CN110061231A - A kind of nickelic tertiary cathode material of modification and preparation method thereof - Google Patents
A kind of nickelic tertiary cathode material of modification and preparation method thereof Download PDFInfo
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- CN110061231A CN110061231A CN201910412431.1A CN201910412431A CN110061231A CN 110061231 A CN110061231 A CN 110061231A CN 201910412431 A CN201910412431 A CN 201910412431A CN 110061231 A CN110061231 A CN 110061231A
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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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- 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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Abstract
The present invention relates to technical field of lithium ion, more particularly, to nickelic tertiary cathode material of a kind of modification and preparation method thereof.The nickelic tertiary cathode material of modification, including core and is at least partly coated on the clad on core surface, and the general formula of the core is LiNixCoyMn(1‑x‑y)O2, the general formula of the clad is LibAmOn, the molar ratio of the Li in Li and clad in the core is 1 ﹕ (0.002b~0.01b)；Wherein, 0.8 < x <, 1,0 < y < 1, b >=1, m >=1,1 < n < 15；A is selected from P, Ti, Zr and Al.The present invention adds a degree of cobalt and manganese in lithium nickelate, form nickelic ternary material, and by way of cladding, on its surface, cladding height leads lithium ion, reduce contact and dissolution of the transition metal element with electrolyte, the diffusion of transition metal element in the electrolytic solution is reduced, improves cycle performance, and increase its high rate performance.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of nickelic tertiary cathode material of modification and its system
Preparation Method.
Background technique
In recent years, because having, specific energy is high, self discharge is small, open-circuit voltage is high, memory-less effect, has extended cycle life, acyclic
The advantages that border is polluted, lithium ion battery is in the consumer electronics markets such as mobile phone, laptop, digital camera and electric car city
Field has obtained significantly popularizing.
Lithium ion battery mainly has the components such as anode, cathode, electrolyte, diaphragm composition, and positive electrode provides lithium source, main
There are cobalt acid lithium, lithium nickelate, LiMn2O4, ternary material and LiFePO4 etc..But cobalt resource is deficient, is more toxic, so
There are production costs to remain high for cobalt acid lithium, and the disadvantages of pollution environment.
Lithium nickelate material resources then enrich much compared to cobalt resource, and have higher theoretical gram volume.But nickel acid
The shortcomings that lithium, is that its cycle performance is poor, and voltage platform is low, and high rate performance difference etc. disadvantage limits answering for its industrialization
With.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of nickelic tertiary cathode material of modification, to solve to exist in the prior art
The technical problem that cannot be considered in terms of material cost and material circulation performance etc..
The second object of the present invention is to provide a kind of preparation method for being modified nickelic tertiary cathode material, the preparation side
Method, simple and easy, mild condition.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of nickelic tertiary cathode material of modification, including core and the clad for being coated on core surface, the general formula of the core is
LiNixCoyMn(1-x-y)O2, the general formula of the clad is LibAmOn, the molar ratio of the Li in Li and clad in the core
For 1 ﹕ (0.002b~0.01b)；Wherein, 0.8 < x <, 1,0 < y < 1, b >=1, m >=1,1 < n < 15；A be selected from P, Ti, Zr and
Al。
The nickelic tertiary cathode material of modification of the invention adds a degree of cobalt and manganese in lithium nickelate, is formed nickelic
Ternary material, and by way of cladding, on its surface, cladding height leads lithium ion, reduces connecing for transition metal element and electrolyte
Touching and dissolution reduce the diffusion of transition metal element in the electrolytic solution, improve cycle performance, and increase its high rate performance.
Each ingredient of the nickelic tertiary cathode material of modification of the invention within the above range, that is, can be improved cycle performance etc., be
The cycle performance and high rate performance for advanced optimizing positive electrode, to material have carried out following improvement:
Preferably, the value range of x is 0.83≤x≤0.95.It is furthermore preferred that the value range of x be 0.85≤x≤
0.92。
As in different embodiments, the value of x can for 0.83,0.84,0.85,0.86,0.87,0.88,0.89,
0.9,0.91,0.92,0.93,0.94,0.95 etc..
Preferably, the value range of y is 0.01≤y≤0.06.It is furthermore preferred that the value range of y be 0.02≤y≤
0.05。
As in different embodiments, the value of y can be 0.01,0.02,0.03,0.04,0.05,0.06 etc..
Preferably, the molar ratio of the Li in the Li and clad in the core is 1 ﹕ (0.0025b~0.0095b).It is more excellent
Choosing, the molar ratio of the Li in Li and clad in the core is 1 ﹕ (0.003b~0.009b).
Preferably, the value range of b is 1≤b≤4.
As in different embodiments, the value of b can be 1,2,3,4 etc..
On this basis, in different embodiments, the molar ratio of the Li in the Li and clad in core can be
0.0025、0.003、0.0035、0.004、0.0045、0.005、0.0055、0.006、0.0065、0.007、0.0075、
0.008,0.0085,0.009,0.01,0.012,0.015,0.018,0.02,0.025,0.03,0.035,0.038 etc..
Preferably, the value range of m is 1≤m≤5.
As in different embodiments, the value of m can be 1,2,3,4,5 etc..It is furthermore preferred that m is 1 or 5.
Preferably, the value range of n is 2≤n≤12.
As in different embodiments, the value of n can be 2,3,4,5,6,7,8,9,10,11,12 etc..More preferably
, n 2,3,4 or 12.
In above-mentioned clad, A is selected from P, Ti, Zr and Al, can be any one of P, Ti, Zr and Al；Be also possible to P,
Any two kinds in Ti, Zr and Al, such as P and Ti, P and Zr, P and Al, Ti and Zr, Ti and Al and Zr and Al；Be also possible to P,
Any three kinds in Ti, Zr and Al, such as P and Ti and Zr, P and Ti and Al, P and Zr and Al, Ti and Zr and Al；Be also possible to P,
Tetra- kinds of Ti, Zr and Al mixing.
When A is P, b=3, m=1, n=4；When A is Al, b=1, m=1, n=2；When A is Zr, b=2, m=1,
N=3；When A is Ti, b=4, m=5, n=12.
Preferably, x, y, z, m and n are selected from any one of following combinations: x=0.88, y=0.03, b=3, m=1, n=
4, the molar ratio of the Li in Li and clad in core is 0.018；X=0.85, y=0.05, b=1, m=1, n=2, in core
The molar ratio of Li and the Li in clad are 0.009；X=0.90, y=0.03, z=0.004, b=2, m=1, n=3；X=
0.92, y=0.02, b=4, m=5, n=12, the molar ratio of the Li in Li and clad in core are 0.012.
The present invention also provides a kind of preparation methods for being modified nickelic tertiary cathode material, include the following steps:
(a) nickel salt, cobalt salt and manganese salt are made into mixed solution according to atomic ratio Ni ﹕ Co ﹕ Mn=x ﹕ y ﹕ (1-x-y), and it is heavy
Shallow lake agent, complexing agent mixing carry out coprecipitation reaction, are dried to obtain presoma NixCoyMn(1-x-y)(OH)2；
(b) under solvent action, by presoma NixCoyMn(1-x-y)(OH)2Atomic ratio Ni ﹕ A=x ﹕ is pressed with the oxide of A
(0.002m~0.01m) mixing, is dried to obtain in NixCoyMn(1-x-y)(OH)2Surface coats the material of the oxide of A；
It (c) is in molar ratio 1 ﹕ (1+0.002b)~1 ﹕ (1+0.06b) by the lithium in material and lithium salts that step (b) obtains
Mixing, sintering, obtains being modified nickelic tertiary cathode material.
Preparation method of the invention, prepares presoma by way of complex coprecipitation, and component proportion is accurate and obtains
Presoma specific surface area is small, and tap density is high；Presoma and cladding material are subjected to material by wet type mixing, covered effect is good.Entire system
Preparation Method is easy to operate, mild condition, and repeatability and stability are good.In step (c), since Li can volatilize damage under pyroreaction
It loses, it is therefore preferable that appropriate excessive.As being in molar ratio 1 ﹕ (1+0.015b), 1 ﹕ (1+0.06b), 1 ﹕ (1+0.04b), 1 ﹕ (1+
0.018b) etc..
Wherein, the oxide of A can be AeOf, wherein e=1 or 2, f=2,3 or 5.
Preferably, in step (a), nickel salt, cobalt salt and manganese salt are respectively one of respective sulfate, nitrate or two
Kind mixing.
Preferably, in step (a), precipitating reagent includes NaOH and Na2CO3Any one of or two kinds mixing.
Preferably, in step (a), complexing agent includes ammonium hydroxide, ammonium chloride, any one or more of mixing of ammonium sulfate.More
Preferably, the concentration of complexing agent is 1-6mol/L.
Preferably, in step (a), coprecipitation reaction temperature is 40-80 DEG C.
The temperature of coprecipitation reaction is higher, and particle forming process is faster, but pyroreaction will lead to waving for the substances such as ammonia
Hair increases a possibility that precursor aoxidizes.It is furthermore preferred that coprecipitation reaction temperature is 50-60 DEG C in step (a).
Preferably, in step (a), the stirring rate of coprecipitation reaction is 600-1200rpm.
In practical coprecipitation reaction, under low mixing speed, second particle assembled by well-developed primary particle and
At, but it is in irregular shape, under relatively high revolving speed, peomote second particle spheroidization and densification.But excessively high
Revolving speed under, will lead to the irregular reunion of particle.The present invention uses above-mentioned stirring rate that can obtain, and specific surface area is small, shakes
The high persursor material of real density, so as to the subsequent performance for improving material.
Preferably, in step (a), the pH of coprecipitation reaction is 9.6-11.4.
Preferably, in step (a), in mixed solution, the concentration of metal is 0.4-4mol/L.
Preferably, in step (b), solvent is selected from short-chain alcohols solvent.It is furthermore preferred that short-chain alcohols solvent includes C1-C3
Alcohols solvent.It is further preferred that short chain alcohol solvent includes methanol, ethyl alcohol, any one or more of mixing of 1- propyl alcohol.
The present invention uses specific short-chain alcohols solvent, presoma and coating is carried out material by wet type mixing, short-chain alcohols are molten
Agent can be improved the wetability of presoma and coating, and keep material evenly dispersed, help to improve cladding uniformity and
Compactness.Solvent has volatility simultaneously, and drying can remove at a proper temperature.
Preferably, it in step (b), is mixed and is dried under an inert atmosphere.By inert atmosphere protection, transition is prevented
The oxidation of metal.Inert nitrogen gas can be used or argon gas provides inert atmosphere.
Preferably, in step (b), mixed temperature is 20-40 DEG C.Water in high mixer interlayer can be passed through in actual operation
Temperature when the control mixed material such as circulation.
Preferably, in step (b), the mixed time is 0.5-2h.Revolving speed when mixed material is 200-800rpm, to protect
The mixing of exhibit material is uniformly dispersed, in presoma coated with uniform material.
Preferably, in step (c), lithium salts includes LiOH and Li2CO3Any one of or two kinds mixing.
Preferably, in step (c), the temperature of sintering is 400-900 DEG C.
In order to further increase the even compact of the material obtained after sintering, improve electric property etc., it is preferred to use two
Section sintering process.
Preferably, double sintering method includes: first segment sintering are as follows: in 450-620 DEG C of sintering 6-12h, second segment sintering are as follows:
In 720-830 DEG C of sintering 10-15h.
It is furthermore preferred that the heating rate of first segment sintering is 2-5 DEG C/min.After first segment is sintered, in 1.2-3.5
DEG C/heating rate of min under be warming up to 720-830 DEG C of progress second segment sintering.
Preferably, further include cooling after sintering in step (c), obtain being modified nickelic tertiary cathode material.It is therein
The mode for the preferably natural cooling of cooling.
Compared with prior art, the invention has the benefit that
(1) the nickelic tertiary cathode material of modification of the invention adds a degree of cobalt and manganese in lithium nickelate, is formed high
Nickel ternary material, and by way of cladding, on its surface, cladding height leads lithium ion, reduces transition metal element and electrolyte
Contact and dissolution reduce the diffusion of transition metal element in the electrolytic solution, improve cycle performance, and increase its high rate performance, solve
It has determined the technical issues of cannot be considered in terms of material cost and performance in the prior art；
(2) preparation method of the invention prepares presoma by way of complex coprecipitation, and component proportion is accurate and obtains
Presoma specific surface area it is small, tap density is high；Presoma and cladding material are subjected to material by wet type mixing, covered effect is good；Entirely
Preparation method is easy to operate, mild condition, and repeatability and stability are good.
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, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the preparation method flow diagram of the embodiment of the present invention.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Fig. 1 is the preparation method flow diagram of the embodiment of the present invention, and with reference to Fig. 1, specific preparation method includes following step
It is rapid:
(a) nickel salt, cobalt salt and manganese salt are made into mixed solution according to atomic ratio Ni ﹕ Co ﹕ Mn=x ﹕ y ﹕ (1-x-y), and it is heavy
Shallow lake agent, complexing agent mixing carry out coprecipitation reaction, are dried to obtain presoma NixCoyMn(1-x-y)(OH)2；
(b) under solvent action, by presoma NixCoyMn(1-x-y)(OH)2With the oxide A of AeOfBy atomic ratio Ni ﹕ A=
X ﹕ (0.002m~0.01m) mixing, is dried to obtain in NixCoyMn(1-x-y)(OH)2Surface coats AeOfMaterial, with
NixCoyMn(1-x-y)(OH)2@AeOfIt indicates, wherein e=1 or 2, f=2,3 or 5；
It (c) is in molar ratio 1 ﹕ (1+0.002b)~1 ﹕ (1+0.06b) by the lithium in material and lithium salts that step (b) obtains
Mixing, sintering, obtains being modified nickelic tertiary cathode material.
Embodiment 1
The preparation method of the nickelic tertiary cathode material of the modification of the present embodiment, includes the following steps:
(1) by nickel sulfate, cobaltous sulfate, manganese sulfate according to 0.03 ﹕ 0.09 of atomic ratio Ni ﹕ Co ﹕ Mn=0.88 ﹕ be made into mixing it is molten
Liquid, nickel ion in mixed solution, cobalt ions and manganese ion concentration and be 3.5mol/L；By mixed solution and 2.0mol/L
The complexing agent NH of NaOH and 4.0mol/L3·H2O is added dropwise in reaction vessel jointly, regulation pH be 10.95, be heated to 55 DEG C into
Row reaction, react 25h after, be filtered, washed, 110 DEG C be dried to obtain precursor powder Ni0.88Co0.03Mn0.09(OH)2。
(2) in the case where argon gas protects atmosphere, in 100mL ethyl alcohol, by Ni0.88Co0.03Mn0.09(OH)2With P2O5According to atom
Ratio than Ni ﹕ P=0.88 ﹕ 0.006 is uniformly mixed (Ni0.88Co0.03Mn0.09(OH)2With P2O5Gross mass be 200g), 95
DEG C constant temperature under dry 2.5h, obtain in Ni0.88Co0.03Mn0.09(OH)2Surface coats P2O5Material
Ni0.88Co0.03Mn0.09(OH)2@(P2O5)0.003。
(3) the material Ni for obtaining step (2)0.88Co0.03Mn0.09(OH)2@(P2O5)0.003With LiOH according to material with
Li molar ratio in lithium salts is progress high temperature sintering after the mixing of 1 ﹕, 1.058 ratio uniform, the condition of sintering are as follows: oxygen atmosphere, 3
DEG C/min is raised to 510 DEG C of heat preservation 6h, then 3 DEG C/min is raised to 790 DEG C of heat preservation 12h, must be modified nickelic tertiary cathode after natural cooling
Material LiNi0.88Co0.03Mn0.09O2@(Li3PO4)0.006；
The positive electrode includes core and the clad for being coated on core surface, and the general formula of core is LiNi0.88Co0.03Mn0.09O2,
The general formula of the clad is Li3PO4, the molar ratio of the Li in Li and clad in the core is 1 ﹕ 0.006.
Embodiment 2
The preparation method of the nickelic tertiary cathode material of the modification of the present embodiment, includes the following steps:
(1) by nickel sulfate, cobaltous sulfate, manganese sulfate according to 0.05 ﹕ 0.1 of atomic ratio Ni ﹕ Co ﹕ Mn=0.85 ﹕ be made into mixing it is molten
Liquid, nickel ion in mixed solution, cobalt ions and manganese ion concentration and be 4.5mol/L；By mixed solution and 3.2mol/L
(the NH of NaOH and 3.5mol/L4)2CO3It is added dropwise in reaction vessel jointly, regulation pH is 11.25, is heated to 55 DEG C and carries out instead
Answer, react 28h after, be filtered, washed, 105 DEG C be dried to obtain precursor powder Ni0.85Co0.05Mn0.1(OH)2。
(2) in the case where argon gas protects atmosphere, in 100mL ethyl alcohol, by Ni0.85Co0.05Mn0.1(OH)2With Al2O3According to atom
Ratio than Ni ﹕ Al=0.85 ﹕ 0.009 is uniformly mixed (Ni0.85Co0.05Mn0.1(OH)2With Al2O3Gross mass be 200g),
Dry 2h, obtains in Ni under 105 DEG C of constant temperature0.85Co0.05Mn0.1(OH)2Surface coats Al2O3Material
Ni0.85Co0.05Mn0.1(OH)2@(Al2O3)0.0045。
(3) the material Ni for obtaining step (2)0.85Co0.05Mn0.1(OH)2@(Al2O3)0.0045With LiOH according to material and lithium
Li molar ratio in salt is progress high temperature sintering after the mixing of 1 ﹕, 1.06 ratio uniform, the condition of sintering are as follows: oxygen atmosphere, 4 DEG C/
Min is raised to 480 DEG C of heat preservation 7h, then 2.5 DEG C/min is raised to 800 DEG C of heat preservation 11h, must be modified nickelic tertiary cathode material after natural cooling
Expect LiNi0.85Co0.05Mn0.1O2@(LiAlO2)0.009；
The positive electrode includes core and the clad for being coated on core surface, and the general formula of core is LiNi0.85Co0.05Mn0.1O2, institute
The general formula for stating clad is LiAlO2, the molar ratio of the Li in Li and clad in the core is 1 ﹕ 0.009.
Embodiment 3
The preparation method of the nickelic tertiary cathode material of the modification of the present embodiment, includes the following steps:
(1) by nickel sulfate, cobaltous sulfate, manganese sulfate according to 0.03 ﹕ 0.07 of atomic ratio Ni ﹕ Co ﹕ Mn=0.9 ﹕ be made into mixing it is molten
Liquid, nickel ion in mixed solution, cobalt ions and manganese ion concentration and be 3.8mol/L；By mixed solution and 4.2mol/L
Na2CO3With the NH of 3.7mol/L3·H2O is added dropwise in reaction vessel jointly, and regulation pH is 11.45, is heated to 60 DEG C and is carried out instead
Answer, react 95h after, be filtered, washed, 95 DEG C be dried to obtain precursor powder Ni0.9Co0.03Mn0.07(OH)2。
(2) in the case where argon gas protects atmosphere, in 100mL methanol, by Ni0.9Co0.03Mn0.07(OH)2With ZrO2According to atom
Ratio than Ni ﹕ Zr=0.9 ﹕ 0.004 is uniformly mixed (Ni0.9Co0.03Mn0.07(OH)2With ZrO2Gross mass be 200g), 85
DEG C constant temperature under dry 3h, obtain in Ni0.9Co0.03Mn0.07(OH)2Surface coats ZrO2Material Ni0.9Co0.03Mn0.07
(OH)2@(ZrO2)0.004。
(3) the material Ni for obtaining step (2)0.9Co0.03Mn0.07(OH)2@(ZrO2)0.004With Li2CO3According to material and lithium
Li molar ratio in salt is progress high temperature sintering after the mixing of 1 ﹕, 1.08 ratio uniform, the condition of sintering are as follows: oxygen atmosphere, 3 DEG C/
Min is raised to 530 DEG C of heat preservation 8h, then 2 DEG C/min is raised to 820 DEG C of heat preservation 13h, must be modified nickelic tertiary cathode material after natural cooling
LiNi0.9Co0.03Mn0.07O2@(Li2ZrO3)0.004；
The positive electrode includes core and the clad for being coated on core surface, and the general formula of core is LiNi0.9Co0.03Mn0.07O2, institute
The general formula for stating clad is Li2ZrO3, the molar ratio of the Li in Li and clad in the core is 1 ﹕ 0.004.
Embodiment 4
The preparation method of the nickelic tertiary cathode material of the modification of the present embodiment, includes the following steps:
(1) by nickel sulfate, cobaltous sulfate, manganese sulfate according to 0.02 ﹕ 0.06 of atomic ratio Ni ﹕ Co ﹕ Mn=0.92 ﹕ be made into mixing it is molten
Liquid, nickel ion in mixed solution, cobalt ions and manganese ion concentration and be 5.2mol/L；By mixed solution and 4.3mol/L
Na2CO3With (the NH of 3.9mol/L4)2CO3It is added dropwise in reaction vessel jointly, regulation pH is 11.15, is heated to 60 DEG C and carries out instead
Answer, react 75h after, be filtered, washed, 120 DEG C be dried to obtain precursor powder Ni0.92Co0.02Mn0.06(OH)2。
(2) in the case where argon gas protects atmosphere, in 100mL 1- propyl alcohol, by Ni0.92Co0.02Mn0.06(OH)2With TiO2According to original
The ratio of son ratio Ni ﹕ Ti=0.92 ﹕ 0.015 is uniformly mixed (Ni0.92Co0.02Mn0.06(OH)2With TiO2Gross mass be 200g),
Dry 3h, obtains in Ni under 85 DEG C of constant temperature0.92Co0.02Mn0.06(OH)2Surface coats TiO2Material
Ni0.92Co0.02Mn0.06(OH)2@(TiO2)0.015。
(3) the material Ni for obtaining step (2)0.92Co0.02Mn0.06(OH)2@(TiO2)0.012With Li2CO3According to material with
Li molar ratio in lithium salts is progress high temperature sintering after the mixing of 1 ﹕, 1.07 ratio uniform, the condition of sintering are as follows: oxygen atmosphere, 3.5
DEG C/min is raised to 470 DEG C of heat preservation 7h, then 4 DEG C/min is raised to 785 DEG C of heat preservation 14h, must be modified nickelic tertiary cathode after natural cooling
Material LiNi0.92Co0.02Mn0.06O2@(Li4Ti5O12)0.003；
The positive electrode includes core and the clad for being coated on core surface, and the general formula of core is LiNi0.92Co0.02Mn0.06O2,
The general formula of the clad is Li4Ti5O12, the molar ratio of the Li in Li and clad in the core is 1 ﹕ 0.003.
Comparative example 1
Presoma Ni is prepared in the method for reference implementation example 10.8Co0.1Mn0.1(OH)2, then by Ni0.8Co0.1Mn0.1
(OH)2With Li2CO3After the mixing of 1 ﹕, 1.06 ratio uniform, high temperature sintering, sintering condition are carried out are as follows: oxygen atmosphere, 3.5 DEG C/
Min is raised to 480 DEG C of heat preservation 8h, then 3 DEG C/min is raised to 800 DEG C of heat preservation 14h, and natural cooling obtains tertiary cathode material
LiNi0.8Co0.1Mn0.1O2。
Experimental example 1
For the performance of comparative illustration various embodiments of the present invention and the tertiary cathode material of comparative example, to each tertiary cathode material
The coating of material, coating content, specific surface area, magnetisable material, granularity are characterized, and test result is shown in Table 1.
Wherein, the test of tap density: test equipment title: tap density meter, instrument model: JZ-1, instrument producer: at
All new powder test equipment Co., Ltds of essence；
Test method: about 10 to 20g positive electrode is weighed with the precision of 0.0001g；Positive electrode is put into graduated cylinder, so
Graduated cylinder is fixed on bracket afterwards；Positive electrode is repeated into 3000 jolt ramming (that is, automatic lifting and whereabouts graduated cylinder), is then measured
Corresponding volume.The volume after quality/jolt ramming after tap density=jolt ramming.Carry out parallel laboratory test three times, the knot listed in table 1
Fruit represents the average value tested three times.
The performance test results of the different tertiary cathode materials of table 1
The performance of positive electrode is influenced in order to further illustrate coating, to each coating height lead lithium ion and it is nickelic just
The parameter of pole material compares, test result is as follows table 2:
2 positive electrode the performance test results of table
| Number | Coating | Lead lithium ion rate (cm2/s) |
| Embodiment 1 | Li3PO4 | 1.68×10-11 |
| Embodiment 2 | LiAlO2 | 2.05×10-11 |
| Embodiment 3 | Li2ZrO3 | 1.93×10-11 |
| Embodiment 4 | Li4Ti5O12 | 1.47×10-11 |
| Comparative example 1 | —— | 7.5×10-12 |
Experimental example 2
For the performance of comparative illustration various embodiments of the present invention and the tertiary cathode material of comparative example, respectively by embodiment 1-
4 and comparative example 1 tertiary cathode material as positive electrode active material, cathode uses metal lithium sheet, and diaphragm uses Celgard 2500
Diaphragm, electrolyte is Suzhou Fo Sai new material Co., Ltd fosai LB-002 electrolyte, according to existing conventional techniques method group
Fill CR2032 model button cell, assembling sequence are as follows: positive cover lays flat, places spring leaf, place stainless steel substrates, place anode
Piece infuses electrolyte, places diaphragm, place lithium piece, cover cathode cap, sealing, is completed.Battery is in the drying for being full of argon gas
It is assembled in glove box.After being completed, battery is tested for the property, test result is shown in Table 2.
Wherein, cycle performance is tested: test equipment title: blue electricity battery testing system, test equipment producer: the blue electricity in Wuhan
Electronics Co., Ltd.；Test method: at 25 DEG C, with 1C constant-current charge to 4.3V, 4.3V constant pressure to 0.05C, then 1C discharges
To 3V, 100 above-mentioned charge and discharge cycles are repeated, when discharge capacity and the 100th circulation when measurement recycles for the first time
Discharge capacity, the capacity retention ratio after calculating circulation 100 times, formula are as follows: capacity retention ratio=(the 100th circulation after circulation
When discharge capacity)/the discharge capacity of when (recycle for the first time) × 100%.
The cycle performance test result of the CR2032 battery of the different tertiary cathode material assemblings of table 2
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of nickelic tertiary cathode material of modification, which is characterized in that including core and be at least partly coated on the cladding on core surface
Layer, the general formula of the core are LiNixCoyMn(1-x-y)O2, the general formula of the clad is LibAmOn, Li and cladding in the core
The molar ratio of Li in layer is 1 ﹕ (0.002b~0.01b)；Wherein, 0.8 < x <, 1,0 < y < 1, b >=1, m >=1,1 < n <
15；A is selected from P, Ti, Zr and Al.
2. the nickelic tertiary cathode material of modification according to claim 1, which is characterized in that the value range of x is 0.83≤x
≤0.95；
Preferably, the value range of x is 0.85≤x≤0.92；
Preferably, the value range of y is 0.01≤y≤0.06；
It is furthermore preferred that the value range of y is 0.02≤y≤0.05.
3. the nickelic tertiary cathode material of modification according to claim 1, which is characterized in that Li and clad in the core
In Li molar ratio be 1 ﹕ (0.0025b~0.0095b)；
Preferably, the molar ratio of the Li in the Li and clad in the core is 1 ﹕ (0.003b~0.009b)；
Preferably, the value range of b is 1≤b≤4；
It is furthermore preferred that b is selected from 1,2,3 or 4.
4. the nickelic tertiary cathode material of modification according to claim 1, which is characterized in that the value range of m be 1≤m≤
5；
Preferably, m is selected from 1 or 5；
Preferably, the value range of n is 2≤n≤12.
5. the nickelic tertiary cathode material of modification according to claim 1, which is characterized in that when A is P, b=3, m=1, n
=4；When A is Al, b=1, m=1, n=2；When A is Zr, b=2, m=1, n=3；When A is Ti, b=4, m=5, n=
12。
6. the preparation method of the nickelic tertiary cathode material of the described in any item modifications of claim 1-5, which is characterized in that including such as
Lower step:
(a) nickel salt, cobalt salt and manganese salt are made into mixed solution according to atomic ratio Ni ﹕ Co ﹕ Mn=x ﹕ y ﹕ (1-x-y), with precipitating reagent,
Complexing agent mixing carries out coprecipitation reaction, is dried to obtain presoma NixCoyMn(1-x-y)(OH)2；
(b) under solvent action, by presoma NixCoyMn(1-x-y)(OH)2Atomic ratio Ni ﹕ A=x ﹕ is pressed with the oxide of A
(0.002m~0.01m) mixing, is dried to obtain in NixCoyMn(1-x-y)(OH)2Surface coats the material of the oxide of A；
It (c) is in molar ratio 1 ﹕ (1+0.002b)~1 ﹕ (1+0.06b) mixed by the lithium in material and lithium salts that step (b) obtains
It closes, sintering obtains being modified nickelic tertiary cathode material.
7. the preparation method of the nickelic tertiary cathode material of modification according to claim 6, which is characterized in that the step
(a) in, nickel salt, cobalt salt and manganese salt are respectively the mixing of one or both of respective sulfate, nitrate；
Preferably, the precipitating reagent includes NaOH and Na2CO3Any one of or two kinds mixing；
Preferably, the complexing agent includes ammonium hydroxide, ammonium chloride, any one or more of mixing of ammonium sulfate；
Preferably, in the step (a), coprecipitation reaction temperature is 40-80 DEG C；
Preferably, in the step (a), the stirring rate of coprecipitation reaction is 600-1200rpm.
8. the preparation method of the nickelic tertiary cathode material of modification according to claim 6, which is characterized in that the step
(b) in, solvent is selected from short-chain alcohols solvent；
Preferably, the short-chain alcohols solvent is selected from the alcohols solvent of C1-C3；
Preferably, the short chain alcohol solvent includes methanol, ethyl alcohol, any one or more of mixing of 1- propyl alcohol.
9. the preparation method of the nickelic tertiary cathode material of modification according to claim 6, which is characterized in that the step
(b) it in, is mixed and is dried under an inert atmosphere；
Preferably, in the step (b), mixed temperature is 20-40 DEG C；
Preferably, in the step (b), the mixed time is 0.5-2h.
10. according to the preparation method of the nickelic tertiary cathode material of the described in any item modifications of claim 6-9, which is characterized in that
In the step (c), lithium salts includes LiOH and Li2CO3Any one of or two kinds mixing；
Preferably, in the step (c), the temperature of sintering is 400-900 DEG C；
It is furthermore preferred that described be sintered to double sintering, the double sintering includes: first segment sintering, in 450-620 DEG C of sintering 6-
12h, second segment sintering, in 720-830 DEG C of sintering 10-15h；
It is furthermore preferred that the heating rate of the first segment sintering is 2-5 DEG C/min；
It is furthermore preferred that being warming up to 720-830 DEG C of progress under the heating rate of 1.2-3.5 DEG C/min after first segment is sintered
Second segment sintering；
Preferably, further include cooling after sintering in the step (c), obtain being modified nickelic tertiary cathode material.
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