass ratio
(NMP) slurry is made in；Then, with scraper plate coating machine by slurry coating in forming electrode slice on aluminium foil, with a thickness of 150 μm, electricity
Pole piece in 120 DEG C of dry 12h, stamps out 1cm in a vacuum drying oven on electrode slice2Cathode disk；Battery assembly is being filled
It is completed in the glove box of full high-purity argon gas, using lithium piece as cathode, Celgard2300 polypropylene porous film is diaphragm, and electrolyte is
1mol/L LiPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1:1) mixed solution.It is assembled into
CR2025 button cell carries out electrochemical property test.
Fig. 3 is the sample for preparing of embodiment 1 in 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density
Under the conditions of first charge-discharge capacitance-voltage curves figure.It can be seen from the figure that first discharge specific capacity is 201.5mAh/g,
Initial charge specific capacity is 222.3mAh/g, and first charge discharge efficiency reaches 90.6%, and polarity effect is also smaller, shows good electrification
Learn performance.
Fig. 4 is the sample of the preparation of embodiment 1 in 3.0-4.3V voltage range, and the circulation under different current densities is bent
Line chart.It can be seen from the figure that under the charging and discharging currents density of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, after circulation 10 times, sample
The specific discharge capacity of product is divided into 200.6,192,180.4,166.2,152.2,125.5mAh/g；When current density turns again to
When 0.2C, discharge capacity is rapidly reached 184.9mAh/g again, and after continuing cycling through 40 times, specific discharge capacity still has 180.6mAh/g；
Show excellent high rate performance and cycle performance.
Embodiment 2:
The present embodiment prepares Sn4+With V5+Codope, Al2O3The tertiary cathode material of cladding, includes the following steps:
(1) weigh 0.02mol SnCl4,0.02mol ammonium metavanadate, be added in 1 liter of water, stirring and dissolving be sufficiently stirred；
The Ni of 9.96mol is weighed again0.6Co0.2Mn0.2(OH)2, 5.15mol lithium carbonate be put into above-mentioned suspension, be heated to 90 DEG C,
And uninterruptedly stirred using high-speed mixer, until solvent is evaporated, obtain a homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's
It under the rate of heat addition, is warming up to 880 DEG C and keeps 20h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) 1 liter of ethyl alcohol is added in the aluminium oxide for weighing 0.025mol, and after being thoroughly mixed, mixture is added to step
(2) in the once sintered product B prepared, 50 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent is evaporated；
It is then transferred in baking oven, dry 10h, obtains mixture C under the conditions of 110 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 2 DEG C/min
Temperature is to 600 DEG C and keeps 8h, then stops heating.Then after natural cooling, broken, screening, metal cation Sn is obtained4+
With V5+Codope, Al2O3The tertiary cathode material of cladding.
The tertiary cathode material sample prepared according to the method for embodiment 1 to embodiment 2 has carried out electrochemical property test.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 188.3mAh/g, and initial charge capacity is 206.4mAh/g, and coulombic efficiency reaches 91.2% for the first time；Circulation
After 100 times, discharge capacity 174.5mAh/g, capacity retention ratio 92.7% shows good chemical property.
Embodiment 3:
The present embodiment prepares Mg2+、Sc3+With Al3+、Ti4+The tertiary cathode material of codope, boron oxide cladding, including it is as follows
Step:
(1) Ni of 9.9mol is weighed0.6Co0.2Mn0.2CO3, the lithium carbonate of 5.20mol, 0.025mol magnesium hydroxide,
Scandium hydroxide, the 0.0125mol aluminum oxide of 0.025mol, the TiO of 0.025mol2, it is placed in high speed mixer, carries out
It is sufficiently mixed, obtains a homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's
It under the rate of heat addition, is warming up to 900 DEG C and keeps 15h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) diboron trioxide for weighing 0.025mol is added in 1 liter of ethyl alcohol, after being thoroughly mixed, mixture is added
Into the once sintered product B of step (2) preparation, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent
It is evaporated；It is then transferred in baking oven, dry 6h, obtains mixture C under the conditions of 110 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 600 DEG C and keeps 8h, stops heating.Then after natural cooling, broken, screening, metal cation Mg is obtained2+、Sc3 +With Al3+、Ti4+The tertiary cathode material of codope, boron oxide cladding.
The tertiary cathode material sample prepared according to the method for embodiment 1 to embodiment 3 has carried out electrochemical property test.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 181.5mAh/g, and initial charge capacity is 199.2mAh/g, and coulombic efficiency reaches 91.1% for the first time；Circulation
After 100 times, discharge capacity 169.7mAh/g, capacity retention ratio 93.5% shows good chemical property.
Embodiment 4:
This implementation prepares Y3+、Ce4+、Eu3+、Gd3+、Er3+With V5+、W6+Codope, TiO2The tertiary cathode material of cladding, packet
Include following steps:
(1) 0.01mol yttria, 0.02mol cerium oxide, 0.01mol gadolinium sesquioxide, tri- oxygen of 0.01mol are weighed
Change two europiums, 0.01mol erbium oxide, 0.02mol ammonium metavanadate, 0.02mol ammonium tungstate, is added in 1 liter of ethyl alcohol, is sufficiently stirred
Mixing；The Ni of 9.8mol is weighed again0.8Co0.1Mn0.1(OH)2, 10.3mol lithium hydroxide be put into above-mentioned suspension, be heated to
60 DEG C, and uninterruptedly stirred using high-speed mixer, until solvent is evaporated, obtain a homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's
It under the rate of heat addition, is warming up to 780 DEG C and keeps 10h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) TiO of 0.05mol is weighed2, 1 liter of ethyl alcohol is added, after being thoroughly mixed, mixture is added to step (2)
In the once sintered product B of preparation, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent is evaporated；Then
It is transferred in baking oven, dry 10h, obtains mixture C under the conditions of 90 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 680 DEG C and keeps 6h, stops heating.Then after natural cooling, broken, screening, Y is obtained3+、Ce4+、Eu3+、Gd3+、
Er3+With V5+、W6+Codope, TiO2The tertiary cathode material of cladding.
Electrochemical property test is carried out to tertiary cathode material sample prepared by embodiment 4 according to the method for embodiment 1.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 202.3mAh/g, and initial charge capacity is 218.5mAh/g, and coulombic efficiency reaches 92.6% for the first time；Circulation
After 100 times, discharge capacity 191.6mAh/g, capacity retention ratio 94.7% shows good chemical property.
Embodiment 5:
The present embodiment prepares Nb5+、Ta5+With Ge4+Codope, vanadic anhydride coating modification tertiary cathode material, including
Following steps:
(1) 0.025mol niobium hydroxide, 0.025mol tantalum hydroxide, 0.05mol germanium dioxide are weighed, 1 liter of ethyl alcohol is added,
It is sufficiently stirred and is mixed；Weigh the Ni of 9.9mol0.8Co0.1Mn0.1(OH)2, 10.3mol lithium hydroxide be put into above-mentioned suspension,
60 DEG C are heated to, and is uninterruptedly stirred using high-speed mixer, until solvent is evaporated, homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's
It under the rate of heat addition, is warming up to 760 DEG C and keeps 20h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) vanadic anhydride for weighing 0.025mol is added 1 liter of ethyl alcohol, after being thoroughly mixed, mixture is added to
In the once sintered product B of step (2) preparation, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent steams
It is dry；It is then transferred in baking oven, dry 10h, obtains mixture C under the conditions of 110 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 600 DEG C and keeps 8h, then stops heating.Then after natural cooling, broken, screening, Nb5+、Ta5+With Ge4+It is co-doped with
Miscellaneous, vanadic anhydride coating modification tertiary cathode material.
The tertiary cathode material sample prepared according to the method for embodiment 1 to embodiment 4 has carried out electrochemical property test.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 210.7mAh/g, and initial charge capacity is 229.3mAh/g, and coulombic efficiency reaches 91.9% for the first time；Circulation
After 100 times, discharge capacity 197.1mAh/g, capacity retention ratio 93.5% shows good chemical property.
Embodiment 6:
The present embodiment prepares In3+With W6+Codope, TiO2The tertiary cathode material of cladding, includes the following steps:
(1) six nitric hydrate indium of 0.02mol, 0.02mol ammonium tungstate are weighed, is added in 1 liter of water, it is molten that stirring is sufficiently stirred
Solution；The Ni of 9.96mol is weighed again0.8Co0.1Mn0.1(OH)2, 10.3mol lithium hydroxide be put into above-mentioned suspension, be heated to
90 DEG C, and uninterruptedly stirred using high-speed mixer, until solvent is evaporated, homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 5 DEG C/min's
It under the rate of heat addition, is warming up to 800 DEG C and keeps 10h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) TiO of 0.05mol is weighed2, 1 liter of ethyl alcohol is added, after being thoroughly mixed, mixture is added to step (2)
In the once sintered product B of preparation, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent is evaporated；Then
It is transferred in baking oven, dry 10h, obtains mixture C under the conditions of 90 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 700 DEG C and keeps 6h, stops heating.Then after natural cooling, broken, screening, In is obtained3+With W6+Codope,
TiO2The tertiary cathode material of cladding.
Electrochemical property test is carried out to tertiary cathode material sample prepared by embodiment 5 according to the method for embodiment 1.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 206.7mAh/g, and initial charge capacity is 228.3mAh/g, and coulombic efficiency reaches 90.5% for the first time；Circulation
After 100 times, discharge capacity 196.5mAh/g, capacity retention ratio 95.1% shows good chemical property.
Comparative example 1:
Embodiment 1 is copied, the tertiary cathode material LiNi undoped with coating modification is prepared0.6Co0.2Mn0.2O2, including it is as follows
Step:
(1) mixing: according to LiNi in tertiary cathode material chemical formula0.6Co0.2Mn0.2O2The molar ratio of each element, weighs
The precursor Ni of 10mol0.6Co0.2Mn0.2(OH)2, the lithium carbonate of 5.15mol；Then be sufficiently mixed, obtain presoma and
The mixture A of lithium carbonate.
(2) high temperature sintering: mixture A prepared by step (1) is placed in high temperature sintering furnace, under oxidizing atmosphere, with
The rate of heat addition of 2 DEG C/min is warming up to 880 DEG C and keeps 20h, then stops heating, by natural cooling, is crushed, sieves, removes
To get metal sun from tertiary cathode material LiNi after iron0.6Co0.2Mn0.2O2。
The tertiary cathode material LiNi according to the method for embodiment 1 prepared by comparative example 10.6Co0.2Mn0.2O2Sample carries out
Electrochemical property test.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 180.3mAh/g, and initial charge capacity is 206.2mAh/g, and coulombic efficiency reaches 87.4% for the first time；Circulation
After 100 times, discharge capacity 161.7mAh/g, capacity retention ratio 89.6%, performance is slightly poor compared with doping vario-property
It is some.
Comparative example 2:
The present embodiment prepares Nb5+The tertiary cathode material of doping, vanadic anhydride coating modification, includes the following steps:
(1) 0.1mol niobium hydroxide is weighed, 1 liter of ethyl alcohol is added, is sufficiently stirred and is mixed；Weigh 9.9mol's
Ni0.8Co0.1Mn0.1(OH)2, 10.3mol lithium hydroxide be put into above-mentioned suspension, be heated to 60 DEG C, and utilize high-speed stirred
Machine uninterruptedly stirs, until solvent is evaporated, homogeneous mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's
It under the rate of heat addition, is warming up to 760 DEG C and keeps 20h, then stop heating.After natural cooling, broken, obtain once sintered
Product B.
(3) vanadic anhydride for weighing 0.025mol is added 1 liter of ethyl alcohol, after being thoroughly mixed, mixture is added to
In the once sintered product B of step (2) preparation, 60 DEG C are heated to, and uninterruptedly stir using high-speed mixer, until solvent steams
It is dry；It is then transferred in baking oven, dry 10h, obtains mixture C under the conditions of 110 DEG C.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, to rise under the rate of heat addition of 5 DEG C/min
Temperature is to 600 DEG C and keeps 8h, then stops heating.Then after natural cooling, broken, screening, Nb5+Doping, five oxidations two
The tertiary cathode material of vanadium coating modification.
The tertiary cathode material sample prepared according to the method for embodiment 1 to comparative example 2 has carried out electrochemical property test.
Test result shows under conditions of 3.0-4.3V voltage range, 0.1C (1C=200mA/g) current density, first
Secondary discharge capacity is 206.8mAh/g, and initial charge capacity is 237.6mAh/g, and coulombic efficiency reaches 87.0% for the first time；Circulation
After 100 times, discharge capacity 189.7mAh/g, capacity retention ratio 91.7%, chemical property and mixture of multi-elements doping
Ternary material (embodiment 5) is compared, slightly weaker.
In conclusion the above is merely preferred embodiments of the present invention, being not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of mixture of multi-elements is mixed with modified tertiary cathode material, chemical formula is Li (NixCoyMnz)1-a-bMaM’bNcO2+c；Wherein, the radius of doped metal ion M and lithium ion are close, are selected from Mg2+、Sc3+、、Y3+、Nb5+、In3+、Sn4+、Ce4 +、Eu3+、Gd3+、Er3+、Ta4+One of or it is a variety of；Transition metal in the radius and ternary material of doped metal ion M ' from
Son (Ni3+、Mn4+、Co3+) radius it is close, be selected from Al3+、Ti4+、Ge4+、W6+、V5+It is one or more；N is ternary material table
The element that bread covers, selection contain Al3+、B3+、Zr4+、Ti4+、Ge4+、W6+、V5+Compound it is one or more；0.5≤x≤
0.9,0 < y≤0.4,0 < z≤0.4, x+y+z=1,0.0001≤a≤0.01,0.0001≤b≤0.01 and a/2≤b≤2a,
0.0001≤c≤0.01。
2. a kind of mixture of multi-elements according to claim 1 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, it is rapid that Bao includes Ru Xia Walk:
(1) according to chemical formula Li (NixCoyMnz)1-a-bMaM’bNcO2+cEach element molar ratio weighs suitable containing nickel cobalt respectively
The presoma of three elements of manganese, lithium source, the ionic compound for containing M and M ', wherein lithium source is measured according to chemical formula than excessive 1-
10%；It is sufficiently mixed, obtains mixture A.
(2) mixture A prepared by step (1), is placed in high temperature sintering furnace, and once sintered, warp is carried out under oxidizing atmosphere
After crossing natural cooling, being crushed, once sintered product B is obtained.
(3) according to chemical Li (NixCoyMnz)1-a-bMaM’bNcO2+cElemental mole ratios weigh a certain amount of compound containing N, are added
To step (2) obtain that a certain amount of solvent is added, is uniformly sufficiently mixed, by further drying in once sintered product B
Afterwards, mixture C is obtained.
(4) mixture C prepared by step (3), is placed in high temperature sintering furnace, double sintering is carried out under oxidizing atmosphere, so
Afterwards after natural cooling, broken, screening, the tertiary cathode material of metal cation M and M ' codope, N oxide cladding is obtained
Expect Li (NixCoyMnz)1-a-bMaM’bNcO2+c。
3. a kind of mixture of multi-elements according to claim 2 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, the presoma containing nickel-cobalt-manganese ternary element described in step (1) can be the hydrogen-oxygen for including nickel-cobalt-manganese ternary element
One of compound, carbonate are a variety of.
4. a kind of mixture of multi-elements according to claim 2 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, lithium source described in step (1) is one of the lithium carbonate containing elemental lithium, lithium hydroxide, lithium acetate or a variety of.
5. a kind of mixture of multi-elements according to claim 2 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, M ionic compound described in step (1) can be comprising Mg2+、Sc3+、Y3+、Nb5+、In3+、Sn4+、Ce4+、Eu3+、
Gd3+、Er3+、Ta4+Oxide, hydroxide, nitrate, acetate, oxalates, carbonate, sulfate, alkoxide one kind or
It is a variety of.
6. a kind of mixture of multi-elements according to claim 2 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, M ' ionic compound described in step (1) is metal ion Al3+、Ti4+、Ge4+、W6+、V5+Oxide, hydrogen-oxygen
Compound, oxalates, carbonate, nitrate, acetate, sulfate, alkoxide it is one or more.
7. a kind of mixture of multi-elements according to claim 2-6 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, step (2) it is described it is once sintered be to be carried out under air or oxygen atmosphere, 700-1100 DEG C of sintering temperature,
1-10 DEG C of heating rate/min, sintering time 5-30h.Preferably, 760-980 DEG C of sintering temperature, 2-5 DEG C of heating rate/min,
Sintering time 15-20h.
8. a kind of mixture of multi-elements according to claim 2-7 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, compound containing N described in step (3) can be and include Al3+、B3+、Zr4+、Ti4+、Ge4+、W6+、V5+Oxidation
Object, hydroxide, nitrate, acetate, oxalates, carbonate, sulfate, organic salt it is one or more.
9. a kind of mixture of multi-elements according to claim 2-8 is mixed with the preparation method of the tertiary cathode material changed,
It is characterized in that, solvent described in step (3) can be one of pure water, ethyl alcohol, acetone or a variety of；The additional amount of solvent is not
Less than the 10% of solid matter mass, not higher than the 20% of solid matter mass.
10. a kind of mixture of multi-elements according to claim 2-9 is mixed with the preparation method of modified tertiary cathode material,
It is characterized in that, step (4) described double sintering is carried out under air or oxygen atmosphere, 400-900 DEG C of sintering temperature, rise
1-10 DEG C of warm speed/min, sintering time 3-10h.
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