CN109755537A - It is a kind of to be mixed with modified rich nickel tertiary cathode material and preparation method thereof - Google Patents
It is a kind of to be mixed with modified rich nickel tertiary cathode material and preparation method thereof Download PDFInfo
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Abstract
Modified rich nickel tertiary cathode material and preparation method thereof is mixed with the present invention relates to a kind of comprising Dopants richness nickel ternary nucleome and the amorphous clad structure of lithium halide, the chemical composition of Dopants richness nickel ternary nucleome are LiNi1‑x‑ yCoyAlxXzO2‑0.5z(X=F, Cl, Br), wherein, 0.030≤x≤0.050,0.100≤y≤0.150,0.001≤z≤0.008, present invention uses the means being mixed with to be modified rich nickel ternary material, part halogen particle, which enters inside particles through gap, improves crystal structure, part halogen particle stay in particle surface formed the amorphous clad structure of lithium halide, avoid rich nickel tertiary cathode material directly and electrolyte contacts, greatly improve stable circulation performance.
Description
Technical field
It is mixed with modified rich nickel tertiary cathode material and preparation method thereof the present invention relates to a kind of, belongs to lithium-ion electric
Pond positive electrode technical field.
Background technique
In recent years, application of the lithium ion battery in energy storage and electric car field gets more and more people's extensive concerning.As lithium
The positive electrode of important component in ion battery, to operating voltage, cycle life, the capacity height of battery, safety etc.
Important performance all plays the role of conclusive.Therefore, research and develop high capacity, the long-life, high security positive electrode be to grind
Study carefully one of the emphasis of lithium ion battery.
The performance of positive electrode is most important to the raising of performance of lithium ion battery in lithium ion battery.Currently, lithium ion
Cell positive material is mainly by cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, LiFePO 4 etc..This year, rich nickel tertiary cathode material
Material (nickle cobalt lithium manganate) is increasingly subject to attract attention, by the material property, such as volume and capacity ratio, weight ratio capacity, circulation, safety
Etc. data test, generally show rich nickel tertiary cathode material as some excellent of emerging anode material of lithium battery
It is anisotropic can, as voltage platform is high, reversible specific capacity is big, stable structure, have a safety feature the advantages that.However, rich nickel tertiary cathode
Material still remains some urgent problems.Showing for position is occupied firstly, remaining in rich nickel tertiary cathode material
As causing material capacity in charge and discharge process to lose, cycle performance decline.Second, it is direct with electrolyte under Charging state
The heat and oxygen that catalytic oxidation generates can still cause safety problem.Third, the high alkalinity essence of rich nickel system base anode material
Cause material to be easy adsorption moisture and carbon dioxide, sharply declines so as to cause the chemical property after material storage.
In the prior art, the solution for being directed to the above problem has following report: CN108899531A is with nickel cobalt aluminium ternary
Positive electrode is coated with phosphate as kernel, on the surface of the kernel, and adds chelating agent during cladding, to promote
Into Phosphate coating on nickel cobalt aluminium tertiary cathode material surface.Positive electrode of the present invention after Phosphate coating possesses higher
Ion transfer ability and electron transmission ability, the material after cladding inhibits the side reaction between positive electrode and electrolyte.
CN108933239A discloses a kind of preparation method of LiMn2O4 cladding nickel-cobalt lithium manganate cathode material, realizes LiMn2O4 cladding
The structure of nickle cobalt lithium manganate also reduces sintering difficulty, while also avoiding the high pH and water absorption issue of certain high-nickel material.
Although the certain solution for obtaining some defects using technological means in the prior art, lithium ion battery is used
Positive electrode performance constantly improve, and is the problem that skilled person constantly studies and overcomes, and therefore, invents and create one kind
Has more excellent cyclical stability, the material for meeting higher requirement is particularly important.
Summary of the invention
It is an object of the invention to solve problems of the prior art, provide it is a kind of have excellent cycle performance,
It is with long service life to be mixed with modified rich nickel tertiary cathode material, and preparation method is provided simultaneously.
To achieve the above object, the technical solution used in the present invention is:
Technical theme one
Be mixed with modified rich nickel tertiary cathode material the present invention provides a kind of, including halogen doping richness nickel ternary nucleome and
The amorphous clad structure of lithium halide, the chemical composition of the Dopants richness nickel ternary nucleome are LiNi1-x- yCoyAlxXzO2-0.5z(X=F, Cl, Br), wherein 0.030≤x≤0.050,0.100≤y≤0.150,0.001≤z≤
0.008。
Further, the amount of the total material of the amorphous clad structure of the lithium halide and Dopants lithium nickel cobalt dioxide core
The mass ratio of the material of body is (0.0005 ~ 0.0040): 1.
Technical theme two
The present invention provides a kind of to be mixed with the preparation of modified rich nickel tertiary cathode material as provided by technical theme one
Method specifically comprises the following steps:
(1) rich nickel ternary precursor and lithium source, halogen source are subjected to mixing and ball milling, obtain ball mill mixing；The richness nickel ternary forerunner
Body is Ni1-x-yCoyAlx(OH)2, wherein 0.030≤x≤0.050,0.100≤y≤0.150, the halogen source be selected from Fluorine source,
The combination in one or both of chlorine source, bromine source or more；
(2) under oxygen atmosphere, the ball mill mixing that the step (2) obtains successively is pre-sintered and is re-sintered, is wrapped
Cover blended positive pole material；The temperature of the pre-sintering is 400 ~ 500 DEG C, and the time of pre-sintering is 4 ~ 6h；The temperature re-sintered
Degree is 700 ~ 800 DEG C, and the time re-sintered is 11 ~ 13h；
Preferably, the temperature being pre-sintered in the step (2) and the temperature re-sintered are reached in a manner of heating, the heating
Rate independently be 1 ~ 5 DEG C/min.
Preferably, lithium source includes the one or more of Lithium hydroxide monohydrate, lithium acetate and lithium carbonate in the step (1).
Preferably, Fluorine source includes one of lithium fluoride, ammonium fluoride and tetrabutyl ammonium fluoride or more in the step (1)
Kind.
Preferably, in the step (1) chlorine source include one of lithium chloride, ammonium chloride and benzyltriethylammoinium chloride or
It is a variety of.
Preferably, bromine source includes one of lithium bromide, ammonium bromide and 4 bromide or more in the step (1)
Kind.
Preferably, the time of mixing and ball milling is 10 ~ 12h in the step (1), and the revolving speed of mixing and ball milling is 100 ~ 150r/
min。
Preferably, in the step (1) in lithium source and step (1) molar ratio of rich nickel ternary precursor be (1.03 ~
1.08): 1；
Halogen source and the molar ratio of nickel ternary precursor rich in step (1) are (0.10 ~ 0.40) in the step (1): 100.
The beneficial effects of adopting the technical scheme are that
Present invention uses the means being mixed with to be modified rich nickel ternary material, and part halogen particle enters through gap
Inside particles improve crystal structure, and part halogen particle stays in particle surface and forms the amorphous clad structure of lithium halide, avoids
Directly and electrolyte contacts, conducive to the promotion of rich nickel tertiary cathode material overall performance, the present invention is logical for rich nickel tertiary cathode material
The rich nickel ternary material that the modified mode combined with the coating modification of surface lithium halide of halogen doping obtains is crossed, in 55 DEG C of hot environments
Under, when charge-discharge magnification is 0.5 C, capacity retention ratio is up to 82% or more after circulation 100 times, greatly improves stable circulation
Performance.
The present invention is fully dispersed by the way that rich nickel ternary precursor and lithium source, halogen source are carried out mixing and ball milling, and passes through control
Sintering temperature and sintering time, realize Uniform Doped and cladding.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the SEM spectrum for the positive electrode that comparative example 1 obtains；
Fig. 2 is the SEM spectrum for the positive electrode that embodiment 2 obtains；
Fig. 3 is the XRD spectrum for the positive electrode that comparative example 1 and embodiment 1 obtain.
Specific embodiment
The present invention is mixed with modified rich nickel tertiary cathode material, including halogen doping lithium nickel cobalt dioxide nucleome and lithium halide
Amorphous clad structure, the chemical composition of Dopants richness nickel ternary nucleome are LiNi1-x-yCoyAlxXzO2-0.5z(X=F,
Cl, Br), wherein 0.030≤x≤0.050,0.100≤y≤0.150,0.001≤z≤0.008.
It is provided by the invention be mixed with modified rich nickel tertiary cathode material include halogen doping richness nickel ternary nucleome and
Clad.In the present invention, the chemical composition of the Dopants lithium nickel cobalt dioxide nucleome is LiNi1-x-yCoyAlxXzO2-0.5z
(X=F, Cl, Br), in which:
0.030≤x≤0.050, further, 0.035≤x≤0.045, further, x=0.40；0.100≤y≤
0.150, further, 0.135≤y≤0.145, further, y=0.130；
0.001≤z≤0.008, further, 0.0020≤z≤0.0070, further, 0.0035≤z≤0.0055；
The group of the clad is divided into lithium halide.
The present invention also provides a kind of preparation methods for being mixed with modified rich nickel tertiary cathode material, including following step
It is rapid:
(1) rich nickel ternary precursor is carried out mixing ball with lithium source, halogen source (Fluorine source, chlorine source, bromine source are one such or several)
Mill, obtains ball mill mixing；The richness nickel ternary precursor is Ni1-x-yCoyAlx(OH)2, wherein 0.030≤x≤0.050,
0.100≤y≤0.150；
(2) under oxygen atmosphere, the ball mill mixing that the step (2) obtains successively is pre-sintered and is re-sintered, is wrapped
Cover blended positive pole material；The temperature of the pre-sintering is 400 ~ 500 DEG C, and the time of pre-sintering is 4 ~ 6h；The temperature re-sintered
Degree is 700 ~ 800 DEG C, and the time re-sintered is 11 ~ 13h；
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention carries out rich nickel ternary precursor and lithium source, halogen source (Fluorine source, chlorine source, bromine source are one such or several)
Mixing and ball milling obtains ball mill mixing.In the present invention, the lithium source preferably includes Lithium hydroxide monohydrate, lithium acetate and lithium carbonate
It is one or more；In terms of lithium content, the molar ratio of the lithium source and nickel cobalt acid aluminium presoma is preferably (1.03 ~ 1.08): 1,
Further preferably 1.05:1.
In the present invention, the rich nickel ternary precursor group is divided into Ni1-x-yCoyAlx(OH)2, wherein 0.030≤x≤
0.050, further, 0.035≤x≤0.045, further, x=0.040；0.100≤y≤0.150, further,
0.135≤y≤0.145, further, y=0.150；In the present invention, x and y in the rich nickel ternary precursor component
It is consistent in value and the rich nickel tertiary cathode material technical solution nucleus component of abovementioned dopant coating modification；In reality of the invention
It applies in example, specially Ni0.82Co0.13Al0.05(OH)2Or Ni0.815Co0.15Al0.035(OH)2。
In the present invention, the Fluorine source includes one of lithium fluoride, ammonium fluoride and tetrabutyl ammonium fluoride or a variety of；It is described
Chlorine source includes one of lithium chloride, ammonium chloride and benzyltriethylammoinium chloride or a variety of；Bromide source preferably include lithium bromide,
One of ammonium bromide and 4 bromide are a variety of；In terms of total halogen content, the halogen source and rich nickel ternary precursor
Molar ratio is preferably (0.10 ~ 0.40): 100, more preferably (0.20 ~ 0.30): 100.
Rich nickel ternary precursor and lithium source, halogen source are carried out mixing and ball milling by the present invention, obtain ball mill mixing.In the present invention
In, the time of the mixing and ball milling is preferably 10 ~ 12h, further preferably 10.5 ~ 11h；The revolving speed of the mixing and ball milling is preferred
For 100 ~ 150r/min, further preferably 120 ~ 145r/min.In the present invention, the mixing and ball milling in the ball mill into
Row；The present invention does not have particular/special requirement to the model of the ball mill, using well-known to those skilled in the art.This hair
It is bright to realize the mixing between raw material during mixing and ball milling, obtain the presoma of mixing halogen source and lithium source.
After obtaining ball mill mixing, the ball mill mixing is successively pre-sintered and is re-sintered by the present invention, obtains primary packet
Cover blended positive pole material.In the present invention, the temperature of the pre-sintering be 400 ~ 500 DEG C, preferably 420 ~ 480 DEG C, further
Preferably 450 ~ 460 DEG C；The time of the pre-sintering is 4 ~ 6h, further preferably 4.2 ~ 4.5h, more preferably 4.3 ~ 4.4h.
In the present invention, the temperature of the pre-sintering is preferably reached in a manner of heating, and the rate of the heating is preferably 1 ~ 5 DEG C/
Min, further preferably 4.5 ~ 4.8 DEG C/min.
In the present invention, the temperature re-sintered be 700 ~ 800 DEG C, preferably 710 ~ 770 DEG C, further preferably
720~750℃；The time re-sintered is 11 ~ 13h, preferably 11.2 ~ 11.5h.In the present invention, the temperature re-sintered
Degree preferably is heated up to obtain by the temperature being pre-sintered；The rate of the heating is preferably 1 ~ 5 DEG C/min, further preferably 1.2 ~ 2
℃/min.The present invention in the pre-sintering and during re-sinter, react with richness nickel ternary precursor, realizes mixing for halogen by halogen source
Miscellaneous, formation group is divided into LiNi1-x-yCoyAlxXzO2-0.5zThe halogen doping richness nickel ternary nucleome of (X=F, Cl, Br)；Part halogen simultaneously
The surface that element remains in rich nickel ternary precursor is reacted at high temperature with lithium generates the amorphous clad structure of lithium halide, is coated
Adulterate rich nickel tertiary cathode material.
In the present invention, it the pre-sintering and re-sinters and is carried out under oxygen atmosphere；The formation of layer structure has with oxygen
It closes, under pure oxygen atmosphere, the layer structure to be formed can be made stronger.The oxygen atmosphere is preferably purity >=99.5%
High purity oxygen gas；The present invention does not have particular/special requirement to the presentation mode of the oxygen atmosphere, and use is well known to those skilled in the art
Mode.
After completion re-sinters, sintered product is preferably carried out Temperature fall by the present invention, is obtaining coating-doping richness nickel ternary just
Pole material.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to it is provided by the invention be mixed with it is modified
Rich nickel tertiary cathode material and preparation method thereof is described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
Comparative example 1
Undoped with uncoated nickel-rich positive pole material LiNi0.815Co0.15Al0.035O2Preparation method:
Rich nickel ternary precursor (Ni0.815Co0.15Al0.035(OH)2) and Lithium hydroxide monohydrate ball mill with the speed of 100r/min
The uniform mixing 10h of degree, obtains mixture, and then 5 DEG C/min is gradually warming up to 450 DEG C of calcining 5h under oxygen atmosphere, and then again 1
DEG C/min is gradually warming up to 750 DEG C of calcining 12h, Temperature fall obtains pure rich nickel tertiary cathode material
(LiNi0.815Co0.15Al0.035O2).
Embodiment 1
The preparation of positive electrode:
(1) by rich nickel ternary precursor, lithium source (Lithium hydroxide monohydrate), ammonium fluoride and ammonium chloride ball mill with 100r/min's
Speed uniformly mixes 10h, obtains the presoma of mixing and doping fluorine chlorine lithium；Wherein, before ammonium fluoride and ammonium chloride respectively account for rich nickel ternary
The molar fraction for driving body is 0.10mol%；Lithium source and the molar ratio of rich nickel ternary precursor are 1.08:1.
(2) presoma of mixing and doping fluorine chlorine lithium obtained in (1) is placed in atmosphere furnace, 5 DEG C under oxygen atmosphere/
Min is gradually warming up to 450 DEG C of calcining 5h, and then 1 DEG C/min is gradually warming up to 750 DEG C of calcining 12h again, and Temperature fall obtains nucleome
For LiNi0.815Co0.15Al0.035F0.001Cl0.001O1.999, surface coats the rich nickel tertiary cathode material of lithium halide.It then will be above-mentioned
Sintering feed is ground up, sieved, and obtains refining primary positive electrode spare.
SEM detection is carried out to the positive electrode that embodiment 1 and comparative example 1 obtain, it is right as a result respectively as shown in Fig. 2 and Fig. 1
Than Fig. 1 and Fig. 2 it is found that not being doped the material that cladding obtains in comparative example 1, surface is smooth.Embodiment 1 is doped to be coated
The positive electrode arrived, surface can see amorphous lithium halide coating.It follows that obtained positive electrode is doping packet
Cover modified rich nickel tertiary cathode material, including halogen doping richness nickel ternary nucleome and clad.It is examined simultaneously by elemental analysis
It surveys, it is known that the component of the halogen doping richness nickel tertiary cathode material nucleome is LiNi0.815Co0.15Al0.035F0.001Cl0.00 1O1.999, the component of clad is lithium fluoride and lithium chloride, and the amount and halogens of the total material of clad adulterate rich nickel ternary core
The mass ratio of the material of body is 0.0005:1.
Embodiment 2
Positive electrode is prepared in the way of embodiment 1, difference is, ammonium fluoride and ammonium chloride respectively account for rich nickel ternary precursor
Molar fraction is 0.20mol%.
Elemental analysis detection equally is carried out to obtained positive electrode, it is known that, obtained positive electrode is to be mixed with to change
The rich nickel tertiary cathode material of property, including halogen doping richness nickel ternary nucleome core clad, the halogen doping richness nickel tertiary cathode
The component of material nucleome is LiNi0.815Co0.15Al0.035F0.002Cl0.002O1.998, the component of clad is lithium fluoride and chlorination
Lithium, the mass ratio of the material that the amount and halogens of the total material of clad adulterate rich nickel ternary nucleome is 0.0010:1.
Embodiment 3
The preparation of positive electrode:
(1) by rich nickel ternary precursor, lithium source (Lithium hydroxide monohydrate), ammonium fluoride and ammonium bromide ball mill with 100r/min's
Speed uniformly mixes 10h, obtains the presoma of mixing and doping fluorine bromine lithium；Wherein, before ammonium fluoride and ammonium bromide respectively account for rich nickel ternary
The molar fraction for driving body is 0.10mol%；Lithium source and the molar ratio of rich nickel ternary precursor are 1.08:1.
(2) presoma of mixing and doping fluorine chlorine lithium obtained in (1) is placed in atmosphere furnace, 5 DEG C under oxygen atmosphere/
Min is gradually warming up to 450 DEG C of calcining 5h, and then 1 DEG C/min is gradually warming up to 750 DEG C of calcining 12h again, and Temperature fall obtains nucleome
For LiNi0.815Co0.15Al0.035F0.001Br0.001O1.999, surface coats the rich nickel tertiary cathode material of lithium halide；It then will be above-mentioned
Sintering feed is ground up, sieved, and obtains refining primary positive electrode spare.
It follows that obtained positive electrode is to be mixed with modified rich nickel tertiary cathode material, including halogen doping
Rich nickel ternary nucleome and clad.It is detected simultaneously by elemental analysis, it is known that the halogen doping richness nickel tertiary cathode material nucleome
Component be LiNi0.815Co0.15Al0.035F0.001 Br0.001O1.999, the component of clad is lithium fluoride and lithium bromide, cladding
The mass ratio of the material that the amount and halogens of the total material of layer adulterate rich nickel ternary nucleome is 0.0005:1.
Embodiment 4
Positive electrode is prepared in the way of embodiment 3, difference is, ammonium fluoride and ammonium bromide respectively account for rich nickel ternary precursor
Molar fraction is 0.20mol%.
Elemental analysis detection equally is carried out to obtained positive electrode, it is known that, obtained positive electrode is to be mixed with to change
The rich nickel tertiary cathode material of property, including halogen doping richness nickel tertiary cathode material nucleome core clad, the halogen doping richness nickel
The component of ternary nucleome is LiNi0.815Co0.15Al0.035F0.002Br0.002O1.998, the component of clad is lithium fluoride and bromination
Lithium, the mass ratio of the material that the amount and halogens of the total material of clad adulterate rich nickel ternary nucleome is 0.0010:1.
Embodiment 5
Positive electrode is prepared in the way of embodiment 1, difference is, ammonium fluoride and ammonium chloride respectively account for rich nickel ternary precursor
Molar fraction is 0.40mol%.
Elemental analysis detection equally is carried out to obtained positive electrode, it is known that, obtained positive electrode is to be mixed with to change
The rich nickel tertiary cathode material of property, including halogen doping richness nickel ternary nucleome core clad, the halogen doping richness nickel tertiary cathode
The component of material nucleome is LiNi0.815Co0.15Al0.035F0.004Cl0.004O1.996, the component of clad is lithium fluoride and chlorination
Lithium, the mass ratio of the material that the amount and halogens of the total material of clad adulterate rich nickel ternary nucleome is 0.0020:1.
Embodiment 6
Positive electrode is prepared in the way of embodiment 3, difference is, ammonium fluoride and ammonium bromide respectively account for rich nickel ternary precursor
Molar fraction is 0.40mol%.
Elemental analysis detection equally is carried out to obtained positive electrode, it is known that, obtained positive electrode is to be mixed with to change
The rich nickel tertiary cathode material of property, including halogen doping richness nickel tertiary cathode material nucleome core clad, the halogen doping richness nickel
The component of ternary nucleome is LiNi0.815Co0.15Al0.035F0.004Br0.004O1.996, the component of clad is lithium fluoride and bromination
Lithium, the mass ratio of the material that the amount and halogens of the total material of clad adulterate rich nickel ternary nucleome is 0.0020:1.
Constant current charge-discharge test is carried out to the positive electrode that embodiment 1 ~ 6 and comparative example obtain, is surveyed in 55 DEG C of hot environments
Under, when charge-discharge magnification is 0.5 C,
The positive electrode first discharge specific capacity that embodiment 1 obtains can reach 200.3mAh/g, still can reach after circulation 100 times
160.7 mAh/g, capacity retention ratio are up to 80.2%；
The positive electrode first discharge specific capacity that embodiment 2 obtains can reach 202.5mAh/g, still can reach after circulation 100 times
169.29 mAh/g, capacity retention ratio are up to 83.6%；
The positive electrode first discharge specific capacity that embodiment 3 obtains can reach 208 mAh/g, still can reach after circulation 100 times
174.9 mAh/g, capacity retention ratio are up to 84.1%；
The positive electrode first discharge specific capacity that embodiment 4 obtains can reach 201.3 mAh/g, still reachable after recycling 100 times
To 170.2mAh/g, capacity retention ratio is up to 84.6%；
The positive electrode first discharge specific capacity that embodiment 5 obtains can reach 200.7 mAh/g, still reachable after recycling 100 times
To 167.2 mAh/g, capacity retention ratio is up to 83.3%；
The positive electrode first discharge specific capacity that embodiment 6 obtains can reach 200.1 mAh/g, still reachable after recycling 100 times
To 165.5 mAh/g, capacity retention ratio is up to 82.7%；
And the positive electrode first discharge specific capacity that comparative example 1 obtains is only 194.2 mAh/g, is 121.6 after circulation 100 times
MAh/g, capacity retention ratio are only 62.6%.
Contrast test is as a result, it is found that the positive electrode specific discharge capacity with higher, excellent that the embodiment of the present invention obtains
Stable circulation performance, big high rate performance and high-temperature behavior.The positive electrode that comparative example 1 and embodiment 3 obtain exists respectively
High rate performance under 0.1C, 0.2C, 1C, 2C, 3C, 4C, 5C multiplying power are as follows: the positive electrode of comparative example 1 respectively 0.1C, 0.2C,
High rate performance under 1C, 2C, 3C, 4C, 5C multiplying power be respectively 188.2mAh/g, 180.3mAh/g, 178.9mAh/g,
173.5mAh/g,166.7mAh/g,161.3mAh/g,155.1mAh/g,150.6mAh/g；The positive electrode of embodiment 3 is distinguished
High rate performance under 0.1C, 0.2C, 1C, 2C, 3C, 4C, 5C multiplying power be respectively 199.1 mAh/g, 184.8mAh/g,
181.9mAh/g、176.3mAh/g、172.6mAh/g、170.0mAh/g、165.4mAh/g、160.7mAh/g。
As seen from the above embodiment, positive electrode provided by the invention has excellent cyclical stability, while using
The means of doping and cladding are modified rich nickel ternary material, while starting with from material internal and outside, both improve inside
Crystal structure, and the erosion of electrolyte side reaction is improved, under the premise of not significantly affecting rich nickel tertiary cathode material capacity,
Effectively improve the cyclical stability of material.
As seen from the above embodiment, positive electrode provided by the invention has excellent cyclical stability, while using
The means of doping are modified rich nickel ternary material, and part halogen particle, which enters inside particles through gap, improves crystal knot
Structure, part halogen particle stay in particle surface and form the amorphous clad structure of lithium halide, we are simultaneously from material internal and outside
Start with, not only improve internal crystal structure, but also improve the erosion of electrolyte side reaction, is not significantly affecting rich nickel tertiary cathode
Under the premise of material capacity, the cyclical stability of material is effectively improved.
Reaction raw material sources used in preparation process of the present invention are abundant, and inexpensively, production cost is low for price, is easy to
Scale business application.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (10)
1. a kind of be mixed with modified rich nickel tertiary cathode material, which is characterized in that including halogen doping richness nickel ternary nucleome
With the amorphous clad structure of lithium halide, the chemical composition of the Dopants richness nickel ternary nucleome is LiNi1-x- yCoyAlxXzO2-0.5z(X=F, Cl, Br), wherein 0.030≤x≤0.050,0.100≤y≤0.150,0.001≤z≤
0.008。
2. a kind of modified rich nickel tertiary cathode material is mixed with according to claim 1, which is characterized in that the halogen
The mass ratio of the material of the amount and Dopants lithium nickel cobalt dioxide nucleome of changing the total material of the amorphous clad structure of lithium is (0.0005
~0.0040):1。
3. one kind is mixed with the preparation method of modified rich nickel tertiary cathode material, feature as claimed in claim 1 or 2
It is, specifically comprises the following steps:
(1) rich nickel ternary precursor and lithium source, halogen source are subjected to mixing and ball milling, obtain ball mill mixing；The richness nickel ternary forerunner
Body is Ni1-x-yCoyAlx(OH)2, wherein 0.030≤x≤0.050,0.100≤y≤0.150, the halogen source be selected from Fluorine source,
The combination in one or both of chlorine source, bromine source or more；
(2) under oxygen atmosphere, the ball mill mixing that the step (2) obtains successively is pre-sintered and is re-sintered, is wrapped
Cover blended positive pole material；The temperature of the pre-sintering is 400 ~ 500 DEG C, and the time of pre-sintering is 4 ~ 6h；The temperature re-sintered
Degree is 700 ~ 800 DEG C, and the time re-sintered is 11 ~ 13h.
4. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, the temperature being pre-sintered in the step (2) and the temperature re-sintered are reached in a manner of heating, the rate of the heating
It independently is 1 ~ 5 DEG C/min.
5. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, lithium source includes the one or more of Lithium hydroxide monohydrate, lithium acetate and lithium carbonate in the step (1).
6. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, Fluorine source includes one of lithium fluoride, ammonium fluoride and tetrabutyl ammonium fluoride or a variety of in the step (1).
7. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, chlorine source includes one of lithium chloride, ammonium chloride and benzyltriethylammoinium chloride or a variety of in the step (1).
8. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, bromine source includes one of lithium bromide, ammonium bromide and 4 bromide or a variety of in the step (1).
9. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, the time of mixing and ball milling is 10 ~ 12h in the step (1), and the revolving speed of mixing and ball milling is 100 ~ 150r/min.
10. a kind of preparation method for being mixed with modified rich nickel tertiary cathode material according to claim 3, feature
It is, lithium source and the molar ratio of nickel ternary precursor rich in step (1) are (1.03 ~ 1.08) in the step (1): 1；
Halogen source and the molar ratio of nickel ternary precursor rich in step (1) are (0.10 ~ 0.40) in the step (1): 100.
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