CN108461737A - A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding - Google Patents
A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding Download PDFInfo
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- CN108461737A CN108461737A CN201810232778.3A CN201810232778A CN108461737A CN 108461737 A CN108461737 A CN 108461737A CN 201810232778 A CN201810232778 A CN 201810232778A CN 108461737 A CN108461737 A CN 108461737A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention provides a kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding, and the chemical formula of the material is (LiaNi1‑x‑yCoxAly)1‑bMbO2, x>0, y>0,1 x y>0,1≤a≤1.1,0 b≤0.02 ＜.The preparation method of the material is first by ternary anode material precursor Ni1‑x‑yCoxAly(OH)2+ySintering；Then lithium source is added in sintering gains to be sintered；Finally addition covering material is sintered, and obtains target product.The nickel cobalt aluminium ternary anode material for lithium-ion batteries of the cladding of preparation method synthesis of the present invention has excellent cycle performance.The preparation method of the present invention is simple for process, and process control is easy to industrial volume production.
Description
Technical field
The present invention relates to electrode material fields, and in particular to a kind of nickel cobalt aluminium ternary lithium ion cell positive material of cladding
Material, Preparation method and use.
Background technology
Nickel cobalt aluminium tertiary cathode material has high-energy density, low temperature performance well, thermal stability good, at low cost and to ring
The features such as border small toxicity is one of the positive electrode of power lithium-ion battery field most market development foreground.But due to nickel
Strong side reaction can occur in wide voltage range with organic bath for cobalt aluminium ternary material, increase battery in charge and discharge
Impedance in journey reduces the cyclical stability of material.Therefore, nickel cobalt aluminium ternary material cyclical stability how must be improved, is become
One of urgent problem to be solved in the industry.
Invention content
We are bright to be designed to provide a kind of nickel cobalt aluminium ternary lithium ion cell positive for the cladding that cycle performance is excellent
Material and preparation method thereof, and the purposes using the lithium ion battery of the positive electrode and the positive electrode is provided.
In order to solve the above-mentioned technical problem, the technical scheme is that：A kind of nickel cobalt aluminium ternary lithium-ion electric of cladding
Pond positive electrode, including nickel cobalt aluminic acid lithium material and the covering material for being coated on the nickel cobalt aluminic acid lithium material surface, it is described
Shown in the chemical formula such as formula (I) of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding：
(LiaNi1-x-yCoxAly)1-bMbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜；
M is selected from alkali metal element, alkali earth metal, the 13rd race's element, the 14th race's element, transition metal element and rare earth
It is one or more in element.
Preferably, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.05,0 b≤0.01 ＜.
Preferably, M is Zr, x=0.15, y=0.035, a=1.035, b=0.0016.
Preferably, M is Zr, x=0.15, y=0.035, a=1.035, b=0.0008.
Preferably, M is Al, x=0.15, y=0.035, a=1.035, b=0.002.
Preferably, M is Al, x=0.15, y=0.035, a=1.035, b=0.0055.
Preferably, M is Zn, x=0.15, y=0.035, a=1.035, b=0.0029.
Preferably, M is Zn, x=0.15, y=0.035, a=1.035, b=0.0007.
Preferably, M is Mg, x=0.15, y=0.035, a=1.035, b=0.0078.
Preferably, M is Mg, x=0.15, y=0.035, a=1.035, b=0.0017.
Preferably, method for coating is one kind in dry method, water phase wet method or organic phase wet method.
Compared with prior art, the nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding provided by the invention, clad
It is not involved in electrochemical reaction, the structural stability of nickel cobalt aluminium ternary anode material for lithium-ion batteries is effectively raised, improves
The chemical property of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the nickel cobalt aluminium ternary lithium ion cell positive material by cladding
Material has higher capacity retention ratio and more stable cycle performance.
In order to solve the above technical problems, the present invention also provides the nickel cobalt aluminium ternary lithium ion cell positive materials of above-mentioned cladding
The preparation method of material, includes the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering；
Step (2) is sintered for second：Lithium source mixed grinding is added in the step (1) sintering gains, grinding is uniform
Afterwards, it is sintered, room temperature is cooled to after the completion of sintering；
Step (3), third time are sintered：Covering material is added in the step (2) sintering gains to be sintered, is wrapped
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li coveredaNi1-x-yCoxAly)1-bMbO2, 0.03≤x≤0.15,0.01≤y≤
0.05,1≤a≤1.1,0 b≤0.02 ＜.
Preferably, in the step (1), sintering time is 6-20 hours, and sintering temperature is 200-1000 DEG C.
Preferably, in the step (2), the lithium source is lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, nitric acid
One kind in lithium, lithium chloride and lithium fluoride.
Preferably, in the step (2), the lithium source is a hydronium(ion) lithia, and a hydronium(ion) lithia is dried
It is mixed to losing completely with the step (1) sintering gains after the crystallization water.
Preferably, in the step (2), sintering time is 8-24 hours, and sintering temperature is 500-1000 DEG C
Preferably, in the step (2), rate of temperature fall is 0.01-2.5 DEG C/min.
Preferably, in the step (2), rate of temperature fall is 0.02-1 DEG C/min
Preferably, in the step (2), the addition of lithium source is Li and (Ni+Co+ in ternary anode material precursor
Al) molar ratio is 1~1.1:1.
Preferably, sintering is carried out in air or oxygen atmosphere in the step (2).
Preferably, step (3) covering material is selected from the oxide of metal M, the fluoride of metal M or metal M's
One kind in sulfide.
Preferably, step (3) sintering time is 1-12 hours, sintering temperature is 500-1000 DEG C.
Compared with prior art, the preparation side of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding provided by the invention
The clad of method, the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the cladding of preparation is not involved in electrochemical reaction, effectively carries
The high structural stability of nickel cobalt aluminium ternary anode material for lithium-ion batteries, improves nickel cobalt aluminium ternary lithium ion cell positive material
The chemical property of material, nickel cobalt aluminium ternary anode material for lithium-ion batteries by cladding have higher capacity retention ratio and more
Stable cycle performance.The preparation method of the present invention is simple for process, and process control is easy to industrial volume production.
In order to solve the above technical problems, the present invention also provides a kind of lithium ion battery, including anode, cathode, electrolyte
And diaphragm, the anode include the nickel cobalt aluminium ternary anode material for lithium-ion batteries of above-mentioned cladding or pass through above-mentioned method system
The nickel cobalt aluminium ternary anode material for lithium-ion batteries of standby obtained cladding.
Compared with prior art, lithium ion battery provided by the invention, anode use the nickel cobalt of cladding provided by the invention
The nickel cobalt aluminium ternary lithium for the cladding that aluminium ternary anode material for lithium-ion batteries or the method provided through the invention are prepared from
Sub- cell positive material, lithium ion battery provided by the invention have good cycle, and service life is long, and capacity retention ratio is high,
Tap density is high, small, it is light-weight the advantages that.
In order to solve the above technical problems, the present invention also provides a kind of above-mentioned nickel cobalt aluminium ternary lithium ion cell positive materials
Material or the nickel cobalt aluminium ternary anode material for lithium-ion batteries being prepared by above-mentioned method are preparing lithium ion battery, electronics
Application in product energy storage, industrial electric power storage energy storage, electric vehicle and electric bicycle power supply.
Compared with prior art, the nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding provided by the invention or pass through this
The nickel cobalt aluminium ternary anode material for lithium-ion batteries that the method for invention is prepared for lithium ion battery, electronic product energy storage,
In industrial electric power storage energy storage, electric vehicle and electric bicycle power supply, preparation with lithium ion battery, electronic product energy storage, industry
The relevant products such as electric power storage energy storage, electric vehicle and electric bicycle power supply have service life long, and cruise duration is long, when charging
Between short, the advantages that weight body is light, power is sufficient.
Description of the drawings
Fig. 1 is the preparation of the embodiment of the present invention 1 using ZrO2The nickel cobalt aluminium tertiary cathode material of cladding is prepared with comparative example 1
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 2 is the preparation of the embodiment of the present invention 2 using ZrO2The nickel cobalt aluminium tertiary cathode material of cladding is prepared with comparative example 2
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 3 is the preparation of the embodiment of the present invention 3 using Al2O3The nickel cobalt aluminium tertiary cathode material of cladding is prepared with comparative example 1
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 4 is the preparation of the embodiment of the present invention 4 using Al2O3The nickel cobalt aluminium tertiary cathode material of cladding is prepared with comparative example 2
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 5 is that the nickel cobalt aluminium tertiary cathode material using ZnO claddings prepared by the embodiment of the present invention 5 is prepared with comparative example 1
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 6 is that the nickel cobalt aluminium tertiary cathode material using ZnO claddings prepared by the embodiment of the present invention 6 is prepared with comparative example 2
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 7 is that the nickel cobalt aluminium tertiary cathode material using MgO claddings prepared by the embodiment of the present invention 7 is prepared with comparative example 1
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 8 is that the nickel cobalt aluminium tertiary cathode material using MgO claddings prepared by the embodiment of the present invention 8 is prepared with comparative example 2
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure.
Specific implementation mode
In order to make goal of the invention, technical solution and the advantageous effect of the present invention be more clear, with reference to embodiments into one
The step detailed description present invention.However, it should be understood that the embodiment of the present invention is not just for the sake of explaining the present invention
The limitation present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.
Shown in the nickel cobalt aluminium ternary anode material for lithium-ion batteries chemical formula such as formula (I) of the cladding of the embodiment of the present invention：
(LiaNi1-x-yCoxAly)1-bMbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜；
M is selected from alkali metal element, alkali earth metal, the 13rd race's element, the 14th race's element, transition metal element and rare earth
It is one or more in element.
The preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the cladding of the embodiment of the present invention, including following step
Suddenly：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering；Sintering time
6-20 hours, 200-1000 DEG C of sintering temperature；
Step (2) is sintered for second：The step (1) sintering gains are added lithium source, before Li and tertiary cathode material
It is=a to drive (Ni+Co+Al) molar ratio in body, and mixed grinding is sintered after grinding uniformly in air or oxygen atmosphere, is burnt
Time 8-24 hour is tied, after the completion of sintering, room is down to 0.01-2.5 DEG C/min rate of temperature fall for 500-1000 DEG C of sintering temperature
Temperature；
Step (3), third time are sintered：Covering material is added in the step (2) sintering gains, in covering material M with
(Ni+Co+Al) molar ratio is b in ternary anode material precursor:(1-b), is sintered, sintering time 1-12 hours, sintering
500-1000 DEG C of temperature, the nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li coatedaNi1-x-yCoxAly)1-bMbO2,
0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 b≤0.02 ＜.
The dosage of lithium source is Li and (Ni+Co+Al) molar ratio in ternary anode material precursor is a, metallic compound
Addition is metal and (Ni+Co+Al) molar ratio in ternary anode material precursor is b:(1-b).
Ternary anode material precursor Ni1-x-yCoxAly(OH)2+yIt is bought for market, art methods can also be used
It prepares.
The lithium source is one in lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, lithium nitrate, lithium chloride and lithium fluoride
Kind；The lithium source can also be a hydronium(ion) lithia, a hydronium(ion) lithia is dried to after losing the crystallization water completely and institute
State step (1) sintering gains mixing.The addition of the lithium source is Li and (Ni+Co+Al) in ternary anode material precursor
Molar ratio is 1~1.1:1.
Covering material be selected from the oxide of metal M, the fluoride of metal M, the sulfide of metal M, metal M tellurides,
It is one or more in the selenides of metal M, the antimonide of metal M, the phosphide of metal M or the composite oxides of metal M.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
Provided in this embodiment is to use covering material ZrO2The nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding is changed
Formula is (Li1.035Ni0.815Co0.15Al0.035)0.9984Zr0.0016O2, M is Zr, x=0.15, y=0.035, a=1.035, b=
0.0016。
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9984Zr0.0016O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mix in proportion, and the dosage of a hydronium(ion) lithia is Li and tertiary cathode in a hydronium(ion) lithia
(Ni+Co+Al) molar ratio is 1.035 in material precursor：It after 1 mixed grinding is uniform, is sintered, heats up in oxygen atmosphere
It is reacted 16.5 hours to 715 DEG C, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：By the step (2) sintering gains and covering material ZrO2Mixing, ZrO2Plus
It is ZrO to enter amount2In Zr and ternary anode material precursor in (Ni+Co+Al) molar ratio be 0.0016：0.9984, it is warming up to
650 DEG C are sintered 3.5 hours, are down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9984Zr0.0016O2,
ICP elemental analysis test results show that each metal molar percentage of Ni, Co, Al, Zr is as follows：
Embodiment 2
Provided in this embodiment is to use covering material ZrO2The nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding is changed
Formula is (Li1.035Ni0.815Co0.15Al0.035)0.9992Zr0.0008O2, M is Zr, x=0.15, y=0.035, a=1.035, b=
0.0008。
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9992Zr0.0008O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775
DEG C reaction 8 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：Covering material ZrO is added in the step (2) sintering gains2, ZrO2Addition
Amount is ZrO2In Zr and ternary anode material precursor in (Ni+Co+Al) molar ratio be 0.0008：0.9992, it is warming up to 615
DEG C sintering 5 hours, is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9992Zr0.0008O2, ICP elements
Analysis test result shows that each metal molar percentage of Ni, Co, Al, Zr is as follows：
Embodiment 3
Provided in this embodiment is to use Al2O3The nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding, chemical formula are
(Li1.035Ni0.815Co0.15Al0.035)0.998Al0.002O2, M is Al, x=0.15, y=0.035, a=1.035, b=0.002.
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.998Al0.002O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715
DEG C reaction 16.5 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：Covering material Al is added in the step (2) sintering gains2O3, Al2O3Plus
It is Al to enter amount2O3In Al and ternary anode material precursor in (Ni+Co+Al) molar ratio be 0.002：0.998, it is warming up to 650
DEG C sintering 3.5 hours, is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.998Al0.002O2, ICP members
Each metal molar percentage of element analysis test Ni, Co, Al is as follows：
Embodiment 4
Provided in this embodiment is to use Al2O3The nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding, chemical formula are
(Li1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2, M is Al, x=0.15, y=0.035, a=1.035, b=0.0055.
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：It after 1 mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775
DEG C reaction 8 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：Covering material Al is added in the step (2) sintering gains2O3, Al2O3Plus
It is Al to enter amount2O3In Al and ternary anode material precursor (Ni+Co+Al) molar ratio be 0.0055：0.9945, it is warming up to 615
DEG C sintering 5 hours, is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2, ICP elements
Analysis test shows that the molar percentage of each metal of Ni, Co, Al is as follows：
Embodiment 5
Provided in this embodiment is using the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings, and chemical formula is
(Li1.035Ni0.815Co0.15Al0.035)0.9971Zn0.0029O2, M is Zn, x=0.15, y=0.035, a=1.035, b=0.0029.
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9971Zn0.0029O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：It after 1 mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715
DEG C reaction 16.5 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are added to the addition of covering material ZnO, ZnO
It is 0.0029 for (Ni+Co+Al) molar ratio in the Zn and ternary anode material precursor in ZnO：0.9971, it is warming up to 650 DEG C
Sintering 3.5 hours is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9971Zn0.0029O2, ICP elements
Analysis test shows that each metal molar percentage of Ni, Co, Al, Zn is as follows：
Embodiment 6
Provided in this embodiment is using the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings, and chemical formula is
(Li1.035Ni0.815Co0.15Al0.035)0.9993Zn0.0007O2, M is Zn, x=0.15, y=0.035, a=1.035, b=0.0007.
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9993Zn0.0007O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775
DEG C reaction 8 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are added to the addition of covering material ZnO, ZnO
It is 0.0007 for (Ni+Co+Al) molar ratio in the Zn and ternary anode material precursor in ZnO：0.9993, it is warming up to 615 DEG C
Sintering 5 hours is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9993Zn0.0007O2, ICP elements point
Analysis test shows that each metal molar percentage of Ni, Co, Al, Zn is as follows：
Embodiment 7
Provided in this embodiment is using the nickel cobalt aluminium ternary anode material for lithium-ion batteries of MgO claddings, and chemical formula is
(Li1.035Ni0.815Co0.15Al0.035)0.9922Mg0.0078O2, M is Mg, x=0.15, y=0.035, a=1.035, b=0.0078
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9922Mg0.0078O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after grinding uniformly, is sintered, is warming up to 715 DEG C and reacts 16.5 hours,
Then room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are added to the addition of covering material MgO, MgO
It is 0.0078 for (Ni+Co+Al) molar ratio in the Mg and ternary anode material precursor in MgO：0.9922, it is warming up to 650 DEG C
Sintering 3.5 hours is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9922Mg0.0078O2, ICP elements
Analysis test shows that the molar percentage of each metal of Ni, Co, Al, Mg is as follows：
Embodiment 8
Provided in this embodiment is using the nickel cobalt aluminium ternary anode material for lithium-ion batteries of MgO claddings, and chemical formula is
(Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2, M is Mg, x=0.15, y=0.035, a=1.035, b=0.0017.
The nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li of the present embodiment cladding1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775
DEG C reaction 8 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are added to the addition of covering material MgO, MgO
It is 0.0017 for (Ni+Co+Al) molar ratio in the Mg and ternary anode material precursor in MgO：0.9983, it is warming up to 615 DEG C
Sintering 5 hours is down to room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2, ICP elements point
Analysis test shows that the molar percentage of each metal of Ni, Co, Al, Mg is as follows：
Comparative example 1
Comparative example 1 provides uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries, and chemical formula is
Li1.035Ni0.815Co0.15Al0.035O2, the uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries of comparative example 1
Li1.035Ni0.815Co0.15Al0.035O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715
DEG C reaction 16.5 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are warming up to 650 DEG C to be sintered 3.5 hours, are down to
Room temperature is to get to contrast material Li1.035Ni0.815Co0.15Al0.035O2。
Comparative example 2
Comparative example 2 provides uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries, and chemical formula is
Li1.035Ni0.815Co0.15Al0.035O2, the uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries of comparative example 2
Li1.035Ni0.815Co0.15Al0.035O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni0.815Co0.15Al0.035(OH)2.035Sintering rises
Temperature to 600 DEG C react 6.5 hours；
Step (2) is sintered for second：One hydronium(ion) lithia is dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, before the dosage of a hydronium(ion) lithia is Li and tertiary cathode material in a hydronium(ion) lithia
It is 1.035 to drive (Ni+Co+Al) molar ratio in body：1, it after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775
DEG C reaction 8 hours, room temperature is then down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered：The step (2) sintering gains are warming up to 615 DEG C to be sintered 5 hours, are down to room
Temperature is to get to contrast material Li1.035Ni0.815Co0.15Al0.035O2。
Table 1：Examples 1 to 8,1~2 reaction condition of comparative example and product.
Button cell assembles
CR2032 model button cells assemble：
The nickel cobalt lithium aluminate tertiary cathode material of the cladding prepared with Examples 1 to 8, comparative example 1~2 prepare uncoated
Nickel cobalt aluminium tertiary cathode material be anode active matter, cathode use metal lithium sheet, diaphragm use 2500 diaphragms of Celgard,
Electrolyte is Suzhou Fo Sai new materials Co., Ltd fosai LB-002 electrolyte, and CR2032 models are assembled by art methods
Button cell, assembling sequence are：Positive cover keeps flat, places spring leaf, place stainless steel substrates, place positive plate, note electrolyte, put
Diaphragm is set, lithium piece is placed, covers cathode cap, seals, is completed.Battery is in the dry glove box full of argon gas into luggage
Match.After being completed, battery is tested for the property, test result is shown in Table 2.
1, ICP Element detections
Test method：Inductivity coupled plasma mass spectrometry method of testing
Test equipment title:Icp ms
Model：Prodigy DC Arc
Test equipment producer：U.S.'s profit is graceful-come Bai Si companies
2, cycle performance
Test equipment title：New prestige battery testing system, model：BTS-5V10mA
Test equipment producer：New Weir Electronics Co., Ltd. of Shenzhen；
Test method：At 25 DEG C, with 1C constant-current charges to 4.3V, 4.3V constant pressures to 0.05C, then 1C be discharged to 3V,
100 above-mentioned charge and discharge cycles are repeated, electric discharge when measuring the discharge capacity and the 100th cycle when recycling for the first time is held
Amount, calculates the capacity retention ratio after recycling 100 times, and formula is：Capacity retention ratio=(putting when the 100th cycle after cycle
Capacitance)/(discharge capacity when recycling for the first time) * 100%.
3, tap density
Test equipment title：Tap density meter
Instrument model：JZ-1
Instrument producer：Jingxin Power Testing Apparatus Co., Ltd., Chengdu
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 holder 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 2
Fruit represents the average value tested three times.
4, surface residual alkali weight testing method：Acid-base titration.
(1) the positive electrode stillness of night is prepared：W is weighed with the precision of 0.0001g1The positive material of (30.0000 ± 0.0040g)
Material weighs W with the precision of 0.01g2(100 ± 0.1g) deionized water mixes positive electrode with deionized water, and argon gas displacement is mixed
The air in liquid is closed, is stirred, filtering obtains filtrate, pipettes 50mL filtrates, is put into 100mL beakers, prepares titration；
(2) LiOH contents are measured：Using phenolphthalein as indicator, titrated with 0.05mol/L hydrochloric acid standard solutions, when titration end-point
The hydrochloric acid standard liquid volume V consumed1；
(3) Li is measured2CO3Content：CO in clear liquid after argon gas displacement step (2) titration2, then with methyl red indicator,
It is titrated with 0.05mol/L hydrochloric acid standard solutions, the hydrochloric acid standard liquid volume V that when titration end-point is consumed2；
Positive electrode Surface L iOH contents (wt%) calculation formula：ω1=(2V1-V2)*0.05*2.395*W2/W1/50；
Positive electrode Surface L i2CO3Content (wt%) calculation formula：ω2=(V2-V1)*0.05*7.389*W2/W1/50；
2.395：With the quality of the comparable LiOH indicated with g of hydrochloric acid standard liquid (1.000mol/L)；
7.389：With the comparable Li indicated with g of hydrochloric acid standard liquid (2.000mol/L)2CO3Quality；
Positive electrode surface residual alkali amount=ω1+ω2。
The battery performance test result of table 2, Examples 1 to 8 and comparative example 1~2
It please refers to Fig.1 and Fig. 2, in conjunction with 1 data of table, it can be seen that：
Embodiment 1 uses ZrO compared with comparison 1 in embodiment 12The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9984Zr0.0016O2Capacity retention ratio 91.50% after recycling 100 times, comparative example 1 are not wrapped
The nickel cobalt aluminium tertiary cathode material that covers recycle 100 times after capacity retention ratio 79.70%, the uncoated nickel cobalt aluminium with comparative example 1
Tertiary cathode material is compared, and ZrO is used in embodiment 12The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9984Zr0.0016O2With more stable cycle performance.
Embodiment 2 uses ZrO compared with comparison 2 in embodiment 22The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9992Zr0.0008O2Capacity retention ratio 91.50% after recycling 100 times, comparative example 2 are not wrapped
The nickel cobalt aluminium tertiary cathode material that covers recycle 100 times after capacity retention ratio 76.20%, the uncoated nickel cobalt aluminium with comparative example 2
Tertiary cathode material is compared, and ZrO is used in embodiment 22The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9992Zr0.0008O2With more stable cycle performance.
Examples 1 to 2 uses ZrO2Nickel cobalt aluminium tertiary cathode material is coated, covering material ZrO2It is easy in main body
The higher position of material surface reactivity preferentially generates, and can effectively eliminate the higher position of bulk material surface reactivity
Point plays the role of rock-steady structure to material of main part, and the reaction in the battery system to effectively reduce positive electrode is lived
Property, it avoids nickel cobalt aluminium tertiary cathode material that side reaction occurs with organic bath, reduces impedance of the battery in charge and discharge process,
To effectively improve the cyclical stability of nickel cobalt aluminium tertiary cathode material.
It please refers to Fig.3 and Fig. 4, in conjunction with 1 data of table, it can be seen that：
Embodiment 3 uses Al compared with comparative example 1 in embodiment 32O3The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.998Al0.002O2Tap density 2.97g/cm3, the capacity retention ratio after recycling 100 times
83.20%, the uncoated nickel cobalt aluminium tertiary cathode material tap density 2.79g/cm of comparative example 13, the capacity after recycling 100 times
Conservation rate 79.70% uses Al compared with the uncoated nickel cobalt aluminium tertiary cathode material of comparative example 1 in embodiment 32O3Cladding
Nickel cobalt aluminium tertiary cathode material Co0.15Al0.035)0.998Al0.002O2With more stable cycle performance, tap density increases.
Embodiment 3 uses Al compared with comparative example 1 in embodiment 32O3The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.998Al0.002O2Surface L iOH weight percent is 0.26%, Surface L i2CO3Weight percent
Than being 0.09%, surface residual alkali amount weight percent is 0.35%, the uncoated nickel cobalt aluminium tertiary cathode material surface of comparative example 1
LiOH contents 0.46%, Surface L i2CO3Content weight percent is 0.37%, and surface residual alkali amount weight percent is 0.83%,
Compared with the uncoated nickel cobalt aluminium tertiary cathode material of comparative example 1, Al is used in embodiment 32O3The nickel cobalt aluminium tertiary cathode of cladding
Material C o0.15Al0.035)0.998Al0.002O2Surface L iOH, Li2CO3Content reduces, to which surface residual alkali amount effectively reduces.
Embodiment 4 uses Al compared with comparative example 2 in embodiment 42O3The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2Tap density 2.96g/cm3, the capacity retention ratio after recycling 100 times
82%, the uncoated nickel cobalt aluminium tertiary cathode material tap density 2.75g/cm of comparative example 23, the capacity holding after recycling 100 times
Rate 76.20% uses Al compared with the uncoated nickel cobalt aluminium tertiary cathode material of comparative example 2 in embodiment 22O3Cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2With more stable cycle performance, tap density increases.
Embodiment 4 uses Al compared with comparison 2 in embodiment 42O3The nickel cobalt aluminium tertiary cathode material of cladding
(Li1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2Surface L iOH content weight percent is 0.26%, Surface L i2CO3Contain
It is 0.15% to measure weight percent, and surface residual alkali amount weight percent is 0.41%, and the uncoated nickel cobalt aluminium ternary of comparative example 2 is just
Pole material surface LiOH content weight percent is 0.49%, Surface L i2CO3Content weight percent is 0.39%, surface residual alkali
It is 0.88% to measure weight percent, compared with the uncoated nickel cobalt aluminium tertiary cathode material of comparative example 2, is used in embodiment 2
Al2O3(the Li of cladding1.035Ni0.815Co0.15Al0.035)0.9945Al0.0055O2Surface L iOH, Li2CO3Content reduces, to surface
Residual alkali amount effectively reduces.
Embodiment 3~4 uses Al2O3Nickel cobalt aluminium tertiary cathode material is coated, covering material Al2O3It is easy in master
The higher position of body material surface reactivity preferentially generates, and it is higher can effectively to eliminate bulk material surface reactivity
Site plays the role of rock-steady structure to material of main part, the reaction in battery system to effectively reduce positive electrode
Activity avoids nickel cobalt aluminium tertiary cathode material that side reaction occurs with organic bath, reduces resistance of the battery in charge and discharge process
It is anti-, to effectively improve the cyclical stability of nickel cobalt aluminium tertiary cathode material, and improve the tap density of material.
CO in the active lithium and air on nickel cobalt aluminium tertiary cathode material surface2、H2O reacts, and generates LiOH, Li2CO3, adopt
Use Al2O3Nickel cobalt aluminium tertiary cathode material is coated, Al2O3It can be anti-with the active lithium on nickel cobalt aluminium tertiary cathode material surface
It answers, generates LiAlO2, reduce the active lithium content on nickel cobalt aluminium tertiary cathode material surface, to reduce nickel cobalt aluminium ternary just
Pole material surface LiOH, Li2CO3Content effectively reduces nickel cobalt aluminium tertiary cathode material surface residual alkali amount, so as to reduce just
In the material configuration process of pole, the attack of the alkaline matter on nickel cobalt aluminium tertiary cathode material surface to binder in positive glue is kept away
Free sticky knot dosage form generates gluing at double bond, avoids causing slurry jelly, improves Painting effect, improves battery core performance.
Fig. 5 and Fig. 6 are please referred to, in conjunction with 1 data of table, it can be seen that：
Embodiment 5 is compared with comparison 1, using the nickel cobalt aluminium tertiary cathode material of ZnO claddings in embodiment 5
(Li1.035Ni0.815Co0.15Al0.035)0.9971Zn0.0029O2Capacity retention ratio 87.30% after recycling 100 times, comparative example 1 are not wrapped
The nickel cobalt aluminium tertiary cathode material that covers recycle 100 times after capacity retention ratio 79.70%, the uncoated nickel cobalt aluminium with comparative example 1
Tertiary cathode material is compared, using the nickel cobalt aluminium tertiary cathode material of ZnO claddings in embodiment 5
(Li1.035Ni0.815Co0.15Al0.035)0.9971Zn0.0029O2With more stable cycle performance.
Embodiment 6 is compared with comparison 2, using the nickel cobalt aluminium tertiary cathode material of ZnO claddings in embodiment 6
(Li1.035Ni0.815Co0.15Al0.035)0.9993Zn0.0007O2Capacity retention ratio 85.90% after recycling 100 times, comparative example 2 are not wrapped
The nickel cobalt aluminium tertiary cathode material that covers recycle 100 times after capacity retention ratio 76.20%, the uncoated nickel cobalt aluminium with comparative example 2
Tertiary cathode material is compared, using the nickel cobalt aluminium tertiary cathode material of ZnO claddings in embodiment 2
(Li1.035Ni0.815Co0.15Al0.035)0.9993Zn0.0007O2With more stable cycle performance.
Embodiment 5~6 coats nickel cobalt aluminium tertiary cathode material using ZnO, and covering material ZnO is easy in main body material
The higher position of material surface reaction activity preferentially generates, and can effectively eliminate the higher position of bulk material surface reactivity
Point plays the role of rock-steady structure to material of main part, and the reaction in the battery system to effectively reduce positive electrode is lived
Property, it avoids nickel cobalt aluminium tertiary cathode material that side reaction occurs with organic bath, reduces impedance of the battery in charge and discharge process,
To effectively improve the cyclical stability of nickel cobalt aluminium tertiary cathode material.
Fig. 7 and Fig. 8 are please referred to, in conjunction with 1 data of table, it can be seen that：
Embodiment 7 is compared with comparison 1, using the nickel cobalt aluminium tertiary cathode material of MgO claddings in embodiment 7
(Li1.035Ni0.815Co0.15Al0.035)0.9922Mg0.0078O2Capacity retention ratio 85.80% after recycling 100 times, comparative example 1 are not wrapped
The nickel cobalt aluminium tertiary cathode material that covers recycle 100 times after capacity retention ratio 79.70%, the uncoated nickel cobalt aluminium with comparative example 1
Tertiary cathode material is compared, using the nickel cobalt aluminium tertiary cathode material of MgO claddings in embodiment 7
(Li1.035Ni0.815Co0.15Al0.035)0.9922Mg0.0078O2With more stable cycle performance.
Embodiment 8 is compared with comparison 2, using the nickel cobalt aluminium tertiary cathode material of MgO claddings in embodiment 8
(Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2Capacity retention ratio 84% after recycling 100 times, comparative example 2 are uncoated
Nickel cobalt aluminium tertiary cathode material recycle 100 times after capacity retention ratio 76.20%, the nickel cobalt aluminium ternary uncoated with comparative example 2
Positive electrode is compared, using the nickel cobalt aluminium tertiary cathode material of MgO claddings in embodiment 2
(Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2With more stable cycle performance.
Embodiment 7~8 coats nickel cobalt aluminium tertiary cathode material using MgO, and covering material MgO is easy in main body material
The higher position of material surface reaction activity preferentially generates, and can effectively eliminate the higher position of bulk material surface reactivity
Point plays the role of rock-steady structure to material of main part, and the reaction in the battery system to effectively reduce positive electrode is lived
Property, it avoids nickel cobalt aluminium tertiary cathode material that side reaction occurs with organic bath, reduces impedance of the battery in charge and discharge process,
To effectively improve the cyclical stability of nickel cobalt aluminium tertiary cathode material.
In conclusion the nickel cobalt aluminium tertiary cathode material that the present invention coats has at least the following advantages：Through the invention
The nickel cobalt aluminium tertiary cathode material of cladding prepared by method, the charge-discharge performance at 3.0V~4.3V have obtained significantly
It improves：Comparative example 1~8 and comparative example 1~2 it can be found that after 100 cycles, packet prepared by the method for the present invention
The capacity retention ratio of the nickel cobalt aluminium tertiary cathode material covered is higher than uncoated nickel cobalt aluminium tertiary cathode material；This illustrates and does not wrap
The nickel cobalt aluminium tertiary cathode material covered is compared, and the nickel cobalt aluminium tertiary cathode material that the present invention coats has more stable cyclicity
Energy.
Since electrochemical reaction is happened at electrode and electrolyte interface, the performance on positive electrode surface influences battery performance
It is very big.Nickel cobalt aluminium tertiary cathode material method for coating provided by the invention, covering material, which is easy to react in bulk material surface, lives
The higher position of property preferentially generates, and the higher site of bulk material surface reactivity can be effectively eliminated, to material of main part
Play the role of rock-steady structure, the reactivity in battery system to effectively reduce positive electrode avoids nickel cobalt aluminium
With organic bath side reaction occurs for tertiary cathode material, reduces impedance of the battery in charge and discharge process, to effectively improve
The cyclical stability of nickel cobalt aluminium tertiary cathode material.The preparation method of the present invention is simple for process, and process control is easy to industrialization amount
Production.
Those skilled in the art can carry out invention spirit and model of the various modification and variations without departing from the present invention
It encloses.In this way, if these modifications and changes of the present invention is within the scope of the claims of the present invention and its equivalent technology, then
The present invention is also intended to including these modification and variations.
Claims (24)
1. a kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding, which is characterized in that including nickel cobalt aluminic acid lithium material with
And it is coated on the covering material on the nickel cobalt aluminic acid lithium material surface, the nickel cobalt aluminium ternary lithium ion cell positive material of the cladding
Shown in the chemical formula of material such as formula (I)：
(LiaNi1-x-yCoxAly)1-bMbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜；
M is selected from alkali metal element, alkali earth metal, the 13rd race's element, the 14th race's element, transition metal element and rare earth element
In it is one or more.
2. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that
0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.05,0 b≤0.01 ＜.
3. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Zr, x
=0.15, y=0.035, a=1.035, b=0.0016.
4. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Zr, x
=0.15, y=0.035, a=1.035, b=0.0008.
5. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Al, x
=0.15, y=0.035, a=1.035, b=0.002.
6. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Al, x
=0.15, y=0.035, a=1.035, b=0.0055.
7. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Zn, x
=0.15, y=0.035, a=1.035, b=0.0029.
8. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Zn, x
=0.15, y=0.035, a=1.035, b=0.0007.
9. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Mg, x
=0.15, y=0.035, a=1.035, b=0.0078.
10. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that M is Mg, x
=0.15, y=0.035, a=1.035, b=0.0017.
11. the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as described in claim 1, which is characterized in that cladding side
Method is one kind in dry method, water phase wet method or organic phase wet method.
12. a kind of system of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the cladding described in claim 1~11 any one
Preparation Method, which is characterized in that include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering；
Step (2) is sintered for second：Lithium source mixed grinding is added in the step (1) sintering gains, after grinding uniformly, into
Row sintering, room temperature is cooled to after the completion of sintering；
Step (3), third time are sintered：Covering material is added in the step (2) sintering gains to be sintered, is coated
Nickel cobalt aluminium ternary anode material for lithium-ion batteries (LiaNi1-x-yCoxAly)1-bMbO2, 0.03≤x≤0.15,0.01≤y≤
0.05,1≤a≤1.1,0 b≤0.02 ＜.
13. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (1), sintering time is 6-20 hours, and sintering temperature is 200-1000 DEG C.
14. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), the lithium source is lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, lithium nitrate, lithium chloride and fluorine
Change one kind in lithium.
15. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), the lithium source is a hydronium(ion) lithia, and a hydronium(ion) lithia is dried to and loses knot completely
It is mixed with the step (1) sintering gains after brilliant water.
16. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), sintering time is 8-24 hours, and sintering temperature is 500-1000 DEG C.
17. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), rate of temperature fall is 0.01-2.5 DEG C/min.
18. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), rate of temperature fall is 0.02-1 DEG C/min.
19. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, in the step (2), the addition of lithium source is Li and (Ni+Co+Al) molar ratio in ternary anode material precursor is 1
~1.1:1.
20. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, sintering is carried out in air or oxygen atmosphere in the step (2).
21. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, step (3) covering material is selected from the oxide of metal M, the fluoride of metal M, the sulfide of metal M, metal M
The selenides of tellurides, metal M, the antimonide of metal M, the phosphide of metal M or one kind in the composite oxides of metal M or
It is a variety of.
22. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries coated as claimed in claim 12, feature
It is, step (3) sintering time is 1-12 hours, and sintering temperature is 500-1000 DEG C.
23. a kind of lithium ion battery, including anode, cathode, electrolyte and diaphragm, which is characterized in that the anode includes right
It is required that the nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding described in 1 to 11 any one or passing through claim 12 to 22
The nickel cobalt aluminium ternary anode material for lithium-ion batteries for the cladding that method described in any one is prepared.
24. a kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries of the cladding described in claim 1 to 11 any one is logical
Cross the nickel cobalt aluminium ternary lithium ion cell positive material for the cladding that the method described in claim 12 to 22 any one is prepared
Expect answering in preparing lithium ion battery, electronic product energy storage, industrial electric power storage energy storage, electric vehicle and electric bicycle power supply
With.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810232778.3A CN108461737A (en) | 2018-03-21 | 2018-03-21 | A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding |
| CN201980000087.3A CN110896674A (en) | 2018-03-21 | 2019-01-07 | Nickel-cobalt-aluminum ternary lithium ion battery positive electrode material, preparation method and application thereof, and lithium ion battery |
| JP2020516709A JP7292265B2 (en) | 2018-03-21 | 2019-01-07 | Cathode material for nickel-cobalt-aluminum ternary lithium-ion battery, its production method, and lithium-ion battery |
| EP19770882.9A EP3667780A4 (en) | 2018-03-21 | 2019-01-07 | Nickel-cobalt-aluminum ternary lithium ion battery anode material, preparation method therefor and application thereof, and lithium ion battery |
| PCT/CN2019/070656 WO2019179219A1 (en) | 2018-03-21 | 2019-01-07 | Nickel-cobalt-aluminum ternary lithium ion battery anode material, preparation method therefor and application thereof, and lithium ion battery |
| US16/840,472 US20200274160A1 (en) | 2018-03-21 | 2020-04-06 | Nickel-cobalt-aluminium ternary lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery |
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| CN201810232778.3A CN108461737A (en) | 2018-03-21 | 2018-03-21 | A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817884A (en) * | 2018-12-29 | 2019-05-28 | 深圳市卓能新能源股份有限公司 | Battery anode slice and preparation method thereof and lithium ion battery |
| WO2019179219A1 (en) * | 2018-03-21 | 2019-09-26 | 浙江林奈新能源有限公司 | Nickel-cobalt-aluminum ternary lithium ion battery anode material, preparation method therefor and application thereof, and lithium ion battery |
| CN110854383A (en) * | 2019-11-08 | 2020-02-28 | 昆山宝创新能源科技有限公司 | Modified ternary cathode material and preparation method thereof |
| CN112038588A (en) * | 2019-06-03 | 2020-12-04 | 贝特瑞（江苏）新材料科技有限公司 | Ternary material, preparation method and application thereof |
| CN114249357A (en) * | 2021-12-27 | 2022-03-29 | 宁波容百新能源科技股份有限公司 | Surface modified high-nickel ternary cathode material and dry preparation process thereof |
| CN114538532A (en) * | 2022-01-11 | 2022-05-27 | 宜宾锂宝新材料有限公司 | Preparation method of high-nickel ternary cathode material and prepared high-nickel ternary cathode material |
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2018
- 2018-03-21 CN CN201810232778.3A patent/CN108461737A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019179219A1 (en) * | 2018-03-21 | 2019-09-26 | 浙江林奈新能源有限公司 | Nickel-cobalt-aluminum ternary lithium ion battery anode material, preparation method therefor and application thereof, and lithium ion battery |
| CN109817884A (en) * | 2018-12-29 | 2019-05-28 | 深圳市卓能新能源股份有限公司 | Battery anode slice and preparation method thereof and lithium ion battery |
| CN112038588A (en) * | 2019-06-03 | 2020-12-04 | 贝特瑞（江苏）新材料科技有限公司 | Ternary material, preparation method and application thereof |
| CN110854383A (en) * | 2019-11-08 | 2020-02-28 | 昆山宝创新能源科技有限公司 | Modified ternary cathode material and preparation method thereof |
| CN114249357A (en) * | 2021-12-27 | 2022-03-29 | 宁波容百新能源科技股份有限公司 | Surface modified high-nickel ternary cathode material and dry preparation process thereof |
| CN114249357B (en) * | 2021-12-27 | 2024-03-01 | 宁波容百新能源科技股份有限公司 | Surface modified high-nickel ternary positive electrode material and dry preparation process thereof |
| CN114538532A (en) * | 2022-01-11 | 2022-05-27 | 宜宾锂宝新材料有限公司 | Preparation method of high-nickel ternary cathode material and prepared high-nickel ternary cathode material |
| CN114538532B (en) * | 2022-01-11 | 2024-03-22 | 宜宾锂宝新材料有限公司 | Preparation method of high-nickel ternary cathode material and prepared high-nickel ternary cathode material |
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Application publication date: 20180828 |