CN104900857A - Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material - Google Patents
Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material Download PDFInfo
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Abstract
The invention relates to a preparation method of a trace Mo-doped lamellar lithium-enriched ternary positive electrode material. The molecular formula of the prepared ternary positive electrode material is Li1.2(Mn0.54Ni0.13Co0.13)(1-x)MoxO2 (x is more than 0 and smaller than 1). The adopted preparation method is an organic co-precipitation method and comprises the steps of stirring an organic precipitator in a water bath with constant temperature, and dissolving the organic precipitator into an organic solvent so as to obtain a solution A; then dissolving soluble cobalt salt, nickel salt, manganese salt, molybdenum salt and lithium salt into deionized water to obtain a solution B; after thorough dissolution, dropwise adding the solution B into the solution A at a constant speed, reacting and drying, increasing the temperature of the obtained solid powder in a high-temperature tube furnace system, and calcining so as to obtain the trace Mo-doped lamellar lithium-enriched ternary positive electrode material. The material has uniform particles and regular polygonal morphology feature, and has relatively good electrochemical performance, the preparation process is relatively simple, and the ternary positive electrode material is suitable for industrialized scale production.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, especially relate to a kind of preparation method of the rich lithium tertiary cathode material of stratiform of micro-Mo doping.
Background technology
Cobalt acid lithium (LiCoO
2) conduct business-like positive electrode the earliest, be used lithium-ions battery is still more, because its material self-capacity is only 50% (140mAh/g) of its theoretical capacity, add cobalt resource scarcity and problem of environmental pollution, scholars deepens continuously research, success has also prepared other transiting metal oxidation positive electrodes, as LiMn2O4 (LiMnO
2), LiFePO4 (LiFePO
4), ternary material (LiCo
xni
ymn
1-x-yo2) etc.
[3]but relatively low specific energy or power become the most fatal shortcoming of this kind of material, hinder further developing of these two materials.
China proposes the energy requirement reaching 230Wh/kg for 2015 in space power application, and in addition on New-energy electric vehicle electrokinetic cell, China and Japan etc. have formulated specific energy is higher than 200Wh/kg target at the year two thousand twenty.Therefore, in the anode material for lithium-ion batteries of novel research and development, a kind of by Li
2mnO
3with stratiform LiMO
2the stratiform that (M=Mn, Ni, Co) is formed rich lithium tertiary cathode material xLi
2mnO
3-(1-x) LiMO
2, due to the specific energy more than 250mAh/g, become positive electrode of future generation and cause and pay close attention to widely.This material except having a clear superiority in specific capacity, and fail safe, production cost are also better than existing positive electrode.
At present, the rich lithium ternary composite cathode material many employings solid phase method of stratiform and liquid phase method, solid reaction process, but use the standby material of this legal system can not reach mixed uniformly level, and easily introduce impurity in the process of preparation; Liquid phase method, the method complex process, needs strictly to control to react (Buchholz protection, pH value, ammonia volume, reaction temperature, mixing speed etc.), is precipitated and also needs long time aging, repeatedly suction filtration cleaning, dries, then with lithium salts ground and mixed.At present, there is the problems such as capacity attenuation is fast, high rate performance is poor in the rich lithium ternary composite cathode material of undeniable stratiform, limits its large-scale application.
Chinese patent CN 103413935A discloses lithium-rich anode material and the preparation method of a kind of Mo that adulterates, and the lithium-rich anode material molecular formula of doping Mo is Li (Li
0.2ni
0.13co
0.13mn
0.54)
0.97mo
0.03o
2.Citric acid joins in deionized water to obtain solution 1 by preparation method; Solution 1 is added drop-wise in metal salt solution 2, adds ammoniacal liquor simultaneously and adjust pH to be 9, stir until form purple gel at 80 DEG C, then successively through 200 DEG C of oven dry, ball milling, calcine by steps, grinding, namely obtain the lithium-rich anode material of doping Mo.The preparation method of this patent is sol-gal process, process is complicated, need to add complexing agent ammoniacal liquor, transition metal Ni, Co, Mn incomplete complexing within the scope of certain pH can only be made, " leavening agent " citric acid simultaneously added, 200 DEG C time, make the fluffy dress that material becomes larger, collecting granules process is loaded down with trivial details, limit by device, industrialized production requirement can not be met.
Summary of the invention
Object of the present invention is exactly the technical problems such as capacity in order to overcome above-mentioned existing positive electrode is low, high rate performance is poor and provides a kind of preparation method of the rich lithium tertiary cathode material of stratiform of micro-Mo doping, it is relatively simple that this preparation method has technique, requires to production equipment the rich lithium tertiary cathode material of stratiform that Mo that is low and that prepare electrochemical performance adulterates.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, the tertiary cathode material prepared contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(0 < x < 1), preparation method adopts following steps:
(1) organic precipitant water bath with thermostatic control stirring is dissolved in organic solvent, obtains solution A;
(2) according to mole metering ratio of material, the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts are dissolved in deionized water, obtain solution B;
(3) solution B is at the uniform velocity added drop-wise in solution A, control temperature 30-90 DEG C, rotating speed is that after reacting 2-6h under 300-800r/min condition, control temperature is 60-120 DEG C of oven dry again, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 200 DEG C of insulation 1-6h, and then to control heating rate be that 2-10 DEG C/min is warming up to 300-600 DEG C of precalcining 3-8h, then controlling heating rate is that 2-10 DEG C/min is warming up to 600-1000 DEG C of calcining 6-20h, cools to the rich lithium tertiary cathode material of stratiform that namely room temperature obtains Mo doping with the furnace.
Described organic precipitant is oxine or oxine derivative.
Described organic solvent is one or more in ethanol, acetone, chloroform, benzene or ore deposit acid.
Organic precipitant mixes with the ratio of organic solvent in 0.5-5mol:1L, then controls that rotating speed is 300-800r/min, temperature is the solution A that at 30-90 DEG C, stirring and dissolving obtains.
The integral molar quantity of the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts: deionized water volume is dissolve the solution B obtained after the ratio mixing of 0.5-5mol:1L under ultrasound condition.
In the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, metal ion mol ratio is 1.2:0.13 (1-x): 0.13 (1-x): 0.54 (1-x): x, 0 < x < 1.
The cobalt salt of solubility is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate or cobalt chloride;
The nickel salt of solubility is one or more in nickelous sulfate, nickel nitrate, nickel acetate or nickel chloride;
The manganese salt of solubility is one or more in manganese sulfate, manganese nitrate, manganese acetate or manganese chloride;
The molybdenum salt of solubility is one or more in ammonium molybdate, sodium molybdate, molybdenum chloride or zinc molybdate;
The lithium salts of solubility is one or more in lithium carbonate, lithium hydroxide, lithium acetate or lithium chloride.
Controlling drop rate is that solution B is added drop-wise in solution A by 0.1-30ml/min.
When solution B and solution A mixing, organic precipitant and soluble cobalt, nickel salt, the ratio of manganese salt, molybdenum salt and lithium salts total mole number is 0.1-10:1.
The application adopts the coprecipitation improved to prepare layed solid-solution lithium-rich anode material, using oxine as coprecipitator, the unoccupied orbital of transition metal Ni, Co, Mn ion can the heteroatomic lone electron pair of N, O of quinoline molecule well combine, form uniform precipitation, lithium salts adds reactor together with transition metal salt simultaneously, meet stoichiometric proportion accurately, building-up process does not need to add complexing agent, do not need to clean suction filtration, the material crystalline degree of preparation is high, electrochemical performance, and preparation technology is simple, is convenient to suitability for industrialized production.
Compared with prior art, the present invention's trace Mo element doping material, make the material after adulterating have better crystal structure, therefore battery has better high rate performance and cycle performance.Due in the building-up process of material, whether transition metal Ni, Co, Mn ion can mix the degree of crystallinity and the chemical property that directly affect later stage material, transition metal Ni, Co, Mn ion has different Ksp values simultaneously, the citric acid that tradition adopts, oxalic acid, NaOH, carbonate and oxalates need to add the complexing agents such as ammoniacal liquor and make that transition metal salt is incomplete to be mixed, and make later stage material property poor.The present invention adopts organic solvent as precipitation reagent, compare with complexing agent with the inorganic precipitant had now, using oxine as coprecipitator, transition metal Ni, Co, the unoccupied orbital of Mn ion can the N of quinoline molecule, the heteroatomic lone electron pair of O well combines, in preparation process ionizable metal salt in the liquid phase with the mixing completely of organic solvent atomic level, form uniform precipitation, lithium salts adds together with transition metal salt simultaneously, pH need not be regulated, ageing, suction filtration cleans, hybrid reaction obtains homogeneous precipitation, make the stratiform rich lithium tertiary cathode material grain diameter of the Mo doping obtained little, be easy to sintering, sintering afterproduct is even, domain size distribution is homogeneous, ensure that the good structure of the rich lithium tertiary cathode material of stratiform that Mo adulterates and degree of crystallinity and chemical property.Mo of the present invention adulterates rich lithium ternary anode material for lithium-ion batteries Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2the preparation method of (0 < x < 1), has preparation technology simple, is suitable for industrialized scale, has higher economic worth.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the rich lithium tertiary cathode material of stratiform of the micro-Mo doping of embodiment 1 gained;
Fig. 2 is the SEM figure of the rich lithium tertiary cathode material of stratiform of the micro-Mo doping of embodiment 1 gained;
Fig. 3 is the cycle performance curve chart of the rich lithium tertiary cathode material of stratiform under 1C multiplying power of the micro-Mo doping of embodiment 1 gained;
Fig. 4 is first with 100 charging and discharging curves of the rich lithium tertiary cathode material of stratiform under 1C multiplying power of the micro-Mo doping of embodiment 1 gained;
Fig. 5 is the cycle performance curve chart of the rich lithium tertiary cathode material of stratiform under different multiplying of the micro-Mo doping of embodiment 1 gained.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, the stratiform rich lithium tertiary cathode battery material of Mo doping contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(0 < x < 1).
The preparation method of the rich lithium tertiary cathode material of stratiform of above-mentioned a kind of micro-Mo doping, specifically comprises the following steps:
(1), by 6.3870g (excessive 1%) organic precipitant and 55ml organic solvent, in organic precipitant: organic solvent is that the ratio of 1mol:1L mixes, then control that rotating speed is 800r/min, temperature is that under 80 DEG C of conditions, stirring and dissolving obtains solution A;
Described organic precipitant is oxine;
Described organic solvent is ethanol;
(2), by the 1.6190g cobalt salt of solubility, 1.6176g nickel salt, 6.61742g manganese salt, 0.2647g molybdenum salt and 6.4273g lithium salts and 50ml deionized water cobalt salt, nickel salt by 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 the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, calculates, i.e. lithium salts: nickel salt: cobalt salt: manganese salt: in molybdenum salt, metal ion ratio is 1.2:0.091:0.091:0.378:0.03 in molar ratio; Wherein, the cobalt salt of solubility is cobalt acetate; The nickel salt of solubility is nickel acetate; The manganese salt of solubility is manganese acetate; The molybdenum salt of solubility is ammonium molybdate; The lithium salts of solubility is lithium acetate;
(3), the solution B of step (2) gained being controlled drop rate is that 0.1ml/min is at the uniform velocity added drop-wise in the solution A of step (1) gained, control temperature 80 DEG C under water bath condition, rotating speed is that after reacting 3h under 500r/min condition, control temperature is 120 DEG C of oven dry, obtains yellow solid powder;
The consumption of above-mentioned solution B and solution A, the organic precipitant oxine by solution A: in solution B, the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts are 1mol:1mol;
(4), the yellow solid powder of step (3) gained is placed in high-temperature tubular furnace system, control ramp to the 200 DEG C insulation 2h that heating rate is 5 DEG C/min, and then control ramp to the 500 DEG C precalcining 4h that heating rate is 5 DEG C/min, then control ramp to the 900 DEG C calcining 12h that heating rate is 5 DEG C/min, cool to the stratiform rich lithium tertiary cathode material Li that namely room temperature obtains Mo doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.03).
By the stratiform rich lithium tertiary cathode material Li of the micro-Mo doping of above-mentioned gained
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
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 stratiform rich lithium tertiary cathode material Li of the micro-Mo doping of embodiment 1 gained thus
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.03) there is good layer structure.
The rich lithium tertiary cathode material of stratiform of the micro-Mo doping of above-mentioned gained is observed by transmission electron microscope, the SEM figure that it obtains under multiplication factor is 30000 times as shown in Figure 2, as can be seen from Figure 2, the stratiform rich lithium tertiary cathode material Li of above-mentioned gained trace Mo doping
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.03) pattern is substantially all the polygon of pattern rule, even particle size distribution.
The rich lithium tertiary cathode material of stratiform of the micro-Mo doping of above-mentioned gained is assembled into battery, and number of assembling steps is as follows:
1, the preparation of anode pole piece
By the ratio mixing that the rich lithium tertiary cathode material of stratiform of above-mentioned gained trace Mo doping, conductive carbon black and bonding polyvinylidene fluoride (PVDF) are 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 battery performance of the rich lithium tertiary cathode material of stratiform of the micro-Mo doping of embodiment 1 gained, by the CR2016 type button cell after assembling, LAND battery test system CT2001A is tested, is adopted the multiplying power condition of 1C, 2C and 5C to test respectively.Test result is shown in shown in Fig. 3, Fig. 4 and Fig. 5.
Fig. 3 is after the rich lithium tertiary cathode material of stratiform of embodiment 1 micro-Mo doping is assembled into experimental button cell, front 100 charging and discharging capacities under 1C multiplying power and cycle efficieny curve.Can draw from Fig. 3, under 1C discharge and recharge condition, the rich lithium ternary anode material for lithium-ion batteries of the stratiform charge and discharge specific capacity first of the micro-Mo doping of embodiment 1 gained is respectively 372.0mAh/g and 260.8mAh/g, coulombic efficiency is 70.1% first, from second time, efficiency for charge-discharge all reaches more than 98.0%.
Fig. 4 is the first with 100th the charging and discharging curve figure that the stratiform rich lithium tertiary cathode battery material of the micro-Mo doping of embodiment 1 gained is assembled into after experimental button cell under 1C multiplying power.In Fig. 41 be charging curve first, 2 be the 100th discharge curve for discharge curve, 3 is first the 100th charging curve, 4.As can be seen from Figure 4, there is obvious 4.5V high-voltage charge platform in the stratiform rich lithium tertiary cathode battery material of embodiment 1 gained trace Mo doping, after 100 discharge and recharges, specific discharge capacity is 202.8mAh/g, and coulombic efficiency is 97.3%.Show thus, the layed solid-solution lithium-rich manganese-based tertiary cathode battery material Li of Mo doping of the present invention
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.03) battery performance is good.
Fig. 5 is front 100 specific discharge capacity curves that the stratiform rich lithium tertiary cathode battery material of the micro-Mo doping of embodiment 1 gained is assembled into after experimental button cell under 2C and 5C multiplying power, and a in Fig. 5 represents front 100 discharge curves under 2C multiplying power, b represents front 100 discharge curves under 5C multiplying power.As can be seen from Figure 5, when discharging under 2C multiplying power, the highest specific discharge capacity is 203.6mAh/g, 100 averaged discharge specific capacities are 177.2mAh/g, when discharging under 5C multiplying power, the highest specific discharge capacity is 163.5mAh/g, and 100 averaged discharge specific capacities are 143.7mAh/g.Show thus, the stratiform rich lithium tertiary cathode battery material of micro-Mo doping of the present invention, under high magnification condition, shows excellent battery performance.
Embodiment 2
A preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, rich lithium ternary anode material for lithium-ion batteries contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.01).
The preparation method of the stratiform rich lithium tertiary cathode battery material of above-mentioned a kind of Mo doping, namely adopts Cobalt method, specifically comprises the following steps:
(1), by organic precipitant with organic solvent in organic precipitant: organic solvent is that the ratio of 0.5mol:1L mixes, and then controls that rotating speed is 800r/min, temperature is that under 40 DEG C of conditions, stirring and dissolving obtains solution A;
Described organic precipitant is oxine;
Described organic solvent is ethanol;
(2), by the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts and deionized water, the integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts: deionized water is obtain solution B after the ratio of 0.5mol:1L mixes under ultrasonic 20min;
The amount of the cobalt salt of described solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, calculates, i.e. lithium salts: nickel salt: cobalt salt: manganese salt: in molybdenum salt, metal ion ratio is 1.2:0.13:0.13:0.54:0.01 in molar ratio; The cobalt salt of solubility is cobalt acetate; The nickel salt of solubility is nickel acetate; The manganese salt of solubility is manganese acetate; The molybdenum salt of solubility is ammonium molybdate; The lithium salts of solubility is lithium acetate;
(3), the solution B of step (2) gained being controlled drop rate is that 0.1ml/min is at the uniform velocity added drop-wise in the solution A of step (1) gained, control temperature 40 DEG C under water bath condition, rotating speed is that after reacting 2h under 800r/min condition, control temperature is 120 DEG C of oven dry, obtains yellow solid powder;
The consumption of above-mentioned solution B and solution A, the organic precipitant by solution A: in solution B, soluble cobalt, nickel salt, manganese salt, molybdenum salt and lithium salts are 0.1mol:1mol;
(4), the yellow solid powder of step (3) gained is placed in high-temperature tubular furnace system, control ramp to the 200 DEG C insulation 2h that heating rate is 5 DEG C/min, and then control ramp to the 400 DEG C precalcining 6h that heating rate is 5 DEG C/min, then control ramp to the 900 DEG C calcining 6h that heating rate is 5 DEG C/min, cool to the stratiform rich lithium ternary anode material for lithium-ion batteries Li that namely room temperature obtains micro-Mo doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.01).
Embodiment 3
A preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, rich lithium ternary anode material for lithium-ion batteries contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.06).
The preparation method of the stratiform rich lithium tertiary cathode battery material of above-mentioned a kind of micro-Mo doping, namely adopts Cobalt method, specifically comprises the following steps:
(1), by organic precipitant with organic solvent in organic precipitant: organic solvent is that the ratio of 2.5mol:1L mixes, and then controls that rotating speed is 500r/min, temperature is that under 60 DEG C of conditions, stirring and dissolving obtains solution 1;
Described organic precipitant is oxine;
Described organic solvent is ethanol;
(2), by the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts and 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 2.5mol:1L mixes under ultrasonic 20min;
The amount of the cobalt salt of described solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, calculates, i.e. lithium salts: nickel salt: cobalt salt: manganese salt: in molybdenum salt, metal ion ratio is 1.2:0.13:0.13:0.54:0.06 in molar ratio; The cobalt salt of solubility is cobalt acetate; The nickel salt of solubility is nickel acetate; The manganese salt of solubility is manganese acetate; The molybdenum salt of solubility is ammonium molybdate; The lithium salts of solubility is lithium acetate;
(3), the solution B of step (2) gained being controlled drop rate is that 10ml/min is at the uniform velocity added drop-wise in the solution A of step (1) gained, control temperature 60 DEG C under water bath condition, rotating speed is that after reacting 3h under 500r/min condition, control temperature is 120 DEG C of oven dry, obtains yellow solid powder;
The consumption of above-mentioned solution B and solution A, the organic precipitant by solution A: in solution B, the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts are 5mol:1mol;
(4), the yellow solid powder of step (3) gained is placed in high-temperature tubular furnace system, control ramp to the 200 DEG C insulation 2h that heating rate is 5 DEG C/min, and then control ramp to the 500 DEG C precalcining 4h that heating rate is 5 DEG C/min, then control ramp to the 900 DEG C calcining 12h that heating rate is 5 DEG C/min, cool to the stratiform rich lithium ternary anode material for lithium-ion batteries Li that namely room temperature obtains micro-Mo doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.06).
Embodiment 4
A preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, the stratiform rich lithium tertiary cathode battery material of Mo doping contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.09).
The preparation method of the stratiform rich lithium tertiary cathode battery material of above-mentioned a kind of micro-Mo doping, namely adopts Cobalt method, specifically comprises the following steps:
(1), by organic precipitant with organic solvent in organic precipitant: organic solvent is that the ratio of 5mol:1L mixes, and then controls that rotating speed is 300r/min, temperature is that under 80 DEG C of conditions, stirring and dissolving obtains solution 1;
Described organic precipitant is oxine;
Described organic solvent is ethanol;
(2), by the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts and deionized water, the integral molar quantity in the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts: deionized water is obtain solution B after the ratio of 5mol:1L mixes under ultrasonic 20min;
The amount of the cobalt salt of described solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, calculates, i.e. lithium salts: nickel salt: cobalt salt: manganese salt: in molybdenum salt, metal ion ratio is 1.2:0.13:0.13:0.54:0.09 in molar ratio; The cobalt salt of solubility is cobalt acetate; The nickel salt of solubility is nickel acetate; The manganese salt of solubility is manganese acetate; The molybdenum salt of solubility is ammonium molybdate; The lithium salts of solubility is lithium acetate;
(3), the solution B of step (2) gained being controlled drop rate is that 20ml/min is at the uniform velocity added drop-wise in the solution A of step (1) gained, control temperature 80 DEG C under water bath condition, rotating speed is that after reacting 4h under 300r/min condition, control temperature is 120 DEG C of oven dry, obtains yellow solid powder;
The consumption of above-mentioned solution B and solution A, the organic precipitant by solution A: in solution B, the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts are 10mol:1mol;
(4), the yellow solid powder of step (3) gained is placed in high-temperature tubular furnace system, control ramp to the 200 DEG C insulation 2h that heating rate is 5 DEG C/min, and then control ramp to the 500 DEG C precalcining 4h that heating rate is 5 DEG C/min, then control ramp to the 900 DEG C calcining 18h that heating rate is 5 DEG C/min, cool to the stratiform rich lithium ternary anode material for lithium-ion batteries Li that namely room temperature obtains micro-Mo doping with the furnace
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(x=0.09).
In sum, stratiform rich lithium tertiary cathode material tool good rate capability, the good cycle of a kind of micro-Mo doping provided by the invention, production technology is simple, and cost is low, is convenient to industrial-scale production etc.Further, 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.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (9)
1. a preparation method for the rich lithium tertiary cathode material of stratiform of micro-Mo doping, it is characterized in that, the tertiary cathode material that the method prepares contains Li, Ni, Co, Mn, Mo and O element, and its molecular formula is Li
1.2(Mn
0.54ni
0.13co
0.13)
1-xmo
xo
2(0 < x < 1), preparation method adopts following steps:
(1) organic precipitant water bath with thermostatic control stirring is dissolved in organic solvent, obtains solution A;
(2) according to mole metering ratio of material, the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts are dissolved in deionized water, obtain solution B;
(3) solution B is at the uniform velocity added drop-wise in solution A, control temperature 30-90 DEG C, rotating speed is that after reacting 2-6h under 300-800r/min condition, control temperature is 60-120 DEG C of oven dry again, gained pressed powder is in high-temperature tubular furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 200 DEG C of insulation 1-6h, and then to control heating rate be that 2-10 DEG C/min is warming up to 300-600 DEG C of precalcining 3-8h, then controlling heating rate is that 2-10 DEG C/min is warming up to 600-1000 DEG C of calcining 6-20h, cools to the rich lithium tertiary cathode material of stratiform that namely room temperature obtains Mo doping with the furnace.
2. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1, it is characterized in that, described organic precipitant is oxine or oxine derivative.
3. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1, it is characterized in that, described organic solvent is one or more in ethanol, acetone, chloroform, benzene or ore deposit acid.
4. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to any one of claim 1-3, it is characterized in that, organic precipitant mixes with the ratio of organic solvent in 0.5-5mol:1L, then controls that rotating speed is 300-800r/min, temperature is the solution A that at 30-90 DEG C, stirring and dissolving obtains.
5. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1, it is characterized in that, the integral molar quantity of the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts: deionized water volume is under ultrasound condition, dissolve the solution B obtained after the ratio mixing of 0.5-5mol:1L.
6. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1 or 5, it is characterized in that, in the cobalt salt of solubility, nickel salt, manganese salt, molybdenum salt and lithium salts, metal ion mol ratio is 1.2:0.13 (1-x): 0.13 (1-x): 0.54 (1-x): x, 0 < x < 1.
7. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 6, is characterized in that,
The cobalt salt of solubility is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate or cobalt chloride;
The nickel salt of solubility is one or more in nickelous sulfate, nickel nitrate, nickel acetate or nickel chloride;
The manganese salt of solubility is one or more in manganese sulfate, manganese nitrate, manganese acetate or manganese chloride;
The molybdenum salt of solubility is one or more in ammonium molybdate, sodium molybdate, molybdenum chloride or zinc molybdate;
The lithium salts of solubility is one or more in lithium carbonate, lithium hydroxide, lithium acetate or lithium chloride.
8. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1, it is characterized in that, controlling drop rate is that solution B is added drop-wise in solution A by 0.1-30ml/min.
9. the preparation method of the rich lithium tertiary cathode material of stratiform of a kind of micro-Mo doping according to claim 1, it is characterized in that, when solution B and solution A mixing, organic precipitant and soluble cobalt, nickel salt, the ratio of manganese salt, molybdenum salt and lithium salts total mole number is 0.1-10:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342398A (en) * | 2017-04-25 | 2017-11-10 | 山东玉皇新能源科技有限公司 | A kind of anode active material of lithium ion battery and preparation method thereof |
| CN107768664A (en) * | 2017-10-23 | 2018-03-06 | 广东工业大学 | A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof |
| CN110642303A (en) * | 2019-08-30 | 2020-01-03 | 广东新凌嘉新能源股份有限公司 | Improved power ternary cylindrical lithium battery positive electrode material and preparation method thereof |
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| CN112670473A (en) * | 2020-12-23 | 2021-04-16 | 中伟新材料股份有限公司 | Ternary precursor, preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621125A (en) * | 2009-02-13 | 2010-01-06 | 成都晶元新材料技术有限公司 | Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof |
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel-manganese-cobalt lithium ion cathode material |
| CN102576869A (en) * | 2009-09-30 | 2012-07-11 | 户田工业株式会社 | Positive electrode active material powder, method for producing same, and nonaqueous electrolyte secondary battery |
| CN103413935A (en) * | 2013-08-27 | 2013-11-27 | 上海电力学院 | Mo-doped lithium-rich positive electrode material and preparation method thereof |
| CN103956477A (en) * | 2014-04-30 | 2014-07-30 | 上海电力学院 | Preparation method of cathode material of lithium-rich ternary compound lithium ion battery |
-
2015
- 2015-06-02 CN CN201510296428.XA patent/CN104900857A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621125A (en) * | 2009-02-13 | 2010-01-06 | 成都晶元新材料技术有限公司 | Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof |
| CN102576869A (en) * | 2009-09-30 | 2012-07-11 | 户田工业株式会社 | Positive electrode active material powder, method for producing same, and nonaqueous electrolyte secondary battery |
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method of nickel-manganese-cobalt lithium ion cathode material |
| CN103413935A (en) * | 2013-08-27 | 2013-11-27 | 上海电力学院 | Mo-doped lithium-rich positive electrode material and preparation method thereof |
| CN103956477A (en) * | 2014-04-30 | 2014-07-30 | 上海电力学院 | Preparation method of cathode material of lithium-rich ternary compound lithium ion battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342398A (en) * | 2017-04-25 | 2017-11-10 | 山东玉皇新能源科技有限公司 | A kind of anode active material of lithium ion battery and preparation method thereof |
| CN107768664A (en) * | 2017-10-23 | 2018-03-06 | 广东工业大学 | A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof |
| WO2019080310A1 (en) * | 2017-10-23 | 2019-05-02 | 广东工业大学 | Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor |
| CN110642303A (en) * | 2019-08-30 | 2020-01-03 | 广东新凌嘉新能源股份有限公司 | Improved power ternary cylindrical lithium battery positive electrode material and preparation method thereof |
| CN111634957A (en) * | 2020-05-28 | 2020-09-08 | 天目湖先进储能技术研究院有限公司 | Carbon-coated mixed solvent thermal-doped lithium-rich manganese material and preparation method and application thereof |
| CN112670473A (en) * | 2020-12-23 | 2021-04-16 | 中伟新材料股份有限公司 | Ternary precursor, preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
| CN114883556A (en) * | 2022-06-29 | 2022-08-09 | 蜂巢能源科技股份有限公司 | Ultrahigh nickel cathode material and preparation method thereof |
| CN114883556B (en) * | 2022-06-29 | 2024-06-14 | 蜂巢能源科技股份有限公司 | Ultra-high nickel anode material and preparation method thereof |
| CN117352710A (en) * | 2023-12-05 | 2024-01-05 | 瑞浦兰钧能源股份有限公司 | Bismuth-carbon negative electrode composite material and preparation method and application thereof |
| CN117352710B (en) * | 2023-12-05 | 2024-02-13 | 瑞浦兰钧能源股份有限公司 | Bismuth-carbon negative electrode composite material and preparation method and application thereof |
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