CN108417807A - A kind of nickel cobalt aluminium tertiary cathode material, the Preparation method and use of Mg doping - Google Patents

A kind of nickel cobalt aluminium tertiary cathode material, the Preparation method and use of Mg doping Download PDF

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CN108417807A
CN108417807A CN201810232790.4A CN201810232790A CN108417807A CN 108417807 A CN108417807 A CN 108417807A CN 201810232790 A CN201810232790 A CN 201810232790A CN 108417807 A CN108417807 A CN 108417807A
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nickel cobalt
cathode material
doping
cobalt aluminium
tertiary cathode
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任东
沈赟
于英超
方艳
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Zhejiang Lin Naixin Energy Co Ltd
Lionano Inc China
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Zhejiang Lin Naixin Energy Co Ltd
Lionano Inc China
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Priority to CN201810232790.4A priority Critical patent/CN108417807A/en
Publication of CN108417807A publication Critical patent/CN108417807A/en
Priority to PCT/CN2019/070656 priority patent/WO2019179219A1/en
Priority to JP2020516709A priority patent/JP7292265B2/en
Priority to EP19770882.9A priority patent/EP3667780A4/en
Priority to CN201980000087.3A priority patent/CN110896674A/en
Priority to US16/840,472 priority patent/US20200274160A1/en
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    • H—ELECTRICITY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • H—ELECTRICITY
    • 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
    • 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
    • H01M4/52—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention provides a kind of nickel cobalt aluminium tertiary cathode material, the Preparation method and use of Mg doping, and the chemical formula of the material is (LiaNi1‑x‑yCoxAly)1‑bMgbO2, x>0, y>0,1 x y>0,1≤a≤1.1,0 b≤0.01 ＜.The preparation method of the material is first by ternary anode material precursor Ni1‑x‑yCoxAly(OH)2+ySintering；Then by lithium source is added in sintering gains, dopant material is sintered；Third time sintering is finally carried out, target product is obtained.The nickel cobalt aluminium tertiary cathode material of the Mg doping of preparation method synthesis of the present invention has excellent cycle performance.The preparation method of the present invention includes sintering step three times, and simple for process, process control is easy to industrial volume production.

Description

A kind of nickel cobalt aluminium tertiary cathode material, the Preparation method and use of Mg doping
Technical field
The present invention relates to electrode material fields, and in particular to a kind of nickel cobalt aluminium tertiary cathode material of Mg doping, preparation side Method and purposes.
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.
The free lithium on nickel cobalt aluminium tertiary cathode material surface, i.e. lithia, lithium hydroxide and lithium carbonate are alkaline matter, In positive electrode configuration process, the attack of the alkaline matter on nickel cobalt aluminium tertiary cathode material surface to binder in positive glue, Cause binder to form double bond, generate gluing, cause slurry jelly, reduces Painting effect, influence battery core performance.
Therefore, nickel cobalt aluminium ternary material cyclical stability how must be improved, it is residual to reduce nickel cobalt aluminium tertiary cathode material surface Alkali number becomes one of urgent problem to be solved in the industry.
Invention content
We are bright to be designed to provide nickel cobalt aluminium ternary anode material for lithium-ion batteries and its preparation of a kind of Mg doping Method improves nickel cobalt aluminium ternary material cyclical stability, reduces nickel cobalt aluminium tertiary cathode material surface residual alkali amount, and provide use The purposes of the lithium ion battery of the positive electrode and the positive electrode.
In order to solve the above-mentioned technical problem, the technical scheme is that：A kind of nickel cobalt aluminium tertiary cathode material of Mg doping Material, shown in the chemical formula such as formula (I) of the nickel cobalt aluminium tertiary cathode material of the Mg doping：
(LiaNi1-x-yCoxAly)1-bMgbO2 (I)
Wherein a, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,
0 b≤0.01 ＜.
Preferably, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.05,0 b≤0.005 ＜.
Preferably, x=0.15, y=0.035, a=1.035, b=0.0017.
Preferably, x=0.15, y=0.035, a=1.035, b=0.0025.
Compared with prior art, the nickel cobalt aluminium tertiary cathode material of Mg doping provided by the invention, effectively raises nickel The structural stability of cobalt aluminium tertiary cathode material reduces nickel cobalt aluminium ternary material and strong side reaction occurs with organic bath, Impedance of the battery in charge and discharge process is reduced, the chemical property of nickel cobalt aluminium tertiary cathode material is improved, is adulterated by Mg Nickel cobalt aluminium tertiary cathode material have higher capacity retention ratio and more stable cycle performance.
The nickel cobalt aluminium tertiary cathode material of Mg doping provided by the invention, using metal Mg to nickel cobalt aluminium tertiary cathode material It is doped, reduces the active lithium content on nickel cobalt aluminium tertiary cathode material surface, to reduce nickel cobalt aluminium tertiary cathode material Expect Surface L iOH, Li2CO3Content effectively reduces nickel cobalt aluminium tertiary cathode material surface residual alkali amount, so as to reduce in positive material Expect in configuration process, the attack of the alkaline matter on nickel cobalt aluminium tertiary cathode material surface to binder in positive glue avoids gluing Dosage form is tied into double bond, generates gluing, avoids causing slurry jelly, improves Painting effect, improve battery core performance.
Doping in order to solve the above technical problems, the present invention also provides a kind of Mg doping nickel cobalt aluminium tertiary cathode material Preparation method, 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, dopant material mixed grinding is added in the step (1) sintering gains, It after grinding uniformly, is sintered, room temperature is cooled to after the completion of sintering；
Step (3), third time are sintered：The step (2) sintering gains are sintered, the nickel cobalt aluminium of Mg doping is obtained Tertiary cathode material (LiaNi1-x-yCoxAly)1-bMgbO2, wherein 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤ 1.05,0 b≤0.005 ＜.
Preferably, in the step (1), sintering time 6-20 hours, 200-1000 DEG C of sintering temperature.
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 8-24 hours, 500-1000 DEG C of sintering temperature.
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 carries out in air or oxygen atmosphere in the step (2).
Preferably, step (2) dopant material is selected from the oxide of metal Mg, the fluoride of metal Mg, metal Mg Sulfide, the tellurides of metal Mg, metal Mg selenides, the antimonide of metal Mg, the phosphide or metal Mg of metal Mg Composite oxides in it is one or more.
Preferably, the step (3) sintering time 1-12 hours, 500-1000 DEG C of sintering temperature.
Compared with prior art, the nickel cobalt aluminium tertiary cathode material preparation method of Mg provided by the invention doping, by Mg metal ions are adulterated in the ternary material lattice of nickel cobalt aluminium tertiary cathode material, can effectively raise nickel cobalt aluminium ternary just The structural stability of pole material reduces nickel cobalt aluminium ternary material and strong side reaction occurs with organic bath, reduces battery and exist Impedance in charge and discharge process, to improve the chemical property of nickel cobalt aluminium tertiary cathode material, by the nickel cobalt of Mg doping Aluminium tertiary cathode material has higher capacity retention ratio and more stable cycle performance.By in nickel cobalt aluminium tertiary cathode material Ternary material lattice in adulterate Mg metal ions, can also reduce effectively reduces nickel cobalt aluminium tertiary cathode material surface residual alkali Amount, so as to reduce in positive electrode configuration process, the alkaline matter on nickel cobalt aluminium tertiary cathode material surface is to positive glue The attack of middle binder avoids binder from forming double bond, generates gluing, avoids causing slurry jelly, improves Painting effect, improves Battery core 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 are prepared using the above-mentioned Mg nickel cobalt aluminium tertiary cathode material adulterated or by above-mentioned method The nickel cobalt aluminium tertiary cathode material of the Mg doping of doping.
Compared with prior art, lithium ion battery provided by the invention, the nickel that anode is adulterated using Mg provided by the invention The nickel cobalt aluminium tertiary cathode material for the Mg doping that cobalt aluminium tertiary cathode material or the method provided through the invention are prepared, this The lithium ion battery that invention provides has good cycle, and service life is long, and capacity retention ratio is high, and battery core performance is good, small, The advantages that light-weight.
In order to solve the above technical problems, the present invention also provides a kind of nickel cobalt aluminium tertiary cathode materials of above-mentioned Mg doping Or the nickel cobalt aluminium tertiary cathode material for the Mg doping being prepared by above-mentioned method is preparing lithium ion battery, electronic product Application in energy storage, industrial electric power storage energy storage, electric vehicle and electric bicycle power supply.
Compared with prior art, the nickel cobalt aluminium tertiary cathode material of Mg provided by the invention doping or side through the invention The nickel cobalt aluminium tertiary cathode material for the Mg doping that method is prepared is for lithium ion battery, electronic product energy storage, industrial electric power storage storage It can, in electric vehicle and electric bicycle power supply, prepare and lithium ion battery, electronic product energy storage, industry electric power storage energy storage, electronic The relevant product such as automobile and electric bicycle power supply has service life long, and cruise duration is long, and the charging time is short, light-weight, The advantages that power is sufficient.
Description of the drawings
Fig. 1 is the nickel cobalt aluminium tertiary cathode material of Mg doping prepared by the embodiment of the present invention 1 (Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2The undoped nickel cobalt aluminium tertiary cathode material prepared with comparative example 1 Cycle performance test and comparison figure；
Fig. 2 is the nickel cobalt aluminium tertiary cathode material of Mg doping prepared by the embodiment of the present invention 2 (Li1.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2The undoped nickel cobalt aluminium tertiary cathode material prepared with comparative example 2 Cycle performance test and 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 chemical formula such as formula (I) of the nickel cobalt aluminium tertiary cathode material of the Mg doping of the embodiment of the present invention：
(LiaNi1-x-yCoxAly)1-bMgbO2 (I)
Wherein a, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.01 ＜.
The preparation method of the nickel cobalt aluminium tertiary cathode material of the Mg doping of the embodiment of the present invention, includes the following steps：
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：Lithium source, dopant material is added according to certain ratio in the step (1) sintering gains Example mixed grinding is sintered, after the completion of sintering, with 0.01-2.5 DEG C/min after grinding uniformly in air or oxygen atmosphere Rate of temperature fall is down to room temperature；
Step (3), third time are sintered：The step (2) sintering gains are sintered, sintering time 1-12 hours, 500-1000 DEG C of sintering temperature obtains the nickel cobalt aluminium tertiary cathode material (Li of Mg dopingaNi1-x-yCoxAly)1-bMgbO2, wherein 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 b≤0.01 ＜.
The dosage of lithium source is：Li is a, the chemical combination of metal Mg with (Ni+Co+Al) molar ratio in ternary anode material precursor The addition of object is metal Mg 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, prior art preparation can also be used.
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 be lithium source in Li in ternary anode material precursor (Ni+Co+Al) molar ratio is 1~1.1:1.
Dopant material is selected from the telluride of the oxide of metal Mg, the fluoride of metal Mg, the sulfide of metal Mg, metal Mg The selenides of object, metal Mg, the antimonide of metal Mg, the phosphide of metal Mg or one kind in the composite oxides of metal Mg or It is a variety of.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
Embodiment 1 provides the nickel cobalt aluminium tertiary cathode material (Li of Mg doping1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2, x=0.15, y=0.035, a=1.035, b=0.0017.The present embodiment provides the nickel cobalt aluminiums three of Mg doping First positive electrode (Li1.035Ni0.815Co0.15Al0.035)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 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) it is sintered gains and dopant material MgO mixed grindings, the dosage of a hydronium(ion) lithia is the Li in a hydronium(ion) lithia It is 1.035 with (Ni+Co+Al) molar ratio in ternary anode material precursor：1, MgO addition is Mg and ternary in MgO (Ni+Co+Al) molar ratio is 0.0017 in positive electrode material precursor：0.9983, after grinding uniformly, it is sintered, 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：By the step (2) sintering obtain product be warming up to 650 DEG C be sintered 3.5 hours, drop To room temperature to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2, ICP elemental analyses, which are tested, to be shown The molar percentage of each metal of Ni, Co, Al, Mg is as follows：
Embodiment 2
Embodiment 2 provides the nickel cobalt aluminium tertiary cathode material (Li of Mg doping1.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2, x=0.15, y=0.035, a=1.035, b=0.0025.The nickel cobalt aluminium of Mg doping provided in this embodiment Tertiary cathode material (Li1.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2Preparation 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) it is sintered gains and dopant material MgO mixed grindings, the dosage of a hydronium(ion) lithia is the Li in a hydronium(ion) lithia It is 1.035 with (Ni+Co+Al) molar ratio in ternary anode material precursor：1, MgO addition is Mg and ternary in MgO (Ni+Co+Al) molar ratio is 0.0025 in positive electrode material precursor:0.9975, after grinding uniformly, it is sintered, is warming up to 775 DEG C sintering 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：By the step (2) sintering obtain product be warming up to 615 DEG C be sintered 5 hours, be down to Room temperature is to get to target product (Li1.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2, ICP elemental analyses test show Ni, The molar percentage of each metal of Co, Al, Mg is as follows：
Comparative example 1
Comparative example 1 provides undoped nickel cobalt aluminium tertiary cathode material, and chemical formula is Li1.035Ni0.815Co0.15Al0.035O2, 1 undoped nickel cobalt aluminium tertiary cathode material of comparative example 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) dosage of sintering gains mixing, a hydronium(ion) lithia is that Li rubs with (Ni+Co+Al) in ternary anode material precursor Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715 DEG C of reactions 16.5 hours, then It is down to room temperature with 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 undoped nickel cobalt aluminium tertiary cathode material, and chemical formula is Li1.035Ni0.815Co0.15Al0.035O2, 2 undoped nickel cobalt aluminium tertiary cathode material of comparative example 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 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) dosage of sintering gains mixing, a hydronium(ion) lithia is that Li rubs with (Ni+Co+Al) in ternary anode material precursor Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, and 775 DEG C of reactions 8 hours are warming up to, then with The rate of temperature fall of 0.3 DEG C/min is down to room temperature；
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 2,1~2 each step reaction condition of comparative example, material rate and product.
CR2032 model button cells assemble：
The nickel cobalt aluminium tertiary cathode material of the Mg doping prepared with Examples 1 to 2, comparative example 1~2 prepare undoped Nickel cobalt aluminium tertiary cathode material is the active matter of anode, and cathode uses metal lithium sheet, diaphragm to use 2500 diaphragms of Celgard, electricity Solution liquid is Suzhou Fo Sai new materials Co., Ltd fosai LB-002 electrolyte, and CR2032 model knobs are assembled by art methods Battery is detained, assembling sequence is：Positive cover keeps flat, places spring leaf, place stainless steel substrates, place positive plate, note electrolyte, place Diaphragm places lithium piece, covers cathode cap, and sealing 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
Instrument title:Icp ms
Instrument model：Prodigy DC Arc
Instrument 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, 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；
LiOH contents (wt%) calculation formula：ω1=(2V1-V2)*0.05*2.395*W2/W1/50；
Li2CO3Content (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 2 and comparative example 1~2
Embodiment/comparative example Capacity retention ratio (%, 1C) after recycling 100 times Surface residual alkali amount (wt%)
Embodiment 1 90.7 0.56
Embodiment 2 88.9 0.59
Comparative example 1 79.7 0.83
Comparative example 2 76.2 0.88
It please refers to Fig.1 and Fig. 2, in conjunction with 2 data of table, it can be seen that：
Doping please refer to Fig.1 and Fig. 2, in conjunction with 2 data of table, it can be seen that：
Embodiment 1 is compared with comparison 1, Mg doping types nickel cobalt aluminium tertiary cathode material in embodiment 1 (Li1.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2Capacity retention ratio 90.7% after recycling 100 times, total residual alkali amount weight Percentage is 0.56%；1 undoped nickel cobalt aluminium tertiary cathode material of comparative example recycle 100 times after capacity retention ratio 79.7%, surface residual alkali amount weight percent is 0.83%, compared with 1 undoped nickel cobalt aluminium tertiary cathode material of comparative example, Mg doping types nickel cobalt aluminium tertiary cathode material (Li in embodiment 11.035Ni0.815Co0.15Al0.035)0.9983Mg0.0017O2With more steady Fixed cycle performance, and surface residual alkali amount effectively reduces.
Embodiment 2 is compared with comparison 2, Mg doping types nickel cobalt aluminium tertiary cathode material in embodiment 2 (Li1.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2Capacity retention ratio 88.9% after recycling 100 times, total residual alkali amount weight Percentage is 0.59%；2 undoped nickel cobalt aluminium tertiary cathode material of comparative example recycle 100 times after capacity retention ratio 76.2%, surface residual alkali amount weight percent is 0.88%, compared with 2 undoped nickel cobalt aluminium tertiary cathode material of comparative example, Mg doping types nickel cobalt aluminium tertiary cathode material (Li in embodiment 21.035Ni0.815Co0.15Al0.035)0.9975Mg0.0025O2With more steady Fixed cycle performance, and surface residual alkali amount effectively reduces.
Examples 1 to 2 is effectively raised by adulterating Mg in the ternary material lattice of nickel cobalt aluminium tertiary cathode material It is anti-to reduce the nickel cobalt aluminium ternary material pair strong with organic bath generation for the structural stability of nickel cobalt aluminium tertiary cathode material It answers, reduces impedance of the battery in charge and discharge process, to improve the chemical property of nickel cobalt aluminium tertiary cathode material, pass through Doping type nickel cobalt aluminium tertiary cathode material has higher capacity retention ratio and more stable cycle performance.
CO in the active lithium and air on nickel cobalt aluminium tertiary cathode material surface2、H2O reacts, and generates LiOH, Li2CO3, adopt Nickel cobalt aluminium tertiary cathode material is doped with Mg, reduces the active lithium content on nickel cobalt aluminium tertiary cathode material surface, from And reduce nickel cobalt aluminium tertiary cathode material Surface L iOH, Li2CO3It is residual effectively to reduce nickel cobalt aluminium tertiary cathode material surface for content Alkali number, so as to reduce in positive electrode configuration process, the alkaline matter on nickel cobalt aluminium tertiary cathode material surface is to positive glue The attack of binder in liquid avoids binder from forming double bond, generates gluing, avoids causing slurry jelly, improves Painting effect, carry High battery core performance.
In conclusion the nickel cobalt aluminium tertiary cathode material of Mg doping provided by the invention has at least the following advantages：Pass through The nickel cobalt aluminium tertiary cathode material of Mg doping prepared by the method for the present invention, the charge-discharge performance at 3V~4.3V obtain Significant raising, comparative example 1~2 and comparative example 1~2 it can be found that after 100 cycles, the method for the present invention The capacity retention ratio of the nickel cobalt aluminium tertiary cathode material of the Mg doping of preparation is higher than undoped nickel cobalt aluminium tertiary cathode material；This Illustrate compared with undoped nickel cobalt aluminium tertiary cathode material, the nickel cobalt aluminium tertiary cathode material of Mg doping of the present invention has more surely Fixed cycle performance.The nickel cobalt aluminium tertiary cathode material of Mg doping provided by the invention, using Mg to nickel cobalt aluminium tertiary cathode material Material is doped, and reduces the active lithium content on nickel cobalt aluminium tertiary cathode material surface, to reduce nickel cobalt aluminium tertiary cathode Material surface LiOH, Li2CO3Content effectively reduces nickel cobalt aluminium tertiary cathode material surface residual alkali amount, so as to reduce in anode In material configuration process, the attack of the alkaline matter on nickel cobalt aluminium tertiary cathode material surface to binder in positive glue avoids Binder forms double bond, generates gluing, avoids causing slurry jelly, improves Painting effect, improves battery core performance.
The nickel cobalt aluminium tertiary cathode material preparation method of doping provided by the invention, by nickel cobalt aluminium tertiary cathode material Ternary material lattice in adulterate Mg metal ions, can effectively improve the structural stability of nickel cobalt aluminium tertiary cathode material, It reduces nickel cobalt aluminium ternary material and strong side reaction occurs with organic bath, reduce impedance of the battery in charge and discharge process, To improve the chemical property of nickel cobalt aluminium tertiary cathode material, have by the Mg nickel cobalt aluminium tertiary cathode materials adulterated Higher capacity retention ratio and more stable cycle performance.By being mixed in the ternary material lattice of nickel cobalt aluminium tertiary cathode material Miscellaneous Mg metal ions, can also reduce effectively reduces nickel cobalt aluminium tertiary cathode material surface residual alkali amount, so as to reduce in anode In material configuration process, the attack of the alkaline matter on nickel cobalt aluminium tertiary cathode material surface to binder in positive glue avoids Binder forms double bond, generates gluing, avoids causing slurry jelly, improves Painting effect, improves battery core performance.The system of the present invention Preparation Method is simple for process, and process control is easy to industrial 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 (17)

1. a kind of nickel cobalt aluminium tertiary cathode material of Mg doping, which is characterized in that the nickel cobalt aluminium tertiary cathode material of the doping Chemical formula such as formula (I) shown in：
(LiaNi1-x-yCoxAly)1-bMgbO2(I)；
Wherein a, b, x, y are molar fraction, x>0, y>0,1-x-y>0,1≤a≤1.1,0 b≤0.01 ＜.
2. the nickel cobalt aluminium tertiary cathode material of Mg doping 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≤0.005 ＜.
3. the nickel cobalt aluminium tertiary cathode material of Mg doping as described in claim 1, which is characterized in that x=0.15, y= 0.035, a=1.035, b=0.0017.
4. the nickel cobalt aluminium tertiary cathode material of Mg doping as described in claim 1, which is characterized in that x=0.15, y= 0.035, a=1.035, b=0.0025.
5. a kind of preparation method of the nickel cobalt aluminium tertiary cathode material of the Mg doping described in Claims 1-4 any one, special Sign is, 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, dopant material mixed grinding, grinding is added in the step (1) sintering gains It after uniformly, is sintered, room temperature is cooled to after the completion of sintering；
Step (3), third time are sintered：The step (2) sintering gains are sintered, the nickel cobalt aluminium ternary of Mg doping is obtained Positive electrode (LiaNi1-x-yCoxAly)1-bMgbO2, 0.03≤x≤0.15,0.01≤y≤0.05,1≤a≤1.1,0 ＜ b≤ 0.01。
6. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that the step Suddenly in (1), sintering time 6-20 hours, 200-1000 DEG C of sintering temperature.
7. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that the step Suddenly in (2), the lithium source is one in lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, lithium nitrate, lithium chloride and lithium fluoride Kind.
8. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that the step Suddenly in (2), the lithium source be a hydronium(ion) lithia, a hydronium(ion) lithia is dried to after losing the crystallization water completely with it is described Step (1) is sintered gains mixing.
9. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that the step Suddenly in (2), sintering time 8-24 hours, 500-1000 DEG C of sintering temperature.
10. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described In step (2), rate of temperature fall is 0.01-2.5 DEG C/min.
11. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described In step (2), rate of temperature fall is 0.02-1 DEG C/min.
12. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described In step (2), the addition of lithium source be in lithium source Li and (Ni+Co+Al) molar ratio in ternary anode material precursor be 1~ 1.1:1。
13. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described Sintering carries out in air or oxygen atmosphere in step (2).
14. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described Step (2) dopant material is selected from the telluride of the oxide of metal Mg, the fluoride of metal Mg, the sulfide of metal Mg, metal Mg The selenides of object, metal Mg, the antimonide of metal Mg, the phosphide of metal Mg or one kind in the composite oxides of metal Mg or It is a variety of.
15. the preparation method of the nickel cobalt aluminium tertiary cathode material of Mg doping as claimed in claim 5, which is characterized in that described Step (3) sintering time 1-12 hours, 500-1000 DEG C of sintering temperature.
16. 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 described in 1 to 4 any one Mg doping nickel cobalt aluminium tertiary cathode material or pass through claim 5 to 15 any one institute The nickel cobalt aluminium tertiary cathode material for the Mg doping that the method stated is prepared.
17. a kind of nickel cobalt aluminium tertiary cathode material of the Mg doping described in Claims 1-4 any one passes through claim The nickel cobalt aluminium tertiary cathode material of Mg that method described in 5 to 15 any one is prepared doping prepare lithium ion battery, Application in electronic product energy storage, industrial electric power storage energy storage, electric vehicle and electric bicycle power supply.
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CN201810232790.4A CN108417807A (en) 2018-03-21 2018-03-21 A kind of nickel cobalt aluminium tertiary cathode material, the Preparation method and use of Mg doping
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
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
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
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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449438A (en) * 2018-11-30 2019-03-08 林奈（中国）新能源有限公司 Quaternary positive electrode, preparation method and purposes
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
CN113241433A (en) * 2021-05-17 2021-08-10 浙江帕瓦新能源股份有限公司 Double-doped coated composite modified ternary cathode material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109449438A (en) * 2018-11-30 2019-03-08 林奈（中国）新能源有限公司 Quaternary positive electrode, preparation method and purposes
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
CN113241433A (en) * 2021-05-17 2021-08-10 浙江帕瓦新能源股份有限公司 Double-doped coated composite modified ternary cathode material and preparation method thereof
CN113241433B (en) * 2021-05-17 2022-06-07 浙江帕瓦新能源股份有限公司 Double-doped coated composite modified ternary cathode material and preparation method thereof

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