CN105098158A - Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material - Google Patents
Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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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- H01M4/525—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 relates to a zirconium-doped lithium-rich cathode material of a lithium ion battery and a preparation method of the zirconium-doped lithium-rich cathode material, and belongs to the technical field of inorganic materials. A chemical formula of the zirconium-doped lithium-rich cathode material of the lithium ion battery provided by the invention is Li1.2(Mn0.54Ni0.13Co0.13)1-xZrxO2 (x is less than 1 and greater than 0); the adopted preparation method is a hydrothermal method; the preparation method is simple; the reaction condition is easy to control; reduction of agglomeration of particles is facilitated; and the chemical reaction in a hydrothermal system has relatively high reaction rate. The zirconium element doped into the zirconium-doped lithium-rich cathode material of the lithium ion battery prepared by the method is relatively low in dosage; the reached effect is very obvious; and compared with the non-doped material, according to the material doped with 3% of zirconium, the performances such as the specific capacity and the rate of the battery are greatly improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery electrode material, especially relate to lithium-enriched cathodic material of lithium ion battery of a kind of zirconium doping and preparation method thereof.
Background technology
Along with the further lifting of lithium ion battery energy density, its application by progressively be applied to electric motor car (electric bicycle, electric automobile, hybrid vehicle), electrical network and other large-scale energy storage fields.The development of anode material for lithium-ion batteries has become the key factor restricting lithium ion battery energy density and promote further.Positive electrode conventional is at present: cobalt acid lithium (LCO), LiMn2O4 (LMO), LiFePO4 (LFP) etc., but the specific capacity of these positive electrodes mostly <160mAh/g.Develop the positive electrode of new high power capacity, be just hopeful the energy density promoting current lithium ion battery further.
Lithium ion battery rich lithium tertiary cathode material receives the extensive concern of researcher because having capacity high (can, up to 250mAh/g, be 91% of theoretical capacity), security performance excellence and the advantage such as cheap.But the poor under high voltages high rate performance of existing lithium ion battery constrains its application & development in lithium ion battery.
Because the radius of nickel ion and lithium ion is close, therefore in the sintering process of the rich lithium tertiary cathode material of lithium ion battery, easily cause nickel to occupy lithium position, occur that Li-Ni mixing makes the coulombic efficiency of material decline; Meanwhile, lithium also can occupy nickel position, causes metal oxygen key average bond length to increase, layer structure is unstable, and therefore in cyclic process, the stripping of metal ion is serious, especially the stripping of manganese is even more serious, and this causes the rich lithium tertiary cathode material of lithium ion battery to be decayed in cyclic process accelerating.Reduce the mixing of lithium nickel, suppress the stripping of manganese and keep lithium ion battery rich lithium tertiary cathode material structural integrity to be improve the key point of the rich lithium tertiary cathode material of lithium ion battery cycle performance and high rate performance under high voltages.
In order to improve cycle performance and the high rate performance of material, the metallic element introducing bond energy stronger is one of method of dealing with problems.Can stabilizing material structure because introduce the stronger metallic element of bond energy, the mixing of lithium nickel can be reduced again.Adulterate the metallic elements such as Zr, Al, Mg in rich lithium tertiary cathode material, allow in material containing keys such as higher Zr-O, Al-O, the Mg-O of bond energy, the structure of material can be made more stable, Mn uses under being no longer easy to stripping and being adapted at high charge cut-ff voltage, uses the lithium ion battery of this material also correspondingly to have better cycle performance and security performance.Rich lithium tertiary cathode material prepared by the present invention possesses higher coulombic efficiency, better layer structure, more strong metal oxygen key bond energy and shorter metal oxygen key bond distance, therefore possess better cycle performance and high rate performance under high voltages, thermal stability have also been obtained very large improvement.
Summary of the invention
The object of the invention is that capacity in order to solve the above-mentioned positive electrode mentioned is low, the technical problem such as high rate performance is poor, cation mixing and lithium-enriched cathodic material of lithium ion battery providing a kind of zirconium to adulterate and preparation method thereof, it is simple that this preparation method has technique, material source is extensive, easy control of reaction conditions, be conducive to subtracting less granular reunion, and the aspect of performance such as battery specific capacity and multiplying power is all greatly improved and improves.
Know-why of the present invention:
Complexing agent stirring at normal temperature is dissolved in deionized water by the present invention, in addition by cobalt salt, nickel salt, manganese salt, zirconates and lithium salts ultrasonic dissolution in deionized water; Then solution in the latter is at the uniform velocity added drop-wise in the former enveloping agent solution, reaction 2-6h, mixed solution is transferred in water heating kettle, 80-250 DEG C of hydro-thermal 6-24h, control temperature is 60-120 DEG C and carries out oven dry and obtain pressed powder, finally by the lithium-enriched cathodic material of lithium ion battery of sintered at high temperature zirconium doping again.This ensure that in hydrothermal system to have reaction rate faster, the particle after sintering reduces, thus the specific area of particle is increased, and lithium ion is spread and is more prone to.
Object of the present invention can be achieved through the following technical solutions:
A lithium-enriched cathodic material of lithium ion battery for zirconium doping, containing Li, Ni, Co, Mn, Zr and O element, its chemical formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2, 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 mixed with salting liquid A;
B, the lithium salts of stoichiometric proportion, manganese salt, nickel salt, cobalt salt and the zirconates shown in the lithium-enriched cathodic material of lithium ion battery chemical formula with zirconium doping to be dissolved in deionized water, be mixed with salting liquid B;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred to hydro-thermal reaction in water heating kettle after reaction, afterwards solution is dried, after the high-temperature calcination of gained pressed powder, cool to the lithium-enriched cathodic material of lithium ion battery that namely room temperature obtains zirconium doping with the furnace.
In step a, described complexing agent be selected from citric acid, oxalic acid, oxalates, tartaric acid or EDTA one or more.
In step a, the concentration of gained salting liquid A is 0.5 ~ 1.5mol/L.
In step b, salting liquid B is by the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts and the deionized water integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts: deionized water volume is dissolve after the ratio of 0.5-5mol:1L mixes to obtain under ultrasound condition;
And the amount of substance of lithium salts exceedes 5% of the stoichiometric proportion shown in lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping.
The cobalt salt of solubility is that one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride are composite;
The nickel salt of solubility is that one or more in nickelous sulfate, nickel nitrate, nickel acetate, nickel chloride are composite;
The manganese salt of solubility is that one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride are composite;
The zirconates of solubility is that one or more in zirconium chloride, zirconium nitrate, zirconium fluoride, zirconium sulfate, propyl alcohol zirconium are composite;
The lithium salts of solubility is that one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride are composite.
In step c, salting liquid A is at the uniform velocity added drop-wise to the speed 0.1-2ml/min in salting liquid B, after salting liquid A is at the uniform velocity added drop-wise to salting liquid B, under rotating speed is 300-800r/min condition, reacts 2-6h.
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 of oven dry controls between 60 ~ 120 DEG C.
In step c, the program of high-temperature calcination is: control heating rate be 2-10 DEG C/min be warming up to 450 DEG C insulation 1-6h, and then control heating rate be 2-10 DEG C/min be warming up to 500-1000 DEG C calcining 6-20h.
Compared with prior art, the present invention has prepared the rich lithium material of pure phase and zirconium doping by simple hydrothermal method and high temperature solid-phase sintering reaction.The inventive method synthesis technique is simple, and production efficiency is high.In addition, the raw material required for the inventive method reactant is easy to get, nontoxic, with low cost, and production process is without the need to special protection, and easy control of reaction conditions, the product obtained has the advantages such as output is large, result is reproducible.Zirconium doping lithium-rich anode material prepared by the inventive method, compared to the material not having to adulterate, has had large increase and improvement in the battery performances such as battery specific capacity and multiplying power.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the lithium-enriched cathodic material of lithium ion battery of Zr doping;
Fig. 2 is the SEM figure of the lithium-enriched cathodic material of lithium ion battery of Zr doping;
Fig. 3 is the cycle performance curve chart of lithium-enriched cathodic material of lithium ion battery under 1C multiplying power of Zr doping;
Fig. 4 is the rich lithium material of Zr doping and battery first discharge specific capacity comparison diagram under 5C multiplying power of unadulterated rich lithium material;
Fig. 5 is rich lithium material and the specific discharge capacity circulation comparison diagram of unadulterated rich lithium material under 5C multiplying power of Zr doping.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A preparation method for the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium-enriched cathodic material of lithium ion battery of described Zr doping contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned Zr doping, specifically comprises the following steps:
A, be dissolved in 20ml deionized water by 2.5214g oxalic acid, ultrasonic 20min, stirring and dissolving obtains solution A;
B, 0.6282g cobalt acetate, 0.6276g nickel acetate, 2.5676g manganese acetate, 0.2576g zirconium nitrate and 2.5709g lithium acetate are dissolved in 40ml deionized water, by cobalt salt, the nickel salt of solubility, the integral molar quantity of manganese salt and lithium salts: deionized water is obtain solution B after the ratio of 1mol:1L mixes under ultrasonic 20min;
The amount of described cobalt acetate, nickel acetate, manganese acetate, zirconium nitrate and lithium acetate, calculates in molar ratio, i.e. lithium acetate: nickel acetate: cobalt acetate: manganese acetate: in zirconium nitrate, metal ion ratio is 1.2:0.091:0.091:0.378:0.03;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred in water heating kettle react 3h under rotating speed is 600r/min condition after, control temperature is hydro-thermal 12h between 180 DEG C, afterwards solution is transferred in beaker, dry at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 2-10 DEG C/min be warming up to 900 DEG C calcining 10h, cool to the lithium-enriched cathodic material of lithium ion battery Li that namely room temperature obtains Zr doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03).
By the lithium-enriched cathodic material of lithium ion battery Li that the Zr of above-mentioned gained adulterates
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) X-ray diffractometer is utilized to scan, result as shown in Figure 1, as can be seen from Figure 1, it is sharp-pointed that it goes out peak, (006) it is obvious that peak is split in/(012) and (108)/(110), and (003) is to the ratio I of (104) peak strength
(003)/ I
(104)be greater than 1.2, indicate the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of embodiment 1 gained thus
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(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 gained
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) observed by scanning electron microscopy, SEM schemes as shown in Figure 2, as can be seen from Figure 2, and the lithium-enriched cathodic material of lithium ion battery Li that above-mentioned gained Zr adulterates
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) pattern is polygon, and granular size is homogeneous, and size is at about 100nm.
By the lithium-enriched cathodic material of lithium ion battery Li that the Zr of above-mentioned gained adulterates
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) be assembled into battery, number of assembling steps is as follows:
1, the preparation of anode pole piece
By the lithium-enriched cathodic material of lithium ion battery Li that above-mentioned gained Zr adulterates
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03), conductive carbon black and bonding polyvinylidene fluoride (PVDF) are the ratio mixing of 80:10:10 in mass ratio, then be placed on magnetic stirring apparatus and stir into uniform sizing material, be spread evenly across on aluminium foil, after 120 DEG C of vacuumize 3h, make the circular anode pole piece that diameter is 14mm;
2, the preparation of battery cathode
In the glove box of drying, scrape off high-purity lithium sheet surface oxide layer, namely the metal surface of exposing gloss obtains battery cathode;
3, experimental button cell assembling
CR2016 type button cell is assembled in the vacuum glove box being full of argon gas.Electrolyte is LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio is 1:1), metal lithium sheet is battery cathode, and barrier film is Celgard2400 polypropylene film.Anode pole piece is put in CR2016 type Snap-type cell positive shell, barrier film is covered on anode pole piece, after dripping electrolyte, again metal lithium sheet and battery cathode are placed on barrier film gently, put into the nickel foam as backing material again, by battery cathode cap on anode cover, and then be assembled into experimental button cell.
The lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of embodiment 1 gained
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) battery performance, by the CR2016 type button cell after assembling, LAND battery test system CT2001A is tested, is tested under the multiplying power condition of 1C and 5C.Test result is shown in 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 doping
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) after being assembled into experimental button cell, front 100 charging and discharging capacities under 1C multiplying power and cycle efficieny curve.Can draw from Fig. 3, the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of embodiment 1 gained under 1C discharge and recharge condition
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) charge and discharge specific capacity is first respectively 308.3mAh/g and 226.1mAh/g, and coulombic efficiency is 73.3% first, and from second time, efficiency for charge-discharge all reaches more than 98.0%.
Fig. 4 is the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of embodiment 1 gained
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) positive electrode and before not adulterating to be assembled into after experimental button cell first charge-discharge curve comparison figure under 5C multiplying power respectively.In Fig. 41 for doping after initial charge curve, 2 be doping after discharge curve first, 3 be unadulterated initial charge curve, 4 be unadulterated discharge curve first.As can be seen from Figure 4, the material after Zr doping significantly improves the high-rate charge-discharge capability of material than unadulterated material, after doping, the first discharge specific capacity of material improves about 50mAh/g than non-dopant material.Show thus, the lithium-enriched cathodic material of lithium ion battery Li of the Zr doping of the present embodiment
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(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 embodiment 1 gained
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.03) unadulterated positive electrode is assembled into the comparison diagram of cycle performance under 5C multiplying power after experimental button cell respectively, in Fig. 51 represents the cycle performance curve of the non-dopant material under 5C multiplying power, and 2 represent the rear cycle performance curve of material under 5C multiplying power of Zr doping.As can be seen from Figure 5, after doping, material property is obviously better than non-dopant material performance.Illustrate that ion channel has been widened in zirconium doping, improve lithium ion diffusion rate, therefore after doping, battery table reveals excellent performance.
Embodiment 2
A preparation method for the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium-enriched cathodic material of lithium ion battery of described Zr doping contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.01).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned a kind of Zr doping, specifically comprises the following steps:
A, be dissolved in 20ml deionized water by 2.5214g oxalic acid, ultrasonic 20min, stirring and dissolving obtains solution A;
B, 0.6411g cobalt acetate, 0.6405g nickel acetate, 2.6205g manganese acetate, 0.08586g zirconium nitrate and 2.5709g lithium acetate are dissolved in 40ml deionized water, by cobalt salt, the nickel salt of solubility, the integral molar quantity of manganese salt and lithium salts: deionized water is obtain solution B after the ratio of 0.5mol:1L mixes under ultrasonic 20min;
The amount of described cobalt acetate, nickel acetate, manganese acetate, zirconium nitrate and lithium acetate, calculates in molar ratio, i.e. lithium acetate: nickel acetate: cobalt acetate: manganese acetate: in zirconium nitrate, metal ion ratio is 1.2:0.1287:0.1287:0.5346:0.01;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred in water heating kettle react 3h under rotating speed is 500r/min condition after, control temperature is hydro-thermal 10h between 180 DEG C, afterwards solution is transferred in beaker, dry at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 2-10 DEG C/min be warming up to 900 DEG C calcining 12h, cool to the lithium-enriched cathodic material of lithium ion battery Li that namely room temperature obtains Zr doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.01).
Embodiment 3
A preparation method for the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium-enriched cathodic material of lithium ion battery of described Zr doping contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.02).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned a kind of Zr doping, specifically comprises the following steps:
A, be dissolved in 20ml deionized water by 2.5214g oxalic acid, ultrasonic 20min, stirring and dissolving obtains solution A;
B, 0.6346g cobalt acetate, 0.6341g nickel acetate, 2.5940g manganese acetate, 0.1717g zirconium nitrate and 2.5709g lithium acetate are dissolved in 40ml deionized water, by cobalt salt, the nickel salt of solubility, the integral molar quantity of manganese salt and lithium salts: deionized water is obtain solution B after the ratio of 0.75mol:1L mixes under ultrasonic 20min;
The amount of described cobalt acetate, nickel acetate, manganese acetate, zirconium nitrate and lithium acetate, calculates in molar ratio, i.e. lithium acetate: nickel acetate: cobalt acetate: manganese acetate: in zirconium nitrate, metal ion ratio is 1.2:0.1274:0.1274:0.5292:0.02;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred in water heating kettle react 4h under rotating speed is 600r/min condition after, control temperature is hydro-thermal 8h between 180 DEG C, afterwards solution is transferred in beaker, dry at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 2-10 DEG C/min be warming up to 900 DEG C calcining 8h, cool to the lithium-enriched cathodic material of lithium ion battery Li that namely room temperature obtains Zr doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.02).
Embodiment 4
A preparation method for the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium-enriched cathodic material of lithium ion battery of described Zr doping contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.04).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned a kind of Zr doping, specifically comprises the following steps:
A, be dissolved in 20ml deionized water by 2.5214g oxalic acid, ultrasonic 20min, stirring and dissolving obtains solution A;
B, 0.6217g cobalt acetate, 0.6211g nickel acetate, 2.5411g manganese acetate, 0.3434g zirconium nitrate and 2.5709g lithium acetate are dissolved in 40ml deionized water, by cobalt salt, the nickel salt of solubility, the integral molar quantity of manganese salt and lithium salts: deionized water is obtain solution B after the ratio of 1.25mol:1L mixes under ultrasonic 20min;
The amount of described cobalt acetate, nickel acetate, manganese acetate, zirconium nitrate and lithium acetate, calculates in molar ratio, i.e. lithium acetate: nickel acetate: cobalt acetate: manganese acetate: in zirconium nitrate, metal ion ratio is 1.2:0.1248:0.1248:0.5184:0.04;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred in water heating kettle react 5h under rotating speed is 800r/min condition after, control temperature is hydro-thermal 14h between 180 DEG C, afterwards solution is transferred in beaker, dry at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 2-10 DEG C/min be warming up to 900 DEG C calcining 14h, cool to the lithium-enriched cathodic material of lithium ion battery Li that namely room temperature obtains Zr doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.04).
Embodiment 5
A preparation method for the lithium-enriched cathodic material of lithium ion battery of Zr doping, the lithium-enriched cathodic material of lithium ion battery of described Zr doping contains Li, Ni, Co, Mn, Zr and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.05).
The preparation method of the lithium-enriched cathodic material of lithium ion battery of above-mentioned a kind of Zr doping, specifically comprises the following steps:
A, be dissolved in 20ml deionized water by 2.5214g oxalic acid, ultrasonic 20min, stirring and dissolving obtains solution A;
B, 0.6152g cobalt acetate, 0.6147g nickel acetate, 2.5146g manganese acetate, 0.4293g zirconium nitrate and 2.5709g lithium acetate are dissolved in 40ml deionized water, by cobalt salt, the nickel salt of solubility, the integral molar quantity of manganese salt and lithium salts: deionized water is obtain solution B after the ratio of 1.5mol:1L mixes under ultrasonic 20min;
The amount of described cobalt acetate, nickel acetate, manganese acetate, zirconium nitrate and lithium acetate, calculates in molar ratio, i.e. lithium acetate: nickel acetate: cobalt acetate: manganese acetate: in zirconium nitrate, metal ion ratio is 1.2:0.1235:0.1235:0.5130:0.05;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred in water heating kettle react 5h under rotating speed is 1000r/min condition after, control temperature is hydro-thermal 16h between 180 DEG C, afterwards solution is transferred in beaker, dry at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 2-10 DEG C/min be warming up to 900 DEG C calcining 16h, cool to the lithium-enriched cathodic material of lithium ion battery Li that namely room temperature obtains Zr doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2(x=0.05).
Embodiment 6
A lithium-enriched cathodic material of lithium ion battery for zirconium doping, containing Li, Ni, Co, Mn, Zr and O element, its chemical formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2, 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 mixed with the salting liquid A that concentration is 0.5mol/L;
B, by zirconium doping lithium-enriched cathodic material of lithium ion battery chemical formula shown in stoichiometric proportion, by the cobalt salt (cobaltous sulfate) of solubility, nickel salt (nickelous sulfate), manganese salt (manganese sulfate), zirconates (zirconium sulfate) and lithium salts (lithium carbonate) and the deionized water integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts: deionized water volume is dissolve under ultrasound condition after the ratio of 0.5mol:1L mixes, and is mixed with salting liquid B;
In this step, the amount of substance of lithium salts exceedes 5% of the stoichiometric proportion shown in lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping;
C, by step a gained salting liquid A at the uniform velocity (0.1ml/min) be added drop-wise in the salting liquid B of step b gained, 6h is reacted under rotating speed is 300r/min condition, again gained mixed solution is transferred in water heating kettle after reaction and carry out hydro-thermal reaction 24h at 80 DEG C, afterwards solution is dried at 60 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2 DEG C/min is warming up to 450 DEG C of insulation 1h, and then control heating rate be 2 DEG C/min be warming up to 500 DEG C calcining 20h, cool to the lithium-enriched cathodic material of lithium ion battery that namely room temperature obtains zirconium doping with the furnace.
Embodiment 7
A lithium-enriched cathodic material of lithium ion battery for zirconium doping, containing Li, Ni, Co, Mn, Zr and O element, its chemical formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2, 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 mixed with the salting liquid A that concentration is 1.0mol/L;
B, by zirconium doping lithium-enriched cathodic material of lithium ion battery chemical formula shown in stoichiometric proportion, by the cobalt salt (cobalt acetate) of solubility, nickel salt (nickel acetate), manganese salt (manganese acetate), zirconates (zirconium fluoride) and lithium salts (lithium acetate) and the deionized water integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts: deionized water volume is dissolve under ultrasound condition after the ratio of 2.5mol:1L mixes, and is mixed with salting liquid B;
In this step, the amount of substance of lithium salts exceedes 5% of the stoichiometric proportion shown in lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping;
C, by step a gained salting liquid A at the uniform velocity (1ml/min) be added drop-wise in the salting liquid B of step b gained, 4h is reacted under rotating speed is 500r/min condition, again gained mixed solution is transferred in water heating kettle after reaction and carry out hydro-thermal reaction 18h at 150 DEG C, afterwards solution is dried at 90 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 6 DEG C/min is warming up to 450 DEG C of insulation 4h, and then control heating rate be 6 DEG C/min be warming up to 800 DEG C calcining 12h, cool to the lithium-enriched cathodic material of lithium ion battery that namely room temperature obtains zirconium doping with the furnace.
Embodiment 8
A lithium-enriched cathodic material of lithium ion battery for zirconium doping, containing Li, Ni, Co, Mn, Zr and O element, its chemical formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2, 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 mixed with the salting liquid A that concentration is 1.5mol/L;
B, by zirconium doping lithium-enriched cathodic material of lithium ion battery chemical formula shown in stoichiometric proportion, by the cobalt salt (cobalt chloride) of solubility, nickel salt (nickel chloride), manganese salt (manganese chloride), zirconates (propyl alcohol zirconium) and lithium salts (lithium hydroxide) and the deionized water integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts: deionized water volume is dissolve under ultrasound condition after the ratio of 5mol:1L mixes, and is mixed with salting liquid B;
In this step, the amount of substance of lithium salts exceedes 5% of the stoichiometric proportion shown in lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping;
C, by step a gained salting liquid A at the uniform velocity (2ml/min) be added drop-wise in the salting liquid B of step b gained, 2h is reacted under rotating speed is 800r/min condition, again gained mixed solution is transferred in water heating kettle after reaction and carry out hydro-thermal reaction 6h at 250 DEG C, afterwards solution is dried at 120 DEG C, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 10 DEG C/min is warming up to 450 DEG C of insulation 6h, and then control heating rate be 10 DEG C/min be warming up to 1000 DEG C calcining 6h, cool to the lithium-enriched cathodic material of lithium ion battery that namely room temperature obtains zirconium doping with the furnace.
In sum, the lithium-enriched cathodic material of lithium ion battery of a kind of Zr doping provided by the invention has the advantages such as specific capacity is high, good rate capability, good cycle.Stratiform rich lithium ternary anode material for lithium-ion batteries has good structure and chemical property, has great practical significance and social value, have good impetus to the development of China's New Energy Industry to the development of lithium ion battery.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a lithium-enriched cathodic material of lithium ion battery for zirconium doping, it is characterized in that, its chemical formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xzr
xo
2, wherein 0 < x < 1.
2. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping as claimed in claim 1, is characterized in that, comprise the following steps:
A, complexing agent is dissolved in deionized water, is mixed with salting liquid A;
B, the lithium salts of stoichiometric proportion, manganese salt, nickel salt, cobalt salt and the zirconates shown in the lithium-enriched cathodic material of lithium ion battery chemical formula with zirconium doping to be dissolved in deionized water, be mixed with salting liquid B;
C, step a gained solution A is at the uniform velocity added drop-wise in the solution B of step b gained, again gained mixed solution is transferred to hydro-thermal reaction in water heating kettle after reaction, afterwards solution is dried, after the high-temperature calcination of gained pressed powder, cool to the lithium-enriched cathodic material of lithium ion battery that namely room temperature obtains zirconium doping with the furnace.
3. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium according to claim 2 doping, is characterized in that, in step a, described complexing agent be selected from citric acid, oxalic acid, oxalates, tartaric acid or EDTA one or more.
4. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 2, it is characterized in that, in step a, the concentration of gained salting liquid A is 0.5 ~ 1.5mol/L.
5. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 2, it is characterized in that, in step b, salting liquid B is by the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts and the deionized water integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, zirconates and lithium salts: deionized water volume is dissolve after the ratio of 0.5-5mol:1L mixes to obtain under ultrasound condition;
And the amount of substance of lithium salts exceedes 5% of the stoichiometric proportion shown in lithium-enriched cathodic material of lithium ion battery chemical formula of zirconium doping.
6. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium according to claim 5 doping, is characterized in that, the cobalt salt of solubility is that one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride are composite;
The nickel salt of solubility is that one or more in nickelous sulfate, nickel nitrate, nickel acetate, nickel chloride are composite;
The manganese salt of solubility is that one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride are composite;
The zirconates of solubility is that one or more in zirconium chloride, zirconium nitrate, zirconium fluoride, zirconium sulfate, propyl alcohol zirconium are composite;
The lithium salts of solubility is that one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride are composite.
7. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterized in that, in step c, salting liquid A is at the uniform velocity added drop-wise to the speed 0.1-2ml/min in salting liquid B, after salting liquid A is at the uniform velocity added drop-wise to salting liquid B, under rotating speed is 300-800r/min condition, reacts 2-6h.
8. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterized in that, in step c, the temperature of hydro-thermal reaction is 80 ~ 250 DEG C, and the time of hydro-thermal reaction is 6 ~ 24h.
9. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterized in that, in step c, the temperature of oven dry controls between 60 ~ 120 DEG C.
10. the preparation method of the lithium-enriched cathodic material of lithium ion battery of zirconium doping according to claim 1, it is characterized in that, in step c, the program of high-temperature calcination is: control heating rate be 2-10 DEG C/min be warming up to 450 DEG C insulation 1-6h, and then control heating rate be 2-10 DEG C/min be warming up to 500-1000 DEG C calcining 6-20h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655554A (en) * | 2016-01-11 | 2016-06-08 | 山东玉皇新能源科技有限公司 | Hydrothermal modification method of lithium-rich manganese-based positive material |
| CN109768232A (en) * | 2018-12-11 | 2019-05-17 | 广东邦普循环科技有限公司 | A kind of complex phase doping nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN110299521A (en) * | 2019-06-24 | 2019-10-01 | 贵州梅岭电源有限公司 | A kind of rich lithium manganese anode material of metal ion mixing and preparation method thereof |
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| CN114497527A (en) * | 2021-12-20 | 2022-05-13 | 江门市科恒实业股份有限公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244237A (en) * | 2011-06-10 | 2011-11-16 | 北京理工大学 | Method for synthesizing cathodic material of high-capacity lithium ion battery |
| CN103441238A (en) * | 2013-08-27 | 2013-12-11 | 上海电力学院 | Mg-doped Li-rich anode material and preparation method for same |
| WO2014190662A1 (en) * | 2013-05-31 | 2014-12-04 | 华为技术有限公司 | Dual-doped lithium-rich solid solution positive electrode composite and preparation method thereof, lithium-ion battery positive electrode plate, and lithium-ion battery |
| CN104518214A (en) * | 2013-09-27 | 2015-04-15 | 北京当升材料科技股份有限公司 | Preparation method of layered lithium-rich sosoloid cathode material |
-
2015
- 2015-08-19 CN CN201510512024.XA patent/CN105098158B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244237A (en) * | 2011-06-10 | 2011-11-16 | 北京理工大学 | Method for synthesizing cathodic material of high-capacity lithium ion battery |
| WO2014190662A1 (en) * | 2013-05-31 | 2014-12-04 | 华为技术有限公司 | Dual-doped lithium-rich solid solution positive electrode composite and preparation method thereof, lithium-ion battery positive electrode plate, and lithium-ion battery |
| CN103441238A (en) * | 2013-08-27 | 2013-12-11 | 上海电力学院 | Mg-doped Li-rich anode material and preparation method for same |
| CN104518214A (en) * | 2013-09-27 | 2015-04-15 | 北京当升材料科技股份有限公司 | Preparation method of layered lithium-rich sosoloid cathode material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655554A (en) * | 2016-01-11 | 2016-06-08 | 山东玉皇新能源科技有限公司 | Hydrothermal modification method of lithium-rich manganese-based positive material |
| CN105655554B (en) * | 2016-01-11 | 2018-05-01 | 山东玉皇新能源科技有限公司 | A kind of hydrothermal modification method of lithium-rich manganese-based anode material |
| CN109768232A (en) * | 2018-12-11 | 2019-05-17 | 广东邦普循环科技有限公司 | A kind of complex phase doping nickel-cobalt-manganternary ternary anode material and its preparation method and application |
| CN110299521A (en) * | 2019-06-24 | 2019-10-01 | 贵州梅岭电源有限公司 | A kind of rich lithium manganese anode material of metal ion mixing and preparation method thereof |
| CN112062167A (en) * | 2020-08-28 | 2020-12-11 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN112062167B (en) * | 2020-08-28 | 2023-09-22 | 常熟理工学院 | Micron-sized binary doped lithium-rich material and preparation method and application thereof |
| CN114497527A (en) * | 2021-12-20 | 2022-05-13 | 江门市科恒实业股份有限公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
| CN114497527B (en) * | 2021-12-20 | 2024-03-29 | 江门市科恒实业股份有限公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
| CN114665086A (en) * | 2022-02-18 | 2022-06-24 | 中国科学院青海盐湖研究所 | Lithium-rich manganese-based positive electrode material and preparation method thereof |
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