CN106711414A - 811-type ternary positive modified material for lithium ion batteries and preparation method thereof - Google Patents

811-type ternary positive modified material for lithium ion batteries and preparation method thereof Download PDF

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CN106711414A
CN106711414A CN201611174060.0A CN201611174060A CN106711414A CN 106711414 A CN106711414 A CN 106711414A CN 201611174060 A CN201611174060 A CN 201611174060A CN 106711414 A CN106711414 A CN 106711414A
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张海朗
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Jiangnan University
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Abstract

The invention relates to an 811-type ternary positive modified material for lithium ion batteries and a preparation method thereof. The 811-type ternary positive modified material comprises a positive material, wherein the outer layer of the positive material is coated with a clad material layer, the mass ratio of the clad material to the positive material is 1 to 5 wt%, the chemical general formula of the positive material is Li(Ni0.8Co0.1Mn0.1)1-xMxO2-yNy, wherein M is Zn, Fe, Ti, Mg, Al or Cr; N is F, Cl or Br, x is greater than 0 and less than or equal to 0.10, y is greater than 0 and less than or equal to 0.10, the clad material is TiO2, Al2O3 or FePO4. The preparation method comprises the following steps: firstly using the raw materials for obtaining a gel with a sol-gel method, after heating and drying, obtaining the positive material after twice firing and grinding, then suspending the positive material and the clad material in deionized water and stirring at a constant temperature, and then carrying out standing, filtering, washing, drying and calcinations so as to obtain the 811-type ternary positive modified material for lithium ion batteries. The preparation method is simple, the steps are easy to operate, prepared and obtained ternary positive modified particles are uniform in distribution, high in degree of crystallinity, smooth in surfaces and good in particle dispersity, and the rate capability and cycle performance of the material are improved.

Description

A kind of type tertiary cathode of lithium ion battery 811 is material modified and preparation method thereof
Technical field
It is material modified and preparation method thereof the present invention relates to a kind of type tertiary cathode of lithium ion battery 811, 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 The further improvement of security with greater need for be positive electrode circulation, the continuous improvement of high rate performance and heat endurance.Ternary Positive electrode is LiCoO2/LiNiO2/LiMn2O4Eutectic system, this eutectic system had LiCoO concurrently2、LiNiO2、 LiMn2O4The characteristics of three class materials, this material is a kind of to contain nickel, cobalt, three kinds of advanced composite material (ACM)s of element of manganese, ternary material There is obvious three elements cooperative effect in material, chemical property is better than any one single group polymerisable compounds.
As (811) type ternary material LiNi a kind of in ternary system0.8Co0.1Mn0.1O2, with traditional (333) type LiNi1/3Mn1/3Co1/3O2Material is compared, and the content of Co is significantly reduced, and can be made the production cost of material and be reduced, while material is given birth to Produce with the process of use to more environment-friendly.The content of Ni is higher, contributes to material to obtain discharge capacity higher.Meanwhile, it is right The content of the maximum Mn of material safety and stability contribution increases, and can make material circulation and security more preferably, and being more suitable for reality should With, thus LiNi0.8Co0.1Mn0.1O2It is a kind of tertiary cathode material with more researching value.
And for the requirement of commercial applications, LiNi0.8Co0.1Mn0.1O2What positive electrode needed raising is vibration density The charging and discharging capabilities of degree, energy force density, circulation ability and big multiplying power.For current LiNi0.8Co0.1Mn0.1O2Tertiary cathode material The deficiency that material is remained, researchers are substantially carried out part doping or surface coating modification to material, and doping vario-property is mainly logical Cross to other metal ions close with bulk transition metal ionic radius that partly adulterated in positive electrode, 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 one layer of material of stable chemical nature on positive electrode surface, be effectively prevented from the directly contact of material and electrolyte, Suppress the interaction between them by such mode 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 positive pole 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 LiNi0.8Co0.1Mn0.1O2The modified synergic that positive electrode is doped or coats.
The content of the invention
The invention aims to solve the above problems, there is provided a kind of simple lithium ion battery 811 of preparation method Type tertiary cathode is material modified and preparation method thereof, and the positive electrode particle diameter distribution for preparing is uniform, and structure is more stablized, material Material high rate performance and cycle performance are preferable.
The present invention is adopted the following technical scheme that：A kind of type tertiary cathode of lithium ion battery 811 is material modified, including doping changes 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 1-5wt% of the positive electrode of doping vario-property, and the chemical general formula of the positive electrode of the doping vario-property is Li (Ni0.8Co012Mn0.1)1-xMxO2-yNy, wherein, M is Zn, 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、Al2O3Or FePO4。
The material modified preparation method of the type tertiary cathode of lithium ion battery 442, comprises 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 Ammoniacal liquor adjusts pH value to 7~8；
(2) solution for obtaining step (1) agitating heating at 60~100 DEG C, obtains gelinite；
(3) will be dried 8~15 hours at step (2) 80~150 DEG C of gelinite of gained, obtain xerogel body；
(4) xerogel body is processed 4~8 hours in 300~600 DEG C of pre- calcinations, is naturally cooled to before grinding at room temperature obtains Drive body；
(5) it is calcined 10~20 hours under the conditions of the presoma that step (4) is obtained is placed in 700~1000 DEG C, is continued after cooling Grinding obtains the positive electrode of doping vario-property；
(6) be by the quality of covering material doping vario-property positive electrode 1-5wt% weigh covering material, covering material It is TiO2、Al2O3Or FePO4；
(7) doping is changed in the positive electrode and covering material of the above-mentioned doping vario-property for preparing being scattered in into water or ethanol Property positive electrode and covering material dissolving it is complete, be stirred vigorously at 40~80 DEG C, and adjust pH 9~10, until solvent Volatilize completely, stirring stands 1~2 hour using quantitative filter paper filtering after terminating, and is washed with deionized 1~2 time after 80 Dried under the conditions of~85 DEG C 12~20 hours, it is to obtain final product finally to calcine 5~10h at 400~500 DEG C.
Further, the lithium source, nickel source, manganese source, cobalt source, M salt, N salt are according to the mol ratio of lithium, nickel, manganese, cobalt, M, N (1-y): (0.8-x): (0.1-x): (0.1-x): x: y adds, wherein 0 ＜ x≤0.10,0 ＜ y≤0.10.
Further, the mol 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 the 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 for preparing is uniform, crystallinity Height, surface is smooth, and particle dispersion is good, because 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 Li high+Diffusion rate, make material surface Li+Abjection is easier with insertion, and doping is served with the comprehensive function of coating modification Material high rate performance and cycle performance are improved, and is adulterated with the cost of material needed for coating modification cheaply, reduce further Cost needed for positive electrode production, is conducive to advancing 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 normal temperature under 0.2C electric currents is bent Line chart, discharge voltage range is 2.5-4.6V.
The positive electrode that Fig. 4 is prepared for comparative example and embodiment 2,3,5, cyclic curve figure during normal 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, the cyclic curve in normal temperature under different multiplying Figure, charging/discharging voltage scope is 2.5-4.6V.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Comparative example：Unmodified LiNi0.4Co0.2Mn0.4O2The preparation of positive electrode.
Analytically pure CH is weighed according to stoichiometric proportion (1.05: 0.8: 0.1: 0.1)3COOLi、Ni(CH3COO)2、Co (CH3COO)2、Mn(CH3COO)2Fully dissolved with deionized water respectively, add citric acid solution, the addition of citric acid solution Equal to the mole sum of transition metal ions, solution ph is adjusted to 7.5,80 DEG C of heating water baths with concentrated ammonia liquor after being well mixed Stirring, makes various ions fully be complexed, and makes moisture evaporation to formation darkviolet gel；Gel is dried under the conditions of 120 DEG C 10 hours, pre-processed 6 hours at being then placed in 500 DEG C, ground after cooling, obtained within 20 hours then at 850 DEG C of roastings LiNi0.8Co0.1Mn0.1O2Positive electrode.
Embodiment 1：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) weighed according to stoichiometric proportion (1.02: 0.798: 0.105: 0.108: 0.03: 0.03) analytically pure CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)·4H2O、Mg(NO3)2· 6H2O, LiF, respectively with deionized water dissolving completely, add the addition of citric acid solution, citric acid solution to be equal to transition metal The mole sum of ion, is adjusted to 7 pH value with concentrated ammonia liquor after being well mixed；
(2) mixed solution that step (1) is obtained is heated in 60 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 80 DEG C, and drying time is 8 hours, obtains dry solidifying Colloid；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 300 DEG C, and burn-in time is 8 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 700 DEG C, and calcination time is 10 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.97Mg0.03O1.97F0.03。
(5) by above-mentioned covering material TiO of the doping vario-property positive electrode and mass fraction for preparing than 1.0wt%2Point Dissipate in amount of alcohol solvent, be stirred vigorously at 40 DEG C, and adjust PH 9, until solvent volatilizees completely, stirring stands 1 after terminating Hour use quantitative filter paper filtering, and 1 drying 20 hour under the conditions of 80 DEG C is washed with deionized, last 400 DEG C are forged It is to obtain final product Surface coating 1.0wt%TiO to burn 10h2Li (Ni0.8Co0.1Mn0.1)0.97Mg0.03O1.97F0.03。
Embodiment 2：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) analytically pure LiNO is weighed according to stoichiometric proportion (1.00: 0.77: 0.10: 0.105: 0.05: 0.05)3、
Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·4H2O、C16H36O4Ti, LiCl, use deionization respectively Water dissolves completely, add citric acid solution, and the addition of citric acid solution is equal to the mole sum of transition metal ions, mixing PH value is adjusted to 7.5 with concentrated ammonia liquor after uniform；
(2) mixed solution that step (1) is obtained is heated in 80 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 100 DEG C, and drying time is 10 hours, is done Gelinite；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 400 DEG C, and burn-in time is 5 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 850 DEG C, and calcination time is 15 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.95Ti0.05O1.95Cl0.05。
(5) the covering material Al by the positive electrode and mass fraction of the above-mentioned doping vario-property for preparing than 2.0wt%2O3 It is scattered in appropriate solvent, is stirred vigorously at 60 DEG C, and adjust PH 9 or so, until solvent volatilizees completely.After stirring terminates 2 hours are stood using quantitative filter paper filtering, and is washed with deionized 2 times and 12 hours, last 450 are dried under the conditions of 85 DEG C DEG C calcining 8h be to obtain final product Surface coating 2.0wt%Al2O3Li (Ni0.8Co0.1Mn0.1)0.95Ti0.05O1.95Cl0.05。
Embodiment 3：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) analytically pure LiOHH is weighed according to stoichiometric proportion (0.95: 0.72: 0.10: 0.10: 0.1: 0.1)2O、 NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、Al(NO3)3, LiBr, respectively with deionized water dissolving completely, add lemon Acid solution, addition is equal to the mole sum of transition metal ions, is adjusted to 8 left sides pH value with concentrated ammonia liquor after being well mixed It is right；
(2) mixed solution that step (1) is obtained is heated in 90 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 120 DEG C, and drying time is 12 hours, is done Gelinite；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 500 DEG C, and burn-in time is 6 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 900 DEG C, and calcination time is 18 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.9Al0.1O1.9Br0.1。
(5) the covering material FePO by the positive electrode and mass fraction of the above-mentioned doping vario-property for preparing than 3.0wt%4 It is scattered in appropriate solvent, is stirred vigorously at 80 DEG C, and adjust PH 9 or so, until solvent volatilizees completely.After stirring terminates Use quantitative filter paper filtering in 1.5 hours is stood, and 2 drying 15 hours under the conditions of 80 DEG C are washed with deionized, finally 500 DEG C of calcining 5h are to obtain final product Surface coating 3.0wt%FePO4Li (Ni0.8Co0.1Mn0.1)0.9Al0.1O1.9Br0.1。
Embodiment 4：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) analytically pure LiNO is weighed according to stoichiometric proportion (1.00: 0.765: 0.105: 0.103: 0.05: 0.05)3、 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 mole sum of transition metal ions, will with concentrated ammonia liquor after being well mixed PH value is adjusted to 7.0 or so；
(2) mixed solution that step (1) is obtained is heated in 100 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 150 DEG C, and drying time is 15 hours, is done Gelinite；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 600 DEG C, and burn-in time is 4 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 1000 DEG C, and calcination time is 20 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.95Cr0.05O1.95F0.05。
(5) the covering material FePO by the positive electrode and mass fraction of the above-mentioned doping vario-property for preparing than 4.0wt%4 It is scattered in appropriate solvent, is stirred vigorously at 80 DEG C, and adjust PH 9, until solvent volatilizees completely.Stirring stands after terminating Filtered using quantitative filter paper within 1 hour, and be washed with deionized 2 times and dried 12 hours under the conditions of 80 DEG C, last 450 DEG C are forged It is to obtain final product Surface coating 4.0wt%FePO to burn 5h4Li (Ni0.8Co0.1Mn0.1)0.95Cr0.05O1.95F0.05。
Embodiment 5：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) analytically pure LiOH is weighed according to stoichiometric proportion (1.00: 0.765: 0.105: 0.106: 0.05: 0.05) H2O、NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、C16H36O4Ti, LiF, respectively with deionized water dissolving completely, add Citric acid solution, addition is equal to the mole sum of transition metal ions, it is well mixed after with concentrated ammonia liquor by pH value adjust to 7.5；
(2) mixed solution that step (1) is obtained is heated in 90 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 120 DEG C, and drying time is 12 hours, is done Gelinite；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 500 DEG C, and burn-in time is 6 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 850 DEG C, and calcination time is 20 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.95Ti0.05O1.95F0.05。
(5) by above-mentioned covering material TiO of the doping vario-property positive electrode and mass fraction for preparing than 2.0wt%2Point Dissipate in alcohol solvent, be stirred vigorously at 80 DEG C, and adjust PH 9, until solvent volatilizees completely, stirring stands 2 after terminating Hour use quantitative filter paper filtering, and 2 drying 15 hours under the conditions of 82 DEG C are washed with deionized, last 480 DEG C are forged It is to obtain final product Surface coating 2.0wt%TiO to burn 6h2Li (Ni0.8Co0.1Mn0.1)0.95Ti0.05O1.95F0.05。
Embodiment 6：A kind of material modified preparation method of the type tertiary cathode of lithium ion battery 811, comprises the following steps：
(1) weighed according to stoichiometric proportion (1.00: 0.801: 0.103: 0.105: 0.03: 0.05) analytically pure CH3COOLi·2H2O、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O、Mn(CH3COO)·4H2O、Al(NO3)2· 9H2O, LiCl, respectively with deionized water dissolving completely, add the addition of citric acid solution, citric acid solution to be equal to transition gold Belong to the mole sum of ion, adjusted to 7 pH value with concentrated ammonia liquor after being well mixed；
(2) mixed solution that step (1) is obtained is heated in 80 DEG C of water-bath to evaporate moisture, and is stirred continuously, obtained To gelinite；
(3) gelinite is dried in air dry oven, drying temperature is 100 DEG C, and drying time is 15 hours, is done Gelinite；
(4) dry gelinite is carried out into pre-burning, calcined temperature is 600 DEG C, and burn-in time is 6 hours, obtains presoma； Presoma is ground after naturally cooling to room temperature, and the presoma after grinding is calcined at 850 DEG C, and calcination time is 20 small When, regrind after room temperature is naturally cooled to after calcining, that is, obtain the positive electrode Li (Ni of doping vario-property0.8Co0.1Mn0.1)0.97Al0.03O1.95Cl0.05。
(5) the covering material TiO by the positive electrode and mass fraction of the above-mentioned doping vario-property for preparing than 5.0wt%2 It is dispersed in water, is stirred vigorously at 80 DEG C, and it is 9 to adjust PH, until solvent volatilizees completely, stirring stands 2 hours after terminating Filtered using quantitative filter paper, and be washed with deionized 2 times and dried under the conditions of 85 DEG C 18 hours, then calcine 5h for 450 DEG C Obtain final product Surface coating 5.0wt%TiO2Li (Ni0.8Co0.1Mn0.1)0.97Al0.03O1.95Cl0.05。
In X-ray diffracting spectrum from comparative example in Fig. 1 and embodiment 2,3,5, synthesize in embodiment 2,3,5 Positive electrode has the hexagonal layer structure of high-sequential, does not occur that to belong to doped chemical miscellaneous with covering material Mass peak, the main peak (1003) of the XRD of each sample and (104) are substantially sharp, and (101) are notable with the division of (006) peak, illustrate this The positive electrode prepared in embodiment 2,3,5 in invention is obvious layer structure, and crystal formation is good, especially the stratiform of embodiment 5 Structure is best.
In scanning electron microscope (SEM) photograph from 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 preferably, through the embodiment after overdoping and coating modification, material granule has increased crystallinity, 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, TiO has been illustrated2、Al2O3With FePO4Covering material is all successfully coated on material granule surface.
The positive electrode powder synthesized in embodiment 1-6, acetylene black, poly- inclined tetrafluoroethene (PVDF) are pressed into mass fraction ratio 80: 12: 8 mixing, uniform sizing material is ground to form after adding appropriate pyrrolidones, is spread evenly across on aluminium foil, is dried at 100 DEG C, blunderbuss Cut (diameter 14mm), 3MPa is rolled, be made pole piece, used after being vacuum dried 12 hours through 80 DEG C, in the glove box full of argon gas It is middle assembling button (CR2032) test battery, negative electricity extremely lithium piece, electrolyte be LB315 [m (DMC): m (EMC): m (EC)=1: 1: 1] solution, barrier film is Celgard2325 holes film.The battery that will be assembled carries out charge-discharge test with LAND-CT2001A. It is 2.5-4.6V that discharge and recharge is interval.
Because Li elements are volatile in high-temperature calcination in the positive electrode that obtains, 5% or so Li losses are had, therefore The actual mole dosage of lithium salts is high compared with theoretical amount by 5% or so.
The battery that comparative example and the positive electrode of the synthesis of embodiment 2,3,5 are assembled into is under normal temperature, 0.2C current densities Electrochemical Characterization result it is as shown in table 1.
The battery that the positive electrode of comparative example and embodiment 2,3,5 is assembled, the filling first under 0.2C electric currents in normal temperature Discharge curve is as shown in Figure 3；From the figure 3, it may be seen that the battery that the present invention implements the positive electrode assembling prepared in 2,3,5 fills Discharge curve is very smooth, the voltage platform of the voltage platform less than comparative example of charging curve, and the discharge curve platform of embodiment 5 Higher than comparative example, also further illustrate best during 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 is 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, and especially cyclical stability during embodiment 5 is most It is good, the battery that the positive electrode of comparative example and embodiment 2,3,5 is assembled, in normal 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, using preparation method of the invention, By cladding, the chemical property of material is all improved the volume positive electrode prepared in each embodiment, and especially 2% The effect of TiO2 claddings is best.
Under the 0.2C current densities of table 1, each embodiment charge-discharge performance test result is as shown in the table：
As shown in Table 1, compared with the positive electrode that comparative example does not have covering material, embodiment 1- embodiments 6 in the present invention In pass through TiO2、Al2O3Or FePO4Cladding of the covering material to positive electrode so that the initial of the positive electrode for preparing is put Electric specific capacity is improved, and cyclical stability is improved, the cladding 2.0wt%TiO for especially being prepared in embodiment 52Li (Ni0.4Co0.2Mn0.4)0.95Ti0.05O1.95F0.05Preferably, capability retention is 99.8% to effect after 50 circulations, the ratio of electric discharge first Capacity is 188.3mAh/g.

Claims (10)

1. a kind of type tertiary cathode of lithium ion battery 811 is material modified and preparation method thereof, it is characterised in that：Including doping vario-property Positive electrode, the outer layer covers of the positive electrode of the doping vario-property have one layer of covering material, the quality of the covering material It is the 1-5wt% of the positive electrode of doping vario-property, the chemical general formula of the positive electrode of the doping vario-property is Li (Ni0.4Co0.2Mn0.4)1-xMxO2-yNy, wherein, M is Zn, 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、Al2O3Or FePO4。
2. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 1 811, it is characterised in that： Comprise 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 are sufficiently mixed, then PH value to 7~8 is adjusted with ammoniacal liquor；
(2) solution for obtaining step (1) agitating heating at 60~100 DEG C, obtains gelinite；
(3) will be dried 8~15 hours at step (2) 80~150 DEG C of gelinite of gained, obtain xerogel body；
(4) xerogel body is processed 4~8 hours in 300~600 DEG C of pre- calcinations, naturally cools to grinding at room temperature and obtain presoma；
(5) it is calcined 10~20 hours under the conditions of the presoma that step (4) is obtained being placed in into 700~1000 DEG C, continues to grind after cooling Mill obtains the positive electrode of doping vario-property；
(6) it is that the 1-5wt% of positive electrode of doping vario-property weighs covering material by the quality of covering material, covering material is TiO2、Al2O3Or FePO4；
(7) doping vario-property is made in the positive electrode and covering material of the above-mentioned doping vario-property for preparing being scattered in into water or ethanol Positive electrode and covering material dissolving are complete, are stirred vigorously at 40~80 DEG C, and adjust pH to 9~10, until solvent is complete Volatilization, stirring stands 1~2 hour using quantitative filter paper filtering after terminating, and is washed with deionized 1~2 time after 80~85 Dried under the conditions of DEG C 12~20 hours, it is to obtain final product finally to calcine 5~10h at 400~500 DEG C.
3. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The lithium source, nickel source, manganese source, cobalt source, M salt, N salt are (1-y): (0.8-x) according to the mol ratio of lithium, nickel, manganese, cobalt, M, N: (0.1-x): (0.1-x): x: y adds, wherein 0 ＜ x≤0.10,0 ＜ y≤0.10.
4. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The integral molar quantity of the nickel salt, cobalt salt and manganese salt and the mol ratio of citric acid are 1: 1~1: 2.
5. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The lithium source is LiNO3、CH3One or more in COOLi, LiOH.
6. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The nickel source is Ni (NO3)2、Ni(CH3COO)2、NiSO4In one or more.
7. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 442, it is characterised in that： The manganese source is Mn (NO3)2、Mn(CH3COO)2、MnSO4In one or more.
8. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 442, it is characterised in that： The cobalt source is Co (NO3)2、Co(CH3COO)2、CoSO4In one or more
9. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The M salt is Mg (NO3)2、C16H36O4Ti、Al(NO3)3Or Cr (NO3)3In one kind.
10. the material modified preparation method of the type tertiary cathode of lithium ion battery as claimed in claim 2 811, it is characterised in that： The N salt is the one kind in LiCl, LiF, LiBr.
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