CN109686940A - Tertiary cathode material and its preparation method and application, lithium ion battery, electric vehicle - Google Patents

Tertiary cathode material and its preparation method and application, lithium ion battery, electric vehicle Download PDF

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Publication number
CN109686940A
CN109686940A CN201811553565.7A CN201811553565A CN109686940A CN 109686940 A CN109686940 A CN 109686940A CN 201811553565 A CN201811553565 A CN 201811553565A CN 109686940 A CN109686940 A CN 109686940A
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tertiary cathode
cathode material
graphene
lithium ion
ion battery
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汤依伟
尚国志
吴剑
杨幸
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Qingyuan New Materials Research Institute Co Ltd
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Qingyuan New Materials Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

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Abstract

The present invention provides a kind of tertiary cathode material and its preparation method and application, lithium ion battery, electric vehicles, belong to technical field of lithium ion.The present invention provides a kind of tertiary cathode materials, and including ternary material and the clad for being coated on ternary material surface, clad includes M1y+2z‑2xM2xR1yR2zAnd graphene；M1 and M2 is metallic element, and R1 and R2 are phosphorous and/or sulfur-bearing anion.The promotion of the excellent electric conductivity of graphene and metal ion to ion mobility, can be effectively reduced the surface impedance of tertiary cathode material；And the clad can be effectively reduced positive electrode surface electrochemistry activity in cyclic process, increase positive electrode surface conductance performance, inhibit electrolyte decomposition product to the corrosiveness on positive electrode surface, inhibit the dissolution of transition metal ions, stablize cathode material structure, improves the cyclical stability and high rate performance of lithium ion battery under high temperature high voltage.

Description

Tertiary cathode material and its preparation method and application, lithium ion battery, electric vehicle
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of tertiary cathode material and preparation method thereof and answer With, lithium ion battery, electric vehicle.
Background technique
Lithium ion battery is as a kind of novel green high-energy battery, and because having, operating voltage is high, specific capacity is big, cycle life It is long, self-discharge rate is low, memory-less effect and it is environmentally friendly the advantages that, be widely used in mobile phone, video camera, notebook The portable devices such as computer.Recently as the universal of portable electronic device, the development of electric tool and electric car, to lithium More stringent requirements are proposed for ion battery --- the cyclical stability and high rate performance of lithium ion battery under high temperature and pressure.
The high-temperature behavior of the ternary material of conventional method preparation is poor, and high-voltage performance is unstable, and transition metal ions is easy In dissolution.Common measure is to be coated on ternary material surface using aluminium oxide, titanium oxide or zirconium oxide, but the prior art pair It not can effectively improve the cyclical stability of ternary material at high temperature, under high voltage in the modification cladding means of ternary material, Transition metal ions is easy to the disadvantages of dissolving out, and preparation process is complex, and manufacturing cost is high.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first purpose of this invention is to provide a kind of tertiary cathode material, can overcome the above problem or at least portion Ground is divided to solve above-mentioned technical problem.
Second object of the present invention is to provide the preparation method of above-mentioned tertiary cathode material；The system of tertiary cathode material It is Preparation Method simple process, reproducible, low in cost, environmental-friendly.
Third object of the present invention is to provide application of the above-mentioned tertiary cathode material in lithium ion battery.
Fourth object of the present invention is to provide a kind of lithium ion battery, including above-mentioned tertiary cathode material.
Of the invention the 5th is designed to provide a kind of electric vehicle, including above-mentioned lithium ion battery.
First aspect according to the present invention, provides a kind of tertiary cathode material, including ternary material and is coated on described The clad on ternary material surface, the clad include M1y+2z-2xM2xR1yR2zAnd graphene；
Wherein, 0≤x≤1,0≤y≤2,0≤z≤1,0≤y+2z-2x≤2, y+z ≠ 0；
The M1 includes at least one of Na, K and Ag metallic element；
The M2 includes at least one of Be, Mg, Ca, Sr, Ba, Cu, Zn and Cd metallic element；
The R1 includes the univalent anion of phosphorous univalent anion and/or sulfur-bearing；
The R2 includes the dianion of phosphorous dianion and/or sulfur-bearing.
Preferably, the M1 includes at least one of Na and K metallic element；
And/or the M2 includes at least one of Mg, Ca and Sr metallic element；
And/or the R1 includes PO2F2 1-And/or HSO3 1-, preferably PO2F2 1-；
And/or the R2 includes H2PO4 2-And/or SO4 2-, preferably H2PO4 2-；
And/or x value is 0 or 1, y value is 0 or 2, z value 0 or 1, y+2z-2x value 0 or 2, y+z ≠ 0；
Preferably, the M1y+2z-2xM2xR1yR2zIncluding Na2H2PO4、K2H2PO4、MgH2PO4、CaH2PO4、NaPO2F2、 KPO2F2、Mg(PO2F2)2With Ca (PO2F2)2At least one of.
Preferably, the M1y+2z-2xM2xR1yR2zMass percentage in tertiary cathode material is 0.1%-10%, Preferably 0.5%-4%；
And/or mass percentage of the graphene in tertiary cathode material is 0.1%-10%, preferably 0.5%-4%；
Preferably, the M1y+2z-2xM2xR1yR2zIt is with mass percentage of the graphene in tertiary cathode material 0.2%-5%.
Preferably, the ternary material is nickelic ternary material, preferably LiNixCoyMnzO2And/or LiNixCoyAlzO2； Wherein, x+y+z=1；
And/or the graphene is single layer or 2-5 layers, the size of the graphene is 10nm-100 μm.
The second aspect according to the present invention provides the preparation method of above-mentioned tertiary cathode material, comprising the following steps:
By ternary material, M1y+2z-2xM2xR1yR2zWith graphene dispersion in alcohols solvent, be isolated to solid phase at Point, it is then heat-treated, the surface of ternary material is made to coat M1y+2z-2xM2xR1yR2zAnd graphene, obtain tertiary cathode material Material.
Preferably, the alcohols solvent is C1-C4Alcohol, preferably methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol and the third three At least one of alcohol.
Preferably, the atmosphere of the heat treatment is inert gas, preferably argon gas or nitrogen；
Preferably, the heat treatment includes successively keeping the temperature 3-8h at 180-220 DEG C and keeping the temperature 2- at 580-620 DEG C 4h。
According to the present invention in terms of third, provide above-mentioned tertiary cathode material or ternary that above-mentioned preparation method obtains just Application of the pole material in lithium ion battery.
4th aspect according to the present invention, provides a kind of lithium ion battery, including above-mentioned tertiary cathode material or above-mentioned The tertiary cathode material that preparation method obtains；
Preferably, the charging voltage of the lithium ion battery is 3-4.5V；
And/or the charge and discharge cycles temperature of the lithium ion battery is 10-70 DEG C.
5th aspect according to the present invention, provides a kind of electric vehicle, including above-mentioned lithium ion battery.
The present invention provides a kind of tertiary cathode materials, including ternary material and the cladding for being coated on ternary material surface Layer, clad includes M1y+2z-2xM2xR1yR2zAnd graphene；Wherein, M1 and M2 is metallic element, R1 and R2 be it is phosphorous and/or The anion of sulfur-bearing.The present invention is with metal cation and phosphorous and/or anions containing sulfur combination substance and graphene Compound coating is carried out to ternary material, the clad of one layer of function admirable can be formed on ternary material surface, which includes M1y+2z-2xM2xR1yR2zAnd graphene.The excellent electric conductivity of graphene and the metal ion being added are able to ascend ion Migration rate can effectively improve the big disadvantage of circulating battery process middle impedance, so that tertiary cathode material surface impedance is low； And the clad can be effectively reduced positive electrode surface electrochemistry activity in cyclic process, accelerate lithium ion mobility rate, Increase positive electrode surface conductance performance, inhibits electrolyte decomposition product to the corrosiveness on positive electrode surface, inhibit simultaneously The dissolution of transition metal ions, stablize cathode material structure, improve high temperature high voltage under lithium ion battery cyclical stability and High rate performance.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is increased variation tendency of discharge capacity of the embodiment 2 at 40 DEG C with circulating ring number；
Fig. 2 is the discharge capacity of embodiment 1 and comparative example 3 (blank sample) with the increased variation tendency of circulating ring number.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with examples and drawings, but those skilled in the art Member will be understood that the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not infused in embodiment Bright actual conditions person, carries out according to conventional conditions or manufacturer's recommended conditions.Production firm is not specified in agents useful for same or instrument Person is the conventional products that can be obtained by commercially available purchase.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the breviary of any real combinings between a to b It indicates, wherein a and b is real number.Such as numberical range " 0.1%-10% " indicates all to list " 0.1%- herein Whole real numbers between 10% ", " 0.1%-10% " are that the breviary of these combinations of values indicates.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
First aspect according to the present invention, provides a kind of tertiary cathode material, including ternary material and is coated on ternary The clad of material surface, clad include M1y+2z-2xM2xR1yR2zAnd graphene；
Wherein, 0≤x≤1,0≤y≤2,0≤z≤1,0≤y+2z-2x≤2, y+z ≠ 0；
M1 includes at least one of Na, K and Ag metallic element；
M2 includes at least one of Be, Mg, Ca, Sr, Ba, Cu, Zn and Cd metallic element；
R1 includes the univalent anion of phosphorous univalent anion and/or sulfur-bearing；
R2 includes the dianion of phosphorous dianion and/or sulfur-bearing.
The present invention provides a kind of tertiary cathode materials, including ternary material and the cladding for being coated on ternary material surface Layer, clad includes M1y+2z-2xM2xR1yR2zAnd graphene；Wherein, M1 and M2 is metallic element, R1 and R2 be it is phosphorous and/or The anion of sulfur-bearing.The present invention is with metal cation and phosphorous and/or anions containing sulfur combination substance and graphene Compound coating is carried out to ternary material, the clad of one layer of function admirable can be formed on ternary material surface, which includes M1y+2z-2xM2xR1yR2zAnd graphene.The excellent electric conductivity of graphene and the metal ion being added are to Ion transfer speed The promotion of rate can effectively improve the big disadvantage of circulating battery process middle impedance, so that tertiary cathode material surface impedance is low； And the clad can be effectively reduced positive electrode surface electrochemistry activity in cyclic process, accelerate lithium ion mobility rate, Increase positive electrode surface conductance performance, inhibits electrolyte decomposition product to the corrosiveness on positive electrode surface, inhibit simultaneously The dissolution of transition metal ions, stablize cathode material structure, improve high temperature high voltage under lithium ion battery cyclical stability and High rate performance.
It should be understood that M1 is monovalent metal element, M2 is divalent metal element, and R1 is univalent anion, M2 bis- Valence anion, at this point, when 0≤x≤1,0≤y≤2,0≤z≤1,0≤y+2z-2x≤2, y+z ≠ 0, M1y+2z-2xM2xR1yR2z It can trim；The typical but non-limiting value of x be 0,0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4, 0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95 or 1；The typical but non-limiting value of y is 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2.0；The typical but non-limiting value of z be 0,0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45, 0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.95 or 1；The typical but non-limiting value of y+2z-2x is 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2.0.It is simultaneously 0 that y+z ≠ 0, which refers to y, z not,.
It is understood that x is 0.3, y 1, and when z is 0.2, M1y+2z-2xM2xR1yR2zFor M10.8M20.3R11R20.2；Again Such as, M1y+2z-2xM2xR1yR2zIt can be M10.2M20.1R20.2、M10.4R20.2、M20.25R11R20.2、M10.8M20.3R11.4、 M10.1M20.3R10.3R20.2、M11.4R11R20.2Deng.
M1 and M2 is metallic element, and metal ion is able to ascend ion mobility, is conducive to improve that impedance is big to be lacked It falls into.M1 includes at least one of Na, K and Ag metallic element；M2 include in Be, Mg, Ca, Sr, Ba, Cu, Zn and Cd at least A kind of metallic element；M1y+2z-2xM2xR1yR2zIn M1 and M2 can exist simultaneously, one kind, i.e. x and y+ can also be contained only 2z-2x can not take 0 simultaneously, only one kind can also not take 0.Relative to Li, Na, K, Ag, Be, Mg, Ca, Sr, Ba, Cu, Zn The diffusion coefficient of lithium ion can more be promoted with Cd.
R1 includes the univalent anion of phosphorous univalent anion and/or sulfur-bearing, and R1 is chosen as PO2F2 1-And/or HSO3 1-； R2 includes the dianion of phosphorous dianion and/or sulfur-bearing, and R2 is chosen as H2PO4 2-And/or SO4 2-。M1y+2z- 2xM2xR1yR2zIn R1 and R2 can exist simultaneously, one kind can also be contained only, i.e. y and z can not take 0 simultaneously, can also be only There is one kind not take 0.
It should be understood that the present invention is not particularly limited the type of M1, M2, R1, R2, for example, M1 can be Na, One of K and Ag, two or three；For another example, M10.1M20.3R10.3R20.2It can be Na0.02K0.08Ca0.3(HSO3)0.3 (H2PO4)0.2。
It should be noted that the present invention does not have the source of ternary material special limitation, using those skilled in the art Each raw material known to member；Ternary material is chosen as nickelic ternary material, for example, it may be LiNixCoyMnzO2And/or LiNixCoyAlzO2；Wherein, x+y+z=1.
It should be noted that the present invention does not have the source of graphene special limitation, using those skilled in the art Known each raw material；Its commercial goods can be such as used, preparation side well known to those skilled in the art can also be used Method is voluntarily prepared.For example, graphene is chosen as single layer or 2-5 layers, the size of graphene is chosen as 10nm-100 μm.
As further preferred embodiment, M1 includes at least one of Na and K metallic element；And/or M2 includes At least one of Mg, Ca and Sr metallic element；And/or R1 includes preferably PO2F2 1-；And/or R2 includes preferably H2PO4 2-；And/or x value is 0 or 1, y value is 0 or 2, z value 0 or 1, y+2z-2x value 0 or 2, y+z ≠ 0.
As further preferred embodiment, M1y+2z-2xM2xR1yR2zIncluding Na2H2PO4、K2H2PO4、MgH2PO4、 CaH2PO4、NaPO2F2、KPO2F2、Mg(PO2F2)2With Ca (PO2F2)2At least one of.
As further preferred embodiment, M1y+2z-2xM2xR1yR2zQuality percentage in tertiary cathode material contains Amount is 0.1%-10%, and/or, mass percentage of the graphene in tertiary cathode material is 0.1%-10%.M1y+2z- 2xM2xR1yR2zIn tertiary cathode material typical but non-limiting mass percentage be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%；Graphene is in tertiary cathode material In typical but non-limiting mass percentage be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%.M1y+2z-2xM2xR1yR2zMass percentage in tertiary cathode material Effect when for 0.1%-10% is more excellent, the study found that M1y+2z-2xM2xR1yR2zUsage amount it is excessively high, it will increase positive material The unstability of material, M1y+2z-2xM2xR1yR2zUsage amount it is too low, it is impossible to form effective protective film layer.Graphene is three Effect when mass percentage in first positive electrode is 0.1%-10% is more excellent, the study found that the use content of graphene It is excessively high, it will to reduce the energy density of positive electrode, the use content of graphene is too low, then cannot form effective protective film Layer.
It should be understood that tertiary cathode material includes ternary material, M1y+2z-2xM2xR1yR2zAnd graphene, " M1y+2z- 2xM2xR1yR2zMass percentage in tertiary cathode material is that 0.1%-10% " refers to M1y+2z-2xM2xR1yR2zWith ternary The weight ratio of positive electrode is 0.1-10:100.
As further preferred embodiment, M1y+2z-2xM2xR1yR2zWith matter of the graphene in tertiary cathode material Amount percentage composition is 0.2%-5%.M1y+2z-2xM2xR1yR2zIt is typical but non-limiting in tertiary cathode material with graphene Mass percentage be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
It should be understood that tertiary cathode material includes ternary material, M1y+2z-2xM2xR1yR2zAnd graphene, " M1y+2z- 2xM2xR1yR2zIt is that 0.2%-5% " refers to M1 with mass percentage of the graphene in tertiary cathode materialy+2z- 2xM2xR1yR2zIt is 0.2-5:100 with the weight ratio of two kinds of substances of graphene and tertiary cathode material.
The second aspect according to the present invention provides the preparation method of above-mentioned tertiary cathode material, comprising the following steps:
By ternary material, M1y+2z-2xM2xR1yR2zWith graphene dispersion in alcohols solvent, be isolated to solid phase at Point, it is then heat-treated, the surface of ternary material is made to coat M1y+2z-2xM2xR1yR2zAnd graphene, obtain tertiary cathode material Material.
Then the present invention is heat-treated by separating after mixing raw material, tertiary cathode material can be prepared.Work Skill process is simple, easy to operate, easy to implement, processing raw material sources it is wide, it is economical and easily available, be nontoxic, environment-friendly type raw material.The present invention To environment, place, equipment etc. without specifically limited, used low in raw material price, safety and environmental protection performance is good, to equipment requirement Low, cost of investment is low, practicability and adaptable, be a kind of environmental protection, energy conservation, efficiently, the preparation of the tertiary cathode material of low cost Method can realize the production of a large amount, application easy to spread at a lower cost.
Compared with existing technology coating modifying, the present invention carries out M1 on ternary material surfacey+2z-2xM2xR1yR2zAnd stone It is low, dense uniform can to form impedance on positive electrode surface for tertiary cathode material made from the compound coating method of black alkene Clad maintains the structure of positive electrode steady to inhibit the oxidative degradation products of electrolyte solvent to the corrosion of positive electrode It is qualitative, improve cyclical stability；Compared with existing covering material technology and the method for replacement main solvent, this kind of method improves Lithium ion battery stability under high temperature high voltage improves cyclical stability and high rate performance, and method is simple, and operation is succinct, addition Amount is smaller, has broad application prospects.
It should be noted that alcohols solvent can be monohydric alcohol, dihydric alcohol, trihydroxylic alcohol or tetrahydroxylic alcohol etc..Optional alcohols Solvent is C1-C4Alcohol, the present invention do not have the source of alcohols solvent special limitation, ripe using those skilled in the art institute Each raw material known；For example, it may be at least one of methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol and glycerine, first Alcohol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol and glycerine purity be 99%-100%.
The present invention does not have the mode of dispersion special limitation, using dispersing mode well-known to those skilled in the art ?；For example, can be by the way of stirring, so that ternary material, M1y+2z-2xM2xR1yR2zIt is molten in alcohols with graphene dispersion In agent, optional mixing speed is 300r/s-2000r/s, and whipping temp is 20-60 DEG C, mixing time 3-24h.
The present invention does not have isolated mode special limitation, using separate mode well-known to those skilled in the art ?；For example, can be separated using the method filtered.
As further preferred embodiment, the atmosphere of heat treatment is inert gas, is chosen as argon gas or nitrogen； Heat treatment includes successively keeping the temperature 3-8h at 180-220 DEG C and keeping the temperature 2-4h at 580-620 DEG C.
According to the present invention in terms of third, provide above-mentioned tertiary cathode material or ternary that above-mentioned preparation method obtains just Application of the pole material in lithium ion battery.
The excellent electric conductivity of the graphene contained in the tertiary cathode material and metal ion are to ion mobility Promotion, the big disadvantage of circulating battery process middle impedance can be effectively improved, so that tertiary cathode material surface impedance is low；And The clad can be effectively reduced positive electrode surface electrochemistry activity in cyclic process, accelerates lithium ion mobility rate, increases Add positive electrode surface conductance performance, inhibits electrolyte decomposition product to the corrosiveness on positive electrode surface, while inhibiting The dissolution of metal ion is crossed, stablizes cathode material structure, and then improve the cyclical stability of lithium ion battery under high temperature high voltage And high rate performance.
4th aspect according to the present invention, provides a kind of lithium ion battery, including above-mentioned tertiary cathode material or above-mentioned The tertiary cathode material that preparation method obtains.
The surface of the tertiary cathode material of the lithium ion battery is coated with the clad of one layer of function admirable, to reduce Positive electrode surface electrochemistry activity in lithium ion battery cyclic process, accelerates lithium ion mobility rate, stablizes positive electrode knot Structure improves the cyclical stability and high rate performance of lithium ion battery under high temperature high voltage.
As further preferred embodiment, the charging voltage of lithium ion battery is 3-4.5V；And/or lithium-ion electric The charge and discharge cycles temperature in pond is 10-70 DEG C.It can be suitable for charging voltage in the section 3-4.5V containing the tertiary cathode material Interior, charge and discharge cycles temperature is the lithium ion battery within the scope of 10-70 DEG C.
5th aspect according to the present invention, provides a kind of electric vehicle, including above-mentioned lithium ion battery.
Above-mentioned lithium ion battery has excellent cycle performance of battery under the voltage of 3-4.5V, by above-mentioned lithium ion battery For in electric car, it can be achieved that the quick charge of electric car.
Technical solution of the present invention is described further below in conjunction with embodiment and comparative example.
Embodiment 1
1, tertiary cathode material
A kind of tertiary cathode material, including ternary material (LiNi0.6Co0.2Mn0.2O2) and be coated on ternary material surface Clad, clad include K2H2PO4And graphene.
Wherein, K2H2PO4Mass percentage in tertiary cathode material is 2%, and graphene is in tertiary cathode material Mass percentage be 1%.
2, the preparation of tertiary cathode material
(1) by ternary material, K2H2PO4In ethanol with graphene dispersion, dispersion is the stirring speed by way of stirring Degree is 800r/s, and temperature is 40 DEG C, mixing time 10h.
(2) solid-phase component is obtained through filtering, then solid-phase component is heat-treated, coats the surface of ternary material K2H2PO4And graphene, obtain tertiary cathode material；The atmosphere of heat treatment is argon gas, keeps the temperature 5 hours at 200 DEG C, is warming up to 600 DEG C heat preservation 3 hours, finally cool down, obtain ternary material.
Embodiment 2-10
Embodiment 2-10 difference from example 1 is that, M1y+2z-2xM2xR1yR2zDifference, it is specific as shown in table 1.
M1 in 1 embodiment 2-10 of tabley+2z-2xM2xR1yR2zSpecific type
Embodiment 11
Embodiment 11 difference from example 1 is that, NaHSO3With quality of the graphene in tertiary cathode material Percentage composition is different, specific as shown in table 2.
Table 2NaHSO3With mass percentage of the graphene in tertiary cathode material
In table 2, "-" indicates identical as the dosage of embodiment 1.
Comparative example 1
Comparative example 1 difference from example 1 is that, clad only has K2H2PO4。
Comparative example 2
Comparative example 2 difference from example 1 is that, clad only has graphene.
Comparative example 3
Comparative example 3 difference from example 1 is that, without clad, i.e., directly using ternary material as ternary just Pole material.
Test example 1
The tertiary cathode material obtained using embodiment 1-18 and comparative example 1-3 as the positive electrode of lithium ion battery, Charge-discharge test is carried out under 1C, 5C, 10C (1C=180mAh/g) multiplying power, obtained specific capacity (mAh/g) is as shown in table 3.
Charge-discharge test of 3 tertiary cathode material of table as the positive electrode of lithium ion battery
Test result shows to have carried out the cladding of the above-mentioned type, and effect will be better than the positive electrode not handled.
Test example 2
Discharge capacity of the embodiment 2 at 40 DEG C is as the increased variation tendency of circulating ring number is as shown in Figure 1, there is Fig. 1 It is found that at high temperature under high pressure, the material capacity conservation rate for having carried out cladding processing is high.
The discharge capacity of embodiment 1 and comparative example 3 (blank sample) with circulating ring number increased variation tendency such as Fig. 2 institute Show there is Fig. 2 it is found that the high rate performance for being added to additive has been significantly improved.
It should be understood that the content being not described in detail in the explanation of above-mentioned preparation method, is those skilled in the art The Common Parameters being readily apparent that, therefore can be omitted detailed description thereof.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of tertiary cathode material, which is characterized in that including ternary material and the cladding for being coated on the ternary material surface Layer, the clad includes M1y+2z-2xM2xR1yR2zAnd graphene；
Wherein, 0≤x≤1,0≤y≤2,0≤z≤1,0≤y+2z-2x≤2, y+z ≠ 0；
The M1 includes at least one of Na, K and Ag metallic element；
The M2 includes at least one of Be, Mg, Ca, Sr, Ba, Cu, Zn and Cd metallic element；
The R1 includes the univalent anion of phosphorous univalent anion and/or sulfur-bearing；
The R2 includes the dianion of phosphorous dianion and/or sulfur-bearing.
2. tertiary cathode material according to claim 1, which is characterized in that the M1 includes at least one of Na and K Metallic element；
And/or the M2 includes at least one of Mg, Ca and Sr metallic element；
And/or the R1 includes PO2F2 1-And/or HSO3 1-, preferably PO2F2 1-；
And/or the R2 includes H2PO4 2-And/or SO4 2-, preferably H2PO4 2-；
And/or x value is 0 or 1, y value is 0 or 2, z value 0 or 1, y+2z-2x value 0 or 2, y+z ≠ 0；
Preferably, the M1y+2z-2xM2xR1yR2zIncluding Na2H2PO4、K2H2PO4、MgH2PO4、CaH2PO4、NaPO2F2、KPO2F2、 Mg(PO2F2)2With Ca (PO2F2)2At least one of.
3. tertiary cathode material according to claim 1, which is characterized in that the M1y+2z-2xM2xR1yR2zIn tertiary cathode Mass percentage in material is 0.1%-10%, preferably 0.5%-4%；
And/or mass percentage of the graphene in tertiary cathode material is 0.1%-10%, preferably 0.5%- 4%；
Preferably, the M1y+2z-2xM2xR1yR2zIt is 0.2%- with mass percentage of the graphene in tertiary cathode material 5%.
4. tertiary cathode material according to claim 1-3, which is characterized in that the ternary material is nickelic three First material, preferably LiNixCoyMnzO2And/or LiNixCoyAlzO2；Wherein, x+y+z=1；
And/or the graphene is single layer or 2-5 layers, the size of the graphene is 10nm-100 μm.
5. the preparation method of the described in any item tertiary cathode materials of claim 1-4, which comprises the following steps:
By ternary material, M1y+2z-2xM2xR1yR2zWith graphene dispersion in alcohols solvent, it is isolated to solid-phase component, then It is heat-treated, the surface of ternary material is made to coat M1y+2z-2xM2xR1yR2zAnd graphene, obtain tertiary cathode material.
6. preparation method according to claim 5, which is characterized in that the alcohols solvent is C1-C4Alcohol, preferably first At least one of alcohol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol and glycerine.
7. preparation method according to claim 5, which is characterized in that the atmosphere of the heat treatment is inert gas, Preferably argon gas or nitrogen；
Preferably, the heat treatment includes successively keeping the temperature 3-8h at 180-220 DEG C and keeping the temperature 2-4h at 580-620 DEG C.
8. the described in any item tertiary cathode materials of claim 1-4 or the described in any item preparation methods of claim 5-7 obtain To application of the tertiary cathode material in lithium ion battery.
9. a kind of lithium ion battery, which is characterized in that including the described in any item tertiary cathode materials of claim 1-4 or right It is required that the tertiary cathode material that the described in any item preparation methods of 5-7 obtain；
Preferably, the charging voltage of the lithium ion battery is 3-4.5V；
And/or the charge and discharge cycles temperature of the lithium ion battery is 10-70 DEG C.
10. a kind of electric vehicle, which is characterized in that including lithium ion battery as claimed in claim 9.
CN201811553565.7A 2018-12-18 2018-12-18 Tertiary cathode material and its preparation method and application, lithium ion battery, electric vehicle Pending CN109686940A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107528050A (en) * 2017-08-08 2017-12-29 上海华普汽车有限公司 Active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery
CN108550803A (en) * 2018-03-21 2018-09-18 北京旭碳新材料科技有限公司 Ternary anode material for lithium-ion batteries and preparation method thereof
CN108899509A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of method of modifying of trielement composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107528050A (en) * 2017-08-08 2017-12-29 上海华普汽车有限公司 Active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery
CN108550803A (en) * 2018-03-21 2018-09-18 北京旭碳新材料科技有限公司 Ternary anode material for lithium-ion batteries and preparation method thereof
CN108899509A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of method of modifying of trielement composite material

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Application publication date: 20190426