CN108470894A - A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of ZnO claddings - Google Patents
A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of ZnO claddings Download PDFInfo
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- CN108470894A CN108470894A CN201810232673.8A CN201810232673A CN108470894A CN 108470894 A CN108470894 A CN 108470894A CN 201810232673 A CN201810232673 A CN 201810232673A CN 108470894 A CN108470894 A CN 108470894A
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- H01M4/00—Electrodes
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- 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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- 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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- 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 provides a kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings, including nickel cobalt aluminic acid lithium material and it is coated on the ZnO on the nickel cobalt aluminic acid lithium material surface, shown in the chemical formula such as formula (I) of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings：(LiaNi1‑x‑yCoxZny)1‑bZnbO2, 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‑yCoxZny(OH)2+ySintering；Then lithium source is added in sintering gains to be sintered；Finally addition covering material ZnO is sintered, and obtains target product.The nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings of preparation method synthesis of the present invention has excellent cycle performance.
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 of ZnO claddings
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 battery of the ZnO that cycle performance is excellent claddings just
Pole 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 of ZnO claddings
Cell positive material, including nickel cobalt aluminic acid lithium material and the ZnO, the ZnO that are coated on the nickel cobalt aluminic acid lithium material surface
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-yCoxZny)1-bZnbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜.
Preferably, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.05,0 b≤0.01 ＜.
Preferably, x=0.15, y=0.035, a=1.035, b=0.0029.
Preferably, x=0.15, y=0.035, a=1.035, b=0.0007.
Compared with prior art, the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings provided by the invention, cladding
Layer is not involved in electrochemical reaction, effectively raises the structural stability of nickel cobalt aluminium ternary anode material for lithium-ion batteries, improves
The chemical property of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the nickel cobalt aluminium ternary lithium ion battery coated by ZnO
Positive electrode has higher capacity retention ratio and more stable cycle performance.
In order to solve the above technical problems, the present invention also provides above-mentioned ZnO cladding nickel cobalt aluminium ternary lithium ion battery just
The preparation method of pole material, includes the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxZny(OH)2+ySintering；Sintering time
6-20 hours, 200-1000 DEG C of sintering temperature；
Step (2) is sintered for second：Lithium source is added in the step (1) sintering gains, mixed grinding, grinding is uniformly
Afterwards, it is sintered in air or oxygen atmosphere, sintering time 8-24 hours, 500-1000 DEG C of sintering temperature, after the completion of sintering,
It is down to room temperature with 0.01-2.5 DEG C/min rate of temperature fall；
Step (3), third time are sintered：Covering material ZnO is added in the step (2) sintering gains, is sintered, burns
It ties time 1-12 hour, 500-1000 DEG C of sintering temperature, obtains the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings
(LiaNi1-x-yCoxZny)1-bZnbO2, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 b≤0.02 ＜.
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), the addition of the lithium source be Li with：(Ni in ternary anode material precursor
+ Co+Al) molar ratio is 1~1.1:1.
Preferably, in the step (2), rate of temperature fall is 0.02-1 DEG C/min
Compared with prior art, the system of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings provided by the invention
The clad of Preparation Method, the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings of preparation is not involved in electrochemical reaction, has
The structural stability for improving nickel cobalt aluminium ternary anode material for lithium-ion batteries of effect, improves nickel cobalt aluminium ternary lithium ion battery
The chemical property of positive electrode, the nickel cobalt aluminium ternary anode material for lithium-ion batteries by ZnO claddings have higher capacity
Conservation rate 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 or pass through above-mentioned side that above-mentioned ZnO is coated
The nickel cobalt aluminium ternary anode material for lithium-ion batteries for the ZnO claddings that method is prepared.
Compared with prior art, lithium ion battery provided by the invention, the nickel that anode is coated using ZnO provided by the invention
The nickel cobalt aluminium ternary for the ZnO claddings that cobalt aluminium ternary anode material for lithium-ion batteries or the method provided through the invention are prepared
Anode material for lithium-ion batteries, lithium ion battery provided by the invention have good cycle, and service life is long, capacity retention ratio
Height, tap density are 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 nickel cobalt aluminium ternary lithium ions of above-mentioned ZnO claddings
Cell positive material or the nickel cobalt aluminium ternary anode material for lithium-ion batteries for the ZnO claddings being prepared by above-mentioned method exist
Prepare the application in lithium ion battery, electronic 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 or logical of ZnO claddings provided by the invention
The nickel cobalt aluminium ternary anode material for lithium-ion batteries that the method for crossing the present invention is prepared is stored up for lithium ion battery, electronic product
Can, industrial electric power storage energy storage, in electric vehicle and electric bicycle power supply, preparation with lithium ion battery, electronic product energy storage, work
The relevant products such as industry electric power storage energy storage, electric vehicle and electric bicycle power supply have service life long, and cruise duration is long, charging
The advantages that time is short, and weight body is light, power is sufficient.
Description of the drawings
Fig. 1 is that the nickel cobalt aluminium tertiary cathode material using ZnO claddings prepared by the embodiment of the present invention 1 is prepared with comparative example 1
Uncoated nickel cobalt aluminium tertiary cathode material cycle performance test comparison figure；
Fig. 2 is that the nickel cobalt aluminium tertiary cathode material using ZnO claddings prepared by the embodiment of the present invention 2 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 ZnO claddings of the embodiment of the present invention：
(LiaNi1-x-yCoxZny)1-bZnbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜.
The preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings of the embodiment of the present invention, including with
Lower step：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxZny(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 sintered
After the completion of sintering, room temperature is down to 0.01-2.5 DEG C/min rate of temperature fall for time 8-24 hour, 500-1000 DEG C of sintering temperature；
Step (3), third time are sintered：Covering material is added in the step (2) sintering gains, in covering material ZnO
Zn is b with (Ni+Co+Al) molar ratio in ternary anode material precursor:(1-b), is sintered, sintering time 1-12 hours,
500-1000 DEG C of sintering temperature, the nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li coatedaNi1-x-yCoxZny)1- bMbO2, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 b≤0.02 ＜.
Ternary anode material precursor Ni1-x-yCoxZny(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 is selected from the telluride of the oxide of metal Zn, the fluoride of metal Zn, the sulfide of metal Zn, metal Zn
The selenides of object, metal Zn, the antimonide of metal Zn, the phosphide of metal Zn or one kind in the composite oxides of metal Zn or
It is a variety of.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
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, 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 2
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, 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：
Comparative example 1
Comparative example 1 provides uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries, and chemical formula is
Li1.035Ni0.815Co0.15Zn0.035O2, the uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries of comparative example 1
Li1.035Ni0.815Co0.15Zn0.035O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxZny(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 Li1.035Ni0.815Co0.15Zn0.035O2。
Comparative example 2
Comparative example 2 provides uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries, and chemical formula is
Li1.035Ni0.815Co0.15Zn0.035O2, the uncoated nickel cobalt aluminium ternary anode material for lithium-ion batteries of comparative example 2
Li1.035Ni0.815Co0.15Zn0.035O2Preparation method, include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni0.815Co0.15Zn0.035(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 Li1.035Ni0.815Co0.15Zn0.035O2。
Table 1：Examples 1 to 2,1~2 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 2, 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%.
The battery performance test result of table 2, Examples 1 to 2 and comparative example 1~2
| Embodiment/comparative example | Capacity retention ratio (%, 1C) after recycling 100 times |
| Embodiment 1 | 87.30 |
| Embodiment 2 | 85.90 |
| Comparative example 1 | 79.70 |
| Comparative example 2 | 76.20 |
It please refers to Fig.1 and Fig. 2, in conjunction with 1 data of table, it can be seen that：
Embodiment 1 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 2 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.
Examples 1 to 2 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.
In conclusion the nickel cobalt aluminium tertiary cathode material of ZnO claddings of the present invention has at least the following advantages：Through the invention
The nickel cobalt aluminium tertiary cathode material of cladding for preparing of method, the charge-discharge performance at 3.0V~4.3V obtained significantly
Raising：Comparative example 1~2 and comparative example 1~2 it can be found that after 100 cycles, prepared by the method for the present invention
The capacity retention ratio of the nickel cobalt aluminium tertiary cathode material of ZnO claddings is higher than uncoated nickel cobalt aluminium tertiary cathode material；This explanation
Compared with uncoated nickel cobalt aluminium tertiary cathode material, the nickel cobalt aluminium tertiary cathode material of ZnO claddings of the present invention is with more stable
Cycle performance.
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 ZnO are easy to react in bulk material surface
The higher position of activity preferentially generates, and the higher site of bulk material surface reactivity can be effectively eliminated, to main body material
Material plays the role of rock-steady structure, and the reactivity in battery system to effectively reduce positive electrode avoids nickel cobalt
With organic bath side reaction occurs for aluminium tertiary cathode material, reduces impedance of the battery in charge and discharge process, to effectively carry
The cyclical stability of high nickel cobalt aluminium tertiary cathode material.The preparation method of the present invention is simple for process, and process control is easy to industrialize
Volume 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 (11)
1. a kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings, which is characterized in that including nickel cobalt aluminic acid lithium material
And it is coated on the ZnO on the nickel cobalt aluminic acid lithium material surface, the nickel cobalt aluminium ternary lithium ion cell positive material of the ZnO claddings
Shown in the chemical formula of material such as formula (I)：
(LiaNi1-x-yCoxZny)1-bZnbO2 (I)
A, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.02 ＜.
2. the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings 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 of ZnO claddings as described in claim 1, which is characterized in that x=
0.15, y=0.035, a=1.035, b=0.0029.
4. the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings as described in claim 1, which is characterized in that x=
0.15, y=0.035, a=1.035, b=0.0007.
5. a kind of system of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings described in Claims 1 to 4 any one
Preparation Method, which is characterized in that include the following steps：
Step (1), first sintering：By ternary anode material precursor Ni1-x-yCoxZny(OH)2+ySintering；Sintering time 6-20
Hour, 200-1000 DEG C of sintering temperature；
Step (2) is sintered for second：By the step (1) sintering gains be added lithium source, mixed grinding, grinding uniformly after,
It is sintered in air or oxygen atmosphere, sintering time 8-24 hours, 500-1000 DEG C of sintering temperature, after the completion of sintering, with
0.01-2.5 DEG C/min rate of temperature fall is down to room temperature；
Step (3), third time are sintered：Covering material ZnO is added in the step (2) sintering gains, is sintered, when sintering
Between 1-12 hours, 500-1000 DEG C of sintering temperature, the nickel cobalt aluminium ternary anode material for lithium-ion batteries (Li coatedaNi1-x- yCoxZny)1-bZnbO2, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 b≤0.02 ＜.
6. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings as claimed in claim 5, 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.
7. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings as claimed in claim 5, 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.
8. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings as claimed in claim 5, feature
It is, in the step (2), the addition of the lithium source is Li and (Ni+Co+Al) molar ratio in ternary anode material precursor
It is 1~1.1:1.
9. the preparation method of the nickel cobalt aluminium ternary anode material for lithium-ion batteries of ZnO claddings as claimed in claim 5, feature
It is, in the step (2), rate of temperature fall is 0.02-1 DEG C/min.
10. a kind of lithium ion battery, it is characterised in that：Including anode, cathode, electrolyte and diaphragm, which is characterized in that it is described just
Pole includes the nickel cobalt aluminium ternary anode material for lithium-ion batteries of the ZnO claddings described in Claims 1-4 any one or passes through power
The nickel cobalt aluminium ternary anode material for lithium-ion batteries that the ZnO that profit requires the method described in 5 to 9 any one to be prepared is coated.
11. described in a kind of Claims 1-4 any one ZnO cladding nickel cobalt aluminium ternary anode material for lithium-ion batteries or
Pass through the nickel cobalt aluminium ternary lithium ion cell positive for the ZnO claddings that the method described in claim 5 to 9 any one is prepared
Material 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 |
|---|---|---|---|
| CN201810232673.8A CN108470894A (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 ZnO claddings |
| 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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| 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 |
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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 |
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