CN108987743A - Ternary cathode material of lithium ion battery and preparation method thereof with hollow structure - Google Patents
Ternary cathode material of lithium ion battery and preparation method thereof with hollow structure Download PDFInfo
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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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- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of ternary cathode material of lithium ion battery and preparation method thereof with hollow structure in technical field of lithium ion, and the chemical general formula of positive electrode is LiNi1/3Co1/ 3Mn1/3O2；Its step includes taking lithium source, nickel source, manganese source, cobalt source, forms uniform solution or suspension after being separately added into solvent, and wherein manganese source is hollow manganese dioxide microballoon；Heating evaporation solvent after solution and suspension are mixed, obtains the anode material for lithium-ion batteries LiNi after calcining and grinding twice is cooled to room temperature1/ 3Co1/3Mn1/3O2.The present invention is easily operated, and the positive electrode particle being prepared is uniform, crystallinity, has the advantages that specific capacity is high, good cycle, good rate capability.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to a kind of lithium ion battery tertiary cathode with hollow structure
Material and preparation method thereof.
Background technique
Due to the limited of fossil fuel and to the serious pollution of environment, exploitation more cleaning, efficient new energy are compeled in eyebrow
Eyelash.Lithium ion battery has been widely used in portable electric because its energy density is big, good cycle, advantages of environment protection
Sub- equipment new-energy automobile industry.
The exploitation of the electrode material of lithium ion battery, especially positive electrode is most important to lithium ion battery.Ternary is just
Pole material LiNixCoyMn1-x-yO2(x+y+z=1) combines LiCoO2、 LiNiO2、LiMnO2The advantages of three kinds of materials and obvious three
Member acts synergistically and is extensively studied.In numerous ternary systems, LiNi1/3Co1/3Mn1/3O2Its at low cost, specific capacity
High, good rate capability and highly-safe, it is considered to be before electric car (EVs) hybrid-electric car (HEVs) power-supply system most has
One of positive electrode of scape.But pass through in recent years studies have shown that in charge and discharge process, LiNi1/3Co1/3Mn1/3O2Material
Material causes its poor cycle performance, special capacity fade and high-temperature behavior poor there are Jahn-Teller effect.
With the fast development of new-energy automobile industry, to lithium ion battery, more stringent requirements are proposed, in order to improve
LiNi1/3Co1/3Mn1/3O2Structural stability, reduce cationic mixing, the major measure that researchers take has ion doping
With surface cladding etc..In addition to this, the partial size and structure for controlling material are also one of important channel, common LiNi1/3Co1/ 3Mn1/3O2Preparation method mainly has high temperature solid-state method, sol-gel method, coprecipitation etc..High temperature solid-state method is easy to operate, but machine
Tool mixing is easy to cause raw material mixing uneven；Sol-gel method can make ion realize nanoscale mixing, but be unable to control material
The pattern of material；The coprecipitation although higher particle of available sphericity, but obtained material is with wider partial size point
Cloth, and experimental method is complicated.
Summary of the invention
The purpose of the present invention is overcoming defect of the existing technology, provide a kind of simple, lithium with hollow structure from
Sub- battery tertiary cathode material and preparation method thereof.
Technical solution according to the invention, the preparation side of the ternary cathode material of lithium ion battery with hollow structure
Method, the chemical general formula of the positive electrode are LiNi1/3Co1/3Mn1/3O2, comprising the following steps:
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:8-12 in molar ratio, and solution is mixed, low whipping speed
It is stirred 2-4 hours under conditions of 200-500 revs/min；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized at least 3 times, anhydrous second
Alcohol washs at least 2 times, obtains manganese carbonate microballoon；
(3) manganese carbonate microballoon is placed in Muffle furnace and is calcined, be warming up to 400-500 DEG C with the heating rate of 4-6 DEG C/min,
Calcining 3-5 hours, obtains hollow manganese dioxide microballoon；
(4) solvent is added in hollow manganese dioxide microballoon, lithium salts, nickel salt and cobalt salt with continuous stirring in molar ratio to be mixed
Uniform suspension；
(5) suspension for obtaining (4) 60-80 DEG C at a temperature of with 200-500 revs/min of speed agitating and heating until molten
Agent volatilization completely, is precipitated；
(6) precipitating that (5) obtain is placed in air dry oven drying 10-12 hours under the conditions of 80-120 DEG C, is driven with evaporating
Except residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 4-6 DEG C/min, calcination temperature 400-
600 DEG C, calcination time is 6-8 hours, obtains presoma；
(8) presoma is placed in ball mill after grinding 1-3 hours and is calcined, calcination temperature is 850-950 DEG C, calcination time
It is 10-20 hours, grinds after cooling to get the ternary cathode material of lithium ion battery LiNi with hollow structure1/3Co1/ 3Mn1/3O2。
Further, the solvent in the step (4) is at least one of dehydrated alcohol, deionized water.
Further, lithium salts in the step (4), hollow manganese dioxide microballoon, nickel salt, cobalt salt molar ratio be 1.05:
1/3 : 1/3 : 1/3。
Further, the lithium salts in the step (4) is lithium carbonate, lithium nitrate, lithium acetate, at least one in lithium hydroxide
Kind.
Further, the nickel salt in the step (4) is at least one of nickelous carbonate, nickel nitrate, nickel acetate.
Further, the cobalt salt in the step (4) is at least one of cobalt carbonate, cobalt nitrate, cobalt acetate.
It is another object of the present invention to provide a kind of lithium ion batteries with hollow structure of above method preparation
Tertiary cathode material LiNi1/3Co1/3Mn1/3O2。
The beneficial effects of the present invention are:
(1) preparation method is simple, easily operated, and prepared positive electrode particle is uniform, has hollow structure, and crystallinity is high,
Specific capacity is high, good cycle, good rate capability.
(2) anode material for lithium-ion batteries made from has the advantages that specific capacity is high, good cycle, good rate capability.
(3) it is suitable for tertiary cathode material LiNixCoyMn1-x-yO2Other systems of (x+y+z=1).
Detailed description of the invention
Fig. 1 is 3 gained positive electrode LiNi of embodiment1/3Co1/3Mn1/3O2XRD diagram.
Fig. 2 is that the SEM of 4 gained hollow manganese dioxide microballoon of embodiment schemes.
Fig. 3 is 2 gained positive electrode LiNi of embodiment1/3Co1/3Mn1/3O2SEM figure.
Fig. 4 is 1 gained positive electrode LiNi of embodiment1/3Co1/3Mn1/3O2First charge-discharge curve (2.5-4.6V,
0.1C, room temperature).
Fig. 5 is 1 gained positive electrode LiNi of embodiment1/3Co1/3Mn1/3O2Cycle performance curve (2.5-4.6V, 0.2C,
Room temperature).
Fig. 6 is 1 gained positive electrode LiNi of embodiment1/3Co1/3Mn1/3O2High rate performance curve (2.5-4.6V, 0.1C,
0.2C, 0.5C, 1C, room temperature).
The abscissa of Fig. 1 is 2 θ of scanning range (10-90 °), and ordinate is the intensity at peak.The times magnification of Fig. 2 is 50K times.
The times magnification of Fig. 3 is 30K times.The abscissa of Fig. 4 is specific capacity, unit mAhg-1, ordinate is voltage, and unit is V, in Fig. 4
Curve A refers to that charging curve, curve B refer to discharge curve.Abscissa is cycle-index in Fig. 5, and ordinate is specific discharge capacity,
Unit is mAhg-1, abscissa is cycle-index in Fig. 6, and ordinate is specific discharge capacity, and unit is mAhg-1。
Specific embodiment
Below with reference to embodiment and attached drawing, technical scheme is described further.
Embodiment 1
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:10 in molar ratio, and solution is mixed, low whipping speed 350
It is stirred 3 hours under conditions of rev/min；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized 3 times, dehydrated alcohol is washed
It washs 2 times, obtains manganese carbonate microballoon；
(3) manganese carbonate being placed in Muffle furnace and is calcined, heating rate is 5 DEG C/min, is warming up to 400 DEG C, it calcines 3 hours,
Obtain hollow manganese dioxide microballoon；
(4) lithium hydroxide, hollow manganese dioxide microballoon, nickel nitrate and nitre are weighed at 1.05: 1/3: 1/3: 1/3 in molar ratio
Dehydrated alcohol is added in sour cobalt, by lithium hydroxide suspension (being slightly soluble in dehydrated alcohol), manganese dioxide suspension (insoluble in anhydrous
Ethyl alcohol), nickel nitrate solution and cobalt nitrate solution be blended in a clean large beaker；Wherein lithium under high-temperature calcination in order to prevent
A small amount of volatilization, the amount of the substance of lithium excessive 5%；
(5) (4) obtained mixture is placed in 80 DEG C of thermostat water baths, continuously stirred with 350 revs/min of speed until
Dehydrated alcohol volatilization completely, is precipitated；
(6) precipitating obtained by (5) is placed in air dry oven drying 12 hours under the conditions of 100 DEG C, to remove residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 5 DEG C/min, is warming up to 500 DEG C, calcining 6
Hour, obtain presoma；
(8) presoma is placed in ball mill to grind to be placed in Muffle furnace for 1 hour and is calcined, calcination temperature is 850 DEG C, is forged
Burning the time is 18 hours, is ground after cooling to get the ternary cathode material of lithium ion battery with hollow structure
LiNi1/3Co1/3Mn1/3O2。
The positive electrode that embodiment 1 obtains is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, and with n-methyl-2-pyrrolidone (NMP) for solvent, 80:12:8 in mass ratio weighs positive material respectively
Material and gathers inclined tetrafluoroethene (PVDF) at acetylene black, after ground and mixed is uniform, is coated on pretreated aluminium foil, and it is dry to be put into vacuum
Positive plate is dried to obtain at 80 DEG C in dry case.Pure metal lithium piece makees cathode, and microporous polypropylene membrane Celgard 2325 is diaphragm,
The mixed solution of LB315 [m(DMC): m(EMC): m(EC)=1:1:1] is as electrolyte, full of (H in argon gas glove box2O contains
Amount < 1ppm) it is assembled into button cell.Constant current cyclic charging and discharging test is carried out to button cell with LAND battery test system；
In test voltage 2.5-4.6V, under the conditions of test voltage 2.5-4.6V, the charge and discharge of 0.1C, room temperature first discharge specific capacity is
192.6 mAh·g-1(shown in Fig. 4), capacity retention ratio is shown in 90.4%(Fig. 5 after charge and discharge 50 circulations under 0.2C), it is different
Specific discharge capacity under multiplying power 0.1C, 0.2C, 0.5C and 1C is respectively 192.6 mAhg-1、181.5 mAh·g-1、165.2
mAh·g-1With 144.6 mAhg-1, when current density turns again to 0.1C, specific discharge capacity still has 186.3 mAhg-1(figure
Shown in 6).
Embodiment 2
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:8 in molar ratio, and solution is mixed, and 200 turns of low whipping speed/
It is stirred 4 hours under conditions of minute；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized 3 times, dehydrated alcohol is washed
It washs 3 times, obtains manganese carbonate microballoon；
(3) manganese carbonate being placed in Muffle furnace and is calcined, heating rate is 4 DEG C/min, is warming up to 450 DEG C, it calcines 4 hours,
Obtain hollow manganese dioxide microballoon；
(4) lithium acetate, hollow manganese dioxide microballoon, nickel acetate and acetic acid are weighed at 1.05: 1/3: 1/3: 1/3 in molar ratio
Dehydrated alcohol is added in cobalt, by manganese dioxide suspension (not dissolving in dehydrated alcohol), lithium acetate solution, Ni-acetate solution and acetic acid
Cobalt liquor is blended in a clean large beaker；
(5) (4) obtained mixture is placed in 70 DEG C of thermostat water baths, continuously stirred with 200 revs/min of speed until
Dehydrated alcohol volatilization completely, is precipitated；
(6) precipitating obtained by (5) is placed in air dry oven drying 12 hours under the conditions of 80 DEG C, to remove residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 4 DEG C/min, is warming up to 400 DEG C, calcining 6
Hour, obtain presoma；
(8) presoma is placed in ball mill to grind to be placed in Muffle furnace for 1 hour and is calcined, calcination temperature is 850 DEG C, is forged
Burning the time is 20 hours, is ground after cooling to get the ternary cathode material of lithium ion battery with hollow structure
LiNi1/3Co1/3Mn1/3O2。
The positive electrode that embodiment 2 obtains is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, and with n-methyl-2-pyrrolidone (NMP) for solvent, 80:12:8 in mass ratio weighs positive material respectively
Material and gathers inclined tetrafluoroethene (PVDF) at acetylene black, after ground and mixed is uniform, is coated on pretreated aluminium foil, and it is dry to be put into vacuum
Positive plate is dried to obtain at 80 DEG C in dry case.Pure metal lithium piece makees cathode, and microporous polypropylene membrane Celgard 2325 is diaphragm,
The mixed solution of LB315 [m(DMC): m(EMC): m(EC)=1:1:1] is as electrolyte, full of (H2O contains in argon gas glove box
Amount < 1ppm) it is assembled into simulated battery.Constant current cyclic charging and discharging test is carried out with LAND battery test system button type battery；
Under the conditions of test voltage 2.5-4.6V, the charge and discharge of 0.1C, room temperature first discharge specific capacity is 190.5 mAhg-1,0.2C
Capacity retention ratio is 88.9% after lower charge and discharge 50 circulations.
Embodiment 3
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:12 in molar ratio, and solution is mixed, low whipping speed 500
It is stirred 3 hours under conditions of rev/min；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized 4 times, dehydrated alcohol is washed
It washs 2 times, obtains manganese carbonate microballoon；
(3) manganese carbonate being placed in Muffle furnace and is calcined, heating rate is 5 DEG C/min, is warming up to 500 DEG C, it calcines 5 hours,
Obtain hollow manganese dioxide microballoon；
(4) lithium carbonate, hollow manganese dioxide microballoon, nickelous carbonate and carbonic acid are weighed at 1.05: 1/3: 1/3: 1/3 in molar ratio
Deionized water is added in cobalt, and lithium hydroxide suspension (being slightly soluble in dehydrated alcohol), manganese dioxide suspension (are not dissolved in anhydrous second
Alcohol), nickel nitrate solution and cobalt nitrate solution be blended in a clean large beaker；
(5) (4) obtained mixture is placed in 60 DEG C of thermostat water baths, continuously stirred with 500 revs/min of speed until
Deionized water volatilization completely, is precipitated；
(6) precipitating obtained by (5) is placed in air dry oven drying 10 hours under the conditions of 120 DEG C, to remove residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 6 DEG C/min, is warming up to 600 DEG C, calcining 7
Hour, obtain presoma；
(8) presoma is placed in ball mill to grind to be placed in Muffle furnace for 2 hours and is calcined, calcination temperature is 950 DEG C, is forged
Burning the time is 12 hours, is ground after cooling to get the ternary cathode material of lithium ion battery with hollow structure
LiNi1/3Co1/3Mn1/3O2。
The positive electrode that embodiment 3 obtains is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, and with n-methyl-2-pyrrolidone (NMP) for solvent, 80:12:8 in mass ratio weighs positive material respectively
Material and gathers inclined tetrafluoroethene (PVDF) at acetylene black, after ground and mixed is uniform, is coated on pretreated aluminium foil, and it is dry to be put into vacuum
Positive plate is dried to obtain at 80 DEG C in dry case.Pure metal lithium piece makees cathode, and microporous polypropylene membrane Celgard 2325 is diaphragm,
The mixed solution of LB315 [m(DMC): m(EMC): m(EC)=1:1:1] is as electrolyte, full of (H in argon gas glove box2O contains
Amount < 1ppm) it is assembled into simulated battery.Constant current cyclic charging and discharging test is carried out with LAND battery test system button type battery；
Under the conditions of test voltage 2.5-4.6V, the charge and discharge of 0.1C, room temperature first discharge specific capacity is 191 mAh/g, is filled under 0.2C
The capacity retention ratio after recycling that discharges 50 is 89.7%.
Embodiment 4
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:9 in molar ratio, and solution is mixed, and low whipping speed 200~
It is stirred 3 hours under conditions of 500 revs/min；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized 3 times, dehydrated alcohol is washed
It washs 2 times, obtains manganese carbonate microballoon；
(3) manganese carbonate is placed in Muffle furnace and is calcined, heating rate is 5 DEG C/min, is warming up to 500 DEG C, calcining 3~5 is small
When, obtain hollow manganese dioxide microballoon；
(4) lithium acetate and lithium nitrate, manganese dioxide, nickel acetate and nitric acid are weighed at 1.05: 1/3: 1/3: 1/3 in molar ratio
Deionized water is added in nickel, cobalt acetate and cobalt nitrate, and manganese dioxide suspension (not soluble in water), lithium acetate solution, nickel acetate is molten
Liquid and acetic acid cobalt liquor are blended in a clean large beaker；
(5) (4) obtained mixture is placed in 80 DEG C of thermostat water baths, is continuously stirred with 200~500 revs/min of speed
It mixes until deionized water volatilization completely, is precipitated；
(6) precipitating obtained by (5) is placed in air dry oven drying 10 hours under the conditions of 110 DEG C, to remove residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 5 DEG C/min, is warming up to 400 DEG C, calcining 8
Hour, obtain presoma；
(8) presoma is placed in ball mill to grind to be placed in Muffle furnace for 3 hours and is calcined, calcination temperature is 850 DEG C, is forged
Burning the time is 10 hours, is ground after cooling to get the ternary cathode material of lithium ion battery with hollow structure
LiNi1/3Co1/3Mn1/3O2。
The positive electrode that embodiment 4 obtains is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, and with n-methyl-2-pyrrolidone (NMP) for solvent, 80:12:8 in mass ratio weighs positive material respectively
Material and gathers inclined tetrafluoroethene (PVDF) at acetylene black, after ground and mixed is uniform, is coated on pretreated aluminium foil, and it is dry to be put into vacuum
Positive plate is dried to obtain at 80 DEG C in dry case.Pure metal lithium piece makees cathode, and microporous polypropylene membrane Celgard 2325 is diaphragm,
The mixed solution of LB315 [m(DMC): m(EMC): m(EC)=1:1:1] is as electrolyte, full of (H in argon gas glove box2O contains
Amount < 1ppm) it is assembled into simulated battery.Constant current cyclic charging and discharging test is carried out with LAND battery test system button type battery；
Under the conditions of test voltage 2.5-4.6V, the charge and discharge of 0.1C, room temperature first discharge specific capacity is 191.5 mAh/g, under 0.2C
Capacity retention ratio is 89% after charge and discharge 50 circulations.
Claims (7)
1. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, which is characterized in that the positive electrode
Chemical general formula be LiNi1/3Co1/3Mn1/3O2, comprising the following steps:
(1) manganese sulfate, ammonium hydrogen carbonate are dissolved in deionized water by 1:8-12 in molar ratio, and solution is mixed, low whipping speed
It is stirred 2-4 hours under conditions of 200-500 revs/min；
(2) suspension obtained by (1) is placed in circulating water type vacuum pump and is filtered, and be washed with deionized at least 3 times, anhydrous second
Alcohol washs at least 2 times, obtains manganese carbonate microballoon；
(3) manganese carbonate microballoon is placed in Muffle furnace and is calcined, be warming up to 400-500 DEG C with the heating rate of 4-6 DEG C/min,
Calcining 3-5 hours, obtains hollow manganese dioxide microballoon；
(4) solvent is added in hollow manganese dioxide microballoon, lithium salts, nickel salt and cobalt salt with continuous stirring in molar ratio to be mixed
Uniform suspension；
(5) suspension for obtaining (4) 60-80 DEG C at a temperature of with 200-500 revs/min of speed agitating and heating until molten
Agent volatilization completely, is precipitated；
(6) precipitating that (5) obtain is placed in air dry oven drying 10-12 hours under the conditions of 80-120 DEG C, is driven with evaporating
Except residual solvent；
(7) precipitating after drying is placed in Muffle furnace and is calcined, heating rate is 4-6 DEG C/min, calcination temperature 400-
600 DEG C, calcination time is 6-8 hours, obtains presoma；
(8) presoma is placed in ball mill after grinding 1-3 hours and is calcined, calcination temperature is 850-950 DEG C, calcination time
It is 10-20 hours, grinds after cooling to get the ternary cathode material of lithium ion battery LiNi with hollow structure1/3Co1/ 3Mn1/3O2。
2. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, feature exist as described in claim 1
In the solvent in the step (4) is at least one of dehydrated alcohol, deionized water.
3. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, feature exist as described in claim 1
In the molar ratio of, lithium salts in the step (4), hollow manganese dioxide microballoon, nickel salt, cobalt salt be 1.05: 1/3: 1/3:
1/3。
4. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, feature exist as described in claim 1
In the lithium salts in the step (4) is at least one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide.
5. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, feature exist as described in claim 1
In the nickel salt in the step (4) is at least one of nickelous carbonate, nickel nitrate, nickel acetate.
6. the preparation method of the ternary cathode material of lithium ion battery with hollow structure, feature exist as described in claim 1
In the cobalt salt in the step (4) is at least one of cobalt carbonate, cobalt nitrate, cobalt acetate.
7. the ternary cathode material of lithium ion battery with hollow structure that the preparation method as described in claim 1-6 is any obtains
LiNi1/3Co1/3Mn1/3O2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463428A (en) * | 2020-04-15 | 2020-07-28 | 江南大学 | Sodium ion doped ternary cathode material and preparation method thereof |
| CN114275827A (en) * | 2021-12-16 | 2022-04-05 | 河源职业技术学院 | Method for preparing ternary composite material by using manganese dioxide nanorod precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450278A (en) * | 2016-11-03 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Ternary positive electrode material with hollow microsphere structure, preparation method and application |
| CN106450284A (en) * | 2016-11-25 | 2017-02-22 | 桂林理工大学 | Method for preparing hollow-microsphere lithium manganate positive electrode material with higher electrochemical properties |
| CN106981654A (en) * | 2017-03-31 | 2017-07-25 | 哈尔滨工业大学（威海） | A kind of preparation method of high-voltage lithium-battery cathode material hollow ball shape nickel ion doped |
-
2018
- 2018-09-04 CN CN201811024154.9A patent/CN108987743A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450278A (en) * | 2016-11-03 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Ternary positive electrode material with hollow microsphere structure, preparation method and application |
| CN106450284A (en) * | 2016-11-25 | 2017-02-22 | 桂林理工大学 | Method for preparing hollow-microsphere lithium manganate positive electrode material with higher electrochemical properties |
| CN106981654A (en) * | 2017-03-31 | 2017-07-25 | 哈尔滨工业大学（威海） | A kind of preparation method of high-voltage lithium-battery cathode material hollow ball shape nickel ion doped |
Non-Patent Citations (1)
| Title |
|---|
| JILI LI等: ""LiNi1/3Co1/3Mn1/3O2 hollow nano-micro hierarchical microspheres with enhanced performances as cathodes for lithium-ion batteries"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463428A (en) * | 2020-04-15 | 2020-07-28 | 江南大学 | Sodium ion doped ternary cathode material and preparation method thereof |
| CN114275827A (en) * | 2021-12-16 | 2022-04-05 | 河源职业技术学院 | Method for preparing ternary composite material by using manganese dioxide nanorod precursor |
| CN114275827B (en) * | 2021-12-16 | 2023-10-31 | 河源职业技术学院 | Method for preparing ternary composite material by manganese dioxide nanorod precursor |
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Application publication date: 20181211 |