CN107910543A - A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof - Google Patents

A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof Download PDF

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CN107910543A
CN107910543A CN201711324080.6A CN201711324080A CN107910543A CN 107910543 A CN107910543 A CN 107910543A CN 201711324080 A CN201711324080 A CN 201711324080A CN 107910543 A CN107910543 A CN 107910543A
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lithium ion
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张海朗
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Jiangnan University
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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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The present invention relates to a kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof, including positive electrode, the outer layer covers of positive electrode have one layer of covering material, and covering material and positive electrode mass ratio are 1 6wt%, and the chemical general formula of positive electrode is Li (Ni0.7Co0.1Mn0.2)1‑xMxO2‑yNy, wherein, M Mo, Fe, Ti, Mg, Al or Cr；N is F, Cl or Br, 0 ＜ x≤0.10,0 ＜ y≤0.10, covering material TiO2、A12O3Or FePO4During preparation, raw material is obtained into gel using sol-gal process first, after heat drying, positive electrode is obtained after the grinding of calcination twice, then positive electrode and covering material are suspended in deionized water, constant temperature stirring, then stand, filter, washing, is dry, 721 type tertiary cathode modified material of lithium ion battery is obtained through calcining.Preparation method of the present invention is simple, and step is easily operated, and the tertiary cathode modification particle diameter distribution being prepared is uniform, and crystallinity is high, improves material high rate performance and cycle performance, capacity significantly improve.

Description

A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof
Technical field
The present invention relates to a kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof, belong to lithium ion Cell positive material technical field.
Background technology
In the element of lithium ion battery, positive electrode all occupies leading factor in price and aspect of performance.Just now Development degree for, development speed of the positive electrode also more than negative material and electrolyte is slow, performance of lithium ion battery and Security it is further improve with greater need for be positive electrode circulation, high rate performance and heat endurance continuous improvement.Ternary Positive electrode is LiCoO2/LiNiO2/LiMn2O4Eutectic system, this eutectic system had LiCoO concurrently2、LiNiO2、 LiMn2O4The characteristics of three classes material.
The content higher of Ni, contributes to material to obtain the discharge capacity of higher.Meanwhile material safety and stability is contributed maximum Mn content increase, material circulation and security can be made more preferable, be more suitable for practical application, thus LiNi0.8Co0.1Mn0.1O2It is a kind of tertiary cathode material with more researching value.
And for the requirement of commercial applications, LiNi0.7Co0.1Mn0.2O2What positive electrode needed to improve is vibration density Degree, can force density, the charging and discharging capabilities of circulation ability and big multiplying power.For current LiNi0.7Co0.1Mn0.2O2Tertiary cathode material Expect the deficiency remained, researchers are substantially carried out material part doping or surface coating modification, and doping vario-property is mainly logical Cross into positive electrode partly doping and other metal ions similar in bulk transition metal ionic radius, or part doping F, The anion such as Cl or Br make material structure more stablize to reach, the more excellent purpose of cycle performance；Coat this modified method Adhere to the material that one layer of chemical property is stablized on positive electrode surface, be effectively prevented from material and contacted with the direct of electrolyte, Mode in this way suppresses the interaction between them, to ensure the complete and stabilization of material structure in cyclic process. In addition, coating modification can also properly increase the electrical conductivity and tap density of positive electrode, make the cathode material after cladding Material high rate performance is more preferable and is conducive to industrial processes.This patent combines two kinds of modified methods, right LiNi0.7Co0.1Mn0.2O2The modified synergic that positive electrode is doped or coats.
The content of the invention
The purpose of the present invention is to solve the above problem, there is provided a kind of 721 type tertiary cathode modified materials and its system Preparation Method, the positive electrode grain high rate performance and cycle performance being prepared are preferable.
The present invention adopts the following technical scheme that：A kind of high-capacity lithium ion cell tertiary cathode modified material, including doping Modified positive electrode, the outer layer covers of the positive electrode of the doping vario-property have one layer of covering material, the covering material Quality is the 1-6wt% of the positive electrode of doping vario-property, and the chemical general formula of the positive electrode of the doping vario-property is Li (Ni0.7Co.01Mn0.2)1-xMxO2-yNy, wherein, M Mo, Fe, Ti,
Mg, Al or Cr；N is F, Cl or Br, and 0 ＜ x≤0.10,0 ＜ y≤0.10, the covering material is TiO2、A12O3Or FePO4。
The preparation method of 721 type tertiary cathode modified material of lithium ion battery, includes the following steps：
(1) by water miscible lithium source, nickel source, manganese source, cobalt source, M salt, N salt and citric acid is soluble in water is sufficiently mixed, then use Ammonium hydroxide adjusts pH value to 7~8；
(2) solution for obtaining step (1) agitating and heating at 60~100 DEG C, obtains gelinite；
(3) by when drying 8~15 is small at 80~150 DEG C of gelinite obtained by step (2), xerogel body is obtained；
(4) by xerogel body when 300~600 DEG C of pre- calcinations processing 4~8 are small, cooled to room temperature is ground before obtaining Drive body；
(5) when roasting 10~20 is small under the conditions of the presoma that step (4) obtains is placed in 700~1000 DEG C, continue after cooling Grinding obtains the positive electrode of doping vario-property；
(6) be by the quality of covering material doping vario-property positive electrode 1-6wt% weigh covering material, covering material For TiO2、A12O3Or FePO4；
(7) positive electrode of the above-mentioned doping vario-property prepared and covering material are scattered in water or ethanol changes doping Property positive electrode and covering material dissolving it is complete, be vigorously stirred at 40~80 DEG C, and adjust pH 9~10, until solvent Volatilization completely, is filtered when standing 1~2 is small after stirring using quantitative filter paper, and is washed with deionized 1~2 time after 80 When drying 12~20 is small under the conditions of~85 DEG C, finally 5~10h are calcined at 400~500 DEG C and obtain final product.
Further, the lithium source, nickel source, manganese source, cobalt source, M salt, N salt are according to the molar ratio of lithium, nickel, manganese, cobalt, M, N (1-y):(0.7-x):(0.2-x):(0.1-x):x:Y is added, wherein 0 ＜ x≤0.10,0 ＜ y≤0.10.
Further, the molar ratio of the integral molar quantity of the nickel salt, cobalt salt and manganese salt and citric acid is 1:1~1:2.
Further, the lithium source is LiNO3、CH3One or more in COOLi, LiOH.
Further, the nickel source is Ni (NO3)2、Ni(CH3COO)2、NiSO4In one or more.
Further, the manganese source is Mn (NO3)2、Mn(CH3COO)2、MnSO4In one or more.
Further, the cobalt source is Co (NO3)2、Co(CH3COO)2、CoSO4In one or more
Further, the M salt is Mg (NO3)2、C16H36O4Ti、Al(NO3)3Or Cr (NO3)3In one kind.
Further, the N salt is one kind in LiCl, LiF, LiBr.
Preparation method of the present invention is simple, and step is easily operated, and the positive electrode particle diameter distribution being prepared is uniform, crystallinity Height, surface is smooth, and particle dispersion is good, since the doping vario-property of anion and cation makes material structure more stablize, and wraps The presence for covering material inhibits the generation of material surface and electrolyte interface side reaction, reduces the impedance in cyclic process, carries High Li+Diffusion rate, make material surface Li+Abjection is easier with insertion, is adulterated the comprehensive function with coating modification and is played Material high rate performance and cycle performance are improved, and doping is cheap with the cost of material needed for coating modification, reduce further Cost needed for positive electrode production, is conducive to promote the process of commercialization.
Brief description of the drawings
Fig. 1 is the x-ray diffraction pattern of positive electrode prepared by comparative example and embodiment 2,3,5.
Fig. 2 is the scanning electron microscope (SEM) photograph of positive electrode prepared by comparative example and embodiment 2,3,5.
Fig. 3 is positive electrode prepared by comparative example and embodiment 2,3,5, and first charge-discharge during room temperature under 0.2C electric currents is bent Line chart, discharge voltage range 2.5-4.6V.
Fig. 4 is positive electrode prepared by comparative example and embodiment 2,3,5, cyclic curve figure during room temperature under 0.2C electric currents, Charging/discharging voltage scope is 2.5-4.6V.
Fig. 5 is positive electrode prepared by comparative example and embodiment 2,3,5, at room temperature the cyclic curve under different multiplying Figure, charging/discharging voltage scope is 2.5-4.6V.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Comparative example：Unmodified LiNi0.7Co0.1Mn0.2O2The preparation of positive electrode.
According to stoichiometric ratio (1.05:0.7:0.1:0.2) analytically pure CH is weighed3COOLi、Ni(CH3COO)2、Co (CH3COO)2、Mn(CH3COO)2Fully dissolved with deionized water respectively, add citric acid solution, the addition of citric acid solution The sum of mole equal to transition metal ions, is adjusted to 7.5,80 DEG C of heating water baths with concentrated ammonia liquor by solution ph after mixing Stirring, makes various ions fully be complexed, and makes moisture evaporation to formation darkviolet gel；The drying under the conditions of 120 DEG C by gel 10 it is small when, and be placed at 500 DEG C pretreatment 6 it is small when, ground after cooling, then at 850 DEG C of roastings 20 it is small when obtain LiNi0.8Co0.1Mn0.1O2Positive electrode.
Embodiment 1：A kind of preparation method of high-capacity lithium ion cell tertiary cathode modified material, includes the following steps：
(1) according to stoichiometric ratio (1.02:0.706:0.105:0.208:0.03:0.03) weigh analytically pure CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)·4H2O、Mg(NO3)2· 6H2O, LiF, it is complete with deionized water dissolving respectively, citric acid solution is added, the addition of citric acid solution is equal to transition metal The sum of mole of ion, is after mixing adjusted pH value to 7 with concentrated ammonia liquor；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 60 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 80 DEG C, when drying time is 8 small, is obtained dry solidifying Colloid；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 300 DEG C, when burn-in time is 8 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 700 DEG C, calcination time is small for 10 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.97Mg0.03O1.97F0.03。
(5) the covering material TiO than 1.0wt% by the above-mentioned doping vario-property positive electrode prepared and mass fraction2Point Dissipate in amount of alcohol solvent, be vigorously stirred at 40 DEG C, and adjust PH 9, until solvent volatilizees completely, 1 is stood after stirring Hour is filtered using quantitative filter paper, and is washed with deionized 1 time when drying 20 is small under the conditions of 80 DEG C, and last 400 DEG C are forged Burn 10h and obtain final product surface cladding 1.0wt%TiO2Li (Ni0.7Co0.1Mn0.2)0.97Mg0.03O1.97F0.03。
Embodiment 2：A kind of preparation method of high-capacity lithium ion cell tertiary cathode modified material, includes the following steps：
(1) according to stoichiometric ratio (1.00:0.705:0.10:0.205:0.05:0.05) analytically pure LiNO is weighed3、 Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·4H2O、C16H36O4Ti, LiCl, it is complete with deionized water dissolving respectively Entirely, citric acid solution is added, the addition of citric acid solution is equal to the sum of mole of transition metal ions, uses after mixing Concentrated ammonia liquor adjusts pH value to 7.5；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 80 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 100 DEG C, when drying time is 10 small, is done Gelinite；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 400 DEG C, when burn-in time is 5 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 850 DEG C, calcination time is small for 15 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.95Ti0.05O1.95Cl0.05。
(5) by the covering material A1 of the positive electrode of the above-mentioned doping vario-property prepared and mass fraction than 2.0wt%2O3 It is scattered in appropriate solvent, is vigorously stirred at 60 DEG C, and adjust PH 9 or so, until solvent volatilizees completely.After stirring Stand 2 it is small when filtered using quantitative filter paper, and be washed with deionized 2 times after under the conditions of 85 DEG C it is dry 12 it is small when, last 450 DEG C calcining 8h i.e. obtain final product surface cladding 2.0wt%A12O3Li (Ni0.7Co0.1Mn0.2)0.95Ti0.05O1.95Cl0.05。
Embodiment 3：A kind of preparation method of 811 type tertiary cathode modified material of lithium ion battery, includes the following steps：
(1) according to stoichiometric ratio (0.95:0.701:0.10:0.20:0.1:0.1) analytically pure LiOHH is weighed2O、 NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、Al(NO3)3, LiBr, it is complete with deionized water dissolving respectively, add lemon Acid solution, addition are equal to the sum of mole of transition metal ions, are after mixing adjusted pH value to 8 left sides with concentrated ammonia liquor It is right；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 90 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 120 DEG C, when drying time is 12 small, is done Gelinite；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 500 DEG C, when burn-in time is 6 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 900 DEG C, calcination time is small for 18 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.9Al0.1O1.9Br0.1。
(5) by the covering material FePO of the positive electrode of the above-mentioned doping vario-property prepared and mass fraction than 3.0wt%4 It is scattered in appropriate solvent, is vigorously stirred at 80 DEG C, and adjust PH 9 or so, until solvent volatilizees completely.After stirring Stand 1.5 it is small when filtered using quantitative filter paper, and be washed with deionized 2 times after under the conditions of 80 DEG C it is dry 15 it is small when, finally 500 DEG C of calcining 5h obtain final product surface cladding 3.0wt%FePO4Li (Ni0.7Co0.1Mn0.2)0.9Al0.1O1.9Br0.1。
Embodiment 4：A kind of preparation method of high-capacity lithium ion cell tertiary cathode modified material, includes the following steps：
(1) according to stoichiometric ratio (1.00:0.696:0.103:0.205:0.05:0.05) analytically pure LiNO is weighed3、 Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·4H2O、Cr(NO3)3·4H2O, LiF, it is molten with deionized water respectively Solution is complete, adds citric acid solution, and addition is equal to the sum of mole of transition metal ions, after mixing will with concentrated ammonia liquor PH value is adjusted to 7.0 or so；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 100 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 150 DEG C, when drying time is 15 small, is done Gelinite；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 600 DEG C, when burn-in time is 4 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 1000 DEG C, calcination time is small for 20 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.95Cr0.05O1.95F0.05。
(5) by the covering material FePO of the positive electrode of the above-mentioned doping vario-property prepared and mass fraction than 5.5wt%4 It is scattered in appropriate solvent, is vigorously stirred at 80 DEG C, and adjust PH 9, until solvent volatilizees completely.Stood after stirring 1 is filtered when small using quantitative filter paper, and is washed with deionized 2 times when drying 12 is small under the conditions of 80 DEG C, and last 450 DEG C are forged Burn 5h and obtain final product surface cladding 5.5wt%FePO4Li (Ni0.7Co0.1Mn0.2)0.95Cr0.05O1.95F0.05。
Embodiment 5：A kind of preparation method of high-capacity lithium ion cell tertiary cathode modified material, includes the following steps：
(1) according to stoichiometric ratio (1.00:0.698:0.103:0.205:0.05:0.05) analytically pure LiOH is weighed H2O、NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、C16H36O4Ti, LiF, it is complete with deionized water dissolving respectively, add Citric acid solution, addition are equal to the sum of mole of transition metal ions, after mixing with concentrated ammonia liquor by pH value adjust to 7.5；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 90 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 120 DEG C, when drying time is 12 small, is done Gelinite；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 500 DEG C, when burn-in time is 6 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 850 DEG C, calcination time is small for 20 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.95Ti0.05O1.95F0.05。
(5) the covering material TiO than 2.0wt% by the above-mentioned doping vario-property positive electrode prepared and mass fraction2Point Dissipate in alcohol solvent, be vigorously stirred at 80 DEG C, and adjust PH 9, until solvent volatilizees completely, 2 are stood after stirring Hour is filtered using quantitative filter paper, and is washed with deionized 2 times when drying 15 is small under the conditions of 82 DEG C, and last 480 DEG C are forged Burn 6h and obtain final product surface cladding 2.0wt%TiO2Li (Ni0.7Co0.1Mn0.2)0.95Ti0.05O1.95F0.05。
Embodiment 6：A kind of preparation method of high-capacity lithium ion cell tertiary cathode modified material, includes the following steps：
(1) according to stoichiometric ratio (1.00：0.702：0.102:0.206:0.03:0.05) weigh analytically pure CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)·4H2O、Al(NO3)2· 9H2O, LiCl, it is complete with deionized water dissolving respectively, citric acid solution is added, the addition of citric acid solution is equal to transition gold Belong to the sum of mole of ion, after mixing adjusted pH value to 7 with concentrated ammonia liquor；
(2) mixed solution for obtaining step (1) is heated to evaporate moisture in 80 DEG C of water-bath, and is stirred continuously, and is obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 100 DEG C, when drying time is 15 small, is done Gelinite；
(4) dry gelinite is subjected to pre-burning, calcined temperature is 600 DEG C, when burn-in time is 6 small, obtains presoma； Ground after presoma cooled to room temperature, the presoma after grinding is calcined at 850 DEG C, calcination time is small for 20 When, regrind after calcining after cooled to room temperature, that is, obtain the positive electrode Li (Ni of doping vario-property0.7Co0.1Mn0.2)0.97Al0.03O1.95Cl0.05。
(5) by the covering material TiO of the positive electrode of the above-mentioned doping vario-property prepared and mass fraction than 5.5wt%2 It is dispersed in water, is vigorously stirred at 80 DEG C, and it is 9 to adjust PH, until solvent volatilizees completely, when standing 2 is small after stirring Filtered using quantitative filter paper, and be washed with deionized 2 times when drying 18 is small under the conditions of 85 DEG C, then 450 DEG C of calcining 5h Obtain final product surface cladding 5.5wt%TiO2Li (Ni0.7Co0.1Mn0.2)0.97Al0.03O1.95Cl0.05。
From in the X-ray diffracting spectrum of comparative example in Fig. 1 and embodiment 2,3,5, being synthesized in embodiment 2,3,5 Positive electrode has the hexagonal layer structure of high-sequential, does not occur and belongs to the miscellaneous of doped chemical and covering material Mass peak, the main peak (1003) of the XRD of each sample and (104) are obvious sharp, and (101) and the division of (006) peak are notable, illustrate this The positive electrode prepared in invention in embodiment 2,3,5 is obvious layer structure, and crystal form is good, especially the stratiform of embodiment 5 Structure is best.
From in the scanning electron microscope (SEM) photograph of comparative example in Fig. 2 and embodiment 2,3,5, comparative example particle is relatively fine and particle diameter divides Cloth is uniform, and surface is smooth, and crystallinity is preferable, and the embodiment after overdoping and coating modification, material granule has increased, Particle agglomeration is even closer, and in addition, the change that becomes apparent from that modified material granule occurs is that material granule surface is all attached Tiny particulate, has illustrated TiO2、A12O3With FePO4Covering material is all successfully coated on material granule surface.
By the positive electrode powder synthesized in embodiment 1-6, acetylene black, gather inclined tetrafluoroethene (PVDF) by mass fraction ratio 80：12：8 mixing, are ground into uniform sizing material after adding appropriate pyrrolidones, are spread evenly across on aluminium foil, dried at 100 DEG C, blunderbuss Cut (diameter 14mm), 3MPa is rolled, and pole piece is made, through 80 DEG C vacuum drying 12 it is small when after use, in the glove box full of argon gas Middle assembling button (CR2032) test battery, negative electricity extremely lithium piece, electrolyte is LB315 [m (DMC):m(EMC):M (EC)=1: 1:1] solution, membrane are Celgard2325 holes film.The battery assembled is subjected to charge-discharge test with LAND-CT2001A. Discharge and recharge section is 2.5-4.6V.
Due in obtained positive electrode Li elements in high-temperature calcination it is volatile, have 5% or so Li losses, therefore The actual mole dosage of lithium salts is high compared with theoretical amount by 5% or so.
The battery that the positive electrode that comparative example and embodiment 2,3,5 synthesize is assembled into is under room temperature, 0.2C current densities Electrochemical Characterization the results are shown in Table 1.
The battery that the positive electrode of comparative example and embodiment 2,3,5 is assembled, at room temperature filling first under 0.2C electric currents Discharge curve is as shown in Figure 3；From the figure 3, it may be seen that the battery for the positive electrode assembling that the present invention implements to be prepared in 2,3,5 fills Discharge curve is very smooth, and the voltage platform of charging curve is less than the voltage platform of comparative example, and the discharge curve platform of embodiment 5 Higher than comparative example, also best during further explanation embodiment 5, the result is consistent with XRD test results above.Comparative example The battery assembled with the positive electrode of embodiment 2,3,5, cyclic curve figure at normal temperatures are as shown in Figure 4；As shown in Figure 4, The circulating battery stability of the material of each embodiment is higher than comparative example, especially embodiment 5 when cyclical stability most Battery good, that the positive electrode of comparative example and embodiment 2,3,5 is assembled, at room temperature respectively 0.2C, 0.5C, 1C, 2.5C, The cyclic curve figure of each circulation 10 times is as shown in figure 5, as shown in Figure 5 under the conditions of 0.2C multiplying powers, preparation method using the present invention, The volume positive electrode prepared in each embodiment is all improved by cladding, the chemical property of material, especially 2% The effect of TiO2 claddings is best.
Under 1 0.2C current densities of table, each embodiment charge-discharge performance test result is as shown in the table：
As shown in Table 1, compared with comparative example does not have the positive electrode of covering material, embodiment 1- embodiments 6 in the present invention In pass through TiO2、A12O3Or FePO4Cladding of the covering material to positive electrode so that the initial of the positive electrode being prepared is put Electric specific capacity is improved, and cyclical stability is improved, the cladding 2.0wt%TiO especially prepared in embodiment 52Li (Ni0.4Co0.2Mn0.4)0.95Ti0.05O1.95F0.05Effect is best, and capacity retention ratio is 99.8% after 50 circulations, and discharge ratio first Capacity is 188.9mAh/g.

Claims (10)

  1. A kind of 1. high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof, it is characterised in that：Change including doping The positive electrode of property, the outer layer covers of the positive electrode of the doping vario-property have one layer of covering material, the matter of the covering material Amount is the 1-6wt% of the positive electrode of doping vario-property, and the chemical general formula of the positive electrode of the doping vario-property is Li (Ni0.4Co0.2Mn0.4)1-xMxO2-yNy, wherein, M Mo, Fe, Ti, Mg, Al or Cr；N is F, Cl or Br, 0 ＜ x≤0.10,0 ＜ y ≤ 0.10, the covering material is TiO2、A12O3Or FePO4。
  2. 2. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 1, it is characterised in that： Include the following steps：
    (1) water miscible lithium source, nickel source, manganese source, cobalt source, M salt, N salt and citric acid are dissolved in deionized water and be sufficiently mixed, then PH value is adjusted to 7~8 with ammonium hydroxide；
    (2) solution for obtaining step (1) agitating and heating at 60~100 DEG C, obtains gelinite；
    (3) by when drying 8~15 is small at 80~150 DEG C of gelinite obtained by step (2), xerogel body is obtained；
    (4) by xerogel body when 300~600 DEG C of pre- calcinations processing 4~8 are small, cooled to room temperature grinds to obtain presoma；
    (5) when roasting 10~20 is small under the conditions of the presoma that step (4) obtains being placed in 700~1000 DEG C, continue to grind after cooling Mill obtains the positive electrode of doping vario-property；
    (6) be by the quality of covering material doping vario-property positive electrode 1-6% weigh covering material, covering material TiO2、 A12O3Or FePO4；
    (7) positive electrode of the above-mentioned doping vario-property prepared and covering material are scattered in water or ethanol makes doping vario-property Positive electrode and covering material dissolving are complete, are vigorously stirred at 40~80 DEG C, and adjust pH to 9~10, until solvent is complete Volatilization, is filtered when standing 1~2 is small after stirring using quantitative filter paper, and is washed with deionized 1~2 time after 80~85 When drying 12~20 is small under the conditions of DEG C, finally 5~10h are calcined at 400~500 DEG C and obtain final product.
  3. 3. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The lithium source, nickel source, manganese source, cobalt source, M salt, N salt are (1-y) according to the molar ratio of lithium, nickel, manganese, cobalt, M, N:(0.7-x): (0.2-x):(0.1-x):x:Y is added, wherein 0 ＜ x≤0.10,0 ＜ y≤0.10.
  4. 4. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The molar ratio of the nickel salt, the integral molar quantity of cobalt salt and manganese salt and citric acid is 1:1~1:2.
  5. 5. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The lithium source is LiNO3、CH3One or more in COOLi, LiOH.
  6. 6. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The nickel source is Ni (NO3)2、Ni(CH3COO)2、NiSO4In one or more.
  7. 7. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The manganese source is Mn (NO3)2、Mn(CH3COO)2、MnSO4In one or more.
  8. 8. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The cobalt source is Co (NO3)2、Co(CH3COO)2、CoSO4In one or more.
  9. 9. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, it is characterised in that： The M salt is Mg (NO3)2、C16H36O4Ti、Al(NO3)3Or Cr (NO3)3In one kind.
  10. 10. the preparation method of high-capacity lithium ion cell tertiary cathode modified material as claimed in claim 2, its feature exist In：The N salt is one kind in LiCl, LiF, LiBr.
CN201711324080.6A 2017-12-13 2017-12-13 A kind of high-capacity lithium ion cell tertiary cathode modified material and preparation method thereof Pending CN107910543A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108682795A (en) * 2018-03-28 2018-10-19 合肥国轩高科动力能源有限公司 A kind of ternary cathode material of lithium ion battery surface acid-washing cladding TiO2Method
CN108807887A (en) * 2018-05-31 2018-11-13 电子科技大学 A kind of dual modified anode material for lithium-ion batteries of aluminium fluorine and preparation method thereof
CN109638258A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of positive electrode and its preparation method and application
CN109817906A (en) * 2018-12-29 2019-05-28 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN109830654A (en) * 2018-12-29 2019-05-31 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN109888199A (en) * 2018-12-29 2019-06-14 深圳市卓能新能源股份有限公司 Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery
CN111261851A (en) * 2018-12-03 2020-06-09 北大先行科技产业有限公司 Ternary cathode material of lithium ion battery and preparation method thereof
CN111342012A (en) * 2020-03-03 2020-06-26 沁新集团(天津)新能源技术研究院有限公司 Mesoporous spherical titanium dioxide coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery
CN111377487A (en) * 2020-03-26 2020-07-07 江苏海基新能源股份有限公司 Preparation method of Al and F co-doped high-nickel ternary cathode material
CN111446433A (en) * 2020-04-23 2020-07-24 华鼎国联四川电池材料有限公司 Positive electrode composite material for lithium battery and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105576236A (en) * 2016-02-25 2016-05-11 江南大学 Lithium ion battery 442 ternary anode modified material and preparing method thereof
CN106711414A (en) * 2016-12-16 2017-05-24 江南大学 811-type ternary positive modified material for lithium ion batteries and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105576236A (en) * 2016-02-25 2016-05-11 江南大学 Lithium ion battery 442 ternary anode modified material and preparing method thereof
CN106711414A (en) * 2016-12-16 2017-05-24 江南大学 811-type ternary positive modified material for lithium ion batteries and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡信国等编著: "《动力电池技术与应用》", 31 January 2013, 北京：化学工业出版社 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108682795B (en) * 2018-03-28 2021-01-08 合肥国轩高科动力能源有限公司 Surface pickling coating TiO of ternary anode material of lithium ion battery2Method (2)
CN108682795A (en) * 2018-03-28 2018-10-19 合肥国轩高科动力能源有限公司 A kind of ternary cathode material of lithium ion battery surface acid-washing cladding TiO2Method
CN108807887A (en) * 2018-05-31 2018-11-13 电子科技大学 A kind of dual modified anode material for lithium-ion batteries of aluminium fluorine and preparation method thereof
CN111261851B (en) * 2018-12-03 2021-07-13 北大先行科技产业有限公司 Ternary cathode material of lithium ion battery and preparation method thereof
CN111261851A (en) * 2018-12-03 2020-06-09 北大先行科技产业有限公司 Ternary cathode material of lithium ion battery and preparation method thereof
CN109638258A (en) * 2018-12-18 2019-04-16 中科廊坊过程工程研究院 A kind of positive electrode and its preparation method and application
CN109638258B (en) * 2018-12-18 2021-09-14 中科廊坊过程工程研究院 Positive electrode material and preparation method and application thereof
CN109817906A (en) * 2018-12-29 2019-05-28 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN109888199A (en) * 2018-12-29 2019-06-14 深圳市卓能新能源股份有限公司 Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery
CN109830654A (en) * 2018-12-29 2019-05-31 深圳市卓能新能源股份有限公司 Anode coating, battery anode slice and lithium ion battery
CN111342012A (en) * 2020-03-03 2020-06-26 沁新集团(天津)新能源技术研究院有限公司 Mesoporous spherical titanium dioxide coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery
CN111342012B (en) * 2020-03-03 2021-08-20 沁新集团(天津)新能源技术研究院有限公司 Mesoporous spherical titanium dioxide coated ternary material, preparation method thereof, lithium ion battery anode and lithium ion battery
CN111377487A (en) * 2020-03-26 2020-07-07 江苏海基新能源股份有限公司 Preparation method of Al and F co-doped high-nickel ternary cathode material
CN111446433A (en) * 2020-04-23 2020-07-24 华鼎国联四川电池材料有限公司 Positive electrode composite material for lithium battery and preparation method thereof

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