CN109216692A - Modified tertiary cathode material and preparation method thereof, lithium ion battery - Google Patents

Modified tertiary cathode material and preparation method thereof, lithium ion battery Download PDF

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CN109216692A
CN109216692A CN201811318171.3A CN201811318171A CN109216692A CN 109216692 A CN109216692 A CN 109216692A CN 201811318171 A CN201811318171 A CN 201811318171A CN 109216692 A CN109216692 A CN 109216692A
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cathode material
tertiary cathode
lini
preparation
modified
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CN109216692B (en
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郑俊超
刘洋
范鑫铭
贺振江
汤林波
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Central South University
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Central South 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

A kind of modified tertiary cathode material and preparation method thereof, lithium ion battery, the general formula of the modification tertiary cathode material are LiNixCoyM1‑x‑yO2@aLiInO2, wherein 0.8≤x < 1,0 < y < 1,0 < 1-x-y < 1, M are Mn and/or Al element, a is the content of metaindic acid lithium clad, on the basis of the total weight for being modified tertiary cathode material, the weight of 0 < a≤10 %.The invention also includes the preparation methods of modified tertiary cathode material, lithium ion battery.The modification tertiary cathode material of the present invention has good cyclical stability and high rate performance, and preparation method operation is simple, low in cost, safe and reliable.On this basis, the lithium ion battery using the modification tertiary cathode material as positive electrode is significantly increased in specific discharge capacity, cycle performance, which can be applied to power battery field.

Description

Modified tertiary cathode material and preparation method thereof, lithium ion battery
Technical field
The present invention relates to power battery technology fields, and in particular to a kind of modified tertiary cathode material and preparation method thereof, Lithium ion battery.
Background technique
Lithium ion battery has the advantages that have extended cycle life, memory-less effect, environmental-friendly, self-discharge rate is low etc., has wide General application prospect.With the popularization of new-energy automobile, power-type lithium ion battery has obtained great development.Therefore, into one Step researches and develops high-energy density, the lithium ion battery material of high power density has become world today's chemistry, material, physics And the hot spot of the subjects such as energy.
In order to realize the conception of lithium ion battery high-energy density and high power density, suitable anode, cathode are found It is needed especially with electrolyte with caution.In recent years, Carbon anode performance successive optimization, novel anode material in continuous explore also was presented The gesture of diversification (such as embedded type, alloy-type and conversion hysteria) development；Multi-functional (height warm type, safety-type and high voltage type etc.), The research of high performance electrolyte also obtains the progress of leap.But as the highest critical material of cost in lithium ion battery, Positive electrode has become the bottleneck that lithium ion battery energy density and power density further increase.Therefore, positive electrode is opened The exploitation of the positive electrode of hair, especially inexpensive, environmental-friendly, high-energy density and high power density is the following lithium ion The main direction of studying of battery development.
Nickelic tertiary cathode material has both traditional positive electrode LiNiO2、LiCoO2And LiMnO2The advantages of three, possesses more Rock-steady structure and superior chemical property, commercialization value are very big.But in practical applications, nickelic tertiary cathode material according to Many problems are so faced, if material water imbibition is strong, storge quality is poor, has seriously affected its industrial production, storage, transport and electricity The preparation process in pond.By taking electrode fabrication as an example, material is easy water suction gum deposit when preparing slurry, and machining property is caused to become Difference.In addition to this, since the lower lithium ion diffusion coefficient of the nickelic tertiary cathode material of stratiform and perveance cause The high rate performance of material is still to be improved.On the other hand, nickelic tertiary cathode material is during removal lithium embedded, Ni4+With electrolyte Side reaction occurs, is easy to happen the phase transformation from layer structure to fused salt structure, material impedance is caused to increase, cycle performance deteriorates. Material is within the scope of 2.7 ~ 4.3 V charge and discharge, and irreversible capacity reaches that 30 ~ 40 mAh/g are even higher, and efficiency is generally low for the first time In 85%.In conclusion to the modification of nickelic tertiary cathode material be very it is necessary to.
Currently, it is a kind of method for being more effectively improved material property that surface, which coats stable nanometer layer,.Wherein, liquid phase packet Not only low in cost, easy to operate but also survivable surface coating layer is covered, material has superior performance after cladding.And Nanometer clad not only will not influence the diffusion of lithium ion in body of material structure, but also can be reduced the direct of material and electrolyte Contact, delays the side reaction of material and electrolyte, to largely improve the chemical property of nickelic tertiary cathode material. Common covering material mainly has simple oxide (TiO now2, Al2O3、ZrO2、MnO2、MoO3And CeO2Deng), phosphate (FePO4、CoPO4And NiPO4Deng), fluoride (CaF2、AlF3And SmF3Deng), organic high molecular polymer, lithium ion good conductor (LiAlO2、Li2ZrO3、Li2TiO3、Li4Ti5O12、Li3VO4And LiNiPO4Deng) and electronics good conductor simple substance (Al and carbon material Deng).As a kind of important multi-element metal oxide containing indium, ternary bimetallic oxide metaindic acid lithium (LiInO2) it is chemically The advantages such as matter is stable, resistivity is low, electron mobility is high, Hall coefficient is low are very suitable to as nickelic ternary material clad. But up to the present, have no that metaindic acid lithium is modified nickelic tertiary cathode material as clad, it is nickelic to improve with this The specific discharge capacity and cyclical stability of tertiary cathode material.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome, cyclical stability of the existing technology is poor, discharge ratio The problems such as capacity is low provides a kind of modification of clad of lithium containing metaindic acid with high specific discharge capacity and good circulation performance Tertiary cathode material.
The present invention is further the technical problem to be solved is that, provide a kind of preparation method of modified tertiary cathode material.
The present invention is further the technical problem to be solved is that, provide a kind of modified ternary prepared by the above method Positive electrode.
The present invention is further the technical problem to be solved is that, provide a kind of high specific discharge capacity, good cycle and peace The high lithium ion battery of full performance.
The technical solution used to solve the technical problems of the present invention is that preparing a kind of modified tertiary cathode material, the modification The general formula of tertiary cathode material is LiNixCoyM1-x-yO2@aLiInO2, wherein 0.8≤x <, 1,0 < y <, 1,0 < 1-x-y < 1, M is Mn and/or Al element, and a is metaindic acid lithium (LiInO2) clad content, be to be modified the total weight of tertiary cathode material Benchmark, 0 < a≤10%.It is LiNi that i.e. the modification tertiary cathode material, which includes general formula,xCoyM1-x-yO2Tertiary cathode material, wherein 0.8≤x <, 1,0 < y < 1,0 < 1-x-y < 1, M are Mn and/or Al element；It further include being located at general formula for LiNixCoyM1-x-yO2 Tertiary cathode material surface metaindic acid lithium clad.
Further, on the basis of the total weight for being modified tertiary cathode material, the weight % of 1≤a≤4 can significantly improve ternary The cyclical stability and high rate performance of positive electrode.
In the present invention, tertiary cathode material LiNixCoyM1-x-yO2After surface coats nanometer metaindic acid lithium layer, so that LiNixCoyM1-x-yO2Material surface is changed into inert NiO layer, is effectively improved surface of active material form, reduces the work on surface Property site, not only obstruct high potential cathode oxidation electrolyte, effectively inhibition LiNixCoyM1-x-yO2Material surface contact air, from And reduce LiNixCoyM1-x-yO2Side reaction occurs for material and electrolyte；And compared to other inertia covering materials such as aluminium oxide, partially The electron conduction and ionic conductivity of indium acid lithium clad are more excellent, material high rate performance performs better than；Simultaneously LiNixCoyM1-x-yO2Material coats the more positive material surface metal of bond energy of In-O key and wanting greatly for oxygen after metaindic acid lithium, thus Coat the LiNi of nanometer metaindic acid lithium layerxCoyM1-x-yO2Material circulation stability is more preferable, also weakens part Li-O at the same time The effect of key.
The present invention further solve its technical problem the technical solution adopted is that, a kind of preparation of modified tertiary cathode material Method, comprising the following steps:
(1) under the first stirring condition, anhydrous organic solvent is dispersed by indium source, forms uniform solution；
(2) under the second stirring condition, it is LiNi that general formula is added in gained uniform solutionxCoyM1-x-yO2Tertiary cathode material Material, makes indium source uniform adsorption in general formula LiNixCoyM1-x-yO2Tertiary cathode material surface, wherein 0.8≤x <, 1,0 < Y < 1,0 < 1-x-y < 1, M are Mn and/or Al element；
(3) products therefrom in step (2) is removed into liquid, drying, obtains the LiNi that adsorption has indium sourcexCoyM1-x-yO2Three First positive electrode solid；
(4) gained adsorption is had to the LiNi in indium sourcexCoyM1-x-yO2Tertiary cathode material solid roasting, obtained general formula are LiNixCoyM1-x-yO2@aLiInO2Modification tertiary cathode material.
The present invention is prepared for the modification tertiary cathode material that metaindic acid lithium coats nickelic ternary material by liquid phase method, significantly Improve the specific discharge capacity and cyclical stability of nickelic tertiary cathode material.
Further, the mass volume ratio of the indium source and anhydrous organic solvent is 0.01~0.03: 1, is conducive to indium source more Easily it is adsorbed onto tertiary cathode material LiNixCoyM1-x-yO2Surface.
Further, the indium source is selected from In (NO3)3、InCl3、In2(SO4)3、In (CH3COO)3、In (CCl3COO)3、 In(CN)3、In(NH2SO3)3With In (BF4)3At least one of soluble-salt may make indium source to be converted into stable metaindic acid Lithium (LiInO2) clad.
Further, the anhydrous organic solvent is selected from least one of methanol, ethyl alcohol, ethylene glycol and propyl alcohol, there is utilization Disperse indium source.
Further, first stirring condition include: mixing speed be 100~800 turns/min, mixing time be 10~ 30min has using dispersion indium source, forms uniform solution.
Further, in step (2), the indium source and general formula are LiNixCoyM1-x-yO2Tertiary cathode material mass ratio It is 0.01~0.1: 1, is conducive to indium source cladding tertiary cathode material LiNixCoyM1-x-yO2, to form the stable indium source of thickness Clad.
In step (2), second stirring condition includes: that whipping temp is 20~40 DEG C, and mixing speed is 100~800 Turn/min, mixing time is 1~20 hour, is conducive to indium source and is adsorbed in tertiary cathode material LiNixCoyM1-x-yO2Surface.
Further, in step (3), it is 100~800 turns/min, temperature that the condition of the removal liquid, which includes: mixing speed, It is 60~90 DEG C；The condition of the drying includes: that temperature is 80~120 DEG C, and the time is 8~20h.
Further, in step (4), the condition of the roasting includes: that temperature is 400~1000 DEG C, and the time is 3~12 small When, atmosphere is air or oxygen.
In the present invention, the partial size of material is indicated with D50 partial size, when D50 partial size is that cumulative distribution is 50% in distribution curve The largest particles equivalent diameter (average grain diameter).
The present invention further solve its technical problem the technical solution adopted is that, a kind of modified tertiary cathode material, by upper The method is stated to be prepared.
The present invention further solve its technical problem the technical solution adopted is that, a kind of lithium ion battery, it is described just extremely Modification tertiary cathode material described above.
Compared with prior art, the metaindic acid lithium of the present invention coats the modification tertiary cathode that nickelic tertiary cathode material obtains Material has good cyclical stability and high rate performance, and preparation method operation is simple, low in cost, safe and reliable, fits For industrialized production.On this basis, the lithium ion battery using the modification tertiary cathode material as positive electrode is being put Electric specific capacity, cycle performance and security performance are significantly increased, which can be applied to power battery field.
Detailed description of the invention
Fig. 1 is tertiary cathode material LiNi in comparative example 1 of the present invention0.8Co0.1Mn0.1O2SEM figure；
Fig. 2 is the SEM figure of modified tertiary cathode material made from the embodiment of the present invention 1；
Fig. 3 is the TEM figure of modified tertiary cathode material made from the embodiment of the present invention 1；
Fig. 4 is the XRD diagram of modified tertiary cathode material made from the embodiment of the present invention 1；
Fig. 5 is tertiary cathode material in modified tertiary cathode material made from the embodiment of the present invention 1 and comparative example 1 LiNi0.8Co0.1Mn0.1O2Cyclic curve comparison diagram under 0.5C discharge-rate；
Fig. 6 is tertiary cathode material in modified tertiary cathode material made from the embodiment of the present invention 1 and comparative example 1 LiNi0.8Co0.1Mn0.1O2First charge-discharge curve comparison figure under 0.1C discharge-rate.
Specific embodiment
The present invention will be described in detail by way of examples below.In following embodiment,
The content of a(metaindic acid lithium clad)=[M (LiInO2) * m (soluble indium salts)/M (soluble indium salts)] (ternary is just by/m Pole material) * 100%, m expression material mass, M expression substance relative molecular mass；
Granularity is measured by PSA- laser particle size analyzer；
Discharge capacity and circulation conservation rate are measured by blue electric battery test system；
Tertiary cathode material LiNi0.8Co0.1Mn0.1O2It is purchased from Zhejiang Pa Wa limited liability company；
Tertiary cathode material LiNi0.8Co0.15Al0.05O2It is purchased from Zhejiang Pa Wa limited liability company；
In case of no particular description, other raw materials used to be all made of commercial product.
Embodiment 1
The preparation of modified tertiary cathode material, comprising the following steps:
(1) 0.1956g In (NO is weighed3)3Powder is added 20mL dehydrated alcohol and is stirred mixing, mixing speed for 100 turns/ Min, mixing time 30min, so that In (NO3)3Powder is completely dissolved, and forms uniform solution；
(2) 10.0000g LiNi is added in gained uniform solution0.8Co0.1Mn0.1O2Powder is stirred mixing, whipping temp It is 30 DEG C, mixing speed is 800 turns/min, and mixing time 1h makes In (NO3)3Uniform adsorption is in LiNi0.8Co0.1Mn0.1O2's Surface；
(3) by products therefrom in step (2) 60 DEG C, mixing speed be 100 turns/min under conditions of be evaporated, then at 120 DEG C Air dry oven in dry 12h, obtain solid powder；
(4) obtained solid powder is calcined into 12h in air atmosphere with 400 DEG C of condition, the metaindic acid of mass fraction 1% is made Lithium coats LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material, i.e. LiNi0.8Co0.1Mn0.1O2@1%LiInO2。
Embodiment 2
The preparation of modified tertiary cathode material, comprising the following steps:
(1) 0.7826g In (NO is weighed3)3Powder is added 40mL dehydrated alcohol and is stirred mixing, mixing speed for 800 turns/ Min, mixing time 10min, so that In (NO3)3Powder is completely dissolved, and forms uniform solution；
(2) 10.0000g LiNi is added in gained uniform solution0.8Co0.1Mn0.1O2Powder is stirred mixing, whipping temp It is 40 DEG C, mixing speed is 100 turns/min, and mixing time 20h makes In (NO3)3Uniform adsorption is in LiNi0.8Co0.1Mn0.1O2 Surface；
(3) by products therefrom in step (2) 80 DEG C, mixing speed be 500 turns/min under conditions of be evaporated, then at 90 DEG C Dry 8h, obtains solid powder in air dry oven；
(4) obtained solid powder is calcined into 3h in air atmosphere with 1000 DEG C of condition, the metaindic acid of mass fraction 4% is made Lithium coats LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material, i.e. LiNi0.8Co0.1Mn0.1O2@4%LiInO2。
Embodiment 3
The preparation of modified tertiary cathode material, comprising the following steps:
(1) 1.9565g In (NO is weighed3)3Powder is added 80mL dehydrated alcohol and is stirred mixing, mixing speed for 500 turns/ Min, mixing time 30min, so that In (NO3)3Powder is completely dissolved, and forms uniform solution；
(2) 10.0000g LiNi is added in gained uniform solution0.8Co0.1Mn0.1O2Powder is stirred mixing, whipping temp It is 30 DEG C, mixing speed is 500 turns/min, and mixing time 10h makes In (NO3)3Uniform adsorption is in LiNi0.8Co0.1Mn0.1O2 Surface；
(3) by products therefrom in step (2) 70 DEG C, mixing speed be 800 turns/min under conditions of be evaporated, then at 100 DEG C Air dry oven in dry 20h, obtain solid powder；
(4) obtained solid powder is calcined into 6h in air atmosphere with 600 DEG C of condition, the metaindic acid of mass fraction 10% is made Lithium coats LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material, i.e. LiNi0.8Co0.1Mn0.1O2@10%LiInO2。
Embodiment 4
The preparation of modified tertiary cathode material, comprising the following steps:
(1) 0.7826g In (NO is weighed3)3Powder is added 40mL dehydrated alcohol and is stirred mixing, mixing speed for 600 turns/ Min, mixing time 20min, so that In (NO3)3Powder is completely dissolved, and forms uniform solution；
(2) 10.0000g LiNi is added in gained uniform solution0.8Co0.15Al0.05O2Powder is stirred mixing, stirring temperature Degree is 35 DEG C, and mixing speed is 600 turns/min, and mixing time 10h makes In (NO3)3Uniform adsorption in LiNi0.8Co0.15Al0.05O2Surface；
(3) by products therefrom in step (2) at 90 DEG C, mixing speed is evaporated under conditions of being 500 turns/min, then at 120 DEG C Air dry oven in dry 8h, obtain solid powder；
(4) obtained solid powder is calcined into 5h in air atmosphere with 500 DEG C of condition, the metaindic acid lithium of mass fraction 4% is made Coat LiNi0.8Co0.15Al0.05O2Modification tertiary cathode material, i.e. LiNi0.8Co0.1Mn0.1O2@4%LiInO2。
Embodiment 5
The preparation of lithium ion battery: the metaindic acid lithium cladding of mass fraction 1% made from 0.4000g embodiment 1 is weighed LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material, be added 0.0500g conductive carbon black make conductive agent and 0.0500g PVDF (Kynoar) makees binder, is coated on aluminium foil and positive plate is made, using metal lithium sheet as cathode in vacuum glove box, with Celgard 2300 is diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button of CR2025 Lithium ion battery.
Embodiment 6
The preparation of lithium ion battery: preparing lithium ion battery according to the method for embodiment 5, unlike, tertiary cathode material is The metaindic acid lithium of mass fraction 4% made from embodiment 2 coats LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material.
Embodiment 7
The preparation of lithium ion battery: preparing lithium ion battery according to the method for embodiment 5, unlike, tertiary cathode material is The metaindic acid lithium of mass fraction 10% made from embodiment 3 coats LiNi0.8Co0.1Mn0.1O2Modification tertiary cathode material.
Embodiment 8
The preparation of lithium ion battery: preparing lithium ion battery according to the method for embodiment 5, unlike, tertiary cathode material is The metaindic acid lithium of mass fraction 4% made from embodiment 4 coats LiNi0.8Co0.15Al0.05O2Modification tertiary cathode material.
Comparative example 1
Lithium ion battery is prepared according to the method for embodiment 5, unlike, tertiary cathode material LiNi0.8Co0.1Mn0.1O2。
Comparative example 2
Lithium ion battery is prepared according to the method for embodiment 6, unlike, tertiary cathode material LiNi0.8Co0.15Al0.05O2。
Test case
Electrochemical property test:
1, material characterization
By tertiary cathode material LiNi in comparative example 10.8Co0.1Mn0.1O2Exist with modified tertiary cathode material made from embodiment 1 Morphology observation is carried out on Japanese JEOL company JSM-7600F type field emission scanning electron microscope.The result of its SEM is respectively such as Fig. 1 and 2 institute Show, can be seen that tertiary cathode material LiNi in comparative example 1 from SEM pattern result in Fig. 1, Fig. 20.8Co0.1Mn0.1O2It is partial size For 10~12 μm of spheric granules, and it is the spheric granules that partial size is 10~12 μm that modified tertiary cathode material, which is made, in embodiment 1, And surface has the unformed shape clad of metaindic acid lithium.Remaining embodiment is similar, is as a result not shown.
By modified tertiary cathode material made from embodiment 1 using Dutch FEI Co.'s Tecnai G2 F30 Flied emission transmission Electron microscope carries out solid surface analysis, and TEM result is as shown in figure 3, TEM test result can be seen that implementation from Fig. 3 Modified tertiary cathode material surface made from example 1 has the clad of one layer of 8~10nm.Remaining embodiment is similar, does not as a result show Out.
Modified tertiary cathode material made from embodiment 1 is carried out using Rigaku SmartLab type X-ray diffractometer Material phase analysis.Operating condition: pipe presses 40kV, pipe stream 20mA, Cu K α line, λ=0.154056nm, using graphite monochromator, step width 0.02 °, residence time 0.2s.Its XRD result as shown in figure 4, from Fig. 4 XRD test result can be seen that embodiment 1 be made Modification tertiary cathode material surface in contain metaindic acid lithium ingredient, and be pure phase.Remaining embodiment is similar, is as a result not shown.
2, electro-chemical test
By lithium ion battery made from embodiment 5-8 and comparative example 1-2 in 25 DEG C of temperature, the voltage range of 2.7-4.3V, It is primary with the multiplying power progress charge and discharge of 0.1C, record initial charge capacity and discharge capacity；And calculate discharging efficiency (%) for the first time； Then charge and discharge cycles 30 are carried out with the multiplying power of 0.5C to enclose, calculates capacity retention ratio (%) after circulation, charge and discharge is carried out with the multiplying power of 1C 30 circle of electricity circulation, calculates capacity retention ratio (%) after circulation.Test result is as shown in table 1, Fig. 5 and Fig. 6.
Table 1
It can be seen that made from embodiment 1-4 the 0.1C of modified tertiary cathode material discharge capacity for the first time from table 1 and Fig. 6 result Greater than 210mAh/g, discharging efficiency is greater than 85% for the first time, and circulation volume is maintained at 90% or more, is all larger than the data of comparative example.
It can be seen that modified tertiary cathode material phase under 0.5C discharge-rate made from embodiment 1-4 from the result of Fig. 5 Than being obviously improved in the data of comparative example 1.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (10)

1. a kind of modified tertiary cathode material, which is characterized in that the general formula of the modification tertiary cathode material is LiNixCoyM1-x- yO2@aLiInO2, wherein 0.8≤x <, 1,0 < y < 1,0 < 1-x-y < 1, M are Mn and/or Al element, and a is metaindic acid lithium packet The content of coating, on the basis of the total weight for being modified tertiary cathode material, the weight of 0 < a≤10 %.
2. modified tertiary cathode material according to claim 1, which is characterized in that be modified the gross weight of tertiary cathode material On the basis of amount, the weight of 1≤a≤4 %.
3. a kind of preparation method of modified tertiary cathode material of any of claims 1 or 2, which is characterized in that including following step It is rapid:
(1) under the first stirring condition, anhydrous organic solvent is dispersed by indium source, forms uniform solution；
(2) under the second stirring condition, it is LiNi that general formula is added in gained uniform solutionxCoyM1-x-yO2Tertiary cathode material Material, makes indium source be adsorbed in general formula LiNixCoyM1-x-yO2Tertiary cathode material surface, wherein 0.8≤x <, 1,0 < y < 1,0 < 1-x-y < 1, M are Mn and/or Al element；
(3) products therefrom in step (2) is removed into liquid, drying, obtains the LiNi that adsorption has indium sourcexCoyM1-x-yO2Ternary Positive electrode solid；
(4) gained adsorption is had to the LiNi in indium sourcexCoyM1-x-yO2Tertiary cathode material solid roasting, obtained general formula are LiNixCoyM1-x-yO2@aLiInO2Modification tertiary cathode material.
4. preparation method according to claim 3, which is characterized in that in step (1), the indium source and anhydrous organic solvent Mass volume ratio be 0.01~0.03: 1；
Preferably, the indium source is selected from In (NO3)3、InCl3、In2(SO4)3、In (CH3COO)3、In (CCl3COO)3、In (CN)3、In(NH2SO3)3With In (BF4)3At least one of soluble-salt；
Preferably, the anhydrous organic solvent is selected from least one of methanol, ethyl alcohol, ethylene glycol and propyl alcohol.
5. preparation method according to claim 3, which is characterized in that in step (1), first stirring condition includes: Mixing speed is 100~800 turns/min, and mixing time is 10~30min.
6. the preparation method according to any one of claim 3-5, which is characterized in that in step (2), the indium source with General formula is LiNixCoyM1-x-yO2Tertiary cathode material mass ratio be 0.01~0.1: 1；
Preferably, it is 20~40 DEG C that second stirring condition, which includes: whipping temp, and mixing speed is 100~800 turns/min, Mixing time is 1~20 hour.
7. the preparation method according to any one of claim 3-5, which is characterized in that in step (3), the removal liquid The condition of body includes: that mixing speed is 100~800 turns/min, and temperature is 60~90 DEG C；The condition of the drying includes: temperature It is 80~120 DEG C, the time is 8~20h.
8. the preparation method according to any one of claim 3-5, which is characterized in that in step (4), the roasting Condition includes: that temperature is 400~1000 DEG C, and the time is 3~12 hours, and atmosphere is air or oxygen.
9. a kind of modified tertiary cathode material, the method as described in any one of claim 3-8 is prepared.
10. a kind of lithium ion battery, which includes anode, which is characterized in that just extremely the claim 1-2,9 Modification tertiary cathode material described in any one.
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