CN105098158B - A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping and preparation method thereof - Google Patents
A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention relates to lithium-enriched cathodic material of lithium ion battery of a kind of zirconium doping and preparation method thereof, belong to technical field of inorganic material.The chemical formula of the lithium-enriched cathodic material of lithium ion battery of zirconium doping in the present invention is Li1.2(Mn0.54Ni0.13Co0.13)1‑xZrxO2(0 ＜ x ＜ 1).Used preparation method is hydro-thermal method, and this method preparation method is simple, easy control of reaction conditions, advantageously reduces the reunion of particle, and the chemical reaction occurred in hydrothermal system has faster reaction rate.The zr element dosage that lithium-enriched cathodic material of lithium ion battery prepared by the present invention is adulterated is less, and the effect reached is clearly, compared with the material of no doping, the aspect of performance such as battery specific capacity and multiplying power is all greatly improved and improved the zirconia material of doping 3%.
Description
Technical field
The present invention relates to a kind of lithium ion battery electrode material, more particularly, to a kind of lithium ion battery richness lithium of zirconium doping
Positive electrode and preparation method thereof.
Background technology
With the further lifting of lithium ion battery energy density, its application field is by progressively applied to electric car (electricity
Dynamic bicycle, electric automobile, hybrid vehicle), power network and other large-scale energy storage fields.Anode material for lithium-ion batteries
Development have become and restrict the key factor that is further lifted of lithium ion battery energy density.Currently used positive electrode
For：Cobalt acid lithium (LCO), LiMn2O4 (LMO), LiFePO4 (LFP) etc., but the specific capacity of these positive electrodes is mostly<160mAh/
g.Develop the positive electrode of new high power capacity, be just hopeful further to lift the energy density of current lithium ion battery.
Lithium ion battery richness lithium tertiary cathode material is because with high (the up to 250mAh/g, for theoretical capacity of capacity
91%) the advantages that, security performance is excellent and cheap and receive the extensive concern of researcher.But existing lithium from
Poor high rate performance constrains its application and development in lithium ion battery to sub- battery under high voltages.
Because nickel ion is close with the radius of lithium ion, therefore in the sintered of lithium ion battery richness lithium tertiary cathode material
Cheng Zhong, easily cause nickel to occupy lithium position, Li-Ni mixings occur and the coulombic efficiency of material is declined；Meanwhile lithium can also occupy nickel
Position, metal oxygen key average bond length is caused to increase, layer structure is unstable, therefore in cyclic process, the dissolution of metal ion is tight
Weight, the dissolution of especially manganese is even more serious, and this causes lithium ion battery richness lithium tertiary cathode material to be decayed in cyclic process change
It hurry up.It is to improve lithium to reduce the mixing of lithium nickel, suppress the dissolution of manganese and keep lithium ion battery richness lithium tertiary cathode material structural integrity
The ion battery richness lithium tertiary cathode material key point of cycle performance and high rate performance under high voltages.
In order to improve the cycle performance of material and high rate performance, it is the side solved the problems, such as to introduce the stronger metallic element of bond energy
One of method.Because introduce the stronger metallic element of bond energy can stabilizing material structure, and can reduces lithium nickel mixing.In rich lithium ternary
The metallic element such as Zr, Al, Mg is adulterated in positive electrode, is allowed in material containing the keys such as bond energy higher Zr-O, Al-O, Mg-O, energy
The structure of material is enough set more to stablize, Mn is no longer easy to dissolution and is adapted to use under high charge blanking voltage, uses the material
Lithium ion battery also correspondingly there is more preferable cycle performance and security performance.Rich lithium tertiary cathode material prepared by the present invention
Possess higher coulombic efficiency, more preferable layer structure, stronger metal oxygen key bond energy and shorter metal oxygen key bond distance, therefore
Possess more preferable cycle performance and high rate performance under high voltage, heat endurance is also greatly improved.
The content of the invention
The invention aims to solve, the capacity of positive electrode mentioned above is low, high rate performance is poor, cation mixes
The technical problems such as row and lithium-enriched cathodic material of lithium ion battery of a kind of zirconium doping and preparation method thereof is provided, preparation method tool
There is technique simple, material source is extensive, easy control of reaction conditions, advantageously reduces the reunion of particle, and battery specific capacity
All it is greatly improved and improves with aspect of performances such as multiplying powers.
The technical principle of the present invention：
The present invention is that complexing agent stirring at normal temperature is dissolved in deionized water, in addition by cobalt salt, nickel salt, manganese salt, zirconates and lithium
Salt ultrasonic dissolution is in deionized water；Then solution in the latter is at the uniform velocity added drop-wise in the former enveloping agent solution, reacts 2-6h, will
Mixed solution is transferred in water heating kettle, 80-250 DEG C of hydro-thermal 6-24h, then controls temperature to be dried to obtain solid for 60-120 DEG C
Powder, the lithium-enriched cathodic material of lithium ion battery adulterated finally by sintered at high temperature zirconium.This ensure that hydrothermal system
In there is faster reaction rate, particle after sintering reduces, so that the specific surface area increase of particle so that lithium ion
Diffusion is more prone to.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping, contains Li, Ni, Co, Mn, Zr and O element, its chemical formula
For Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2, wherein 0 ＜ x ＜ 1.
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned zirconium doping, comprises the following steps：
A, complexing agent is dissolved in deionized water, is configured to salting liquid A；
B, by the lithium salts of the stoichiometric proportion shown in the lithium-enriched cathodic material of lithium ion battery chemical formula adulterated with zirconium,
Manganese salt, nickel salt, cobalt salt and zirconates dissolving in deionized water, are configured to salting liquid B；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, again by gained mixed solution after reaction
Hydro-thermal reaction in water heating kettle is transferred to, afterwards dries solution, after gained solid powder high-temperature calcination, cools to room temperature with the furnace i.e.
Obtain the lithium-enriched cathodic material of lithium ion battery of zirconium doping.
In step a, one or more of the complexing agent in citric acid, oxalic acid, oxalates, tartaric acid or EDTA.
In step a, gained salting liquid A concentration is 0.5~1.5mol/L.
In step b, salting liquid B is by solvable by cobalt salt, nickel salt, manganese salt, zirconates and the lithium salts of solubility and deionized water
The cobalt salt of property, nickel salt, manganese salt, the integral molar quantity of zirconates and lithium salts：Deionized water volume is 0.5-5mol:1L ratio is mixed
Close what is obtained after dissolving under ultrasound condition；
And the amount of the material of lithium salts exceedes the change shown in the lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping
Learn the 5% of metering ratio.
Soluble cobalt salt is more than one or both of cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride to compound；
Soluble nickel salt is more than one or both of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride to compound；
Soluble manganese salt is more than one or both of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride to compound；
Soluble zirconates is more than one or both of zirconium chloride, zirconium nitrate, zirconium fluoride, zirconium sulfate, propyl alcohol zirconium multiple
Match somebody with somebody；
Soluble lithium salts is more than one or both of lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride to compound.
In step c, the speed 0.1-2ml/min that salting liquid A is at the uniform velocity added drop-wise in salting liquid B, by salting liquid A at the uniform velocity
After being added drop-wise to salting liquid B 2-6h is reacted under the conditions of rotating speed is 300-800r/min.
In step c, the temperature of hydro-thermal reaction is 80~250 DEG C, and the time of hydro-thermal reaction is 6~24h.
In step c, the temperature control of drying is between 60~120 DEG C.
In step c, the program of high-temperature calcination is：Heating rate is controlled to be warming up to 450 DEG C of insulation 1-6h for 2-10 DEG C/min,
Then heating rate is controlled to be warming up to 500-1000 DEG C of calcining 6-20h for 2-10 DEG C/min again.
Compared with prior art, the present invention has prepared pure phase by simple hydrothermal method and high temperature solid-phase sintering reaction
With the rich lithium material of zirconium doping.The inventive method synthesis technique is simple, and production efficiency is high.In addition, the inventive method reactant institute
The raw material needed is easy to get, is nontoxic, cost is cheap, and production process is without special protection, easy control of reaction conditions, resulting production
Thing has the advantages that yield is big, result is reproducible.Zirconium doping lithium-rich anode material prepared by the inventive method is not compared to having
The material of doping, there are large increase and improvement in terms of the battery performance such as battery specific capacity and multiplying power.
Brief description of the drawings
Fig. 1 is the XRD of the lithium-enriched cathodic material of lithium ion battery of Zr doping；
Fig. 2 is the SEM figures of the lithium-enriched cathodic material of lithium ion battery of Zr doping；
Fig. 3 is cycle performance curve map of the lithium-enriched cathodic material of lithium ion battery of Zr doping under 1C multiplying powers；
Fig. 4 be Zr doping rich lithium material with undoped with rich lithium material battery under 5C multiplying powers first discharge specific capacity
Comparison diagram；
Fig. 5 be Zr doping rich lithium material with undoped with specific discharge capacity of the rich lithium material under 5C multiplying powers circulate and contrast
Figure.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium ion battery of described Zr doping
Lithium-rich anode material contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.03).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically includes following steps：
A, 2.5214g oxalic acid is dissolved in 20ml deionized waters, ultrasonic 20min, stirring and dissolving obtains solution A；
B, by 0.6282g cobalt acetates, 0.6276g nickel acetates, 2.5676g manganese acetates, 0.2576g zirconium nitrates and 2.5709g
Lithium acetate is dissolved in 40ml deionized waters, by the cobalt salt of solubility, nickel salt, the integral molar quantity of manganese salt and lithium salts：Deionized water is
1mol:1L ratio is mixed after obtaining solution B under ultrasonic 20min；
Described cobalt acetate, nickel acetate, manganese acetate, the amount of zirconium nitrate and lithium acetate, for calculation in the molar ratio, i.e. lithium acetate：
Nickel acetate：Cobalt acetate：Manganese acetate：Metal ion ratio is 1.2 in zirconium nitrate:0.091:0.091:0.378：0.03；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, under the conditions of rotating speed is 600r/min
Gained mixed solution is transferred in water heating kettle again after reaction 3h, temperature hydro-thermal 12h between 180 DEG C is controlled, afterwards by solution
Be transferred in beaker, dried at 120 DEG C, gained solid powder in high-temperature tubular furnace system, control heating rate for 2-10 DEG C/
Min is warming up to 450 DEG C of insulation 4h, then controls heating rate to be warming up to 900 DEG C for 2-10 DEG C/min again and calcines 10h, cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery Li of Zr doping to room temperature1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=
0.03)。
The lithium-enriched cathodic material of lithium ion battery Li that the Zr of above-mentioned gained is adulterated1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2
(x=0.03) it is scanned using X-ray diffractometer, as a result as shown in figure 1, from figure 1 it appears that its appearance is sharp,
(006)/(012) and (108)/(110) split that peak is obvious, the ratio I of (003) to (104) peak strength(003)/I(104)More than 1.2,
It has been indicated above the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the gained of embodiment 11.2(Mn0.54Ni0.13Co0.13)1- xZrxO2(x=0.03) there is good layer structure.
The lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of above-mentioned gained1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.03) observed by SEM, SEM schemes as shown in Figure 2, figure it is seen that above-mentioned gained Zr is adulterated
Lithium-enriched cathodic material of lithium ion battery Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=0.03) pattern is polygon,
Grain size is homogeneous, and size is in 100nm or so.
The lithium-enriched cathodic material of lithium ion battery Li that the Zr of above-mentioned gained is adulterated1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2
(x=0.03) battery is assembled into, number of assembling steps is as follows：
1st, the preparation of anode pole piece
The lithium-enriched cathodic material of lithium ion battery Li that above-mentioned gained Zr is adulterated1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.03), conductive carbon black and bonding polyvinylidene fluoride (PVDF) are 80 in mass ratio：10：10 ratio mixing, is subsequently placed in
Uniform sizing material is stirred on magnetic stirring apparatus, is spread evenly across on aluminium foil, after 120 DEG C of vacuum drying 3h, a diameter of 14mm is made
Circular anode pole piece；
2nd, the preparation of GND
High pure metal lithium piece surface oxide layer is scraped off in dry glove box, the metal surface for exposing gloss produces battery
Negative pole；
3rd, experimental button cell assembles
CR2016 type button cells are assembled into the vacuum glove box full of argon gas.Electrolyte is LiPF6/ ethylene carbonate
Ester (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), metal lithium sheet is GND, and barrier film is Celgard2400 poly- third
Alkene film.Anode pole piece is put into CR2016 type Snap-type cell positive shells, barrier film is covered on anode pole piece, electrolysis is added dropwise
After liquid, then by metal lithium sheet it is that GND is gently placed on barrier film, places into the nickel foam as backing material, battery is born
Pole cap is assembled into experimental button cell on anode cover.
The lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the gained of embodiment 11.2(Mn0.54Ni0.13Co0.13)1-xZrxO2
(x=0.03) battery performance is enterprising in LAND battery test systems CT2001A by the CR2016 type button cells after assembling
Row test, is tested under the conditions of 1C and 5C multiplying power.Test result is as shown in Fig. 3, Fig. 4 and Fig. 5.
Fig. 3 is the lithium-enriched cathodic material of lithium ion battery Li of embodiment 1Zr doping1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2
(x=0.03) after being assembled into experimental button cell, preceding 100 charging and discharging capacities and cycle efficieny curve under 1C multiplying powers.
It can be drawn from Fig. 3, the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the gained of embodiment 1 under the conditions of 1C discharge and recharges1.2
(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=0.03) charge and discharge specific capacity is respectively 308.3mAh/g and 226.1mAh/g first,
Coulombic efficiency is 73.3% first, and since second, efficiency for charge-discharge reaches more than 98.0%.
Fig. 4 is the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the gained of embodiment 11.2
(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=0.03) and undoped with preceding positive electrode it is assembled into respectively after experimental button cell
First charge-discharge curve comparison figure under 5C multiplying powers.1 in Fig. 4 be doping after initial charge curve, 2 be doping after putting first
Electric curve, 3 be undoped with initial charge curve, 4 be undoped with discharge curve first.Figure 4, it is seen that Zr is adulterated
Material afterwards than undoped with material significantly improve the high-rate charge-discharge capability of material, the ratio of electric discharge first of material after doping
Capacity Ratio improves 50mAh/g or so undoped with material.It is indicated above that the lithium ion battery richness lithium of the Zr doping of the present embodiment is just
Pole material Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=0.03) battery high-rate charge-discharge capability is good.
Fig. 5 is the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the gained of embodiment 11.2
(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=0.03) undoped with positive electrode be assembled into respectively after experimental button cell at 5C times
The comparison diagram of cycle performance under rate, 1 in Fig. 5 represents the cycle performance curve undoped with material under 5C multiplying powers, and 2 expression Zr mix
Cycle performance curve of the material under 5C multiplying powers after miscellaneous.From figure 5 it can be seen that doping after material property be substantially better than undoped with
Material property.Illustrate that ion channel has been widened in zirconium doping, improve lithium ion diffusion rate, thus after adulterating battery show it is excellent
Different performance.
Embodiment 2
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium ion battery of described Zr doping
Lithium-rich anode material contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.01).
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically includes following steps：
A, 2.5214g oxalic acid is dissolved in 20ml deionized waters, ultrasonic 20min, stirring and dissolving obtains solution A；
B, by 0.6411g cobalt acetates, 0.6405g nickel acetates, 2.6205g manganese acetates, 0.08586g zirconium nitrates and 2.5709g
Lithium acetate is dissolved in 40ml deionized waters, by the cobalt salt of solubility, nickel salt, the integral molar quantity of manganese salt and lithium salts：Deionized water is
0.5mol:1L ratio is mixed after obtaining solution B under ultrasonic 20min；
Described cobalt acetate, nickel acetate, manganese acetate, the amount of zirconium nitrate and lithium acetate, for calculation in the molar ratio, i.e. lithium acetate：
Nickel acetate：Cobalt acetate：Manganese acetate：Metal ion ratio is 1.2 in zirconium nitrate:0.1287:0.1287:0.5346：0.01；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, under the conditions of rotating speed is 500r/min
Gained mixed solution is transferred in water heating kettle again after reaction 3h, temperature hydro-thermal 10h between 180 DEG C is controlled, afterwards by solution
Be transferred in beaker, dried at 120 DEG C, gained solid powder in high-temperature tubular furnace system, control heating rate for 2-10 DEG C/
Min is warming up to 450 DEG C of insulation 4h, then controls heating rate to be warming up to 900 DEG C for 2-10 DEG C/min again and calcines 12h, cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery Li of Zr doping to room temperature1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=
0.01)。
Embodiment 3
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium ion battery of described Zr doping
Lithium-rich anode material contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.02).
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically includes following steps：
A, 2.5214g oxalic acid is dissolved in 20ml deionized waters, ultrasonic 20min, stirring and dissolving obtains solution A；
B, by 0.6346g cobalt acetates, 0.6341g nickel acetates, 2.5940g manganese acetates, 0.1717g zirconium nitrates and 2.5709g
Lithium acetate is dissolved in 40ml deionized waters, by the cobalt salt of solubility, nickel salt, the integral molar quantity of manganese salt and lithium salts：Deionized water is
0.75mol:1L ratio is mixed after obtaining solution B under ultrasonic 20min；
Described cobalt acetate, nickel acetate, manganese acetate, the amount of zirconium nitrate and lithium acetate, for calculation in the molar ratio, i.e. lithium acetate：
Nickel acetate：Cobalt acetate：Manganese acetate：Metal ion ratio is 1.2 in zirconium nitrate:0.1274:0.1274:0.5292：0.02；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, under the conditions of rotating speed is 600r/min
Gained mixed solution is transferred in water heating kettle again after reaction 4h, controls temperature hydro-thermal 8h between 180 DEG C, afterwards turns solution
Move on in beaker, dried at 120 DEG C, gained solid powder in high-temperature tubular furnace system, control heating rate for 2-10 DEG C/
Min is warming up to 450 DEG C of insulation 4h, then controls heating rate to be warming up to 900 DEG C of calcining 8h, furnace cooling for 2-10 DEG C/min again
It is to obtain the lithium-enriched cathodic material of lithium ion battery Li of Zr doping to room temperature1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=
0.02)。
Embodiment 4
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium ion battery of described Zr doping
Lithium-rich anode material contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.04).
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically includes following steps：
A, 2.5214g oxalic acid is dissolved in 20ml deionized waters, ultrasonic 20min, stirring and dissolving obtains solution A；
B, by 0.6217g cobalt acetates, 0.6211g nickel acetates, 2.5411g manganese acetates, 0.3434g zirconium nitrates and 2.5709g
Lithium acetate is dissolved in 40ml deionized waters, by the cobalt salt of solubility, nickel salt, the integral molar quantity of manganese salt and lithium salts：Deionized water is
1.25mol:1L ratio is mixed after obtaining solution B under ultrasonic 20min；
Described cobalt acetate, nickel acetate, manganese acetate, the amount of zirconium nitrate and lithium acetate, for calculation in the molar ratio, i.e. lithium acetate：
Nickel acetate：Cobalt acetate：Manganese acetate：Metal ion ratio is 1.2 in zirconium nitrate:0.1248:0.1248:0.5184：0.04；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, under the conditions of rotating speed is 800r/min
Gained mixed solution is transferred in water heating kettle again after reaction 5h, temperature hydro-thermal 14h between 180 DEG C is controlled, afterwards by solution
Be transferred in beaker, dried at 120 DEG C, gained solid powder in high-temperature tubular furnace system, control heating rate for 2-10 DEG C/
Min is warming up to 450 DEG C of insulation 4h, then controls heating rate to be warming up to 900 DEG C for 2-10 DEG C/min again and calcines 14h, cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery Li of Zr doping to room temperature1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=
0.04)。
Embodiment 5
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium ion battery of described Zr doping
Lithium-rich anode material contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x
=0.05).
A kind of preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically includes following steps：
A, 2.5214g oxalic acid is dissolved in 20ml deionized waters, ultrasonic 20min, stirring and dissolving obtains solution A；
B, by 0.6152g cobalt acetates, 0.6147g nickel acetates, 2.5146g manganese acetates, 0.4293g zirconium nitrates and 2.5709g
Lithium acetate is dissolved in 40ml deionized waters, by the cobalt salt of solubility, nickel salt, the integral molar quantity of manganese salt and lithium salts：Deionized water is
1.5mol:1L ratio is mixed after obtaining solution B under ultrasonic 20min；
Described cobalt acetate, nickel acetate, manganese acetate, the amount of zirconium nitrate and lithium acetate, for calculation in the molar ratio, i.e. lithium acetate：
Nickel acetate：Cobalt acetate：Manganese acetate：Metal ion ratio is 1.2 in zirconium nitrate:0.1235:0.1235:0.5130：0.05；
C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, is 1000r/min conditions in rotating speed
Gained mixed solution is transferred in water heating kettle again after lower reaction 5h, controls temperature hydro-thermal 16h between 180 DEG C, afterwards will be molten
Liquid is transferred in beaker, is dried at 120 DEG C, and for gained solid powder in high-temperature tubular furnace system, it is 2-10 to control heating rate
DEG C/min be warming up to 450 DEG C insulation 4h, then control again heating rate for 2-10 DEG C/min be warming up to 900 DEG C calcining 16h, with stove
It is cooled to the lithium-enriched cathodic material of lithium ion battery Li that room temperature obtains Zr doping1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2(x=
0.05)。
Embodiment 6
A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping, contains Li, Ni, Co, Mn, Zr and O element, its chemical formula
For Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2, wherein x=0.1.
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned zirconium doping, comprises the following steps：
A, complexing agent (citric acid) is dissolved in deionized water, is configured to the salting liquid A that concentration is 0.5mol/L；
B, the stoichiometric proportion shown in the lithium-enriched cathodic material of lithium ion battery chemical formula by zirconium doping, by solubility
Cobalt salt (cobaltous sulfate), nickel salt (nickel sulfate), manganese salt (manganese sulfate), zirconates (zirconium sulfate) and lithium salts (lithium carbonate) are pressed with deionized water
Soluble cobalt salt, nickel salt, manganese salt, the integral molar quantity of zirconates and lithium salts：Deionized water volume is 0.5mol:1L ratio is carried out
Mixing is dissolved after under ultrasound condition, is configured to salting liquid B；
In this step, the amount of the material of lithium salts exceedes shown in the lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping
Stoichiometric proportion 5%；
C, salting liquid A at the uniform velocity (0.1ml/min) obtained by step a is added drop-wise in the salting liquid B obtained by step b, in rotating speed
To react 6h under the conditions of 300r/min, after reaction again by gained mixed solution be transferred in water heating kettle at 80 DEG C carry out hydro-thermal it is anti-
24h is answered, afterwards dries solution at 60 DEG C, for gained solid powder in high-temperature tubular furnace system, it is 2 to control heating rate
DEG C/min be warming up to 450 DEG C insulation 1h, then control again heating rate for 2 DEG C/min be warming up to 500 DEG C calcining 20h, it is cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery of zirconium doping to room temperature.
Embodiment 7
A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping, contains Li, Ni, Co, Mn, Zr and O element, its chemical formula
For Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2, wherein x=0.5.
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned zirconium doping, comprises the following steps：
A, complexing agent (oxalates A) is dissolved in deionized water, is configured to the salting liquid A that concentration is 1.0mol/L；
B, the stoichiometric proportion shown in the lithium-enriched cathodic material of lithium ion battery chemical formula by zirconium doping, by solubility
Cobalt salt (cobalt acetate), nickel salt (nickel acetate), manganese salt (manganese acetate), zirconates (zirconium fluoride) and lithium salts (lithium acetate) are pressed with deionized water
Soluble cobalt salt, nickel salt, manganese salt, the integral molar quantity of zirconates and lithium salts：Deionized water volume is 2.5mol:1L ratio is carried out
Mixing is dissolved after under ultrasound condition, is configured to salting liquid B；
In this step, the amount of the material of lithium salts exceedes shown in the lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping
Stoichiometric proportion 5%；
C, salting liquid A at the uniform velocity (1ml/min) obtained by step a is added drop-wise in the salting liquid B obtained by step b, is in rotating speed
4h is reacted under the conditions of 500r/min, after reaction again by gained mixed solution be transferred in water heating kettle at 150 DEG C carry out hydro-thermal it is anti-
18h is answered, afterwards dries solution at 90 DEG C, for gained solid powder in high-temperature tubular furnace system, it is 6 to control heating rate
DEG C/min be warming up to 450 DEG C insulation 4h, then control again heating rate for 6 DEG C/min be warming up to 800 DEG C calcining 12h, it is cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery of zirconium doping to room temperature.
Embodiment 8
A kind of lithium-enriched cathodic material of lithium ion battery of zirconium doping, contains Li, Ni, Co, Mn, Zr and O element, its chemical formula
For Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2, wherein x=0.9.
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned zirconium doping, comprises the following steps：
A, complexing agent (EDTA) is dissolved in deionized water, is configured to the salting liquid A that concentration is 1.5mol/L；
B, the stoichiometric proportion shown in the lithium-enriched cathodic material of lithium ion battery chemical formula by zirconium doping, by solubility
Cobalt salt (cobalt chloride), nickel salt (nickel chloride), manganese salt (manganese chloride), zirconates (propyl alcohol zirconium) and lithium salts (lithium hydroxide) and deionized water
By the integral molar quantity of the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts：Deionized water volume is 5mol:1L ratio is carried out
Mixing is dissolved after under ultrasound condition, is configured to salting liquid B；
In this step, the amount of the material of lithium salts exceedes shown in the lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping
Stoichiometric proportion 5%；
C, salting liquid A at the uniform velocity (2ml/min) obtained by step a is added drop-wise in the salting liquid B obtained by step b, is in rotating speed
2h is reacted under the conditions of 800r/min, after reaction again by gained mixed solution be transferred in water heating kettle at 250 DEG C carry out hydro-thermal it is anti-
6h is answered, afterwards dries solution at 120 DEG C, for gained solid powder in high-temperature tubular furnace system, it is 10 to control heating rate
DEG C/min be warming up to 450 DEG C insulation 6h, then control again heating rate for 10 DEG C/min be warming up to 1000 DEG C calcining 6h, it is cold with stove
But it is to obtain the lithium-enriched cathodic material of lithium ion battery of zirconium doping to room temperature.
In summary, a kind of lithium-enriched cathodic material of lithium ion battery of Zr doping provided by the invention have specific capacity it is high,
The advantages that good rate capability, good cycle.Stratiform richness lithium ternary anode material for lithium-ion batteries has preferable structure and electricity
Chemical property, the development to lithium ion battery has great practical significance and social value, to the hair of China's New Energy Industry
Exhibition has good impetus.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (7)
- A kind of 1. preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping, it is characterised in thatThe lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2, wherein 0 ＜ x ＜ 1,Preparation method comprises the following steps：A, complexing agent is dissolved in deionized water, is configured to solution A "；B, by lithium salts, the manganese of the stoichiometric proportion shown in the lithium-enriched cathodic material of lithium ion battery chemical formula adulterated with zirconium Salt, nickel salt, cobalt salt and zirconates dissolving in deionized water, are configured to salting liquid B；C, step a resulting solutions A is at the uniform velocity added drop-wise in the solution B obtained by step b, again shifted gained mixed solution after reaction The hydro-thermal reaction into water heating kettle, afterwards dries solution, after gained solid powder high-temperature calcination, cools to room temperature with the furnace and obtains The lithium-enriched cathodic material of lithium ion battery of zirconium doping；In step c, the temperature of hydro-thermal reaction is 80~250 DEG C, and time of hydro-thermal reaction is 6~24h, the program of high-temperature calcination For：Heating rate is controlled to be warming up to 450 DEG C of insulation 1-6h for 2-10 DEG C/min, it is 2-10 DEG C/min then to control heating rate again It is warming up to 500-1000 DEG C of calcining 6-20h.
- 2. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterised in that In step a, one or more of the complexing agent in citric acid, oxalic acid, oxalates, tartaric acid or EDTA.
- 3. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterised in that In step a, resulting solution A concentration is 0.5~1.5mol/L.
- 4. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterised in that In step b, salting liquid B be by cobalt salt, nickel salt, manganese salt, zirconates and lithium salts and the deionized water of solubility by solubility cobalt salt, Nickel salt, manganese salt, the integral molar quantity of zirconates and lithium salts：Deionized water volume is 0.5-5mol:1L ratio is mixed after super Dissolving obtains under the conditions of sound；And the amount of the material of lithium salts exceedes the chemistry meter shown in the lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping Measure the 5% of ratio.
- 5. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 4, it is characterised in that Soluble cobalt salt is more than one or both of cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride to compound；Soluble nickel salt is more than one or both of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride to compound；Soluble manganese salt is more than one or both of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride to compound；Soluble zirconates is more than one or both of zirconium chloride, zirconium nitrate, zirconium fluoride, zirconium sulfate, propyl alcohol zirconium to compound；Soluble lithium salts is more than one or both of lithium carbonate, lithium acetate, lithium chloride to compound.
- 6. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterised in that In step c, solution A is at the uniform velocity being added drop-wise to salting liquid by the speed 0.1-2ml/min that solution A is at the uniform velocity added drop-wise in salting liquid B After B 2-6h is reacted under the conditions of rotating speed is 300-800r/min.
- 7. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterised in that In step c, the temperature control of drying is between 60~120 DEG C.
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