CN103943863A - Anion doped modified lithium-excess (5:3:2) type ternary lithium ion battery cathode material - Google Patents

Anion doped modified lithium-excess (5:3:2) type ternary lithium ion battery cathode material Download PDF

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CN103943863A
CN103943863A CN201310023686.1A CN201310023686A CN103943863A CN 103943863 A CN103943863 A CN 103943863A CN 201310023686 A CN201310023686 A CN 201310023686A CN 103943863 A CN103943863 A CN 103943863A
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张海朗
宋腾飞
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Jiangnan University
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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
    • H01M4/362—Composites
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention relates to an anion doped modified lithium-excess (5:3:2) type ternary lithium ion battery cathode material and a preparing method thereof. The chemical formula of the cathode material is Li<1+x>(Ni<0.5>Mn<0.3>Co<0.2>)O<2-y>My, wherein the M is F, Cl or S; 0.02<=x<=0.15; and 0.02<=y<=0.1. The preparing method of the cathode material is characterized in that: an oxalate co-precipitation method is adopted, so that the three elements are uniformly mixed at the atom level, and a disadvantage that inert gas protection is needed in a process of a hydroxide co-precipitation method is overcome. In addition, a LiNi<0.5>Mn<0.3>Co<0.2>)O<2> material is subjected to modification by anion doping, thus further enhancing the cyclic performance and the rate capability of the material. The cathode material has characteristics of uniform particles, smooth surfaces, high tap density, high volume energy density, high specific capacity and good cyclic performance.

Description

Lithium (5:3:2) type of the crossing ternary anode material for lithium-ion batteries of anion doped modification
Technical field
The invention belongs to technical field of lithium ion, be specifically related to anode material for lithium-ion batteries of lithium (5: 3: 2) type ternary excessively of a kind of anion doped modification and preparation method thereof.
Background technology
Along with the aggravation of fossil energy crisis, the new material of finding alternative new forms of energy and can be used for energy storage has become an important scientific research direction., since coming out, just the advantage such as grow with its high voltage, high power capacity, memory-less effect and life-span and be widely used in the electronic product such as mobile phone, digital camera, and will be applied to gradually electric automobile field as the lithium ion battery of new forms of energy.But with regard to business-like several anode material for lithium-ion batteries at present, all, because of its some intrinsic shortcomings, be difficult to meet the requirement of power lithium-ion battery.
LiNi 0.5mn 0.3co 0.2o 2material has been assembled the advantage of cobalt acid lithium, LiMn2O4 and three kinds of positive electrodes of lithium nickelate, all has advantage aspect price, capacity and thermal stability, is a kind of very promising positive electrode.But this material is yet needing further lifting aspect cycle performance, high rate performance, anion doped is the very resultful method of modifying of one.In addition, nickel, manganese, three kinds of element distributing inhomogeneities of cobalt in the synthetic material of current preparation method, particle is irregular, and the material stacking density making is lower, and is difficult to ensure batch stability.
Summary of the invention
The object of the invention is for LiNi 0.5mn 0.3co 02o 2the shortcoming that material is intrinsic, and existing preparation method's deficiency, correspondingly propose following solution:
1, adopt oxalate coprecipitation method, by nickel, manganese, the homogeneous precipitation simultaneously of cobalt three components out, make three kinds of elements reach the even mixing on atomic level.Overcome the deficiency that needs blanketing with inert gas in hydroxide coprecipitation step process simultaneously.
2, to LiNi 0.5mn 0.3co 0.2o 2material has carried out crossing lithiumation processing, has reduced the mixing of lithium nickel, and material capacity is further improved.Carry out anion doped modification simultaneously, further promoted cycle performance and the high rate performance of material.
Another object of the present invention is to provide the preparation method of described material.
The anode material for lithium-ion batteries of lithium (5: 3: 2) type ternary excessively of anion doped modification, has following chemical general formula Li 1+x(Ni 05mn 0.3co 0.2) O 2-ym y, wherein, M is F, Cl or S, 0.02≤x≤0.15,0.02≤y≤0.1.
The preparation method of lithium (5-3-2) type of the crossing ternary anode material for lithium-ion batteries of described anion doped modification, comprises the steps:
(1) water miscible nickel salt, cobalt salt and manganese salt are dissolved in deionized water, are made into the solution that concentration of metal ions is 0.4～1.0mol/L;
(2) (the NH that compound concentration is 0.2～0.5mol/L 4) 2c 2o 4solution;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit control solution is 6.5～8.0, and regulating the rotating speed of blender is 300～500r/min, and reaction temperature is 40～60 DEG C;
(4), to the material continuous stirring 6-10 hour in reactor in step (3), reacted rear one-tenth continuation ageing and within 6 hours, obtained shallow grey blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) precursor and Li source compound, M salt are ground 1 hour on ball mill, then pre-burning 6 hours at 400～600 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour again, compressing tablet fully contacts it, high-temperature calcination at last 800～950 DEG C.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+xni 0.5mn 0.3co 0.2o 2-ym ymaterial, wherein, M is F, Cl or S, 0.02≤x≤0.15,0.02≤y≤0.1.
Further, integral molar quantity and the precipitation reagent (NH of the described nickel salt of step (3), cobalt salt and manganese salt 4) 2c 2o 4mol ratio be 1: (1～1.2).
Further, the described M salt of step (5) is LiF, LiCl or S powder.
Further, in step (5), the time of calcining is 12～20 hours, and heating rate is 3～5 DEG C/min.
Further, described nickel salt is Ni (CH 3cOOH) 2, Ni (NO 3) 2, NiSO 4in at least one, described cobalt salt is Co (CH 3cOOH) 2, Co (NO 3) 2, CoSO 4in at least one, described manganese salt is Mn (CH 3cOOH) 2, Mn (NO 3) 2, MnSO 4in at least one, described lithium salts is CH 3cOOLi, LiNO 3, Li 2cO 3or at least one in LiOH.
Beneficial effect of the present invention:
(1) the prepared positive electrode uniform particles of the present invention, smooth surface, crystal property is good;
(2) the present invention is to LiNi 0.5mn 0.3co 0.2o 2material has carried out crossing lithiumation processing, has reduced the mixing of lithium nickel, and material capacity is further improved; Pass through to LiNi simultaneously 0.5mn 0.3co 0.2o 2in mix anion replace part O, the cycle performance of material and high rate performance are improved.Prepared material specific capacity is high, good cycle, and under 55 DEG C, 0.1C, (in 2.5～4.6V voltage range) first discharge specific capacity is more than 200.0mAh/g, and after 50 circulations, capability retention is more than 93%.
Brief description of the drawings
The XRD collection of illustrative plates of Fig. 1 positive electrode of the present invention, wherein curve a, b, c, d, e are respectively
Li 1+0.02(Ni 05Mn 0.3Co 0.2)O 2-002F 0.02、Li 1+0.05(Ni 0.5Mn 0.3Co 0.2)O 2-0.05F 005、
Li 1+0.15(Ni 0.5Mn 0.3Co 0.2)O 2-0.1F 01、Li 1+0.05(Ni 0.5Mn 0.3Co 0.2)O 2-0.05Cl 005、
Li 1+01(Ni 0.5Mn 0.3Co 0.2)O 2-0.05S 0.05
Fig. 2 is the prepared Li of the embodiment of the present invention two 1+0.05(Ni 0.5mn 0.3co 0.2) O 2-005f 0.05sEM figure.
Fig. 3 is the prepared Li of the embodiment of the present invention two 1+005(Ni 05mn 0.3co 02) O 2-0.05f 0.05first charge-discharge curve chart.
Fig. 4 is the prepared Li of the embodiment of the present invention five 1+0.05(Ni 0.5mn 03co 0.2) O 2-0.05cl 0.05sEM figure.
Fig. 5 is the cyclic curve figure of positive electrode of the present invention, and wherein curve a, b are respectively
Li 1+0.05(Ni 0.5Mn 0.3Co 0.2)O 2-0.05Cl 0.05、Li 1+0.1(Ni 0.5Mn 0.3Co 0.2)O 2-005S 005。
Fig. 6 is the curve of double curvature figure of positive electrode of the present invention, and wherein curve a, b, c are respectively
Li 1+0.05(Ni 05Mn 0.3Co 0.2)O 2-005F 0.05、Li 1+0 .05(Ni 0.5Mn 03Co 0.2)O 2-005Cl 0.05、
Li 1+0.1(Ni 0.5Mn 0.3Co 0.2)O 2-0.05S 0.05。
Embodiment
Below in conjunction with concrete drawings and Examples, the invention will be further described.
Embodiment mono-Li 1+0.02(Ni 0.5mn 0.3co 0.2) O 2-002f 0.02
(1) by 0.1mol Ni (CH 3cOOH) 24H 2o, 0.06mol Mn (CH 3cOOH) 24H 2o, 0.04molCo (CH 3cOOH) 24H 2o is dissolved in 500mL deionized water, is made into the solution that concentration of metal ions is 0.4mol/L;
(2) by 0.2mol (NH 4) 2c 2o 4be dissolved in 1000mL deionized water, form the solution of 0.2mol/L;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 6.5, and regulating the rotating speed of blender is 300r/min, and reaction temperature is 40 DEG C;
(4), to the material continuous stirring in reactor in step (3) 10 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain shallow grey blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.2molCH 3cOOLi2H 2o, 0.004molLiF grind 1 hour on ball mill, and then pre-burning 6 hours at 400 DEG C is cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 12 hours at last 950 DEG C, heating rate is 3 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+002(Ni 0.5mn 0.3co 0.2) O 2-0.02f 0.02material.
Embodiment bis-Li 1+0.05(Ni 0.5mn 0.3co 0.2) O 2-005f 005
(1) by 0.1mol Ni (NO 3) 26H 2o, 0.06mol Mn (NO 3) 26H 2o, 0.04mol Co (NO 3) 26H 2o is dissolved in 400mL deionized water, is made into the solution that concentration of metal ions is 0.5mol/L;
(2) by 0.22mol (NH 4) 2c 2o 4be dissolved in 800mL deionized water, form the solution (precipitation reagent (NH of 0.275mol/L 4) 2c 2o 4excess coefficient is 1.1);
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 7.0, and regulating the rotating speed of blender is 400r/min, and reaction temperature is 50 DEG C;
(4), to the material continuous stirring in reactor in step (3) 8 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain shallow grey blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.2mol LiNO 3, 0.01molLiF grinds 1 hour on ball mill, then pre-burning 6 hours at 500 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 15 hours at last 900 DEG C, heating rate is 3 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.05(Ni 0.5mn 0.3co 0.2) O 2-0.05f 0.05material.
The positive electrode that the present embodiment is made carries out XRD, SEM and detects, and result is respectively as shown in the curve b of Fig. 1 and Fig. 2.The abscissa of Fig. 1 is sweep limits 2 θ (10～90 °), the intensity that ordinate is peak.(006) the two groups of peak divisions in/(102) and (108)/(110) obviously, show that positive electrode degree of crystallinity is good, have complete layer structure.Fig. 2 is the SEM figure of this material, shows that the particle of this positive electrode is tiny, is evenly distributed, and is class spherical.Material is assembled into button cell and carries out charge-discharge test, and as shown in Figure 3, in 2.5～4.6V voltage range, under 55 DEG C, 0.1C, first discharge specific capacity and coulomb efficiency are respectively 203.6mAh/g and 96.7%.The ordinate of Fig. 3 is voltage, and abscissa is specific discharge capacity, and unit is mAh/g.In Fig. 6, curve a is this material under 55 DEG C, 2.5～4.6V, 0.1C, and 0.5C, 20 multiplying power cycle performance curves under 1C and 2C different multiplying, under 2C, the capacity of the 20th circulation is 156.2mAh/g, demonstrates good high rate performance.
Embodiment tri-Li 1+0.1(Ni 0.5mn 0.3co 0.2) O 2-0.1f 0.1
(1) by 0.1mol NiSO 44H 2o, 0.06mol MnSO 4h 2o, 0.04mol CoSO 47H 2o is dissolved in 300mL deionized water, is made into the solution that concentration of metal ions is 0.67mol/L;
(2) by 0.24mol (NH 4) 2c 2o 4be dissolved in 600mL deionized water, form the solution (precipitation reagent (NH of 0.4mol/L 4) 2c 2o 4excess coefficient is 1.2);
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 7.5, and regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C;
(4), to the material continuous stirring in reactor in step (3) 6 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.1mol Li 2cO 3, 0.02molLiF grinds 1 hour on ball mill, then pre-burning 6 hours at 600 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 20 hours at last 850 DEG C, heating rate is 4 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.1(Ni 0.5mn 0.3co 02) O 2-0.1f 0.1material.
Embodiment tetra-Li 1+0.15(Ni 0.5mn 0.3co 0.2) O 2-0.1f 0.1
(1) by 0.1mol Ni (CH 3cOOH) 24H 2o, 0.06molMn (CH 3cOOH) 24H 2o, 0.04molCo (CH 3cOOH) 24H 2o is dissolved in 200mL deionized water, is made into the solution that concentration of metal ions is 1.0mol/L;
(2) by 0.2mol (NH 4) 2c 2o 4be dissolved in 400mL deionized water, form the solution of 0.5mol/L;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 8.0, and regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C;
(4), to the material continuous stirring in reactor in step (3) 8 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) above-mentioned precursor and 0.21mol LiOH, 0.02mol LiF are ground 1 hour on ball mill, then pre-burning 6 hours at 500 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 20 hours at last 800 DEG C, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.15(Ni 0.5mn 03co 02) O 2-0.1f 0.1material.
Embodiment five Li 1+0.05(Ni 0.5mn 0.3co 0.2) O 2-0.05cl 0.05
(1) by 0.1mol Ni (CH 3cOOH) 24H 2o, 0.06mol Mn (CH 3cOOH) 24H 2o, 0.04molCo (CH 3cOOH) 24H 2o is dissolved in 500mL deionized water, is made into the solution that concentration of metal ions is 0.4mol/L;
(2) by 0.2mol (NH 4) 2c 2o 4be dissolved in 1000mL deionized water, form the solution of 0.2mol/L;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 6.5, and regulating the rotating speed of blender is 300r/min, and reaction temperature is 40 DEG C;
(4), to the material continuous stirring in reactor in step (3) 10 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.2molCH 3cOOLi2H 2o, 0.01molLiCl grind 1 hour on ball mill, and then pre-burning 6 hours at 400 DEG C is cooling with stove.By the mixed oxide obtaining after pre-burning again ball milling 1 hour, compressing tablet it is fully contacted, high-temperature calcination 12 hours at last 950 DEG C, heating rate is 3 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.05(Ni 0.5mn 0.3co 0.2) O 2-0.05cl 0.05material.
The positive electrode that the present embodiment is made carries out XRD, SEM and detects, and result is respectively as shown in the curve d of Fig. 1 and Fig. 4.(006) the two groups of peak divisions in/(102) and (108)/(110) obviously, show that positive electrode degree of crystallinity is good, have complete layer structure.Fig. 4 is the SEM figure of this material, shows that the particle of this positive electrode is tiny, is evenly distributed, and is class spherical.Curve a in Fig. 5 be this material in 2.5～4.6V voltage range, the cycle performance curve under 55 DEG C, 0.1C, the capacity after 50 circulations and capability retention 190.2mAh/g and 93.5% respectively.In Fig. 6, curve b is material under 55 DEG C, 2.5～4.6V, 0.1C, and 0.5C, 20 multiplying power cycle performance curves under 1C and 2C different multiplying, under 2C, the capacity of the 20th circulation is 151.1mAh/g, demonstrates good high rate performance.
Embodiment six Li 1+015(Ni 0.5mn 0.3co 0.2) O 2-01cl 0.1
(1) by 0.1mol Ni (NO 3) 26H 2o, 0.06mol Mn (NO 3) 26H 2o, 0.04mol Co (NO 3) 26H 2o is dissolved in 400mL deionized water, is made into the solution that concentration of metal ions is 0.5mol/L;
(2) by 0.22mol (NH 4) 2c 2o 4be dissolved in 800mL deionized water, form the solution (precipitation reagent (NH of 0.275mol/L 4) 2c 2o 4excess coefficient is 1.1);
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 7.0, and regulating the rotating speed of blender is 400r/min, and reaction temperature is 50 DEG C;
(4), to the material continuous stirring in reactor in step (3) 8 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain shallow grey blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.2mol LiNO 3, 0.02molLiCl grinds 1 hour on ball mill, then pre-burning 6 hours at 500 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 15 hours at last 900 DEG C, heating rate is 3 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.15(Ni 0.5mn 03co 0.2) O 2-0.1cl 0.1material.
Embodiment seven Li 1+0.02(Ni 05mn 03co 0.2) O 2-002s 0.02
(1) by 0.1mol NiSO 44H 2o, 0.06mol MnSO 4h 2o, 0.04mol CoSO 47H 2o is dissolved in 300mL deionized water, is made into the solution that concentration of metal ions is 0.67mol/L;
(2) by 0.24mol (NH 4) 2c 2o 4be dissolved in 600mL deionized water, form the solution (precipitation reagent (NH of 0.4mol/L 4) 2c 2o 4excess coefficient is 1.2);
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 7.5, and regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C;
(4), to the material continuous stirring in reactor in step (3) 6 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) by above-mentioned precursor and 0.102mol Li 2cO 3, 0.02mol S powder grinds 1 hour on ball mill, then pre-burning 6 hours at 600 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 20 hours at last 850 DEG C, heating rate is 4 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+002(Ni 0.5mn 0.3co 0.2) O 2-0.02s 0.02material.
Embodiment eight Li 1+0.1(Ni 0.5mn 0.3co 0.2) O 2-005s 0.05
(1) by 0.1molNi (CH 3cOOH) 24H 2o, 0.06molMn (CH 3cOOH) 24H 2o, 0.04mol Co (CH 3cOOH) 24H 2o is dissolved in 200mL deionized water, is made into the solution that concentration of metal ions is 1.0mol/L;
(2) by 0.2mol (NH 4) 2c 2o 4be dissolved in 400mL deionized water, form the solution of 0.5mol/L;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and to drip mass percentage concentration be that the pH value of 15% ammonia spirit regulator solution is 8.0, and regulating the rotating speed of blender is 500r/min, and reaction temperature is 60 DEG C;
(4), to the material continuous stirring in reactor in step (3) 8 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain light blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) above-mentioned precursor and 0.22mol LiOH, 0.05mol S powder are ground 1 hour on ball mill, then pre-burning 6 hours at 500 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour, compressing tablet again, high-temperature calcination 20 hours at last 800 DEG C, heating rate is 5 DEG C/min.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+0.1(Ni 0.5mn 0.3dEG C o 0.2) O 2-0.05s 0.05material.
The positive electrode that the present embodiment is made carries out XRD detection, and result is as shown in curve e in Fig. 1.(006) the two groups of peak divisions in/(102) and (108)/(110) are more clear, show that positive electrode degree of crystallinity is good, have complete layer structure.Curve b in Fig. 5 be this material in 2.5～4.6V voltage range, the cycle performance curve under 55 DEG C, 0.1C, the capacity after 50 circulations and capability retention 194.7mAh/g and 94.5% respectively.In Fig. 6, curve c is material under 55 DEG C, 2.5～4.6V, 0.1C, and 0.5C, 20 multiplying power cycle performance curves under 1C and 2C different multiplying, under 2C, the capacity of the 20th circulation is 155.2mAh/g, demonstrates good high rate performance.

Claims (9)

1. the anode material for lithium-ion batteries of lithium (5: 3: 2) type ternary excessively of anion doped modification, is characterized in that: have following chemical general formula Li 1+x(Ni 0.5mn 0.3co 02) O 2-ym y, wherein, M is F, Cl or S, 0.02≤x≤0.15,0.02≤y≤0.1.
2. the preparation method who crosses lithium (5: 3: 2) type ternary anode material for lithium-ion batteries of anion doped modification described in claim 1, is characterized in that, adopts following processing step:
(1) water miscible nickel salt, cobalt salt and manganese salt are dissolved in deionized water, are made into the solution that concentration of metal ions is 0.4～1.0mol/L;
(2) (the NH that compound concentration is 0.2～0.5mol/L 4) 2c 2o 4solution;
(3) by the metallic solution, (NH that prepare respectively in step (1) (2) 4) 2c 2o 4solution is slowly added drop-wise in the reactor of continuous stirring, and drips the pH value that mass percentage concentration is 15% ammonia spirit control solution, regulates rotating speed and the reaction temperature of blender simultaneously;
(4), to the material continuous stirring in reactor in step (3) 6～10 hours, reacted rear one-tenth and continued ageing and within 6 hours, obtain shallow grey blue precipitation.By sedimentation and filtration, washing with dryly obtain the oxalate coprecipitation precursor that nickel, cobalt, manganese are evenly distributed.
(5) precursor and Li source compound, M salt are ground 1 hour on ball mill, then pre-burning 6 hours at 400～600 DEG C, cooling with stove.By the mixed oxide obtaining after pre-burning ball milling 1 hour again, compressing tablet fully contacts it, final high temperature calcining.Quenching, crosses 300 mesh sieves, obtains the spherical Li of class that crystal formation is intact 1+xni 0.5mn 03co 0.2o 2-ym ymaterial, wherein, M is F, Cl or S, 0.02≤x≤0.15,0.02≤y≤0.1.
3. the preparation method who crosses lithium (5: 3: 2) type ternary anode material for lithium-ion batteries of anion doped modification according to claim 2, it is characterized in that: described lithium salts, nickel salt, manganese salt, cobalt salt and M salt are (1+x-y) according to mol ratio: 0.5: 0.3: 0.2: y adds, wherein 0.02≤x≤0.15,0.02≤y≤0.1.
4. the preparation method who crosses lithium (5: 3: 2) type ternary anode material for lithium-ion batteries of anion doped modification according to claim 2, is characterized in that: integral molar quantity and the precipitation reagent (NH of the described nickel salt of step (3), cobalt salt and manganese salt 4) 2c 2o 4mol ratio be 1: (1～1.2).
5. according to the preparation method who crosses lithium (5: 3: 2) type ternary anode material for lithium-ion batteries of the arbitrary described anion doped modification of claim 2～4, it is characterized in that: described nickel salt is Ni (CH 3cOOH) 2, Ni (NO 3) 2, NiSO 4in at least one, described cobalt salt is Co (CH 3cOOH) 2, Co (NO 3) 2, CoSO 4in at least one, described manganese salt is Mn (CH 3cOOH) 2, Mn (NO 3) 2, MnSO 4in at least one.
6. preparation method according to claim 2, is characterized in that: the described pH value of step (3) is 6.5～8.0, and regulating the rotating speed of blender is 300～500r/min, and reaction temperature is 40～60 DEG C.
7. according to the preparation method described in claim 2 or 3, it is characterized in that: described lithium salts is CH 3cOOLi, LiNO 3, Li 2cO 3or at least one in LiOH.
8. according to the preparation method described in claim 2 or 3, it is characterized in that: described M salt is LiF, LiCl or S powder.
9. preparation method according to claim 2, is characterized in that: in step (5), the temperature of high-temperature calcination is 800～950 DEG C, and the time is 15～25 hours, and heating rate is 3～5 DEG C/min.
CN201310023686.1A 2013-01-23 2013-01-23 Anion doped modified lithium-excess (5:3:2) type ternary lithium ion battery cathode material Pending CN103943863A (en)

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CN104733732A (en) * 2015-02-11 2015-06-24 江苏科捷锂电池有限公司 Preparation method for F-substituted 523 ternary material
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CN111225877A (en) * 2017-09-19 2020-06-02 加利福尼亚大学董事会 Cation disordered rock salt lithium metal oxide and oxyfluoride and preparation method thereof
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CN114284499A (en) * 2021-12-20 2022-04-05 中国科学院物理研究所 Spinel structure coated modified lithium cobaltate-based material, preparation method and lithium battery
CN114284499B (en) * 2021-12-20 2023-05-12 中国科学院物理研究所 Spinel structure coated modified lithium cobaltate-based material, preparation method and lithium battery

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