CN104810519A - Lithium ion battery cathode material rich in lithium and manganese and preparation method thereof - Google Patents
Lithium ion battery cathode material rich in lithium and manganese and preparation method thereof Download PDFInfo
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- CN104810519A CN104810519A CN201510184875.6A CN201510184875A CN104810519A CN 104810519 A CN104810519 A CN 104810519A CN 201510184875 A CN201510184875 A CN 201510184875A CN 104810519 A CN104810519 A CN 104810519A
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- lithium
- anode material
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- lithium manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery cathode material rich in lithium and manganese and a preparation method thereof, and belongs to the technical field of preparation of the lithium ion battery cathode material. The chemical formula of the cathode material rich in lithium and manganese, provided by the invention is xLi2MnO3. (1-x)LiNi(0.5-a/2)Mn(0.5-a/2)FeaO2, wherein the x is not smaller than 0.1 and not greater than 0.9 and the a is not smaller than 0.002 and not greater than 0.008. When the accumulative particle size distribution percentage of the cathode material rich in lithium and manganese reaches 50%, the corresponding particle size is 0.1-0.8 micrometer. The particle size of the cathode material rich in lithium and manganese, provided by the invention is submicron level. Comparatively fine particle size facilitates that the cathode material rich in lithium and manganese is in full contact with electrolyte, can shorten the diffusion path of Li+, and results in the good rate performance of the lithium ion battery using the cathode material rich in lithium and manganese, provided by the invention as the positive active material, wherein the specific discharge capacity of the lithium ion battery at the rate of 5C keeps over 150 mAh/g.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, particularly rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery, as a kind of high-energy battery, has that energy density is high, long service life, good cycle and advantages such as memory-less effect.Anode material for lithium-ion batteries is the important component part in lithium ion battery, and it has important impact for the chemical property of lithium ion battery.General anode material for lithium-ion batteries (LiCoO
2, LiMn
2o
4, LiFePO
4) can not meet the demand of people to high power capacity, high-energy-density electronic product.Stratiform rich lithium manganese anode material xLi
2mnO
3(1-x) LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) be a kind of α-NaFeO
2type solid-solution material, by the Li of stratiform
2mnO
3and LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) formed, with performances such as its distinctive height ratio capacity (200 ~ 300mAh/g), outstanding circulation abilities, become the study hotspot of current lithium ion secondary battery anode material.Such as, CN102013481A (application number: 201010522413.8) disclose a kind of spherical gradient rich lithium manganese anode material xLi
2mnO
3(1-x) Li [Ni
0.4co
0.2mn
0.4] O
2the synthetic method of (0.1≤x≤0.4), with existing commercialization spherical precursor [Ni
0.4co
0.2mn
0.4] (OH)
2carry out Mn element coated, then with the process of the lithium hydroxide heat of mixing.The particle diameter of gained positive electrode is about 10 μm, 0.2C multiplying power current charge-discharge electricity, and the specific capacitance that discharges first is 242mAh/g; Under 1C multiplying power, the specific capacitance that discharges first is 171mAh/g; Under 2C multiplying power, the specific capacitance that discharges first is 162mAh/g.
Realizing in process of the present invention, the present inventor finds at least there is following problem in prior art: existing rich lithium manganese anode material is lower compared with the specific discharge capacity under high magnification, and high rate performance is poor.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of rich lithium manganese anode material of lithium ion battery with good high rate performance and preparation method thereof.
Specifically, following technical scheme is comprised:
First aspect present invention provides a kind of lithium ion battery rich lithium manganese anode material, and the chemical formula of described rich lithium manganese anode material is xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08; When the accumulative particle size distribution in percentage of described rich lithium manganese anode material reaches 50%, corresponding particle diameter is 0.1 ~ 0.8 μm.
Further, the specific area of described rich lithium manganese anode material is 0.8 ~ 2.0m
2/ g, tap density is 1.8 ~ 2.3g/cm
3.
Second aspect present invention provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery of first aspect present invention, and described preparation method comprises the following steps:
Step (1), according to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2stoichiometric proportion by lithium salts, nickel salt, molysite and manganese salt is soluble in water obtains aqueous metallic ions, in described aqueous metallic ions, metal ion total concentration is 0.2 ~ 3mol/L;
Step (2), added in described aqueous metallic ions by chelating agent, dispersed with stirring is even; The amount of substance of described chelating agent and the ratio of the total amount of substance of described metal ion are 1 ~ 1.2:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 180 ~ 220 DEG C, and the leaving air temp of described spray dryer is 100 ~ 120 DEG C;
Step (4), calcines after the compacting of step (3) gained persursor material in air atmosphere; Calcination condition is: be incubated 3 ~ 15h after being first warming up to 350 ~ 500 DEG C with the speed of 0.5 ~ 10 DEG C/min, and then is incubated 5 ~ 24h after being warming up to 650 ~ 900 DEG C with the speed of 1 ~ 10 DEG C/min; Namely described rich lithium manganese anode material is obtained after being cooled to room temperature.
Preferably, in step (3), the inlet temperature of described spray dryer is 180 ~ 210 DEG C, and the leaving air temp of described spray dryer is 100 ~ 110 DEG C.
Preferably, the calcination condition in step (4) is: be incubated 3 ~ 10h after being first warming up to 350 ~ 450 DEG C with the speed of 2 ~ 6 DEG C/min, and then is incubated 5 ~ 15h after being warming up to 750 ~ 900 DEG C with the speed of 1 ~ 6 DEG C/min.
Preferably, described in step (1), lithium salts is selected from least one in lithium hydroxide, lithium acetate, lithium nitrate and lithium chloride.
Preferably, described in step (1), manganese salt is selected from least one in manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
Preferably, described in step (1), molysite is selected from least one in ferric sulfate, ferric nitrate and iron chloride.
Preferably, described in step (1), nickel salt is selected from least one in nickelous sulfate, nickel nitrate, nickel chloride and nickel acetate.
Preferably, described in step (2), chelating agent is selected from least one in citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid and oxalic acid.
The beneficial effect of the technical scheme that the embodiment of the present invention provides:
1, the embodiment of the present invention is in the preparation process of the rich lithium manganese anode material of lithium ion battery, spray dryer is adopted to carry out spraying dry to metal ion solution, calcine after obtaining persursor material, and the inlet temperature of spray dryer, leaving air temp and calcination condition are optimized, obtain the rich lithium manganese anode material of submicron order of particle diameter 0.1 ~ 0.8 μm.Because gained rich lithium manganese anode material particle diameter is little, fully can contact with electrolyte, and less particle shortens Li
+the evolving path, make the rich lithium manganese anode material that provides using the embodiment of the present invention have good high rate performance as the lithium ion battery of positive electrode active materials, the specific discharge capacity under 5C multiplying power can remain on more than 150mAh/g.
2, owing to have employed spray-dired method, enable in the rich lithium manganese anode material of gained metallic element---iron, manganese, nickel and lithium distribute uniformly, make the ratio of iron, manganese, nickel and lithium in rich lithium manganese anode material can meet xLi accurately
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2the stoichiometric ratio of (wherein, 0.1≤x≤0.9,0.002≤a≤0.08).
3, not containing metal cobalt in the rich lithium manganese anode material of the lithium ion battery of the embodiment of the present invention, and the abundance of iron, manganese, nickel, lithium, reduce the cost of rich lithium manganese anode material.Meanwhile, owing to being doped with iron, improve the stability of rich lithium manganese anode material structure, thus improve its cyclical stability first in coulombic efficiency and charge and discharge process.
4, the preparation technology of the rich lithium manganese anode material of the lithium ion battery that provides of the embodiment of the present invention is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of the rich lithium manganese anode material of the embodiment of the present invention 1 gained lithium ion battery;
Fig. 2 is the embodiment of the present invention 1 gained lithium ion battery rich lithium manganese anode material first charge-discharge cycle performance curve;
Fig. 3 is the cycle performance curve that discharges under the embodiment of the present invention 1 gained lithium ion battery rich lithium manganese anode material different multiplying;
Fig. 4 is the embodiment of the present invention 1 gained lithium ion battery rich lithium manganese anode material discharge cycles performance curve.
Embodiment
For making technical scheme of the present invention and advantage clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
First aspect present invention provides a kind of lithium ion battery rich lithium manganese anode material, and the chemical formula of described rich lithium manganese anode material is xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08; When the accumulative particle size distribution in percentage of described rich lithium manganese anode material reaches 50%, corresponding particle diameter is 0.1 ~ 0.8 μm.
When the accumulative particle size distribution in percentage of the rich lithium manganese anode material that the embodiment of the present invention provides reaches 50%, corresponding particle diameter (hereinafter referred to as D50) is 0.1 ~ 0.8 μm, reach sub-micron rank, because particle diameter is little, rich lithium manganese anode material is fully contacted with electrolyte, and less particle shorten Li
+the evolving path, make the lithium ion battery using above-mentioned rich lithium manganese anode material as positive electrode active materials have good high rate performance, the specific discharge capacity under 5C multiplying power can remain on more than 150mAh/g.In addition, not containing metal cobalt in the rich lithium manganese anode material of the embodiment of the present invention, reduces the cost of rich lithium manganese anode material.And owing to being doped with iron, improve the stability of rich lithium manganese anode material structure, thus improve its cyclical stability first in coulombic efficiency and charge and discharge process.
In above-mentioned rich lithium manganese anode material, the specific area of described rich lithium manganese anode material is 0.8 ~ 2.0m
2/ g, tap density is 1.8 ~ 2.3g/cm
3, larger specific area is conducive to the contact area increasing rich lithium manganese anode material and electrolyte, improves the performance of lithium ion battery; Higher tap density can make to hold more rich lithium manganese anode material in the lithium ion battery of unit volume, is conducive to the capacity improving lithium ion battery.
Second aspect present invention provides the preparation method of the rich lithium manganese anode material of a kind of lithium ion battery of first aspect present invention, and described preparation method comprises the following steps:
Step (1), according to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2stoichiometric proportion by lithium salts, nickel salt, molysite and manganese salt is soluble in water obtains aqueous metallic ions, in described aqueous metallic ions, metal ion total concentration is 0.2 ~ 3mol/L;
Step (2), added in described aqueous metallic ions by chelating agent, dispersed with stirring is even; The amount of substance of described chelating agent and the ratio of the total amount of substance of described metal ion are 1 ~ 1.2:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 180 ~ 220 DEG C, and the leaving air temp of described spray dryer is 100 ~ 120 DEG C;
Step (4), calcines after the compacting of step (3) gained persursor material in air atmosphere; Calcination condition is: be incubated 3 ~ 15h after being first warming up to 350 ~ 500 DEG C with the speed of 0.5 ~ 10 DEG C/min, and then is incubated 5 ~ 24h after being warming up to 650 ~ 900 DEG C with the speed of 1 ~ 10 DEG C/min; Namely described rich lithium manganese anode material is obtained after being cooled to room temperature.
In the preparation method that the embodiment of the present invention provides, adopt spray dryer to carry out drying to metal ion solution and obtain persursor material, after being calcined by persursor material, obtain the rich lithium manganese anode material of first aspect present invention.Spray-dired operation principle is: pass through mechanism, by the particulate as mist needing dry material dispersion to become very thin, with hot air, because disengagement area is large, instantaneously most of moisture can removed, thus the solid matter in material is being dried to powder.The spray-dried solid powder particle obtained is less and be uniformly dispersed.In spray-drying process, the inlet temperature of spray dryer and leaving air temp affect rate of drying and the drying effect of material, and then affect the character of final gained pressed powder.Therefore, the embodiment of the present invention is on the spray-dired basis of employing, be optimized the inlet temperature of spray dryer and leaving air temp, make the particle diameter of gained rich lithium manganese anode material persursor material little, iron, manganese, nickel and lithium are uniformly dispersed and their ratio can meet xLi accurately
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2stoichiometric ratio.The embodiment of the present invention is also optimized the calcination condition in rich lithium manganese anode material preparation process.The condition of calcining can affect the character such as pattern, crystal structure of the rich lithium manganese anode material of final gained, and then affects the electric property such as high rate performance, stable circulation performance of rich lithium manganese anode material.To sum up, by optimizing the technological parameter of spraying dry and calcination process in the embodiment of the present invention, the rich lithium manganese anode material that D50 is the submicron order of 0.1 ~ 0.8 μm is obtained.And preparation method's technique of the embodiment of the present invention is simple, is conducive to suitability for industrialized production.
In above-mentioned preparation method, in step (3), the inlet temperature of described spray dryer preferably 180 ~ 210 DEG C such as, can be 185 DEG C, 190 DEG C, 200 DEG C, 205 DEG C etc.; The leaving air temp of described spray dryer preferably 100 ~ 110 DEG C can be such as 102 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 108 DEG C etc.
In above-mentioned preparation method, in step (4), preferred calcination condition is: be incubated 3 ~ 10h after being first warming up to 350 ~ 450 DEG C with the speed of 2 ~ 6 DEG C/min, and then is incubated 5 ~ 15h after being warming up to 750 ~ 900 DEG C with the speed of 1 ~ 6 DEG C/min.Wherein, temperature during first time insulation can be 360 DEG C, 380 DEG C, 400 DEG C, 420 DEG C etc.; Temperature during second time insulation can be 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 850 DEG C, 860 DEG C, 880 DEG C etc.
In above-mentioned preparation method, described in step (1), lithium salts does not have strict restriction, as long as can be soluble in water, can be such as lithium hydroxide, lithium acetate, lithium nitrate or lithium chloride etc., can be used alone by often kind of lithium salts, also can two kinds or two or more lithium salts used in combination.
In above-mentioned preparation method, described in step (1), manganese salt does not have strict restriction yet, can be arbitrary solubility, such as manganese nitrate, manganese acetate, manganese sulfate or manganese chloride etc., can be used alone by often kind of manganese salt, also can two kinds or two or more manganese salt used in combination.
In above-mentioned preparation method, described in step (1), molysite does not have considered critical yet, as long as soluble ferric iron salt, can be ferric sulfate, ferric nitrate or iron chloride etc., can be used alone by often kind of molysite, also can two kinds or two or more molysite used in combination.
In above-mentioned preparation method, described in step (1), nickel salt does not have considered critical equally, soluble nickel salt, such as nickelous sulfate, nickel nitrate, nickel chloride or nickel acetate etc., similar with above-mentioned lithium salts, manganese salt, molysite, can be used alone by often kind of nickel salt, also can two kinds or two or more nickel salts used in combination.
In above-mentioned preparation method, chelating agent in step (2) can be any chelating agent that this area is commonly used, such as citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid, oxalic acid etc., can be used alone by often kind of chelating agent, also can two kinds or two or more chelating agents used in combination.Wherein, the not special requirement of concrete kind of aliphatic acid, aliphatic acid is commonly used in this area, such as oleic acid, linoleic acid, stearic acid etc.
In above-mentioned preparation method, in step (4) can just described persursor material to be compacted to compacted density be 0.5 ~ 1.8g/cm
3after calcine.
In above-mentioned preparation method, because lithium salts has a small amount of volatilization when high-temperature calcination, therefore in order to make each constituent content in the rich lithium manganese anode material of final gained more accurate, can in the step (1) during preparing metal deionized water solution, make lithium salts excessive 1% ~ 8% to compensate a small amount of volatilization of lithium salts when high-temperature calcination.
Following examples 1 ~ 4 prepare the rich lithium manganese anode material of lithium ion battery according to preparation method provided by the invention, rich for gained lithium manganese anode material is assembled in lithium ion battery, and the high rate performance of gained lithium ion battery, the first character such as coulombic efficiency and cyclical stability are tested.Wherein, the assembly method of lithium ion battery is as follows:
The rich lithium manganese anode material of gained in embodiment 1 ~ 4 is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar), with NMP (1-Methyl-2-Pyrrolidone), said mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven, dry 3h for 110 DEG C, take out and be washed into pole piece; 85 DEG C of vacuumizes carried out compressing tablet after 12 hours, vacuumize 12 hours at 85 DEG C again after compressing tablet, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is 1.0mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2325 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
Embodiment 1
The present embodiment provides rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof, and the chemical formula of prepared rich lithium manganese anode material is: 0.5Li
2mnO
30.5LiNi
0.49mn
0.49fe
0.02o
2, preparation method is as follows:
Step (1), according to the ratio of Li:Ni:Fe:Mn=1.575:0.245:0.01:0.745 (mol ratio, lower same), lithium acetate, nickel chloride, iron chloride and manganese nitrate are dissolved in deionized water and obtain the aqueous metallic ions that metal ion total concentration is 1mol/L; Wherein, lithium salts excessive 5%, to compensate a small amount of volatilization when lithium salts is at high temperature calcined;
Step (2), added in described aqueous metallic ions by citric acid, dispersed with stirring is even; The amount of substance of citric acid and the ratio of the total amount of substance of described metal ion are 1.05:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 180 DEG C, and the leaving air temp of described spray dryer is 100 DEG C;
Step (4), it is 0.5g/cm that step (3) gained persursor material is compacted to compacted density
3after calcine in air atmosphere; Calcination condition is: be incubated 4h after being first warming up to 400 DEG C with the speed of 5 DEG C/min, and then is incubated 5h after being warming up to 750 DEG C with the speed of 2 DEG C/min; Namely 0.5Li is obtained after being cooled to room temperature
2mnO
30.5LiNi
0.49mn
0.49fe
0.02o
2rich lithium manganese anode material.
Carry out sem test to the rich lithium manganese anode material of gained, gained stereoscan photograph as shown in Figure 1.As can be seen from Figure 1, the rich lithium manganese anode material of gained is spherical or class ball shape particle, and even particle size, D50 is 0.6 μm.The specific area of the rich lithium manganese anode material of gained is 0.85m
2/ g, tap density is 1.98g/cm
3.
First charge-discharge loop test is carried out to using above-mentioned rich lithium manganese material as the button cell of positive electrode, test condition: charging/discharging voltage scope is 4.8 ~ 2.0V, be 0.1C (1C=250mA/g, lower same) at charging and discharging currents, result as shown in Figure 2.Be respectively 278.337mAh/g, 247.162mAh/g using above-mentioned rich lithium manganese material as the first charge-discharge specific capacity of the button cell of positive electrode, initial coulomb efficiency is 88.8%, and efficiency is higher first.
Test as the high rate performance of the button cell of positive electrode using above-mentioned rich lithium manganese material, charging/discharging voltage scope is 4.8 ~ 2.0V, charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each circulation 5 times.As shown in Figure 3, under 1C multiplying power, specific discharge capacity remains on about 200mAh/g to high rate performance test result; Under 2C multiplying power, specific discharge capacity remains on about 180mAh/g; Under 5C multiplying power, specific discharge capacity still can remain on more than 154mAh/g.As can be seen here, the rich lithium manganese anode material of submicron order can shorten Li
+the evolving path, make gained battery have good high rate performance.
Test as the stable circulation performance of the button cell of positive electrode using above-mentioned rich lithium manganese material, charging and discharging currents is 0.2C.As shown in Figure 4, first discharge specific capacity is 243.236mAh/g, and 50 specific capacities that circulate are 241.63mAh/g, and capability retention is 99.34%, and cyclical stability is better.
Embodiment 2
The present embodiment provides rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof, and the chemical formula of prepared rich lithium manganese anode material is: 0.2Li
2mnO
30.8LiNi
0.48mn
0.48fe
0.04o
2, preparation method is as follows:
Step (1), to be dissolved in lithium nitrate, nickel acetate, iron chloride and manganese sulfate in deionized water according to the ratio of Li:Ni:Fe:Mn=1.224:0.384:0.032:0.584 and to obtain the aqueous metallic ions that metal ion total concentration is 2.0mol/L; Wherein, lithium salts excessive 2%, to compensate a small amount of volatilization when lithium salts is at high temperature calcined;
Step (2), added in described aqueous metallic ions by acrylic acid, dispersed with stirring is even; The ratio of acrylic acid amount of substance and the total amount of substance of described metal ion is 1.01:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 195 DEG C, and the leaving air temp of described spray dryer is 105 DEG C;
Step (4), it is 1.0g/cm that step (3) gained persursor material is compacted to compacted density
3after calcine in air atmosphere; Calcination condition is: be incubated 6h after being first warming up to 350 DEG C with the speed of 3 DEG C/min, and then is incubated 8h after being warming up to 850 DEG C with the speed of 3 DEG C/min; Namely 0.2Li is obtained after being cooled to room temperature
2mnO
30.8LiNi
0.48mn
0.48fe
0.04o
2rich lithium manganese anode material.
ESEM result shows, and the rich lithium manganese material of the present embodiment gained is spherical or class ball shape particle, and even particle size, D50 is 0.4 μm.The specific area of the rich lithium manganese anode material of gained is 0.96m
2/ g, tap density is 2.1g/cm
3.
According to the test condition of embodiment 1, test using the rich lithium manganese material of the present embodiment gained as the first charge-discharge cycle performance of the button cell of positive electrode, high rate performance and cyclical stability.Result shows, first discharge specific capacity is 266.68mAh/g, first coulombic efficiency 85.68%; Specific discharge capacity under 5C multiplying power remains on more than 148mAh; 50 capability retentions that circulate are 98.45%, and cyclical stability is better.As can be seen here, the rich lithium manganese anode material of submicron order can shorten Li
+the evolving path, make gained battery have good high rate performance.
Embodiment 3
The present embodiment provides rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof, and the chemical formula of prepared rich lithium manganese anode material is: 0.7Li
2mnO
30.3LiNi
0.495mn
0.495fe
0.01o
2, preparation method is as follows:
Step (1), to be dissolved in lithium nitrate, nickel acetate, iron chloride and manganese sulfate in deionized water according to the ratio of Li:Ni:Fe:Mn=1.717:0.1485:0.003:0.8485 and to obtain the aqueous metallic ions that metal ion total concentration is 1.5mol/L; Wherein, lithium salts excessive 1%, to compensate a small amount of volatilization when lithium salts is at high temperature calcined;
Step (2), added in described aqueous metallic ions by citric acid, dispersed with stirring is even; The amount of substance of citric acid and the ratio of the total amount of substance of described metal ion are 1.05:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 200 DEG C, and the leaving air temp of described spray dryer is 100 DEG C;
Step (4), it is 1.5g/cm that step (3) gained persursor material is compacted to compacted density
3after calcine in air atmosphere; Calcination condition is: be incubated 4h after being first warming up to 400 DEG C with the speed of 5 DEG C/min, and then is incubated 10h after being warming up to 900 DEG C with the speed of 5 DEG C/min; Namely 0.7Li is obtained after being cooled to room temperature
2mnO
30.3LiNi
0.495mn
0.495fe
0.01o
2rich lithium manganese anode material.
ESEM result shows, and the rich lithium manganese material of the present embodiment gained is spherical or class ball shape particle, and even particle size, D50 is 0.7 μm.The specific area of the rich lithium manganese anode material of gained is 1.06m
2/ g, tap density is 2.05g/cm
3.
According to the test condition of embodiment 1, test using the rich lithium manganese material of the present embodiment gained as the first charge-discharge cycle performance of the button cell of positive electrode, high rate performance and cyclical stability.Result shows, first discharge specific capacity is 215.235mAh/g, first coulombic efficiency 83.2%; Specific discharge capacity under 5C multiplying power remains on more than 165mAh; 50 capability retentions that circulate are 97.62%, and cyclical stability is better.As can be seen here, the rich lithium manganese anode material of submicron order can shorten Li
+the evolving path, make gained battery have good high rate performance.
Embodiment 4
The present embodiment provides rich lithium manganese anode material of a kind of lithium ion battery and preparation method thereof, and the chemical formula of prepared rich lithium manganese anode material is: 0.4Li
2mnO
30.6LiNi
0.47mn
0.47fe
0.06o
2, preparation method is as follows:
Step (1), to be dissolved in lithium nitrate, nickel acetate, iron chloride and manganese sulfate in deionized water according to the ratio of Li:Ni:Fe:Mn=1.484:0.282:0.036:0.682 and to obtain the aqueous metallic ions that metal ion total concentration is 2.1mol/L; Wherein, lithium salts excessive 6%, to compensate a small amount of volatilization when lithium salts is at high temperature calcined;
Step (2), added in described aqueous metallic ions by triethanolamine, dispersed with stirring is even; The amount of substance of triethanolamine and the ratio of the total amount of substance of described metal ion are 1:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 205 DEG C, and the leaving air temp of described spray dryer is 110 DEG C;
Step (4), it is 1.8g/cm that step (3) gained persursor material is compacted to compacted density
3after calcine in air atmosphere; Calcination condition is: be incubated 6h after being first warming up to 500 DEG C with the speed of 5 DEG C/min, and then is incubated 8h after being warming up to 750 DEG C with the speed of 3 DEG C/min; Namely 0.4Li is obtained after being cooled to room temperature
2mnO
30.6LiNi
0.47mn
0.47fe
0.06o
2rich lithium manganese anode material.
ESEM result shows, and the rich lithium manganese material of the present embodiment gained is spherical or class ball shape particle, and even particle size, D50 is 0.75 μm.The specific area of the rich lithium manganese anode material of gained is 1.65m
2/ g, tap density is 2.2g/cm
3.
According to the test condition of embodiment 1, test using the rich lithium manganese material of the present embodiment gained as the first charge-discharge cycle performance of the button cell of positive electrode, high rate performance and cyclical stability.Result shows, first discharge specific capacity is 257.652mAh/g, first coulombic efficiency 87.51%; Specific discharge capacity under 5C multiplying power remains on more than 158mAh; 50 capability retentions that circulate are 98.75%, and cyclical stability is better.As can be seen here, the rich lithium manganese anode material of submicron order can shorten Li
+the evolving path, make gained battery have good high rate performance.
Table 1 embodiment 1 ~ 4 gained rich lithium manganese anode material performance gathers
To sum up, the embodiment of the present invention obtains persursor material by adopting spray-dired method to carry out drying to metal ion solution, and the condition of spraying dry and persursor material calcining is optimized, obtain the rich lithium manganese anode material of submicron order that particle diameter is 0.1 ~ 0.8 μm.Because less particle diameter can shorten Li
+the evolving path, the rich lithium manganese anode material therefore provided using the embodiment of the present invention has good high rate performance as the lithium ion battery of positive electrode active materials, and the specific discharge capacity under 5C multiplying power can remain on more than 150mAh/g.
The above is only understand technical scheme of the present invention for the ease of those skilled in the art, not in order to limit the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the rich lithium manganese anode material of lithium ion battery, it is characterized in that, the chemical formula of described rich lithium manganese anode material is xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2, wherein, 0.1≤x≤0.9,0.002≤a≤0.08; When the accumulative particle size distribution in percentage of described rich lithium manganese anode material reaches 50%, corresponding particle diameter is 0.1 ~ 0.8 μm.
2. rich lithium manganese anode material according to claim 1, is characterized in that, the specific area of described rich lithium manganese anode material is 0.8 ~ 2.0m
2/ g, tap density is 1.8 ~ 2.3g/cm
3.
3. a preparation method for the rich lithium manganese anode material of lithium ion battery, it is characterized in that, described preparation method comprises the following steps:
Step (1), according to xLi
2mnO
3(1-x) LiNi
0.5-a/2mn
0.5-a/2fe
ao
2stoichiometric proportion by lithium salts, nickel salt, molysite and manganese salt is soluble in water obtains aqueous metallic ions, in described aqueous metallic ions, metal ion total concentration is 0.2 ~ 3mol/L;
Step (2), added in described aqueous metallic ions by chelating agent, dispersed with stirring is even; The amount of substance of described chelating agent and the ratio of the total amount of substance of described metal ion are 1 ~ 1.2:1;
Step (3), carries out drying with spray dryer to step (2) gained mixed solution, obtains the persursor material of described rich lithium manganese anode material; The inlet temperature of described spray dryer is 180 ~ 220 DEG C, and the leaving air temp of described spray dryer is 100 ~ 120 DEG C;
Step (4), calcines after the compacting of step (3) gained persursor material in air atmosphere; Calcination condition is: be incubated 3 ~ 15h after being first warming up to 350 ~ 500 DEG C with the speed of 0.5 ~ 10 DEG C/min, and then is incubated 5 ~ 24h after being warming up to 650 ~ 900 DEG C with the speed of 1 ~ 10 DEG C/min; Namely described rich lithium manganese anode material is obtained after being cooled to room temperature.
4. preparation method according to claim 3, is characterized in that, in step (3), the inlet temperature of described spray dryer is 180 ~ 210 DEG C, and the leaving air temp of described spray dryer is 100 ~ 110 DEG C.
5. preparation method according to claim 3, it is characterized in that, calcination condition in step (4) is: be incubated 3 ~ 10h after being first warming up to 350 ~ 450 DEG C with the speed of 2 ~ 6 DEG C/min, and then is incubated 5 ~ 15h after being warming up to 750 ~ 900 DEG C with the speed of 1 ~ 6 DEG C/min.
6. preparation method according to claim 3, is characterized in that, described in step (1), lithium salts is selected from least one in lithium hydroxide, lithium acetate, lithium nitrate and lithium chloride.
7. preparation method according to claim 3, is characterized in that, described in step (1), manganese salt is selected from least one in manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
8. preparation method according to claim 3, is characterized in that, described in step (1), molysite is selected from least one in ferric sulfate, ferric nitrate and iron chloride.
9. preparation method according to claim 3, is characterized in that, described in step (1), nickel salt is selected from least one in nickelous sulfate, nickel nitrate, nickel chloride and nickel acetate.
10. preparation method according to claim 3, is characterized in that, described in step (2), chelating agent is selected from least one in citric acid, glycolic, triethanolamine, acrylic acid, aliphatic acid and oxalic acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111600012A (en) * | 2020-04-30 | 2020-08-28 | 孚能科技(赣州)股份有限公司 | Cobalt-free lithium-rich manganese-based positive electrode material, composite positive electrode piece and lithium ion battery |
| CN113097475A (en) * | 2021-04-02 | 2021-07-09 | 上海科技大学 | Lithium-rich layered cathode material, preparation method thereof, battery cathode formed by lithium-rich layered cathode material and battery |
| CN113991102A (en) * | 2021-12-29 | 2022-01-28 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich cathode material and preparation method and application thereof |
| CN116344791A (en) * | 2023-05-26 | 2023-06-27 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111600012A (en) * | 2020-04-30 | 2020-08-28 | 孚能科技(赣州)股份有限公司 | Cobalt-free lithium-rich manganese-based positive electrode material, composite positive electrode piece and lithium ion battery |
| CN111600012B (en) * | 2020-04-30 | 2023-09-26 | 孚能科技(赣州)股份有限公司 | Cobalt-free lithium-rich manganese-based positive electrode material, composite positive electrode plate and lithium ion battery |
| CN113097475A (en) * | 2021-04-02 | 2021-07-09 | 上海科技大学 | Lithium-rich layered cathode material, preparation method thereof, battery cathode formed by lithium-rich layered cathode material and battery |
| CN113991102A (en) * | 2021-12-29 | 2022-01-28 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich cathode material and preparation method and application thereof |
| CN116344791A (en) * | 2023-05-26 | 2023-06-27 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
| CN116344791B (en) * | 2023-05-26 | 2023-08-08 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
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