CN106129348A - 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

Info

Publication number
CN106129348A
CN106129348A CN201610471240.9A CN201610471240A CN106129348A CN 106129348 A CN106129348 A CN 106129348A CN 201610471240 A CN201610471240 A CN 201610471240A CN 106129348 A CN106129348 A CN 106129348A
Authority
CN
China
Prior art keywords
solution
naalo
stirring
ultrasonic disperse
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610471240.9A
Other languages
Chinese (zh)
Other versions
CN106129348B (en
Inventor
常丽娟
王体龙
贾元波
伍建军
高娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Non Ferrous Metallurgy Research Co ltd
Original Assignee
Sichuan Non Ferrous Metallurgy Research Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Non Ferrous Metallurgy Research Co ltd filed Critical Sichuan Non Ferrous Metallurgy Research Co ltd
Priority to CN201610471240.9A priority Critical patent/CN106129348B/en
Publication of CN106129348A publication Critical patent/CN106129348A/en
Application granted granted Critical
Publication of CN106129348B publication Critical patent/CN106129348B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The open a kind of Al of the present invention2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps: (1) solution is prepared；(2) nickel ion doped is scattered in deionized water formation suspension, adds anion surfactant, ultrasonic disperse 15～30min；(3) in ultrasonic disperse solution, Al (NO is added3)3Solution, ultrasonic disperse 15～30min, then add NaAlO while stirring2Solution；(4) adding concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution；(5) aging, clean, dry；(6) high temperature pyrolysis.In preparation process, rate of crystalline growth is consistent with nucleation rate, is evenly coated；The material safety prepared is high, low cost, and energy density, charge/discharge capacity under high voltages are obviously improved, and under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention reaches 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, be specifically related to a kind of Al2O3The nickel lithium manganate cathode material of coating modification and Its preparation method.
Background technology
The severe contamination of depleted, the environment of the whole world Fossil fuel such as main energy sources coal, oil, natural gas is to the mankind's Existence constitutes great threat, therefore, carrys out substitute fossil fuels in the urgent need to seeking a kind of reproducible clean energy resource, and this just promotes People look for the renewable new forms of energy of cleaning.Have high working voltage, wide operating range, high-energy-density, length in service life, zero The lithium rechargeable battery of the advantages such as pollution is increasingly paid close attention to by people, and it is not only widely used in energy storage, communication and state The fields such as anti-construction, the popularization in new energy field, have been raised to national strategy height, from the point of view of long-range development trend, It has wide application prospect.
In the manufacture field of lithium rechargeable battery, the development of positive electrode relatively lags behind, and it is also the heat of research at present Point and difficult point.The positive electrode of most study is lithium-transition metal oxide material at present, mainly includes LiCoO2、LiMn2O4、 LiNi0.5Mn1.5O4、Li[NixCoyMn1-x-y]O2、LiFePO4With LiMnPO4Deng.Wherein, there is high voltage, high-energy-density Nickel ion doped (LiNi0.5Mn1.5O4) enjoy the concern of people in the industry, the diffusion admittance of its three-dimensional, it is more beneficial for the biography of lithium ion Defeated, theoretical discharge specific capacity is up to 147mAh/g, and energy density is up to 700Wh/Kg it is considered to be following lithium ion battery develops In one of the positive electrode of most future.
The nickel lithium manganate cathode material of commercialization at present is deposited discharge and recharge surface electrolyte under high voltages and is easily decomposed, by material Circulation that oxygen defect itself causes and the problem that high-temperature behavior is deteriorated.Following approach is generally used to solve the problems referred to above: (1) opens Send out electrolyte system high voltage withstanding；(2) nickel ion doped surface is coated with.Under higher charging/discharging voltage, nickel ion doped The protective layer that Surface coating is stable, can avoid or slow down electrode and contact with the direct of electrolyte, reduce decomposition and the Mn of electrolyte3+ The dissolving of element, is effectively improved the chemical stability of material, and the material being typically used as protective layer includes some metal-oxides, phosphorus Hydrochlorate or metal etc..The employing Al element doping ZnO that Li Decheng etc. propose in Chinese invention patent CN201210556546.6 Nickel ion doped material surface is modified by thin film；Wang Li etc. propose to use in Chinese invention patent CN201510171987.8 CO2The method of gas precipitation meta-aluminic acid root is at nickel ion doped surface-coated aluminum oxide.Though above method can be at nickel ion doped material Surface Creation metal-oxide clad, but the rate of crystalline growth that there is coating is inconsistent with nucleation rate, causes cladding Composition granule is excessive and uneven, and clad is the most fluffy, and in charge and discharge process, clad there will be and subsides and dissociate；CO2 The use of gas needs to put into more cost of material and experimental facilities, and the consideration of safety, is unfavorable for large-scale business Industry metaplasia is produced.
Summary of the invention
For the above-mentioned problems in the prior art, the present invention provides a kind of Al2O3The nickel ion doped positive pole of coating modification Material and preparation method thereof, can effectively solve rate of crystalline growth inconsistent with nucleation rate, the problems such as clad is uneven.
For achieving the above object, the technical solution adopted for the present invention to solve the technical problems is:
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps:
(1) preparation of solution: according to Al2O3Covering amount is nickel ion doped quality 1～5%, calculate aluminium element mole 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)3Solution and the NaAlO of 0.4～0.7mol/L2Solution；
(2) nickel ion doped ultrasonic disperse is formed in deionized water suspension, in suspension, add anionic surface Activating agent, continues ultrasonic disperse 15～30min；Wherein nickel ion doped: water=1g:30～60mL；Anion surfactant Addition is the 0.5～4% of nickel ion doped quality；
(3) in step (2) ultrasonic disperse solution, Al (NO is added3)3Solution, and continue ultrasonic disperse 15～30min, so After add NaAlO the most while stirring2Solution；
(4) being slowly added to concentration in step (3) gained mixed liquor while stirring is 0.5mol/L citric acid solution, and continues Continuous stirring 30～40min, the AlO to solution2 -Ion precipitates completely；
(5) gained mixture in step (4) is stood aging 4～5h, filters, except filtrate, be then washed with deionized, It is placed in 90～100 DEG C again and dries 1～2h, obtain the nickel ion doped material of aluminium hydroxide cladding；
(6) the nickel ion doped material that aluminium hydroxide is coated with is placed under the hot environment of argon shield and is pyrolyzed, obtain Al2O3Bag Cover the nickel lithium manganate cathode material of modification；Wherein pyrolysis temperature is 300～400 DEG C, and pyrolysis time is 1～2h.
Further, in step (2) anion surfactant be dodecylbenzene sodium sulfonate, sodium cetanesulfonate and In sodium lauryl sulphate at least one.
Further, the concrete operations adding solution in step (3) are: add institute in step (2) ultrasonic disperse solution Al (the NO of preparation3)3The 30% of liquor capacity, ultrasonic disperse 15～30min, add the NaAlO prepared the most while stirring2 The 30% of liquor capacity, continues stirring 1～2h, is further continued for adding residue Al (NO3)3The 50% of liquor capacity, ultrasonic disperse 15～ 30min, adds residue NaAlO the most while stirring2The 50% of liquor capacity, continues stirring 1～2h, is eventually adding residue Al (NO3)3Solution, ultrasonic disperse 15～30min, then add residue NaAlO while stirring2Solution, continues stirring 1～2h.
Further, dropping NaAlO in step (3)2The speed of solution need to control to be 15～20mL/min.
Further, in step (4), the speed of dropping citric acid solution need to control to be 10～15mL/min.
A kind of Al that the present invention provides2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof, having following has Benefit effect:
(1) nickel ion doped forms the suspension of homogenizing after ultrasonic disperse, more modified through anion surfactant, when adding Enter the Al (NO of certain concentration3)3After solution, continue ultrasonic disperse, its objective is to make through the modified nickel of anion surfactant LiMn2O4 is to Al3+There is more preferable adsorptivity, and adsorb more uniform；When continuing to add the NaAlO of certain concentration2Solution, makes Al3+With AlO2 -React, be partially formed Al (OH) on nickel ion doped surface3Crystal seed, this crystal seed continues nucleation and grows, and crystal The speed of growth keeps consistent with nucleation rate, this and the Al (NO of certain concentration3)3Solution and the NaAlO of certain concentration2Solution Addition sequence, is dividedly in some parts and suitable pH environment is all closely-related.
(2) use and successively add Al (NO3)3、NaAlO2Method, and limit its rate of addition, thus Al can be controlled (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, it is provided that H+, can be with the AlO of excess2 -React formation Al (OH)3 Precipitation, and the addition of citric acid is to prepared Al2O3The nickel lithium manganate cathode material of coating modification will not produce unfavorable shadow Ring.
(4) Al formed after pyrolysis2O3The nickel lithium manganate cathode material of coating modification energy density under high voltages, fill Discharge capacity is obviously improved, and under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capacitance conservation rate reaches 86.3%.
(5) the lithium metal battery safety that the positive electrode that the present invention prepares assembles is high, through acupuncture, falls, short circuit, Occur without on fire, explosive event after 3C/12V overcharge test.
(6) this preparation method is simple to operation, low cost, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of uncoated nickel lithium manganate cathode material；
Fig. 2 is Al2O3The SEM figure of the nickel lithium manganate cathode material of coating modification；
Fig. 3 is Al2O3The XRD figure of the nickel lithium manganate cathode material before and after cladding；Before wherein figure a is for cladding, figure b is cladding After；
Fig. 4 is with Al2O3Before and after cladding, nickel ion doped is the charging and discharging curve figure of the lithium metal battery of positive electrode；Wherein Before figure a is for cladding, after figure b is for cladding；
Fig. 5 is with Al2O3Before and after cladding, nickel ion doped is the 1C cyclic curve figure of the lithium metal battery of positive electrode；Wherein Before figure a is for cladding, after figure b is for cladding.
Detailed description of the invention
Reaction equation used in preparation process has:
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, its preparation method comprises the following steps:
(1) with Al2O3Covering amount is nickel ion doped quality of materials 1% calculating aluminium element molal quantity, then according to change Learn metering ratio and converse Al (NO3)3、NaAlO2Molal quantity and quality；Al (NO is weighed respectively according to result of calculation3)3With NaAlO2, and it is configured to Al (the NO that concentration is 0.2mol/L respectively3)3Solution, the NaAlO of 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped: the ratio ultrasonic disperse of water=1g:30mL is in deionized water Form suspension, in suspension, add the dodecylbenzene sodium sulfonate that quality is nickel ion doped quality 1.5%, ultrasonic disperse 15min；
(3) in step (2) ultrasonic disperse solution, prepared Al (NO it is slowly added to3)3The 30% of liquor capacity, and ultrasonic 15min, more while stirring with the speed of 15mL/min drip in mixed liquor preparation NaAlO2The 30% of liquor capacity, and slowly Stirring 1h, is then followed by adding residue Al (NO3)3The 50% of liquor capacity, and continue ultrasonic 15min, more while stirring with The speed of 15mL/min drips residue NaAlO in mixed liquor2The 50% of liquor capacity, and stir 1h slowly, it is eventually adding residue Al (NO3)3Solution ultrasonic 15min, be eventually adding remaining NaAlO2Solution, and stir 1h slowly；
(4) being slowly added to concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution, controls Rate of addition is 10mL/min, and continues to stir 30min slowly, to guarantee the AlO in solution2 -Ion precipitates completely；
(5) after gained mixture in step (4) being stood aging 4h, filter, remove filtrate, be washed with deionized After, dry 1～2h in 90 DEG C, obtain Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3The nickel ion doped material of cladding is inserted in the Muffle furnace of argon shield, in 400 DEG C of heat treatment 1h, Obtain Al2O3Modified nickel lithium manganate cathode material.
With this material as positive pole, the 0.1C first discharge specific capacity that lithium metal designs 2.5Ah lithium metal battery for negative pole is 132.4mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention is 83.2%, and energy density is 526.3Wh/kg。
Embodiment 2
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps:
(1) with Al2O3Covering amount is nickel ion doped quality of materials 3% calculating aluminium element molal quantity, then according to change Learn metering ratio and converse Al (NO3)3、NaAlO2Molal quantity and quality；Al (NO is weighed respectively according to result of calculation3)3With NaAlO2, and it is configured to Al (the NO that concentration is 0.2mol/L respectively3)3Solution, the NaAlO of 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped: the ratio ultrasonic disperse of water=1g:30mL is in deionized water Form suspension, in suspension, add the dodecylbenzene sodium sulfonate that quality is nickel ion doped quality 2.5%, ultrasonic disperse 20min；
(3) in step (2) ultrasonic disperse solution, prepared Al (NO it is slowly added to3)3The 30% of liquor capacity, and ultrasonic 20min, more while stirring with the speed of 15mL/min drip in mixed liquor preparation NaAlO2The 30% of liquor capacity, and slowly Stirring 1h, is then followed by adding residue Al (NO3)3The 50% of liquor capacity, and continue ultrasonic 25min, more while stirring with The speed of 15mL/min drips residue NaAlO in mixed liquor2The 50% of liquor capacity, and stir 1.5h slowly, it is eventually adding surplus Remaining Al (NO3)3Solution ultrasonic 25min, be eventually adding remaining NaAlO2Solution, and stir 1.5h slowly；
(4) being slowly added to concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution, controls Rate of addition is 10mL/min, and continues to stir 30min slowly, to guarantee the AlO in solution2 -Ion precipitates completely；
(5) after gained mixture in step (4) being stood aging 4h, filter, remove filtrate, be washed with deionized After, dry 1～2h in 90 DEG C, obtain Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3The nickel ion doped material of cladding is inserted in the Muffle furnace of argon shield, in 400 DEG C of heat treatment 1h, Obtain Al2O3Modified nickel lithium manganate cathode material.
Before and after cladding, the SEM figure of nickel ion doped material is shown in Fig. 1 and Fig. 2, respectively from Fig. 1 and Fig. 2, compared to cladding Before, through Al2O3After cladding, nickel ion doped still keeps good chondritic, and clad is uniformly complete, but grain diameter substantially increases Greatly.
Fig. 3 is Al2O3The XRD figure of the nickel lithium manganate cathode material before and after cladding；Before wherein figure a is for cladding, figure b is cladding After；From the figure 3, it may be seen that the crystal structure of material does not changes before and after Bao Fu.
With this material as positive pole, the 0.1C first discharge specific capacity that lithium metal designs 2.5Ah lithium metal battery for negative pole is 137.6mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention is 86.3%, and energy density is 601.4Wh/kg, the energy density of uncoated nickel lithium manganate cathode material is 472.8Wh/kg, under the conditions of 1C, room temperature charge and discharge After electricity circulation 500 times, capability retention is 62%, the nickel ion doped positive pole material that after cladding, the capability retention of material is more uncoated Material raising 24.3%.
Embodiment 3
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps:
(1) with Al2O3Covering amount is nickel ion doped quality of materials 5% calculating aluminium element molal quantity, then according to change Learn metering ratio and converse Al (NO3)3、NaAlO2Molal quantity and quality；Al (NO is weighed respectively according to result of calculation3)3With NaAlO2, and it is configured to Al (the NO that concentration is 0.2mol/L respectively3)3Solution, the NaAlO of 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped: the ratio ultrasonic disperse of water=1g:30mL is in deionized water Form suspension, in suspension, add the dodecylbenzene sodium sulfonate that quality is nickel ion doped quality 3.5%, ultrasonic disperse 30min；
(3) in step (2) ultrasonic disperse solution, prepared Al (NO it is slowly added to3)3The 30% of liquor capacity, and ultrasonic 30min, more while stirring with the speed of 15mL/min drip in mixed liquor preparation NaAlO2The 30% of liquor capacity, and slowly Stirring 1.5h, is then followed by adding residue Al (NO3)3The 50% of liquor capacity, and continue ultrasonic 30min, more while stirring with The speed of 15mL/min drips residue NaAlO in mixed liquor2The 50% of liquor capacity, and stir 2h slowly, it is eventually adding residue Al (NO3)3Solution ultrasonic 30min, be eventually adding remaining NaAlO2Solution, and stir 2h slowly；
(4) being slowly added to concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution, controls Rate of addition is 15mL/min, and continues to stir 30min slowly, to guarantee the AlO in solution2 -Ion precipitates completely；
(5) after gained mixture in step (4) being stood aging 4h, filter, remove filtrate, be washed with deionized After, dry 1～2h in 90 DEG C, obtain Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3The nickel ion doped material of cladding is inserted in the Muffle furnace of argon shield, in 400 DEG C of heat treatment 1h, Obtain Al2O3Modified nickel lithium manganate cathode material.
With this material as positive pole, the 0.1C first discharge specific capacity that lithium metal designs 2.5Ah lithium metal battery for negative pole is 132.3mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention is 82.6%, and energy density is 552.5Wh/kg。
Embodiment 4
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps:
(1) with Al2O3Covering amount is nickel ion doped quality of materials 3% calculating aluminium element molal quantity, then according to change Learn metering ratio and converse Al (NO3)3、NaAlO2Molal quantity and quality；Al (NO is weighed respectively according to result of calculation3)3With NaAlO2, and it is configured to Al (the NO that concentration is 0.2mol/L respectively3)3Solution, the NaAlO of 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped: the ratio ultrasonic disperse of water=1g:30mL is in deionized water Form suspension, in suspension, add the sodium cetanesulfonate that quality is nickel ion doped quality 2.5%, ultrasonic disperse 20min；
(3) in step (2) ultrasonic disperse solution, prepared Al (NO it is slowly added to3)3The 30% of liquor capacity, and ultrasonic 20min, more while stirring with the speed of 15mL/min drip in mixed liquor preparation NaAlO2The 30% of liquor capacity, and slowly Stirring 1h, is then followed by adding residue Al (NO3)3The 50% of liquor capacity, and continue ultrasonic 25min, more while stirring with The speed of 15mL/min drips residue NaAlO in mixed liquor2The 50% of liquor capacity, and stir 1.5h slowly, it is eventually adding surplus Remaining Al (NO3)3Solution ultrasonic 25min, be eventually adding remaining NaAlO2Solution, and stir 1.5h slowly；
(4) being slowly added to concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution, controls Rate of addition is 15mL/min, and continues to stir 30min slowly, to guarantee the AlO in solution2 -Ion precipitates completely；
(5) after gained mixture in step (4) being stood aging 4h, filter, remove filtrate, be washed with deionized After, dry 1～2h in 90 DEG C, obtain Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3The nickel ion doped material of cladding is inserted in the Muffle furnace of argon shield, in 400 DEG C of heat treatment 1h, Obtain Al2O3Modified nickel lithium manganate cathode material.
With this material as positive pole, the 0.1C first discharge specific capacity that lithium metal designs 2.5Ah lithium metal battery for negative pole is 134.5mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention is 84.6%, and energy density is 538.1Wh/kg。
Embodiment 5
A kind of Al2O3The nickel lithium manganate cathode material of coating modification, its preparation method comprises the following steps:
(1) with Al2O3Covering amount is nickel ion doped quality of materials 3% calculating aluminium element molal quantity, then according to change Learn metering ratio and converse Al (NO3)3、NaAlO2Molal quantity and quality；Al (NO is weighed respectively according to result of calculation3)3With NaAlO2, and it is configured to Al (the NO that concentration is 0.2mol/L respectively3)3Solution, the NaAlO of 0.5mol/L2Solution；
(2) nickel ion doped is weighed, and according to nickel ion doped: the ratio ultrasonic disperse of water=1g:30mL is in deionized water Form suspension, in suspension, add the sodium lauryl sulphate that quality is nickel ion doped quality 2.5%, ultrasonic disperse 20min；
(3) in step (2) ultrasonic disperse solution, prepared Al (NO it is slowly added to3)3The 30% of liquor capacity, and ultrasonic 20min, more while stirring with the speed of 15mL/min drip in mixed liquor preparation NaAlO2The 30% of liquor capacity, and slowly Stirring 1h, is then followed by adding residue Al (NO3)3The 50% of liquor capacity, and continue ultrasonic 25min, more while stirring with The speed of 15mL/min drips residue NaAlO in mixed liquor2The 50% of liquor capacity, and stir 1.5h slowly, it is eventually adding surplus Remaining Al (NO3)3Solution ultrasonic 25min, be eventually adding remaining NaAlO2Solution, and stir 1.5h slowly；
(4) being slowly added to concentration while stirring in step (3) gained mixed liquor is 0.5mol/L citric acid solution, controls Rate of addition is 15mL/min, and continues to stir 30min slowly, to guarantee the AlO in solution2 -Ion precipitates completely；
(5) after gained mixture in step (4) being stood aging 4h, filter, remove filtrate, be washed with deionized After, dry 1～2h in 90 DEG C, obtain Al (OH)3The nickel ion doped material of cladding；
(6) by Al (OH)3The nickel ion doped material of cladding is inserted in the Muffle furnace of argon shield, in 400 DEG C of heat treatment 1h, Obtain Al2O3Modified nickel lithium manganate cathode material.
With this material as positive pole, the 0.1C first discharge specific capacity that lithium metal designs 2.5Ah lithium metal battery for negative pole is 131.4mAh/g, under the conditions of 1C, after room temperature charge and discharge cycles 500 times, capability retention is 81.6%, and energy density is 508.1Wh/kg。
The Al that the present invention prepares2O3The nickel lithium manganate cathode material of coating modification, the 0.1C after lithium metal battery is first Under the conditions of secondary specific discharge capacity, room temperature 1C, after charge and discharge cycles 500 times, capability retention and energy density results see table, its Middle comparative example is uncoated Al2O3Positive electrode, for lithium metal battery:
In sum, this patent is by using two-way Hydrolyze method at nickel ion doped Surface coating Al (OH)3, after high temperature pyrolysis Formed and slow down the Al that nickel ion doped surface electrolyte decomposes2O3Protective layer, makes the charge and discharge electric capacity of the lithium metal battery of nickel ion doped Amount, energy density, cycle performance be improved significantly, in new energy field actual application provide technological guidance, have weight Big production practices meaning.

Claims (5)

1. an Al2O3The preparation method of the nickel lithium manganate cathode material of coating modification, it is characterised in that comprise the following steps:
(1) preparation of solution: according to Al2O3Covering amount is nickel ion doped quality 1～5%, calculate aluminium element mole, Then Al (NO is 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 is formed in deionized water suspension, in suspension, add anion surface active Agent, continues ultrasonic disperse 15～30min；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) in step (2) ultrasonic disperse solution, Al (NO is added3)3Solution, and continue ultrasonic disperse 15～30min, the most again Add NaAlO while stirring2Solution；
(4) being slowly added to concentration in step (3) gained mixed liquor while stirring is 0.5mol/L citric acid solution, and continues to stir Mix 30～40min, the AlO to solution2 -Ion precipitates completely；
(5) gained mixture in step (4) is stood aging 4～5h, filter, except filtrate, be then washed with deionized, then put Dry 1～2h in 90～100 DEG C, obtain the nickel ion doped material of aluminium hydroxide cladding；
(6) the nickel ion doped material that aluminium hydroxide is coated with is placed under the hot environment of argon shield 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.
Al the most according to claim 12O3The preparation method of the nickel lithium manganate cathode material of coating modification, it is characterised in that In step (2), anion surfactant is in dodecylbenzene sodium sulfonate, sodium cetanesulfonate and sodium lauryl sulphate At least one.
Al the most according to claim 12O3The preparation method of the nickel lithium manganate cathode material of coating modification, it is characterised in that Step (3) is added the concrete operations of solution by: in step (2) ultrasonic disperse solution, add the Al (NO prepared3)3Solution The 30% of volume, ultrasonic disperse 15～30min, add the NaAlO prepared the most while stirring2The 30% of liquor capacity, continues Continuous stirring 1～2h, is further continued for adding residue Al (NO3)3The 50% of liquor capacity, ultrasonic disperse 15～30min, then limit stirring Limit adds residue NaAlO2The 50% of liquor capacity, continues stirring 1～2h, is eventually adding residue Al (NO3)3Solution, ultrasonic disperse 15～30min, then add residue NaAlO while stirring2Solution, continues stirring 1～2h.
Al the most according to claim 12O3The preparation method of the nickel lithium manganate cathode material of coating modification, it is characterised in that Dropping NaAlO in step (3)2The speed of solution need to control to be 15～20mL/min.
Al the most according to claim 12O3The preparation method of the nickel lithium manganate cathode material of coating modification, it is characterised in that In step (4), the speed of dropping citric acid solution need to control to be 10～15mL/min.
CN201610471240.9A 2016-06-23 2016-06-23 A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof Active CN106129348B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610471240.9A CN106129348B (en) 2016-06-23 2016-06-23 A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610471240.9A CN106129348B (en) 2016-06-23 2016-06-23 A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106129348A true CN106129348A (en) 2016-11-16
CN106129348B CN106129348B (en) 2018-10-30

Family

ID=57269733

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610471240.9A Active CN106129348B (en) 2016-06-23 2016-06-23 A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106129348B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106684361A (en) * 2017-01-19 2017-05-17 新乡天力锂能股份有限公司 Preparation method of Ni-Co-Al precursor
CN106848298A (en) * 2017-03-31 2017-06-13 中南大学 A kind of method of anode material for lithium-ion batteries surface clad oxide
CN108365183A (en) * 2018-01-02 2018-08-03 乳源东阳光磁性材料有限公司 Ternary material with surface coated with aluminum oxide and preparation method thereof
CN110492061A (en) * 2018-05-15 2019-11-22 湖南师范大学 A kind of method for coating of water-soluble additives auxiliary positive material interface growth boron aluminum oxide thin layer
WO2020029029A1 (en) * 2018-08-06 2020-02-13 中天新兴材料有限公司 Preparation method for positive electrode material, positive electrode material and lithium ion battery
CN111430711A (en) * 2020-03-30 2020-07-17 新乡天力锂能股份有限公司 Coated lithium ion battery positive electrode active material and preparation method thereof
CN114824242A (en) * 2022-05-10 2022-07-29 哈尔滨工业大学（威海） Preparation method of metal oxide coated lithium ion battery anode material

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

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106684361A (en) * 2017-01-19 2017-05-17 新乡天力锂能股份有限公司 Preparation method of Ni-Co-Al precursor
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
CN106848298A (en) * 2017-03-31 2017-06-13 中南大学 A kind of method of anode material for lithium-ion batteries surface clad oxide
CN108365183A (en) * 2018-01-02 2018-08-03 乳源东阳光磁性材料有限公司 Ternary material with surface coated with aluminum oxide and preparation method thereof
CN108365183B (en) * 2018-01-02 2020-10-20 乳源东阳光磁性材料有限公司 Ternary material with surface coated with aluminum oxide and preparation method thereof
CN110492061A (en) * 2018-05-15 2019-11-22 湖南师范大学 A kind of method for coating of water-soluble additives auxiliary positive material interface growth boron aluminum oxide thin layer
WO2020029029A1 (en) * 2018-08-06 2020-02-13 中天新兴材料有限公司 Preparation method for positive electrode material, positive electrode material and lithium ion battery
CN111010887A (en) * 2018-08-06 2020-04-14 中天新兴材料有限公司 Preparation method of anode material, anode material and lithium ion battery
CN111010887B (en) * 2018-08-06 2022-07-08 中天新兴材料有限公司 Preparation method of anode material, anode material and lithium ion battery
CN111430711A (en) * 2020-03-30 2020-07-17 新乡天力锂能股份有限公司 Coated lithium ion battery positive electrode active material and preparation method thereof
CN114824242A (en) * 2022-05-10 2022-07-29 哈尔滨工业大学（威海） Preparation method of metal oxide coated lithium ion battery anode material
CN114824242B (en) * 2022-05-10 2023-09-15 哈尔滨工业大学（威海） Preparation method of metal oxide coated lithium ion battery anode material

Also Published As

Publication number Publication date
CN106129348B (en) 2018-10-30

Similar Documents

Publication Publication Date Title
CN106129348B (en) A kind of Al2O3Nickel lithium manganate cathode material of coating modification and preparation method thereof
CN104201323B (en) The preparation method of alumina-coated lithium cobaltate cathode material
CN110459736B (en) Positive electrode material, positive electrode plate containing positive electrode material and lithium ion battery
US9281516B2 (en) Cathode material of lithium ion secondary battery and method for manufacturing the same
CN110931797A (en) High-nickel positive electrode material with composite coating layer and preparation method thereof
CN108172803B (en) Surface-modified coated lithium-rich material, preparation method thereof and lithium ion battery
CN101969110A (en) Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN110931781A (en) Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material
CN108199011B (en) Preparation method of lithium titanate negative electrode material
CN107221661A (en) A kind of preparation method of graphite negative material of lithium ion battery
CN107994226A (en) A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof
WO2020098275A1 (en) Sio2-covered ternary positive electrode material and preparation method therefor
CN103236518A (en) Lithium ion battery negative nanometer material SnO2/MCMB (Mesophase Carbon Micro Beads) shell, and preparation method and application thereof
CN112614978B (en) Cage-shaped eutectic high-entropy oxide lithium ion battery cathode material and preparation method thereof
CN106450306A (en) Preparation method and application of negative electrode material of tin phosphide sodium ion battery
CN103794761A (en) Preparation method of silicon/lithium titanate composite negative electrode material of lithium ion battery
CN105826568A (en) Lithium-rich positive electrode material with hypoxic metallic oxide coating layer structure, preparation method and application
CN113772718B (en) SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof
CN113991084A (en) SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof
CN204885286U (en) Lithium metal negative pole of high security
WO2023226555A1 (en) Modified iron phosphate precursor, modified lithium iron phosphate, and preparation methods therefor
CN115261662B (en) High-entropy alloy CuSnZnAlCD/C carbon-based composite material and preparation method and application thereof
CN111137871A (en) Tin antimony oxide coated lithium cobalt fluorophosphate and surface deposition in-situ coating method and application thereof
CN114142010B (en) Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant