CN106129348B - A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof - Google Patents

A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof Download PDF

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CN106129348B
CN106129348B CN201610471240.9A CN201610471240A CN106129348B CN 106129348 B CN106129348 B CN 106129348B CN 201610471240 A CN201610471240 A CN 201610471240A CN 106129348 B CN106129348 B CN 106129348B
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naalo
stirring
ion doped
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常丽娟
王体龙
贾元波
伍建军
高娟
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SICHUAN NONFERROUS METALLURGY INSTITUTE Co Ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
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    • 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

Abstract

The present invention discloses a kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：(1) solution is prepared；(2) nickel ion doped is scattered in deionized water and forms suspension, add anion surfactant, 15~30min of ultrasonic disperse；(3) Al (NO are added into ultrasonic disperse solution3)3Solution, 15~30min of ultrasonic disperse, then NaAlO is added while stirring2Solution；(4) a concentration of 0.5mol/L citric acid solutions are added into mixed liquor obtained by step (3) while stirring；(5) aging is cleaned, drying；(6) high temperature pyrolysis.Rate of crystalline growth is consistent with nucleation rate in preparation process, is evenly coated；The material safety prepared is high, and at low cost, energy density under high voltages, charge/discharge capacity are obviously improved, and under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio is up to 86.3%.

Description

A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of Al2O3The nickel lithium manganate cathode material of coating modification and Preparation method.
Background technology
Depleted, environment the serious pollution of the fossil fuels such as global main energy sources coal, oil, natural gas is to the mankind's Existence constitutes great threat, and therefore, there is an urgent need to seek a kind of reproducible clean energy resource to carry out substitute fossil fuels, this just promotes People look for clean renewable new energy.With high working voltage, wide operating range, high-energy-density, service life length, zero The lithium rechargeable battery of the advantages that pollution has been to be concerned by more and more people, and is not only widely used in energy storage, communication and state Fields, the popularizations in new energy field such as anti-construction have been raised to national strategy height, from the point of view of long-range development trend, It is with wide application prospect.
It relatively lags behind in the development of the manufacturing field of lithium rechargeable battery, positive electrode, is also the heat studied at present Point and difficult point.The positive electrode of most study is lithium-transition metal oxide material at present, includes mainly LiCoO2、LiMn2O4、 LiNi0.5Mn1.5O4、Li[NixCoyMn1-x-y]O2、LiFePO4With LiMnPO4Deng.Wherein, with high voltage, high-energy density Nickel ion doped (LiNi0.5Mn1.5O4) concern of people in the industry is received, three-dimensional diffusion admittance is more advantageous to the biography of lithium ion Defeated, theoretical discharge specific capacity is up to 700Wh/Kg up to 147mAh/g, energy density, it is considered to be the following lithium ion battery hair Most one of the positive electrode of future in exhibition.
The nickel lithium manganate cathode material being commercialized at present is deposited charge and discharge surface electrolyte under high voltages and is easily decomposed, by material The problem of cycle caused by the oxygen defect of itself and high-temperature behavior are deteriorated.The following approach of generally use solves the above problems：(1) it opens Send out electrolyte system high voltage withstanding；(2) nickel ion doped surface is coated.Under higher charging/discharging voltage, nickel ion doped Cladding stable protective layer in surface can avoid or slow down being in direct contact for electrode and electrolyte, reduces decomposition and the Mn of electrolyte3+ The dissolving of element effectively improves the chemical stability of material, and the substance for being typically used as protective layer includes some metal oxides, phosphorus Hydrochlorate or metal etc..What Li Decheng etc. was proposed in Chinese invention patent CN201210556546.6 uses Al element dopings ZnO Film is modified nickel ion doped material surface；Wang Li etc. proposes to use in Chinese invention patent CN201510171987.8 CO2The method of gas precipitation meta-aluminic acid root is in nickel ion doped surface-coated aluminum oxide.Though above method can be in nickel ion doped material Surface Creation metal oxide clad, but that there are the rate of crystalline growths of coating is inconsistent with nucleation rate, causes to coat Composition granule is excessive and uneven, and clad is too fluffy, and in charge and discharge process, clad, which will appear, to be collapsed and dissociate；CO2 The use of gas needs the considerations of putting into more costs of material and experimental facilities and safety, is unfavorable for large-scale quotient Industry metaplasia is produced.
Invention content
For the above-mentioned problems in the prior art, the present invention provides a kind of Al2O3The nickel ion doped anode of coating modification Material and preparation method thereof can effectively solve the problems such as rate of crystalline growth is inconsistent with nucleation rate, and clad is uneven.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is：
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) preparation of solution：According to Al2O3Covering amount be nickel ion doped quality 1~5%, calculate mole of aluminium element Amount, then calculates Al (NO3)3、NaAlO2Mole and quality, weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of 0.1~0.3mol/L3)3The NaAlO of solution and 0.4~0.7mol/L2Solution；
(2) nickel ion doped ultrasonic disperse in deionized water is formed into suspension, anionic surface is added into suspension Activating agent continues 15~30min of ultrasonic disperse；Wherein nickel ion doped：Water=1g：30~60mL；Anion surfactant Addition is the 0.5~4% of nickel ion doped quality；
(3) Al (NO are added into step (2) ultrasonic disperse solution3)3Solution, and continue 15~30min of ultrasonic disperse, so NaAlO is added while stirring again afterwards2Solution；
(4) it is slowly added to a concentration of 0.5mol/L citric acid solutions into mixed liquor obtained by step (3) while stirring, and after 30~40min of continuous stirring, until the AlO in solution2 -Ion precipitates completely；
(5) gained mixture in step (4) being stood into 4~5h of aging, filtering removes filtrate, is then washed with deionized, It is placed in 90~100 DEG C of 1~2h of baking again, obtains the nickel ion doped material of aluminium hydroxide cladding；
(6) the nickel ion doped material that aluminium hydroxide coats is placed under the hot environment of argon gas protection and is pyrolyzed, obtain Al2O3Packet Cover modified nickel lithium manganate cathode material；Wherein pyrolysis temperature is 300~400 DEG C, and pyrolysis time is 1~2h.
Further, in step (2) anion surfactant be neopelex, sodium cetanesulfonate and At least one of lauryl sodium sulfate.
Further, the concrete operations of addition solution are in step (3)：Institute is added into step (2) ultrasonic disperse solution Al (the NO of preparation3)3Prepared NaAlO is then added in the 30% of liquor capacity, 15~30min of ultrasonic disperse while stirring2 The 30% of liquor capacity continues 1~2h of stirring, is further continued for that remaining Al (NO are added3)3The 50% of liquor capacity, ultrasonic disperse 15 Residue NaAlO is then added in~30min while stirring2The 50% of liquor capacity continues 1~2h of stirring, is eventually adding remaining Al (NO3)3Solution, 15~30min of ultrasonic disperse, then residue NaAlO is added while stirring2Solution continues 1~2h of stirring.
Further, NaAlO is added dropwise in step (3)2The speed of solution need to control as 15~20mL/min.
Further, the speed of citric acid solution is added dropwise in step (4) need to control as 10~15mL/min.
A kind of Al provided by the invention2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof has with following Beneficial effect：
(1) nickel ion doped forms the suspension of homogeneous after ultrasonic disperse, then is modified through anion surfactant, when adding Enter the Al (NO of certain concentration3)3After solution, continue ultrasonic disperse, the purpose is to make through the modified nickel of anion surfactant LiMn2O4 is to Al3+There is better adsorptivity, and adsorbs more uniform；As the NaAlO for continuing addition certain concentration2Solution makes Al3+With AlO2 -It reacts, Al (OH) is partially formed on nickel ion doped surface3Crystal seed, which continues to be nucleated and grow, and crystal The speed of growth is consistent with nucleation rate, the Al (NO of this and certain concentration3)3The NaAlO of solution and certain concentration2Solution Addition sequence, is added portionwise and suitable pH environment is all closely related.
(2) using successively addition Al (NO3)3、NaAlO2Method, and its rate of addition is limited, to controllable Al (OH)3The speed of growth of crystal seed makes material surface form the Al (OH) of even compact3Clad.
(3) citric acid solution is organic monoacid solution, provides H+, can be with excessive AlO2 -It reacts to form Al (OH)3 Precipitation, and the addition of citric acid is to prepared Al2O3The nickel lithium manganate cathode material of coating modification not will produce unfavorable shadow It rings.
(4) Al formed after being pyrolyzed2O3The nickel lithium manganate cathode material of coating modification energy density under high voltages is filled Discharge capacity is obviously improved, and under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacitance conservation rate is up to 86.3%.
(5) lithium metal battery for the positive electrode assembling that the present invention prepares is safe, pierces, falls through needle, short circuit, Occur without on fire, explosive event after 3C/12V overcharge tests.
(6) preparation method is simple to operation, at low cost, is suitble to industrialized production.
Description of the drawings
Fig. 1 is that the SEM of uncoated nickel lithium manganate cathode material schemes；
Fig. 2 is Al2O3The SEM of the nickel lithium manganate cathode material of coating modification schemes；
Fig. 3 is Al2O3The XRD diagram of the front and back nickel lithium manganate cathode material of cladding；Wherein figure a is before coating, and figure b is cladding Afterwards；
Fig. 4 is with Al2O3The front and back nickel ion doped of cladding is the charging and discharging curve figure of the lithium metal battery of positive electrode；Wherein It is before coating, after figure b is cladding to scheme a；
Fig. 5 is with Al2O3The front and back nickel ion doped of cladding is the 1C cyclic curve figures of the lithium metal battery of positive electrode；Wherein It is before coating, after figure b is cladding to scheme a.
Specific implementation mode
There is used reaction equation in preparation process：
Al3++3AlO2 -+12H2O=4Al (OH)3↓
H++AlO2 -+H2O=Al (OH)3↓
Embodiment 1
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) with Al2O3Covering amount be nickel ion doped quality of materials 1% calculate aluminium element molal quantity, then according to change It learns metering ratio and converses Al (NO3)3、NaAlO2Molal quantity and quality；Weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of a concentration of 0.2mol/L respectively3)3The NaAlO of solution, 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped：Water=1g：The ratio ultrasonic disperse of 30mL is in deionized water Suspension is formed, the neopelex that quality is nickel ion doped quality 1.5%, ultrasonic disperse are added into suspension 15min；
(3) prepared Al (NO are slowly added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, and ultrasound 15min, then prepared NaAlO is added dropwise into mixed liquor with the speed of 15mL/min while stirring2The 30% of liquor capacity, and it is slow 1h is stirred, is then followed by and residue Al (NO is added3)3The 50% of liquor capacity, and continue ultrasonic 15min, then while stirring with Residue NaAlO is added dropwise into mixed liquor for the speed of 15mL/min2The 50% of liquor capacity, and 1h is stirred slowly, it is eventually adding residue Al (NO3)3Solution and ultrasound 15min, are eventually adding remaining NaAlO2Solution, and 1h is stirred slowly；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, controlled Rate of addition is 10mL/min, and continues slow stirring 30min, to ensure the AlO in solution2 -Ion precipitates completely；
(5) it by after gained mixture standing aging 4h in step (4), is filtered, removes filtrate, be washed with deionized Afterwards, 1~2h is dried in 90 DEG C, obtains Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3In the Muffle furnace of the nickel ion doped material merging argon gas protection of cladding, it is heat-treated 1h in 400 DEG C, Obtain Al2O3Modified nickel lithium manganate cathode material.
It is anode with this material, the 0.1C first discharge specific capacities that lithium metal designs 2.5Ah lithium metal batteries for cathode are 132.4mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio 83.2%, energy density is 526.3Wh/kg。
Embodiment 2
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) with Al2O3Covering amount be nickel ion doped quality of materials 3% calculate aluminium element molal quantity, then according to change It learns metering ratio and converses Al (NO3)3、NaAlO2Molal quantity and quality；Weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of a concentration of 0.2mol/L respectively3)3The NaAlO of solution, 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped：Water=1g：The ratio ultrasonic disperse of 30mL is in deionized water Suspension is formed, the neopelex that quality is nickel ion doped quality 2.5%, ultrasonic disperse are added into suspension 20min；
(3) prepared Al (NO are slowly added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, and ultrasound 20min, then prepared NaAlO is added dropwise into mixed liquor with the speed of 15mL/min while stirring2The 30% of liquor capacity, and it is slow 1h is stirred, is then followed by and residue Al (NO is added3)3The 50% of liquor capacity, and continue ultrasonic 25min, then while stirring with Residue NaAlO is added dropwise into mixed liquor for the speed of 15mL/min2The 50% of liquor capacity, and 1.5h is stirred slowly, it is eventually adding surplus Remaining Al (NO3)3Solution and ultrasound 25min, are eventually adding remaining NaAlO2Solution, and 1.5h is stirred slowly；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, controlled Rate of addition is 10mL/min, and continues slow stirring 30min, to ensure the AlO in solution2 -Ion precipitates completely；
(5) it by after gained mixture standing aging 4h in step (4), is filtered, removes filtrate, be washed with deionized Afterwards, 1~2h is dried in 90 DEG C, obtains Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3In the Muffle furnace of the nickel ion doped material merging argon gas protection of cladding, it is heat-treated 1h in 400 DEG C, Obtain Al2O3Modified nickel lithium manganate cathode material.
The SEM figures of the front and back nickel ion doped material of cladding are shown in Fig. 1 and Fig. 2 respectively, by Fig. 1 and Fig. 2 it is found that compared to cladding Before, through Al2O3Nickel ion doped still keeps good chondritic after cladding, and clad is uniformly complete, but grain diameter obviously increases Greatly.
Fig. 3 is Al2O3The XRD diagram of the front and back nickel lithium manganate cathode material of cladding；Wherein figure a is before coating, and figure b is cladding Afterwards；From the figure 3, it may be seen that the crystal structure of the front and back material of cladding does not change.
It is anode with this material, the 0.1C first discharge specific capacities that lithium metal designs 2.5Ah lithium metal batteries for cathode are 137.6mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio 86.3%, energy density is The energy density of 601.4Wh/kg, uncoated nickel lithium manganate cathode material are 472.8 Wh/kg, and under the conditions of 1C, room temperature fills After discharge cycles 500 times, capacity retention ratio 62%, the more uncoated nickel ion doped anode of the capacity retention ratio of material after cladding Material improves 24.3%.
Embodiment 3
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) with Al2O3Covering amount be nickel ion doped quality of materials 5% calculate aluminium element molal quantity, then according to change It learns metering ratio and converses Al (NO3)3、NaAlO2Molal quantity and quality；Weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of a concentration of 0.2mol/L respectively3)3The NaAlO of solution, 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped：Water=1g：The ratio ultrasonic disperse of 30mL is in deionized water Suspension is formed, the neopelex that quality is nickel ion doped quality 3.5%, ultrasonic disperse are added into suspension 30min；
(3) prepared Al (NO are slowly added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, and ultrasound 30min, then prepared NaAlO is added dropwise into mixed liquor with the speed of 15mL/min while stirring2The 30% of liquor capacity, and it is slow 1.5h is stirred, is then followed by and residue Al (NO is added3)3The 50% of liquor capacity, and continue ultrasonic 30min, then while stirring with Residue NaAlO is added dropwise into mixed liquor for the speed of 15mL/min2The 50% of liquor capacity, and 2h is stirred slowly, it is eventually adding residue Al (NO3)3Solution and ultrasound 30min, are eventually adding remaining NaAlO2Solution, and 2h is stirred slowly；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, controlled Rate of addition is 15mL/min, and continues slow stirring 30min, to ensure the AlO in solution2 -Ion precipitates completely；
(5) it by after gained mixture standing aging 4h in step (4), is filtered, removes filtrate, be washed with deionized Afterwards, 1~2h is dried in 90 DEG C, obtains Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3In the Muffle furnace of the nickel ion doped material merging argon gas protection of cladding, it is heat-treated 1h in 400 DEG C, Obtain Al2O3Modified nickel lithium manganate cathode material.
It is anode with this material, the 0.1C first discharge specific capacities that lithium metal designs 2.5Ah lithium metal batteries for cathode are 132.3mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio 82.6%, energy density is 552.5Wh/kg。
Embodiment 4
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) with Al2O3Covering amount be nickel ion doped quality of materials 3% calculate aluminium element molal quantity, then according to change It learns metering ratio and converses Al (NO3)3、NaAlO2Molal quantity and quality；Weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of a concentration of 0.2mol/L respectively3)3The NaAlO of solution, 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped：Water=1g：The ratio ultrasonic disperse of 30mL is in deionized water Suspension is formed, the sodium cetanesulfonate that quality is nickel ion doped quality 2.5%, ultrasonic disperse are added into suspension 20min；
(3) prepared Al (NO are slowly added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, and ultrasound 20min, then prepared NaAlO is added dropwise into mixed liquor with the speed of 15mL/min while stirring2The 30% of liquor capacity, and it is slow 1h is stirred, is then followed by and residue Al (NO is added3)3The 50% of liquor capacity, and continue ultrasonic 25min, then while stirring with Residue NaAlO is added dropwise into mixed liquor for the speed of 15mL/min2The 50% of liquor capacity, and 1.5h is stirred slowly, it is eventually adding surplus Remaining Al (NO3)3Solution and ultrasound 25min, are eventually adding remaining NaAlO2Solution, and 1.5h is stirred slowly；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, controlled Rate of addition is 15mL/min, and continues slow stirring 30min, to ensure the AlO in solution2 -Ion precipitates completely；
(5) it by after gained mixture standing aging 4h in step (4), is filtered, removes filtrate, be washed with deionized Afterwards, 1~2h is dried in 90 DEG C, obtains Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3In the Muffle furnace of the nickel ion doped material merging argon gas protection of cladding, it is heat-treated 1h in 400 DEG C, Obtain Al2O3Modified nickel lithium manganate cathode material.
It is anode with this material, the 0.1C first discharge specific capacities that lithium metal designs 2.5Ah lithium metal batteries for cathode are 134.5mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio 84.6%, energy density is 538.1Wh/kg。
Embodiment 5
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, preparation method includes the following steps：
(1) with Al2O3Covering amount be nickel ion doped quality of materials 3% calculate aluminium element molal quantity, then according to change It learns metering ratio and converses Al (NO3)3、NaAlO2Molal quantity and quality；Weigh Al (NO respectively according to result of calculation3)3With NaAlO2, and it is configured to the Al (NO of a concentration of 0.2mol/L respectively3)3The NaAlO of solution, 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped：Water=1g：The ratio ultrasonic disperse of 30mL is in deionized water Suspension is formed, the lauryl sodium sulfate that quality is nickel ion doped quality 2.5%, ultrasonic disperse are added into suspension 20min；
(3) prepared Al (NO are slowly added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, and ultrasound 20min, then prepared NaAlO is added dropwise into mixed liquor with the speed of 15mL/min while stirring2The 30% of liquor capacity, and it is slow 1h is stirred, is then followed by and residue Al (NO is added3)3The 50% of liquor capacity, and continue ultrasonic 25min, then while stirring with Residue NaAlO is added dropwise into mixed liquor for the speed of 15mL/min2The 50% of liquor capacity, and 1.5h is stirred slowly, it is eventually adding surplus Remaining Al (NO3)3Solution and ultrasound 25min, are eventually adding remaining NaAlO2Solution, and 1.5h is stirred slowly；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, controlled Rate of addition is 15mL/min, and continues slow stirring 30min, to ensure the AlO in solution2 -Ion precipitates completely；
(5) it by after gained mixture standing aging 4h in step (4), is filtered, removes filtrate, be washed with deionized Afterwards, 1~2h is dried in 90 DEG C, obtains Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3In the Muffle furnace of the nickel ion doped material merging argon gas protection of cladding, it is heat-treated 1h in 400 DEG C, Obtain Al2O3Modified nickel lithium manganate cathode material.
It is anode with this material, the 0.1C first discharge specific capacities that lithium metal designs 2.5Ah lithium metal batteries for cathode are 131.4mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacity retention ratio 81.6%, energy density is 508.1Wh/kg。
The Al that the present invention prepares2O3The nickel lithium manganate cathode material of coating modification, for the 0.1C after lithium metal battery Capacity retention ratio and energy density results see the table below after charge and discharge cycles 500 times under the conditions of first discharge specific capacity, room temperature 1C, Wherein comparative example is uncoated Al2O3Positive electrode, be used for lithium metal battery：
In conclusion this patent coats Al (OH) by using two-way Hydrolyze method on nickel ion doped surface3, after high temperature pyrolysis Form the Al for slowing down the decomposition of nickel ion doped surface electrolyte2O3Protective layer makes the charge and discharge capacitance of the lithium metal battery of nickel ion doped Amount, energy density, cycle performance be improved significantly, provide technological guidance for the practical application in new energy field, have weigh Big production practices meaning.

Claims (2)

1. a kind of Al2O3The preparation method of the nickel lithium manganate cathode material of coating modification, which is characterized in that include the following steps：
(1) preparation of solution：According to Al2O3Covering amount be nickel ion doped quality 1~5%, calculate the mole of aluminium element, Then Al (NO are calculated3)3、NaAlO2Mole and quality, weigh Al (NO respectively according to result of calculation3)3And NaAlO2, and It is configured to 0.1~0.3mol/L Al (NO3)3Solution and 0.4~0.7mol/L NaAlO2Solution；
(2) nickel ion doped ultrasonic disperse in deionized water is formed into suspension, anion surface active is added into suspension Agent continues 15~30min of ultrasonic disperse；Wherein nickel ion doped：Water=1g：30~60mL；The addition of anion surfactant Amount is the 0.5~4% of nickel ion doped quality；
(3) prepared Al (NO are added into step (2) ultrasonic disperse solution3)3The 30% of liquor capacity, ultrasonic disperse 15~ Prepared NaAlO is then added in 30min while stirring2The 30% of liquor capacity continues 1~2h of stirring, is further continued for being added surplus Remaining Al (NO3)3Residue NaAlO is then added in the 50% of liquor capacity, 15~30min of ultrasonic disperse while stirring2Liquor capacity 50%, continue 1~2h of stirring, be eventually adding remaining Al (NO3)3Solution, 15~30min of ultrasonic disperse, then be added while stirring Remaining NaAlO2Solution continues 1~2h of stirring；Wherein, NaAlO is added dropwise2The speed of solution need to control as 15~20mL/min；
(4) a concentration of 0.5mol/L citric acid solutions are slowly added into mixed liquor obtained by step (3) while stirring, and continue to stir 30~40min is mixed, until the AlO in solution2 -Ion precipitates completely；Wherein, the speed of adding citric acid solution need to control as 10~ 15mL/min；
(5) gained mixture in step (4) is stood into 4~5h of aging, filtering removes filtrate, is then washed with deionized, then set 1~2h is dried in 90~100 DEG C, obtains the nickel ion doped material of aluminium hydroxide cladding；
(6) the nickel ion doped material that aluminium hydroxide coats is placed under the hot environment of argon gas protection and is pyrolyzed, obtain Al2O3Cladding changes The nickel lithium manganate cathode material of property；Wherein pyrolysis temperature is 300~400 DEG C, and pyrolysis time is 1~2h.
2. Al according to claim 12O3The preparation method of the nickel lithium manganate cathode material of coating modification, which is characterized in that Anion surfactant is in neopelex, sodium cetanesulfonate and lauryl sodium sulfate in step (2) It is at least one.
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CN106684361B (en) * 2017-01-19 2020-05-19 新乡天力锂能股份有限公司 Preparation method of nickel-cobalt-aluminum precursor
CN106848298B (en) * 2017-03-31 2020-04-21 中南大学 Method for coating metal oxide on surface of lithium ion battery anode material
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007018743A (en) * 2005-07-05 2007-01-25 Sony Corp Positive electrode active material and manufacturing method of same, and battery
CN104241636A (en) * 2014-10-20 2014-12-24 上海空间电源研究所 Lithium ion battery manganese anode material with surface wrapped with LiAlO2 and preparation method thereof
KR20150052652A (en) * 2013-11-06 2015-05-14 건국대학교 산학협력단 Preparation method of yolk-shell structured material by spray drying and yolk-shell structured materials prepared thereby
CN104766960A (en) * 2015-04-13 2015-07-08 河北工业大学 Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery
CN105226287A (en) * 2014-06-26 2016-01-06 中兴通讯股份有限公司 Anode material for lithium-ion batteries and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007018743A (en) * 2005-07-05 2007-01-25 Sony Corp Positive electrode active material and manufacturing method of same, and battery
KR20150052652A (en) * 2013-11-06 2015-05-14 건국대학교 산학협력단 Preparation method of yolk-shell structured material by spray drying and yolk-shell structured materials prepared thereby
CN105226287A (en) * 2014-06-26 2016-01-06 中兴通讯股份有限公司 Anode material for lithium-ion batteries and preparation method thereof
CN104241636A (en) * 2014-10-20 2014-12-24 上海空间电源研究所 Lithium ion battery manganese anode material with surface wrapped with LiAlO2 and preparation method thereof
CN104766960A (en) * 2015-04-13 2015-07-08 河北工业大学 Method for modifying lithium nickel manganese oxide positive electrode material for lithium ion battery

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