CN109336193A - Multielement original position codope ternary material precursor and its preparation method and application - Google Patents

Multielement original position codope ternary material precursor and its preparation method and application Download PDF

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CN109336193A
CN109336193A CN201811225811.6A CN201811225811A CN109336193A CN 109336193 A CN109336193 A CN 109336193A CN 201811225811 A CN201811225811 A CN 201811225811A CN 109336193 A CN109336193 A CN 109336193A
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ternary material
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CN109336193B (en
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闫东伟
赵宜男
吴志坚
谷丰宏
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Saint Glory (beijing) Technology 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
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    • 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
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Abstract

The invention discloses a kind of multielement original position codope ternary material precursors and its preparation method and application.The chemical formula of the presoma are as follows: (NixCoyMnz)1‑a‑cMaNc(OH)2+k, wherein 1/3≤x≤0.9,0 < y≤1/3,0 < z≤0.4, x+y+z=1,0.0001≤a≤0.01,0.0001≤c≤0.01；The radius and lithium ion of Doped ions M is close, is selected from Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+It is one or more；The radius of metal ion manganese and cobalt in the radius and ternary material of Doped ions N is close, is selected from Al3+、Ti4+、Ge4+、W6+、V5+It is one or more.During preparing ternary material precursor, the metal ion in situ for introducing two class different ions radiuses is uniformly distributed in doped metal ion in presoma body phase, realizes the uniform mixing of atomic level the present invention.The metal ion of two class different radiis carries out the doping of different location, and cell parameter collaborative variation can expand the channel of lithium ion transport, and ternary material can be made to keep good lattice structure, to obtain the ternary material with excellent electrochemical performance.

Description

Multielement original position codope ternary material precursor and its preparation method and application
Technical field
The invention belongs to technical field of lithium ion battery electrode, and in particular to a kind of multielement original position codope ternary Material precursor and preparation method thereof is preparing the application in ternary cathode material of lithium ion battery with it.
Background technique
Anode material for lithium-ion batteries currently used, that exploitation is more mature mainly has cobalt acid lithium (LiCoO2), nickel acid Lithium, LiMn2O4 (LixMn2O4), LiFePO 4 (LiFePO4) etc., carry out a large amount of basic research and substantially real to this both at home and abroad Existing industrialization.Compared with above-mentioned traditional positive electrode, Layered Lithium nickel, cobalt, manganese and oxygen positive electrode (hereinafter referred to as " ternary material " or " NCM ") the advantages of preferably having had both cobalt acid lithium, lithium nickelate, LiMn2O4, trielement synergistic effect makes its comprehensive performance better than any One-component compound.Because it has many advantages, such as that height ratio capacity, stable cycle performance, advantage of lower cost, security performance are preferable, It is proved to be the ideal positive electrode of power battery.
However, ternary material similarly there are problems that some needing to overcome: (1) material crystal structure is unstable, is filling Crystal structure easily changes in discharge process；(2) poor compatibility of material surface structural instability, material and electrolyte, by In LiPF6Transition metal ions is caused to dissolve containing HF corroding electrode material in electrolyte；(3)Ni2+Radius and Li+Radius phase Closely, so Ni2+It is dissolved in very much and Li+Mutual occupy-place, so as to cause the generation of cationic mixing phenomenon, Ni2+In Li+Layer not only reduces Specific discharge capacity, and hinder Li+Diffusion, the disordered state of this structure directly becomes the chemical property of material Difference；(4) thermal stability of ternary material is poor；(5) compacted density of material needs further improve.
In view of the above-mentioned problems, researcher improves the performance of ternary material using element doping.Metal cation adulterates A kind of common method for improving ternary material chemical property, common foreign cation have Zn2+、Zr2+、Al3+、Ti4+、V5 +、Mo6+Deng lattice defect will be caused in the lattice of these ion dopings to material, or increase the crystalline substance of interlamellar spacing or stabilizing material Body structure, so that the chemical property of material be made to get a promotion.For example, the patent application No. is CN201410110848.X passes through After rare earth oxide and ternary material precursor ball milling, rear-earth-doped ternary material is obtained by being sintered three times；Application No. is The patent of CN201510672398 discloses step sintering Ca2+The preparation method for adulterating ternary material, by by nickel, cobalt, manganese, calcium Compound and lithium salts grinding and sintering be made ternary material.Application No. is the patents of CN201710121639.9 to disclose a kind of benefit Al is prepared with sol-gel method3+、Zr2+、Ti4+The method of the ternary material of equal doping.
It is well known that being known as the cation altogether there are five types of different valence state and radius: Li at present in ternary material+(half Diameter:)、Ni2+(radius:)、Ni3+(radius:)、Mn4+(radius:)、Co3+(radius:)；In this five kinds of cations, can be divided into two classes by ionic radius size: one kind is that cation radius is larger and close Li+And Ni2+, the another kind of transition metal ions Ni smaller and close for ionic radius3+、Mn4+、Co3+。
And the method for above-mentioned ternary material doping vario-property, on the one hand it is difficult to ensure that Doped ions are evenly distributed in ternary material In Material phase；On the other hand, single to introduce a kind of ion, or ion similar in different kinds of ions radius is introduced, lead to ternary The out-of-proportion variation of the cell parameter of material causes lattice lopsided, it is difficult to ensure that the performance of ternary material is greatly improved Or it improves.
Summary of the invention
In order to overcome the deficiencies of the prior art, the present invention provides a kind of multielement original position codope ternary precursor preparation sides Method is preparing the application in ternary cathode material of lithium ion battery with it.So-called multielement original position codope, i.e., using chemistry During coprecipitation prepares ternary precursor, while the metal cation of two class different ions radiuses is added, so that two classes Metal cation with different ions radius is uniformly distributed in presoma body phase.Further, by the ternary precursor It mixes and is sintered with lithium source, to obtain the modification tertiary cathode material with excellent high rate performance and cycle performance.
To achieve the above object, the invention adopts the following technical scheme:
The chemical formula of a kind of multielement original position codope ternary material precursor and ternary material is respectively (NixCoyMnz)1-a-cMaNc(OH)2+kWith Li (NixCoyMnz)1-a-cMaNcO2；The radius and lithium ion of metal ions M in chemical formula It is close, it is selected from Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+It is one or more；The radius of metal ion N With the transition metal ions (Mn in ternary material4+、Co3+) radius it is close, be selected from Al3+、Ti4+、Ge4+、W6+、V5+It is a kind of or more Kind.Wherein 1/3≤x≤0.9,0 < y≤1/3,0 < z≤0.4, x+y+z=1,0.0001≤a≤0.01,0.0001≤c≤ 0.01, k value is determined by metal ions M and N valent state and doping a and c.
A kind of multielement original position codope ternary material precursor and its preparation method and application, it is rapid that Bao includes Ru Xia Walk:
(1) metal salt solution is prepared: by M salt corresponding to soluble nickel salt, manganese salt, cobalt salt, doped chemical M, doping member N salt corresponding to plain N is made into aqueous solution according to molar ratio Ni:Co:Mn:M:N=x:y:z:a:c, final all metal ions Concentration summation is the metal salt solution A of 0.1-3mol/L.
(2) precipitating reagent is prepared: using water soluble alkali as precipitating reagent, being taken suitable water soluble alkali, is dissolved in pure water, configures At the aqueous slkali B of concentration 1-8mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 2-12mol/L.
(4) chemical coprecipitation prepares ternary precursor (NixCoyMnz)1-a-cMaNc(OH)2+k: step (1) is prepared The ammonia spirit C that the aqueous slkali B and step (3) that metal salt solution A, step (2) are prepared are prepared is pumped into stirred autoclave simultaneously In, under inert gas protection, carry out chemical precipitation reaction.After reaction, it by ageing, centrifugation, washing, drying, obtains The spherical codoping modified ternary precursor (Ni of multielement of micronxCoyMnz)1-a-cMaNc(OH)2+k。
(5) tertiary cathode material Li (NixCoyMnz)1-a-cMaNcO2Preparation: step (4) preparation multielement in situ altogether Adulterate presoma (NixCoyMnz)1-a-cMaNc(OH)2+kIt is used to prepare lithium ion battery ternary material.According to ternary material chemistry Formula Li (NixCoyMnz)1-a-cMaNcO2The molar ratio of middle each element weighs the presoma of appropriate step (4) preparation respectively (NixCoyMnz)1-a-cMaNc(OH)2+kAnd lithium source；It after being sufficiently mixed, is placed in high temperature sintering furnace, under oxidizing atmosphere High-temperature calcination is carried out, the ternary codoping modified to get metal cation M and N after natural cooling, broken, screening, except iron Positive electrode Li (NixCoyMnz)1-a-cMaNcO2。
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (1) Stating nickel salt, manganese salt, cobalt salt is respectively one of sulfate corresponding to each metal ion, villaumite, nitrate or a variety of.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (1) Stating doped chemical M is metal ions M g2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+One of or it is a variety of； The soluble M salt is metal ions M g2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+Institute is corresponding One of soluble sulphate, villaumite, nitrate, oxalates or other corresponding soluble-salts.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (1) Stating doped chemical N is metal ion Al3+、Ti4+、Ge4+、W4+、V5+One of or it is a variety of；The N salt is metal ion Al3+、 Ti4+、Ge4+、W6+、V5+One of the corresponding sulfate of institute, villaumite, nitrate or other corresponding soluble-salts.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (1) Stating concentration of metal ions summation in metal salt solution A is 0.1-3mol/L, it is preferable that the concentration summation of all metal ions is 1-2mol/L。
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (2) Stating precipitating reagent is one of sodium hydroxide, potassium hydroxide or lithium hydroxide or a variety of；The concentration of the precipitant solution be 1~ 8mol/L, it is preferred that the concentration of the precipitating reagent is 4~6mol/L.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, institute in step (3) Stating complexing agent is ammonium hydroxide, concentration 2-12mol/L；Preferably, the concentration of the complexing agent is 6-10mol/L.
A kind of preparation method of multielement codoping modified tertiary cathode material in situ, chemistry described in step (4) Coprecipitation prepares ternary precursor (NixCoyMnz)1-a-cMaNc(OH)2+k, the inert gas is one in nitrogen or argon gas Kind；In the coprecipitation reaction, mixing speed 100-800rpm, at 40-80 DEG C, pH value is controlled in 9- heating and temperature control 12；Preferably, inert gas is nitrogen, and mixing speed 200-600rpm, at 50-80 DEG C, pH value controls heating and temperature control In 10-11.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, step (5) are described Lithium source is one of the lithium carbonate containing elemental lithium, lithium hydroxide, lithium acetate.According to stoichiometric ratio, lithium source excessive 2%- 10%, i.e., lithium ion and presoma (Ni in lithium sourcexCoyMnz)1-a-cMaNc(OH)2+kThe molar ratio of middle metal ion be (1.02~ 1.1):1；Preferably, lithium source excess 3%-5%, i.e., lithium ion and presoma (Ni in lithium sourcexCoyMnz)1-a-cMaNc(OH)2+kIn The molar ratio of metal ion is (1.03~1.05): 1.
Described a kind of multielement original position codope ternary material precursor and its preparation method and application, step (6) are described High temperature sintering is carried out under air or oxygen atmosphere, 650-1100 DEG C of sintering temperature, 1-5 DEG C of heating rate/min, and sintering Time 10-30h；Preferably, 750-980 DEG C of sintering temperature, 2-5 DEG C of heating rate/min, sintering time, 15-20h.
Compared with prior art, the invention has the following beneficial effects:
1, the codoping modified tertiary cathode material of multielement prepared by the present invention, before preparing ternary material using coprecipitation It is in situ to introduce doped metal ion during driving body, it is uniformly distributed in doped metal ion in presoma body phase, realizes The uniform mixing of atomic level, to obtain higher building matter activity and the ternary material precursor compared with high-tap density.
2, the present invention selectively introduces two class different radii metal ions using the method adulterated in situ: one kind doping Metal ion radius is suitable or close with lithium ion radius, the transition metal in another kind of doped metal ion and ternary material from Sub- radius is suitable or close.In high-temperature sintering process, in the lattice of the involvement ternary material of two class doped chemicals faster more evenly, The doping of different location is carried out, cell parameter collaborative variation can expand the channel of lithium ion transport, and can make ternary material Material keeps good lattice structure, to prepare the tertiary cathode material with excellent cycling performance and high rate performance.
3, a variety of doped metal ions are introduced in situ during preparing ternary precursor, substantially reduce preparation work Skill improves production efficiency, is easy to scale industrial production.
Detailed description of the invention
Fig. 1: 1 ternary precursor (Ni of embodiment0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01The scanning electricity of sample Mirror figure.
Fig. 2: 1 tertiary cathode material Li (Ni of embodiment0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The scanning electron microscope of sample Figure.
Fig. 3: 1 tertiary cathode material Li (Ni of embodiment0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The XRD diagram of sample.
Fig. 4: 1 tertiary cathode material Li (Ni of embodiment0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The charge and discharge for the first time of sample Electric curve graph.
Fig. 5: 1 tertiary cathode material Li (Ni of embodiment0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The circulation of sample Curve graph.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without For limiting the scope of the invention.Externally it should be understood that after reading the contents of the present invention, those skilled in the art are to this hair Various changes made by bright or modification, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1:
The present embodiment prepares Zr4+With Al3+Codoping modified ternary precursor (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01With tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2, including walk as follows It is rapid:
(1) metal salt solution is prepared: weigh 8.937mol nickel sulfate hexahydrate respectively, 2.979mol cobalt sulfate, 2.979mol manganese sulfate monohydrate, 0.03mol aluminum sulfate octadecahydrate, 0.045mol tetrahydrated zirconium sulfate, are dissolved in suitable pure water, match 10 liters of salting liquid A is made, total concentration of metal ions in salting liquid is 1.5mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 40mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 4mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Zr4+With Al3+Codoping modified ternary precursor (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01: the aqueous slkali B and step of metal salt solution A, step (2) preparation that step (1) is prepared (3) the ammonia spirit C prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, mixing speed 200-800rpm, heating At 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12 for temperature control.After reaction, by ageing, centrifugation, Washing, drying, obtain Zr4+With Al3+Ternary precursor (the Ni of codope0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01。
(5) tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Preparation: according to tertiary cathode material Expect chemical formula Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The molar ratio of middle each element weighs the precursor of 2mol (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01, the lithium carbonate of 1.015mol；Then it is sufficiently mixed, before obtaining Drive the mixture of body and lithium carbonate.Mixture is placed in high temperature sintering furnace, under oxidizing atmosphere, with the heating of 2 DEG C/min Rate is warming up to 860 DEG C and keeps 20h, then stops heating, arrives Zr after natural cooling, broken, screening, except iron4+ With Al3+Codoping modified tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2。
Using scanning electron microscope (SEM) to ternary precursor (Ni in embodiment 10.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01With tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Carry out table pattern Characterization, as depicted in figs. 1 and 2.It will be seen from figure 1 that gained presoma is in micron chondritic, sphericity is preferable, and partial size is equal One, 4-8 μm of particle size range.Each micron particles are made of nanometer sheet, the thickness of nanometer sheet from several nanometers to tens nanometers not Deng.From figure 2 it can be seen that after mixing lithium high temperature sintering, tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Still maintain preferable spheric granules, partial size is more uniform, most particles at 6 μm or so, Monocrystalline micron chip of each micron particles by thickness at 1 μm is constituted.
Tertiary cathode material Li (the Ni using x-ray powder diffraction instrument prepared by embodiment 10.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Structural characterization is carried out, as a result as shown in Figure 3.It can be seen that diffraction maximum and α-NaFeO2The goodness of fit is higher, There is no dephasign peak, there is good layer structure, I003/I104Value 2.05, illustrate showing for nickelous and the mutual occupy-place of lithium ion As less.
Zr manufactured in the present embodiment4+With Al3+Tertiary cathode material Li (the Ni of codope0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2, chemical property test method it is as follows:
With the tertiary cathode material sample of this example preparation by Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2It is positive Pole active material is assembled into CR2025 button cell: firstly, being in mass ratio 8:1:1 by Li (Ni0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2, acetylene black and PVDF be scattered in N-Methyl pyrrolidone (NMP) and slurry be made；Then, scraper plate is used Coating machine is by slurry coating in forming electrode slice on aluminium foil, with a thickness of 150 μm, electrode slice is dry in 120 DEG C in a vacuum drying oven Dry 12h, stamps out 1cm on electrode slice2Cathode disk；Battery assembly is completed in the glove box full of high-purity argon gas, with Lithium piece is cathode, and Celgard2300 polypropylene porous film is diaphragm, and electrolyte is 1mol/L LiPF6Ethylene carbonate (EC) mixed solution of/dimethyl carbonate (DMC) (volume ratio 1:1).It is assembled into CR2025 button cell, carries out electrochemistry It can test.
Fig. 4 is the sample for preparing of embodiment 1 in 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density Under the conditions of first charge-discharge capacitance-voltage curves figure.It can be seen from the figure that first discharge specific capacity is 185.6mAh/g, Initial charge specific capacity is 203.8mAh/g, and first charge discharge efficiency reaches 91.06%, and polarity effect is also smaller, shows good electricity Chemical property.
Fig. 5 is the sample of the preparation of embodiment 1 in 2.8-4.3V voltage range, and the circulation under different current densities is bent Line chart.It can be seen from the figure that the capacity of putting of sample is 128.9mAh/g, when current density is returned under the high current density of 5C When to 0.1C, discharge capacity reaches 179.3mAh/g again, and after continuing cycling through 130 times, discharge capacity still has 168.5mAh/g；Performance Excellent high rate performance and cycle performance are gone out.
Embodiment 2:
The present embodiment is with tertiary cathode material LiNi0.5Co0.2Mn0.3O2(NCM523) it is matrix, prepares Zr4+、Zn2+With Al3 +Tertiary cathode material Li (the Ni of codope0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2, include the following steps:
(1) metal salt solution is prepared: weigh 9.9mol six hydration nickel sulfate respectively, 3.96mol Cobalt monosulfate heptahydrate, 5.94mol Manganous sulfate monohydrate, 0.05mol Patent alum, 0.06mol Zirconium bis(sulfate) tetrahydrate, seven water sulfuric acid of 0.04mol Zinc is dissolved in suitable pure water, is configured to 10 liters of aqueous metal salt A, and total concentration of metal ions in solution is 2.0mol/ L。
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 60mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 6mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 10mol/L.
(4) chemical coprecipitation prepares Zr4+、Zn2+With Al3+The ternary material precursor of codope (Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.011: the metal salt solution A of step (1) preparation, step (2) are matched The ammonia spirit C that the aqueous slkali B and step (3) of system are prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, stirring speed Degree is 200-800rpm, and for heating and temperature control at 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12.Reaction knot Shu Hou obtains Zr by ageing, centrifugation, washing, drying4+、Zn2+With with Al3+The ternary material precursor of codope (Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.011。
(5) tertiary cathode material Li (Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.0023Al0.005O2Preparation: just according to ternary Pole materials chemistry formula Li (Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.0023Al0.005O2The molar ratio of middle each element, weighs 2mol's Precursor Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.011, the lithium carbonate of 1.015mol；Then it is sufficiently mixed It closes, obtains the mixture of presoma and lithium carbonate.Mixture is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/ It under the rate of heat addition of min, is warming up to 880 DEG C and keeps 20h, then stop heating, by natural cooling, broken, screening, remove iron Afterwards to get metal cation Zr4+、Zn2+With Al3+Tertiary cathode material Li (the Ni of codope0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2。
Prepared by tertiary cathode material Li (Ni to embodiment 2 according to the method for embodiment 10.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2Electrochemical property test is carried out.
The result shows that under conditions of 0.1C (1C=180mA/g) current density, being put for the first time in 2.8-4.3V voltage range Capacitance is 170.8mAh/g, and initial charge capacity is 184.5mAh/g, and coulombic efficiency reaches 92.6% for the first time, recycles 100 times Afterwards, discharge capacity 160.2mAh/g, capacity retention ratio 93.8% show good chemical property.
Embodiment 3:
The present embodiment is with tertiary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) it is matrix, prepares Mg2+、Sc3+、Al3+ With Ti4+Tertiary cathode material Li (the Ni of codope0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O 2, including it is as follows Step:
(1) metal salt solution is prepared: weighing 5.94mol nickel sulfate hexahydrate, 1.98mol cobalt sulfate, 1.98mol respectively Manganese sulfate monohydrate, the magnesium sulfate of 0.03mol, 0.02mol aluminum sulfate octadecahydrate, eight water scandium sulfate of 0.01mol, 0.01mol tetrachloro Change titanium, is dissolved in suitable pure water, is configured to 10 liters of aqueous metal salt A, total concentration of metal ions in salting liquid is 1mol/L。
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Mg2+、Sc3+、Al3+With Ti4+The ternary material precursor of codope (Ni0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.008: metal salt solution A, step step (1) preparation (2) the ammonia spirit C that the aqueous slkali B and step (3) prepared is prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, Mixing speed is 200-800rpm, and for heating and temperature control at 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12. After reaction, by ageing, centrifugation, washing, drying, Mg is obtained2+、Sc3+、Al3+With Ti4+The ternary material forerunner of codope Body (Ni0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.008。
(5) tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2Preparation: according to Tertiary cathode material chemical formula Li (Ni0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2The molar ratio of middle each element, Weigh the precursor (Ni of 2mol0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.008, the carbonic acid of 1.015mol Lithium；Then it is sufficiently mixed, obtains the mixture of presoma and lithium carbonate.The mixture of preparation, it is placed in high temperature sintering In furnace, under oxidizing atmosphere, under the rate of heat addition of 2 DEG C/min, to be warming up to 860 DEG C and keep 20h, then stop heating, warp To get metal cation Zr after crossing natural cooling, broken, screening, removing iron4+With Al3+The tertiary cathode material Li of codope (Ni0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 30.6Co0.2Mn0.2)0.99Mg0.003 Sc0.002Al0.004Ti0.001O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 188.1mAh/g, and initial charge capacity is 204.7mAh/g, and coulombic efficiency reaches 91.89% for the first time；Circulation After 100 times, discharge capacity 175.7mAh/g, capacity retention ratio 93.4% shows good chemical property.
Embodiment 4:
The present embodiment is with tertiary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) it is matrix, prepares Nb5+With Al3+It is co-doped with Miscellaneous tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2, include the following steps:
(1) metal salt solution is prepared: weighing 5.94mol nickel sulfate hexahydrate, 1.98mol cobalt sulfate, 1.98mol respectively Manganese sulfate monohydrate, six water niobium oxalate of 0.06mol, 0.0035mol aluminum sulfate octadecahydrate, are dissolved in suitable pure water, are configured to 10 The aqueous metal salt A risen, total concentration of metal ions in salting liquid are 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares standby Nb5+With Al3+Ternary material precursor (the Ni of codope0.6Co0.2Mn0.2)0.987Nb0.006Al0.007(OH)2.025: the aqueous slkali B and step of metal salt solution A, step (2) preparation that step (1) is prepared (3) the ammonia spirit C prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, mixing speed 200-800rpm, heating At 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12 for temperature control.After reaction, by ageing, centrifugation, Washing, drying, obtain Nb5+With Mo6+Ternary material precursor (the Ni of codope0.6Co0.2Mn0.2)0.987Nb0.006Al0.007 (OH)2.046。
(5) tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2Preparation: according to tertiary cathode material Expect chemical formula Li (Ni0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2The molar ratio of middle each element weighs the precursor of 2mol (Ni0.6Co0.2Mn0.2)0.987Nb0.006Al0.007(OH)2.025, the lithium carbonate of 1.015mol；Then it is sufficiently mixed, before obtaining Drive the mixture of body and lithium carbonate.It said mixture, is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's It under the rate of heat addition, is warming up to 860 DEG C and keeps 20h, then stop heating, after natural cooling, broken, screening, except iron, i.e., Obtain metal cation Nb5+With Al3+Tertiary cathode material Li (the Ni of codope0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 40.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 181.2mAh/g, and initial charge capacity is 198.5mAh/g, and coulombic efficiency reaches 91.28% for the first time；Circulation After 100 times, discharge capacity 172.3mAh/g, capacity retention ratio 95.08% shows good chemical property.
Embodiment 5:
The present embodiment is with tertiary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) it is matrix, prepares In3+、Ta5+With Al3 +、Ge4+Tertiary cathode material Li (the Ni of codope0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O 2, including it is as follows Step:
(1) metal salt solution is prepared: weighing 5.94mol nickel sulfate hexahydrate, 1.98mol cobalt sulfate, 1.98mol respectively Manganese sulfate monohydrate, nine hydrated sulfuric acid indium of 0.015mol, 0.02mol potassium tantalifluoride, 0.015mol aluminum sulfate octadecahydrate, 0.02mol germanium dioxide is dissolved in suitable pure water, is configured to 10 liters of aqueous metal salt A, total metal in salting liquid from Sub- concentration is 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares In3+、Ta5+With Al3+、Ge4+The ternary material precursor of codope (Ni0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003(OH)2.016: metal salt solution A, step step (1) preparation (2) the ammonia spirit C that the aqueous slkali B and step (3) prepared is prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, Mixing speed is 200-800rpm, and for heating and temperature control at 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12. After reaction, by ageing, centrifugation, washing, drying, In is obtained3+、Ta5+With Cr3+、Ge4+The ternary material forerunner of codope Body (Ni0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al 0.003(OH)2.016。
(5) tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2Preparation: according to Tertiary cathode material chemical formula Li (Ni0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2The molar ratio of middle each element, Weigh the precursor (Ni of 2mol0.6Co0.2Mn0.2)0.99In0.003Ta0.02Ge0.002Al 0.003(OH)2.016, the carbonic acid of 1.015mol Lithium；Then it is sufficiently mixed, obtains the mixture of presoma and lithium carbonate.The mixture of the above-mentioned preparation of step is placed in height In warm sintering furnace, under oxidizing atmosphere, under the rate of heat addition of 2 DEG C/min, to be warming up to 860 DEG C and keep 20h, then stop adding Heat, to get metal cation In after natural cooling, broken, screening, except iron3+、Ta5+With Al3+、Ge4+The ternary of codope Positive electrode Li (Ni0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 50.6Co0.2Mn0.2)0.99In0.003 Ta0.002Ge0.002Al0.003O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 188.5mAh/g, and initial charge capacity is 206.8mAh/g, and coulombic efficiency reaches 91.15% for the first time；Circulation After 100 times, discharge capacity 178.7mAh/g, capacity retention ratio 94.8% shows good chemical property.
Embodiment 6:
The present embodiment is with tertiary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) it is matrix, prepares Y3+、Ce4+、Gd3+ With V5+、W6+Tertiary cathode material Li (the Ni of codope0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2, packet Include following steps:
(1) metal salt solution is prepared: weighing 5.94mol nickel sulfate hexahydrate, 1.98mol cobalt sulfate, 1.98mol respectively Manganese sulfate monohydrate, eight water yttrium sulfate of 0.01mol, tetra- water cerous sulfate of 0.02mol, eight water Digadolinium trisulfate of 0.01mol, tetra- water of 0.02mol Cerous sulfate, 0.02mol ammonium metavanadate, 0.02mol ammonium tungstate, are dissolved in suitable pure water, and it is water-soluble to be configured to 10 liters of metal salt Liquid A, total concentration of metal ions in salting liquid are 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Y3+、Ce4+、Gd3+With V5+、W6+The ternary material precursor of codope (Ni0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.022: step (1) prepare metal salt solution A, The ammonia spirit C that the aqueous slkali B and step (3) that step (2) is prepared are prepared is pumped into stirred autoclave simultaneously, in nitrogen protection Under, mixing speed 200-800rpm, for heating and temperature control at 50-80 DEG C, it is anti-to carry out chemical precipitation in 10-12 for pH value control It answers.After reaction, by ageing, centrifugation, washing, drying, Y is obtained3+、Ce4+、Gd3+With V5+、W6+The ternary material of codope Presoma (Ni0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.022。
(5) tertiary cathode material Li (Ni0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2Preparation: press According to tertiary cathode material chemical formula Li (Ni0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2Middle each element is rubbed That ratio, weighs the precursor Li (Ni of 2mol0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.022, 1.015mol lithium carbonate；Then it is sufficiently mixed, obtains the mixture of presoma and lithium carbonate；Mixture is placed in height In warm sintering furnace, under oxidizing atmosphere, under the rate of heat addition of 2 DEG C/min, to be warming up to 860 DEG C and keep 20h, then stop adding Heat, to get metal cation Y after natural cooling, broken, screening, except iron3+、Ce4+、Gd3+With V5+、W6+The three of codope First positive electrode Li (Ni0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 60.6Co0.2Mn0.2)0.99Y0.002 Ce0.002Gd0.002V0.002W0.002O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 180.6mAh/g, and initial charge capacity is 203.1mAh/g, and coulombic efficiency reaches 88.92% for the first time；Circulation After 100 times, discharge capacity 166.1mAh/g, capacity retention ratio 91.97% shows good chemical property.
Embodiment 7:
The present embodiment is with tertiary cathode material LiNi0.8Co0.1Mn0.1O2(NCM811) it is matrix, prepares Zr4+With Al3+It is co-doped with Miscellaneous tertiary cathode material, Li (Ni0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2, include the following steps:
(1) metal salt solution is prepared: weigh 7.944mol nickel sulfate hexahydrate respectively, 0.993mol cobalt sulfate, 0.993mol manganese sulfate monohydrate, 0.02mol aluminum sulfate octadecahydrate, 0.03mol tetrahydrated zirconium sulfate, are dissolved in suitable pure water, match 10 liters of aqueous metal salt A is made, total concentration of metal ions in salting liquid is 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Zr4+With Al3+Ternary material precursor (the Ni of codope0.8Co0.1Mn0.1)0.993Zr0.003Al0.004(OH)2.01: the aqueous slkali B and step of metal salt solution A, step (2) preparation that step (1) is prepared (3) the ammonia spirit C prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, mixing speed 200-800rpm, heating At 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12 for temperature control.After reaction, by ageing, centrifugation, Washing, drying, obtain Zr4+With Al3+Ternary material precursor (the Ni of codope0.8Co0.1Mn0.1)0.993Zr0.003Al0.004 (OH)2.01。
(5) tertiary cathode material Li (Ni0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2Preparation: according to tertiary cathode material Expect chemical formula Li (Ni0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2The molar ratio of middle each element weighs the precursor of 2mol (Ni0.8Co0.1Mn0.1)0.993Zr0.003Al0.004(OH)2.01, the lithium hydroxide of 2.05mol；Then it is sufficiently mixed, before obtaining Drive the mixture of body and lithium hydroxide.Mixture is placed in high temperature sintering furnace, under oxidizing atmosphere, with adding for 2 DEG C/min Under hot rate, be warming up to 760 DEG C and keep 20h, then stop heating, after natural cooling, broken, screening, except iron to get Metal cation Zr4+With Al3+Tertiary cathode material Li (the Ni of codope0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 70.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=200mA/g) current density, first Secondary discharge capacity is 216.2mAh/g, and initial charge capacity is 238.6mAh/g, and coulombic efficiency reaches 90.61% for the first time；Circulation After 100 times, discharge capacity 198.9mAh/g, capacity retention ratio 92.0% shows good chemical property.
Embodiment 8:
The present embodiment is with tertiary cathode material LiNi0.8Co0.1Mn0.1O2(NCM811) it is matrix, prepares Zr4+With Al3+It is co-doped with Miscellaneous tertiary cathode material, Li (Ni0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2, include the following steps:
(1) metal salt solution is prepared: weighing 7.92mol nickel sulfate hexahydrate, 0.99mol cobalt sulfate, 0.99mol respectively Manganese sulfate monohydrate, 0.01mol aluminum sulfate octadecahydrate, 0.08mol tetrahydrated zirconium sulfate, are dissolved in suitable pure water, are configured to 10 liters Aqueous metal salt A, total concentration of metal ions in salting liquid is 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, is configured to 10 liters of sodium hydroxide Aqueous solution B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Zr4+With Al3+Ternary material precursor (the Ni of codope0.8Co0.1Mn0.1)0.99Zr0.008Al0.002(OH)2.018: the aqueous slkali B and step of metal salt solution A, step (2) preparation that step (1) is prepared (3) the ammonia spirit C prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, mixing speed 200-800rpm, heating At 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12 for temperature control.After reaction, by ageing, centrifugation, Washing, drying, obtain Zr4+With Al3+Ternary material precursor (the Ni of codope0.8Co0.1Mn0.1)0.99Zr0.008Al0.002 (OH)2.018。
(5) tertiary cathode material Li (Ni0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2Preparation: according to tertiary cathode material Chemical formula Li (Ni0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2The molar ratio of middle each element weighs the precursor of 2mol (Ni0.8Co0.1Mn0.1)0.99Zr0.008Al0.002(OH)2.018, the lithium hydroxide of 2.05mol；Then it is sufficiently mixed, before obtaining Drive the mixture of body and lithium carbonate.Then, mixture is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min's It under the rate of heat addition, is warming up to 750 DEG C and keeps 20h, then stop heating, after natural cooling, broken, screening, except iron, i.e., Obtain metal cation Zr4+With Al3+Tertiary cathode material Li (the Ni of codope0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 80.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 215.7mAh/g, and initial charge capacity is 235.1mAh/g, and coulombic efficiency reaches 91.75% for the first time；Circulation After 100 times, discharge capacity 200.6mAh/g, capacity retention ratio 93.0% shows good chemical property.
Embodiment 9:
The present embodiment is with tertiary cathode material LiNi0.85Co0.05Mn0.1O2For matrix, Zr is prepared4+With Al3+The three of codope First positive electrode Li (Ni0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2, include the following steps:
(1) metal salt solution is prepared: weighing 8.33mol nickel sulfate hexahydrate, 0.49mol cobalt sulfate, 0.98mol respectively Manganese sulfate monohydrate, 0.005mol aluminum sulfate octadecahydrate, 0.01mol tetrahydrated zirconium sulfate, are dissolved in suitable pure water, are configured to 10 liters Aqueous metal salt A, total concentration of metal ions in salting liquid is 1mol/L.
(2) precipitating reagent is prepared: being weighed the sodium hydroxide of 30mol, is dissolved in pure water, it is water-soluble to be configured to 10 liters of sodium hydroxide Liquid B, concentration 3mol/L.
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to The ammonia spirit C of 10 liters of 8mol/L.
(4) chemical coprecipitation prepares Zr4+With Al3+Ternary material precursor (the Ni of codope0.85Co0.05Mn0.1)0.98Zr0.01Al0.01(OH)2.03: the aqueous slkali B and step of metal salt solution A, step (2) preparation that step (1) is prepared (3) the ammonia spirit C prepared is pumped into stirred autoclave simultaneously, under nitrogen protection, mixing speed 200-800rpm, heating At 50-80 DEG C, pH value control carries out chemical precipitation reaction in 10-12 for temperature control.After reaction, by ageing, centrifugation, Washing, drying, obtain Zr4+With Al3+Ternary material precursor (the Ni of codope0.85Co0.05Mn0.1)0.98Zr0.01Al0.01 (OH)2.03。
(5) tertiary cathode material Li (Ni0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2Preparation: according to tertiary cathode material Chemical formula Li (Ni0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2The molar ratio of middle each element weighs the precursor of 2mol (Ni0.85Co0.05Mn0.1)0.98Zr0.01Al0.01(OH)2.03, the lithium hydroxide of 2.06mol；Then it is sufficiently mixed, before obtaining Drive the mixture of body and lithium carbonate.Then, it mixture, is placed in high temperature sintering furnace, under oxidizing atmosphere, with 2 DEG C/min The rate of heat addition under, be warming up to 740 DEG C and keep 20h, then stop heating, after natural cooling, broken, screening, except iron, Up to metal cation Zr4+With Al3+Tertiary cathode material Li (the Ni of codope0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2。。
Tertiary cathode material Li (the Ni according to the method for embodiment 1 prepared by embodiment 90.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2Sample has carried out electrochemical property test.
Test result shows under conditions of 2.8-4.3V voltage range, 0.1C (1C=180mA/g) current density, first Secondary discharge capacity is 220.6mAh/g, and initial charge capacity is 239.2mAh/g, and coulombic efficiency reaches 92.1% for the first time；Circulation After 100 times, discharge capacity 206.7mAh/g, capacity retention ratio 93.7% shows good chemical property.
In conclusion the above is merely preferred embodiments of the present invention, being not intended to limit the scope of the present invention. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention Within protection scope.

Claims (10)

1. a kind of multielement original position codope ternary material precursor, chemical formula are as follows: (NixCoyMnz)1-a-cMaNc(OH)2+k, In 1/3≤x≤0.9,0 < y≤1/3,0 < z≤0.4, x+y+z=1,0.0001≤a≤0.01,0.0001≤c≤0.01；Chemistry The radius of doped metal ion M and lithium ion are close in formula, are selected from Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4 +、Gd3+It is one or more；Transition metal ions (Mn in the radius and ternary material of doped metal ion N4+、Co3+) radius It is close, it is selected from Al3+、Ti4+、Ge4+、W6+、V5+It is one or more.The value of k is determined by metal ions M and N valent state and doping It is fixed.
2. a kind of preparation method of multielement original position codope ternary material precursor according to claim 1, including it is as follows Walk is rapid:
(1) metal salt solution is prepared: by M salt corresponding to soluble nickel salt, manganese salt, cobalt salt, doped chemical M, doped chemical N institute Corresponding N salt is made into aqueous solution, the concentration of final all metal ions according to molar ratio Ni:Co:Mn:M:N=x:y:z:a:c Summation is the metal salt solution A of 0.1-3mol/L；
(2) precipitating reagent is prepared: using water soluble alkali as precipitating reagent, being taken suitable water soluble alkali, is dissolved in pure water, be configured to dense Spend the aqueous slkali B of 1-8mol/L；
(3) complexing agent is prepared: using ammonium hydroxide as complexing agent, taking suitable concentrated ammonia liquor, suitable pure water is added, is configured to 2- The ammonia spirit C of 12mol/L；
(4) chemical coprecipitation prepares ternary precursor (NixCoyMnz)1-a-cMaNc(OH)2+k: the metal salt that step (1) is prepared The ammonia spirit C that the aqueous slkali B and step (3) that solution A, step (2) are prepared are prepared is pumped into stirred autoclave simultaneously, lazy Property gas shield under, carry out chemical precipitation reaction；After reaction, by ageing, centrifugation, washing, drying, it is spherical to obtain micron The codoping modified ternary precursor (Ni of multielementxCoyMnz)1-a-cMaNc(OH)2+k。
3. a kind of multielement original position codope ternary material precursor (Ni according to claim 1 to 2xCoyMnz)1-a-cMaNc (OH)2+kPreparation method, which is characterized in that nickel salt described in step (1), manganese salt, cobalt salt are respectively corresponding to each metal ion Sulfate, villaumite, one of nitrate or a variety of；Doped chemical M described in step (1) is metal ions M g2+、Zn2+、 Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+One of or it is a variety of；The soluble M salt is metal ions M g2+、 Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+The corresponding soluble sulphate of institute, villaumite, nitrate, grass One of hydrochlorate or other corresponding soluble-salts are a variety of；Doped chemical N described in step (1) is metal ion Al3+、 Ti4+、Ge4+、W4+、V5+One of or it is a variety of；The N salt is metal ion Al3+、Ti4+、Ge4+、W6+、V5+Institute is corresponding One of sulfate, villaumite, nitrate or other corresponding soluble-salts are a variety of.
4. a kind of preparation method of multielement original position codope ternary material precursor according to claim 1 to 3, special Sign is that the concentration of metal ions summation in metal salt solution A described in step (1) is 0.1-3mol/L, it is preferred that Suo Youjin The concentration summation for belonging to ion is 1-2mol/L.
5. a kind of preparation method of multielement original position codope ternary material precursor described in -4 according to claim 1, special Sign is that precipitating reagent described in step (2) is one of sodium hydroxide, potassium hydroxide or lithium hydroxide or a variety of；It is described heavy The concentration of shallow lake agent solution is 1~8mol/L, it is preferred that the concentration of the precipitating reagent is 4~6mol/L；Network described in step (3) Mixture is ammonium hydroxide, concentration 2-12mol/L；Preferably, the concentration of the complexing agent is 6-10mol/L.
6. a kind of preparation method of multielement original position codope ternary material precursor described in -5 according to claim 1, special Sign is that inert gas described in step (4) is one of nitrogen or argon gas；In the coprecipitation reaction, mixing speed is 100-800rpm, at 40-80 DEG C, pH value is controlled in 9.5-12 heating and temperature control；Preferably, inert gas is nitrogen, stirring Speed is 200-600rpm, and at 50-80 DEG C, pH value is controlled in 10-11 heating and temperature control；Step (4) described chemical coprecipitation After completion of the reaction, by ageing, centrifugation, washing, drying etc. to get arrive multielement original position codope ternary material precursor ((NixCoyMnz)1-a-cMaNc(OH)2+k。
7. a kind of preparation method of multielement original position codope ternary material precursor described in -6 according to claim 1, special Sign is that the invention further relates to the multielement original position codope ternary material precursor (NixCoyMnz)1-a-cMaNc(OH)2+k Application, be used for preparing ternary cathode material of lithium ion battery.
8. a kind of application of multielement original position codope ternary material precursor, feature described in -7 exist according to claim 1 In utilizing the multielement original position codope ternary material precursor (NixCoyMnz)1-a-cMaNc(OH)2+kWith lithium source according to one It after fixed stoichiometric ratio is mixed, is placed in high temperature sintering furnace, high-temperature calcination is carried out under oxidizing atmosphere, by nature Cooling, broken, screening, except after iron to get arriving the codoping modified ternary cathode material of lithium ion battery Li of multielement (NixCoyMnz)1-a-cMaNcO2。
9. a kind of preparation side of the codoping modified ternary cathode material of lithium ion battery of multielement according to claim 8 Method, which is characterized in that the lithium source is one of the lithium carbonate containing elemental lithium, lithium hydroxide, lithium acetate；In the lithium source Lithium ion and presoma (NixCoyMnz)1-a-cMaNc(OH)2+kThe molar ratio of middle metal ion is (1.02~1.1): 1, it is preferable that (1.03~1.05): 1.
10. a kind of preparation of the codoping modified ternary cathode material of lithium ion battery of multielement according to claim 8-9 Method, which is characterized in that the high temperature sintering is carried out under air or oxygen atmosphere, 650-1100 DEG C of sintering temperature, is risen 1-5 DEG C of warm speed/min, sintering time 10-30h；Preferably, 750-980 DEG C of sintering temperature, 2-5 DEG C of heating rate/min are burnt Tie time, 15-20h.
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