CN105336944A - High-capacity cathode material for lithium ion batteries and preparation method thereof - Google Patents
High-capacity cathode material for lithium ion batteries and preparation method thereof Download PDFInfo
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- CN105336944A CN105336944A CN201510906729.XA CN201510906729A CN105336944A CN 105336944 A CN105336944 A CN 105336944A CN 201510906729 A CN201510906729 A CN 201510906729A CN 105336944 A CN105336944 A CN 105336944A
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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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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 high-capacity cathode material for lithium ion batteries and a preparation method thereof. The high-capacity cathode material is LiNi1-x-yCoxAlyO2. While Nickel sulfate solution rich in nickel is added into mixed solution of nickel, cobalt and aluminum poor in nickel, the mixed solution is added to a reaction tank; sodium hydroxide and ammonia-water solution are added into the reaction tank, and a coprecipitate Ni1-x-yCoxAly(OH)2+y precursor is prepared; the precursor undergoes ageing, filtration, washing and drying and then is mixed with a lithium source, and the mixed material is formed by compression; the material formed by compression is placed in a tube furnace to be presintered and sintered in oxygen airflow or oxygen-enriched air flow, and a target product is obtained. The prepared high-capacity cathode material for the lithium ion batteries is free of impure phase and high in crystallization quality, the product particle size distribution is uniform, the high-capacity cathode material has very high discharged specific capacity and cycling stability, an operation process is simple, raw material sources are extensive, the manufacturing cost is low, and large-scale industrial production is achieved easily.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of anode material for lithium ion battery with high power capacity and preparation method thereof.
Background technology
Along with going from bad to worse and the exhaustion of the resource such as oil of global environment, the research and development of energy-saving and emission-reduction and green energy resource are extremely urgent, all pay much attention to the development & application about new forms of energy and renewable and clean energy resource both at home and abroad.Lithium ion battery is the energy of wherein a kind of more promising novel environmental protection.Owing to having, energy density is high, quickly-chargeable, self discharge are little, can the advantage such as long-time storage, cycle performance is superior, memory-less effect, working temperature are wide, lightweight, lithium ion battery has been widely used on various portable electric appts, is also expected to the power source being applied to electric automobile and hybrid vehicle soon.For lithium-ion-power cell, energy density is its important indicator parameter, because it is directly connected to the course continuation mileage of electric automobile and the stream time of electrical source of power.And the energy density of lithium ion battery depends primarily on it manufactures positive electrode used.The energy density lithium ion power battery positive electrode that Tesla (CS) Koncern, Podebradska 186, Praha 9, Czechoslovakia of the current U.S. uses is also blank at present at home substantially.The positive electrode being applied to lithium ion battery at present in batches mainly contains cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2), LiFePO4 (LiFePO
4), nickle cobalt lithium manganate and (LiMn
2o
4).Wherein, cobalt acid lithium realizes commercial applications the earliest, have ripe large-scale production technology, and be widely used on lower powered mobile electronic products, but cobalt resource is deficient, expensive, and toxicity is comparatively large not environmentally; The aboundresources of lithium manganate battery manganese, cheap, environmentally safe, deintercalation current potential is high, and power density is comparatively large, but low capacity and unstable cycle performance limit its application; Lithium iron phosphate positive material environment-protecting asepsis, rich in mineral resources, low raw-material cost, temperature tolerance is splendid, stable circulation performance is superior, but its conductivity is poor, and density is little, volume is large, and energy density is low and cryogenic property is not good enough, and its application and development is all restricted.Lithium nickelate (LiNiO
2) positive electrode and LiCoO
2positive electrode is all the material with layer structure, its specific discharge capacity is very high ~ and 210mAh/g (LiCoO
2~ 140mAh/g), power density and energy density are large, good electric conductivity, relatively cheap price and lower toxicity, the lithium nickelate positive electrode made get a good chance of replace lithium cobaltate cathode material, especially electric automobile and mixed power electric car application prospect better.But lithium nickelate preparation condition is harsh, the not easily product of obtained ideal stoichiometric ratio, has the safety problem of the precipitation of oxygen, limits the process that it is practical in the poor and charging process of thermal stability.
Existing lithium ionic cell nickel acid lithium (LiNiO
2) positive electrode electrochemistry cycle performance is poor, poor heat stability, poor safety performance.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium ion battery with high power capacity and preparation method thereof, be intended to solve existing lithium ionic cell nickel acid lithium (LiNiO
2) positive electrode electrochemistry cycle performance is poor, the problem of poor heat stability, poor safety performance.
The present invention is achieved in that a kind of preparation method of anode material for lithium ion battery with high power capacity, and the preparation method of described anode material for lithium ion battery with high power capacity comprises the following steps:
Step one, by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is dissolved in appropriate amount of deionized water, joins mol ratio is Ni
2+: Co
2+: Al
3+rich nickel solution A (0.1≤m≤0.4) of 1.5mol/L of=(1-x-y-m): x:y=(1-m): 0:0;
Step 2, by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is Ni in molar ratio
2+: Co
2+: Al
3+=m:x:y=(20m): 3:1 is dissolved in appropriate amount of deionized water, joins to obtain isopyknic poor nickel solution B (0.1≤m≤0.4);
Step 3, add in solution B by solution A with the speed of 10mL ~ 10L/min (V), strong agitation makes it mix;
Step 4, simultaneously by the solution that mixes at N
2add in reactive tank (container C) with the speed (2V) doubling solution A under protection, isopyknic A liquid and B liquid are exhausted simultaneously;
Step 5, simultaneously in step 4 gained mixed solution and drip adds the NaOH solution of ammoniacal liquor and 4mol/L, adjust ph is 11.0, and reaction temperature of simultaneously controlling well is 50 DEG C and mixing speed is 600rpm;
Step 6, by the still aging 12h of step 5 gained co-precipitation liquid, after ageing liquid being filtered and repeatedly washing, vacuumize 24h at 105 DEG C;
Step 7, fully mixes dry for step 6 gained presoma with lithium source, compressing after mixing;
Step 8, by step 7 gained molding materials product pre-burning 4h ~ 8h at 450 ~ 550 DEG C, sinters 16h ~ 24h at 680 DEG C ~ 850 DEG C temperature, namely obtains target product LiNi under oxygen flow or oxygen-enriched air air-flow
1-x-yco
xal
yo
2.
Further, 0<x≤0.2,0≤y≤0.1,0<x+y≤0.3, x >=3y; 0.1≤m≤0.4.
Further, the mol ratio of described lithium source raw material, nickel source raw material, cobalt source raw material and aluminium source raw material is (1.05 ~ 1.15): (1-x-y): x: y, x >=3y.
Further, described LiNi
1-x-yco
xal
yo
2anode material series adopts liquid phase method to prepare in conjunction with solid phase method.
Further, described lithium source raw material is at least one in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium citrate, lithium oxalate.
Further, described nickel source raw material is at least one in nickel nitrate, nickelous sulfate, nickel oxide, nickel chloride, nickel hydroxide, nickel acetate.
Further, described cobalt source raw material is at least one in cobalt nitrate, cobaltous sulfate, cobalt oxide, cobalt chloride, cobalt hydroxide, cobalt acetate.
Further, described aluminium source raw material is at least one in aluminum nitrate, aluminium oxide, aluminum sulfate, aluminium chloride, aluminum trifluoride, aluminum phosphate.
Another object of the present invention is to the anode material for lithium-ion batteries providing a kind of preparation method of described anode material for lithium ion battery with high power capacity to prepare, described anode material for lithium-ion batteries LiNi
1-x-yco
xal
yo
2, be the ternary layered positive electrode of cobalt, aluminium doped and substituted nickel; And the positive electrode obtained is the controlled gradient anode material of a kind of surface and body phase Co and Al concentration.
Anode material for lithium ion battery with high power capacity provided by the invention and preparation method thereof, compared with prior art, has following advantage:
1, the anode material for lithium-ion batteries LiNi of synthesis
0.8co
0.15al
0.05o
2there is very high specific discharge capacity and excellent stable circulation performance, the energy density of lithium-ion-power cell can be significantly improved and meet lithium-ion-power cell high rate charge-discharge demand, its preparation method overcomes solid-phase synthesis preparation time length, is difficult to control stoichiometric proportion, particle size skewness and the shortcoming such as chemical property is poor, the product purity of preparation is high, crystalline quality is high, regular appearance, product grain density large and be evenly distributed, excellent electrochemical performance and low cost of manufacture.Be particularly suitable for making current electric automobile lithium-ion-power cell.
2, the present invention obtains anode material for lithium-ion batteries LiNi by the elemental nickel (Ni) that doping triad aluminium (Al) and diad cobalt (Co) replace in positive electrode simultaneously
0.8co
0.15al
0.05o
2.Aluminium is III Main Group Metal Elements, and its valence state is+3 valencys, and the trivalent aluminium ion nickel element replaced in positive electrode can improve the thermal stability of positive electrode.Cobalt is the transition metal close with nickel, and its valence state is+divalent.The introducing of cobalt ions can improve the structure of nickel system layered cathode material and the difficulty of preparation; Improve the structural stability of nickel system positive electrode, improve conductivity, increase the cycle life of positive electrode.
3, the present invention adopts graded concentration (solubility gradient) co-precipitation-solid-phase synthesis to prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2and LiNi
0.75co
0.2al
0.05o
2.Compared with pure solid-phase synthesis, the preparation technology of graded concentration (solubility gradient) co-precipitation-solid-phase synthesis is simple, the time shorten of sintering, the temperature of sintering reduces, therefore power consumption significantly reduces, and product has good spherical morphology, is evenly distributed, processing coating (coating) easy to use, is convenient to suitability for industrialized production application.
4, the present invention adopts graded concentration (solubility gradient) coprecipitation, Ni in the process of reaction
2+solubility increase gradually, Co
2+, Al
3+solubility gradually reduce, the speed of precipitation is controlled by ammoniacal liquor complexing agent, reaction raw materials fully precipitates, and overcomes the shortcoming of conventional solid synthetic method and coprecipitation method, the product crystalline quality of preparation is excellent, chemical composition close to theoretical value, product phase purity is high, layer structure is excellent.
5, the layered lithium ion battery positive electrode LiNi for preparing of the present invention
0.8co
0.15al
0.05o
2in, doping+divalent metallic cobalt element ,+3 valency aluminium elements, fully by means of the advantage of each doped chemical, can improve the combination property of positive electrode.
6, the layered lithium ion battery positive electrode LiNi for preparing of the present invention
0.8co
0.15al
0.05o
2there is very high specific discharge capacity and more excellent stable circulation performance, be applicable to the demand of electric automobile high-energy-density, high power discharge; Under room temperature environment, when constant current charge-discharge multiplying power is 0.2C, when voltage range is 2.75-4.3V, the first discharge specific capacity of this lithium ion battery positive electrode material in layer structure can reach 217mAh/g, circulate after 32 times, specific discharge capacity still can reach 195mAh/g, and capability retention is 90%.
7, in technique of the present invention, reaction raw material used are all general chemical products, and comparatively horn of plenty of originating, relative low price, manufacturing cost is lower.
8, in technique of the present invention, device therefor is simple, produces, both met environmental protection concept in preparation process without poisonous and harmful substance, is easy to again to realize large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the anode material for lithium ion battery with high power capacity that the embodiment of the present invention provides.
Fig. 2 be the embodiment of the present invention provide prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2xRD figure.
Fig. 3 be the embodiment of the present invention provide prepare precursor of lithium ionic cell positive material Ni
0.8co
0.15al
0.05(OH)
2+ δsEM figure.
Fig. 4 be the embodiment of the present invention provide prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2first charge-discharge curve chart under 0.2C multiplying power.
Fig. 5 be the embodiment of the present invention provide prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2cycle performance curve chart under 0.2C multiplying power.
Fig. 6 be the embodiment of the present invention provide prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2coulombic efficiency curve chart under 0.2C multiplying power.
Fig. 7 be the embodiment of the present invention provide prepare anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2first charge-discharge curve chart under 0.5C multiplying power.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Below in conjunction with accompanying drawing, application principle of the present invention is further described.
The anode material for lithium-ion batteries LiNi of the embodiment of the present invention
1-x-yco
xal
yo
2, the ternary layered positive electrode of cobalt, aluminium doped and substituted nickel.Wherein: 0<x≤0.2,0≤y≤0.1,0<x+y≤0.3, x >=3y.
As shown in Figure 1, the preparation method of the anode material for lithium-ion batteries of the embodiment of the present invention comprises the following steps:
S101: by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is dissolved in appropriate amount of deionized water, joins mol ratio is Ni
2+: Co
2+: Al
3+rich nickel solution A (0.1≤m≤0.4) of 1.5mol/L of=(1-x-y-m): x:y=(1-m): 0:0;
S102: by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is Ni in molar ratio
2+: Co
2+: Al
3+=m:x:y=(20m): 3:1 is dissolved in appropriate amount of deionized water, joins to obtain isopyknic poor nickel solution B (0.1≤m≤0.4);
S103: add in solution B by solution A with the speed of 10mL/min ~ 10L/min (V), strong agitation makes it mix;
S104: simultaneously by the solution that mixes at N
2add in reactive tank (container C) with the speed (2V) doubling solution A under protection, isopyknic A liquid and B liquid are exhausted simultaneously;
S105: simultaneously in step S104 gained mixed solution and drip adds the NaOH solution of ammoniacal liquor and 4mol/L, adjust ph is 11.0, reaction temperature of simultaneously controlling well is 50 DEG C and mixing speed is 600rpm;
S106: by the still aging 12h of step S105 gained co-precipitation liquid, after ageing liquid being filtered and repeatedly washing, vacuumize 24h at 105 DEG C;
S107: dry for step S106 gained presoma is fully mixed with lithium source, compressing after mixing;
S108: by step S107 gained shaped article pre-burning 4h ~ 8h at 450 ~ 550 DEG C, sinters 16h ~ 24h at 680 DEG C ~ 850 DEG C temperature, namely obtains target product LiNi under oxygen flow or oxygen-enriched air air-flow
1-x-yco
xal
yo
2(0<x≤0.2,0≤y≤0.1,0<x+y≤0.3, x>=3y).
The mol ratio of described lithium source raw material, nickel source raw material, cobalt source raw material and aluminium source raw material is (1.05 ~ 1.15): (1-x-y): x: y.
Described LiNi
1-x-yco
xal
yo
2anode material series adopts liquid phase method to prepare in conjunction with solid phase method.
Described lithium source raw material is at least one in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium citrate, lithium oxalate.
Described nickel source raw material is at least one in nickel nitrate, nickelous sulfate, nickel oxide, nickel chloride, nickel hydroxide, nickel acetate.
Described cobalt source raw material is at least one in cobalt nitrate, cobaltous sulfate, cobalt oxide, cobalt chloride, cobalt hydroxide, cobalt acetate.
Described aluminium source raw material is at least one in aluminum nitrate, aluminium oxide, aluminum sulfate, aluminium chloride, aluminum trifluoride, aluminum phosphate.
Below in conjunction with specific embodiment, application principle of the present invention is further described.
Embodiment 1:
Technical scheme of the present invention is: anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2and LiNi
0.75co
0.2al
0.05o
2.
Anode material for lithium-ion batteries LiNi
0.8co
0.15al
0.05o
2preparation method, it is characterized in that, comprise the following steps:
Step 1.NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is Ni in molar ratio
2+: Co
2+: Al
3+=(1-x-y-m): x:y=(1-m): 0:0 is dissolved in appropriate amount of deionized water, joins to obtain 1.5mol/L solution A; (0.1≤m≤0.4)
Step 2.NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is Ni in molar ratio
2+: Co
2+: Al
3+=m:x:y=(20m): 3:1=2:3:1 (m=0.1) is dissolved in appropriate amount of deionized water, joins to obtain solution B isopyknic with solution A;
Solution A adds in solution B according to the speed of 20mL/min by step 3., and vigorous stirring makes it mix;
The solution mixed adds in reactive tank (container C) according to the speed of 40mL/min by step 4., and isopyknic A liquid and B liquid are exhausted simultaneously;
Step 5. is in step 4 gained mixed solution and drip adds the NaOH solution of ammoniacal liquor and 4mol/L, and adjust ph is 11.0, the speed that reaction temperature of simultaneously controlling well is 50 DEG C and stirs;
Step 6. by the still aging 12h of step 5 gained precipitated liquid, by ageing liquid filter and repeatedly washing after, vacuumize 24h at 105 DEG C;
Dry for step 6 gained presoma fully mixes with excessive hydrogen lithia by step 7., is pressed into given shape after mixing;
Step 8., by step 7 gained molding materials pre-burning 4h at 480 DEG C, sinters 16h ~ 24h at 690 DEG C ~ 820 DEG C temperature, namely obtains target product LiNi under Oxygen Flow
0.8co
0.15al
0.05o
2.
Embodiment 2
0.30mol nickelous sulfate is dissolved in 200mL deionized water, makes it dissolve completely and obtain (rich nickel) solution A; 0.10mol nickelous sulfate, 0.075mol cobaltous sulfate and 0.025mol aluminum nitrate are dissolved in 200mL deionized water and prepare to obtain salt-mixture (poor nickel) solution B;
Solution A is joined in mixing salt solution B with the speed of 10mL/min, and constantly stir, the mixed solution adding the B liquid of A liquid is joined in the stirred tank (container C) under nitrogen protection with the speed of 20mL/min simultaneously, also stream adds the agent of 4mol/L sodium hydroxide pellets and 1mol/L ammoniacal liquor complexing agent simultaneously, and adjust ph is 11, it is 50 DEG C that reaction temperature controls, and mixing speed is 600rpm; Then the sediment at room temperature ageing 12h will obtained, then filters, washs multipass with hot deionized water, finally 105 DEG C of dry 24h in air dry oven.By dried presoma with excessive 8% ~ 12% lithium hydroxide mortar mix, compressing by powder compressing machine is given shape, be put in 450-550 DEG C of low temperature presintering 4h-8h in tube furnace again, then in oxygen/oxygen-enriched air air-flow, sinter 16-24h at (flow velocity is 200mL/min) 680-850 DEG C temperature, the lithium ion battery target positive electrode LiNi of layer structure can be obtained
0.8co
0.15al
0.05o
2.
To the lithium ion battery target positive electrode LiNi of preparation
0.8co
0.15al
0.05o
2carry out constant current charge-discharge test, can find out that this positive electrode has very high specific discharge capacity and comparatively excellent stable circulation performance from test result; Under room temperature environment, when constant current charge-discharge multiplying power is 0.2C, when voltage range is 2.75-4.3V, the first discharge specific capacity of this layered lithium ion battery positive electrode can reach 217mAh/g, circulate after 32 times, specific discharge capacity still can reach 195mAh/g, and capability retention is 90%.
Embodiment 3
0.30mol (80.056g) nickelous sulfate is dissolved in 200mL deionized water, makes it dissolve completely and obtain (rich nickel) solution A;
0.10mol (26.685g) nickelous sulfate, 0.075mol (21.1884g) cobaltous sulfate and 0.025mol (9.3783g) aluminum nitrate are dissolved in 200mL deionized water and prepare to obtain salt-mixture (poor nickel) solution B;
Mixing salt solution B is added in solution A with the speed of 15mL/min, and constantly stir, the mixed liquor of A liquid and B liquid is joined in the stirred tank (container C) under nitrogen protection with the speed of 30mL/min, simultaneously and stream adds the agent of 4mol/L sodium hydroxide pellets and 1mol/L ammoniacal liquor complexing agent adjust ph is 11, it is 50 DEG C that reaction temperature controls, and mixing speed is 600rpm; Then by ageing 12h under the sediment room temperature that obtains, then filter, wash multipass with hot deionized water, finally 105 DEG C of dry 24h in air dry oven.By dried presoma with excessive 8% lithium hydroxide 0.54mol (22.695g) mix with mortar, compressing by powder compressing machine, be put in 450-550 DEG C of low temperature presintering 4h-8h in tube furnace again, then in oxygen/oxygen-enriched air air-flow, sinter 16-24h at (200mL/min) 690-820 DEG C of temperature, the lithium ion battery target positive electrode LiNi of layer structure can be obtained
0.8co
0.15al
0.05o
2.
To the lithium ion battery target positive electrode LiNi of preparation
0.8co
0.15al
0.05o
2carry out constant current charge-discharge test, can find out that this positive electrode has very high specific discharge capacity and comparatively excellent stable circulation performance from test result; Under room temperature environment, when constant current charge-discharge multiplying power is 0.2C, when voltage range is 2.75-4.3V, the first discharge specific capacity of this layered lithium ion battery positive electrode can reach 217.5mAh/g, circulate after 30 times, specific discharge capacity still can reach 194.5mAh/g, and capability retention is 90%.
Embodiment 4
0.30mol nickelous sulfate is dissolved in 200mL deionized water, makes it dissolve completely and obtain (rich nickel) solution A; 0.075mol nickelous sulfate, 0.10mol cobaltous sulfate and 0.025mol aluminum nitrate are dissolved in 200mL deionized water and prepare to obtain salt-mixture (poor nickel) solution B;
Solution A is joined in mixing salt solution B with the speed of 10mL/min, and constantly stir, the mixed solution adding the B liquid of A liquid is joined in the stirred tank (container C) under nitrogen protection with the speed of 20mL/min simultaneously, also stream adds the agent of 4mol/L sodium hydroxide pellets and 1mol/L ammoniacal liquor complexing agent simultaneously, and adjust ph is 11, it is 50 DEG C that reaction temperature controls, and mixing speed is 600rpm; Then the sediment at room temperature ageing 12h will obtained, then filters, washs multipass with hot deionized water, finally 105 DEG C of dry 24h in air dry oven.By dried presoma with excessive 8% lithium hydroxide mortar mix, compressing by powder compressing machine is given shape, be put in 450-550 DEG C of low temperature presintering 4h-8h in tube furnace again, then in oxygen/oxygen-enriched air air-flow, sinter 16-24h at (flow velocity is 200mL/min) 690-850 DEG C temperature, the lithium ion battery target positive electrode LiNi of layer structure can be obtained
0.75co
0.20al
0.05o
2.
To the lithium ion battery target positive electrode LiNi of preparation
0.75co
0.20al
0.05o
2carry out constant current charge-discharge test, can find out that this positive electrode still has very high specific discharge capacity and comparatively excellent stable circulation performance from test result; Under room temperature environment, when constant current charge-discharge multiplying power is 0.2C, when voltage range is 2.75-4.3V, the first discharge specific capacity of this layered lithium ion battery positive electrode can reach 210mAh/g, circulate after 30 times, specific discharge capacity still can reach 190mAh/g, and capability retention is greater than 90%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for anode material for lithium ion battery with high power capacity, is characterized in that, the preparation method of described anode material for lithium ion battery with high power capacity comprises the following steps:
Step one, by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is dissolved in appropriate amount of deionized water, joins mol ratio is Ni
2+: Co
2+: Al
3+the rich nickel solution A of 1.5mol/L of=(1-x-y-m): x:y=(1-m): 0:0,0.1≤m≤0.4;
Step 2, by NiSO
46H
2o, CoSO
47H
2o and Al (NO
3)
39H
2o is Ni in molar ratio
2+: Co
2+: Al
3+=m:x:y=(20m): 3:1 is dissolved in appropriate amount of deionized water, joins to obtain isopyknic poor nickel solution B, 0.1≤m≤0.4;
Step 3, adds in solution B by solution A with the speed V of 10mLmin ~ 10L/min, and strong agitation makes it mix;
Step 4, simultaneously by the solution that mixes at N
2add in reactive tank with the speed 2V doubling solution A under protection, isopyknic A liquid and B liquid are exhausted simultaneously;
Step 5, simultaneously in step 4 gained mixed solution and drip adds the NaOH solution of ammoniacal liquor and 4mol/L, adjust ph is 11.0, and reaction temperature of simultaneously controlling well is 50 DEG C and mixing speed is 600rpm;
Step 6, by the still aging 12h of step 5 gained co-precipitation liquid, after ageing liquid being filtered and repeatedly washing, vacuumize 24h at 105 DEG C;
Step 7, fully mixes dry for step 6 gained presoma with lithium source, compressing after mixing;
Step 8, by step 7 gained shaped article pre-burning 4h ~ 8h at 450 ~ 550 DEG C, sinters 16h ~ 24h at 680 DEG C ~ 850 DEG C temperature, namely obtains target product LiNi under oxygen flow or oxygen-enriched air air-flow
1-x-yco
xal
yo
2.
2. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, is characterized in that, 0<x≤0.2,0≤y≤0.1,0<x+y≤0.3, x >=3y.
3. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, it is characterized in that, the mol ratio of described lithium source raw material, nickel source raw material, cobalt source raw material and aluminium source raw material is (1.05 ~ 1.15): (1-x-y): x: y, x >=3y.
4. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, is characterized in that, described LiNi
1-x-yco
xal
yo
2anode material series adopts liquid phase method to prepare in conjunction with solid phase method.
5. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, it is characterized in that, described lithium source raw material is at least one in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium citrate, lithium oxalate.
6. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, it is characterized in that, described nickel source raw material is at least one in nickel nitrate, nickelous sulfate, nickel oxide, nickel chloride, nickel hydroxide, nickel acetate.
7. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, it is characterized in that, described cobalt source raw material is at least one in cobalt nitrate, cobaltous sulfate, cobalt oxide, cobalt chloride, cobalt hydroxide, cobalt acetate.
8. the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, it is characterized in that, described aluminium source raw material is at least one in aluminum nitrate, aluminium oxide, aluminum sulfate, aluminium chloride, aluminum trifluoride, aluminum phosphate.
9. the anode material for lithium-ion batteries prepared of the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, is characterized in that, described anode material for lithium-ion batteries LiNi
1-x-yco
xal
yo
2, the ternary layered positive electrode of cobalt, aluminium doped and substituted nickel.
10. the anode material for lithium-ion batteries prepared of the preparation method of anode material for lithium ion battery with high power capacity as claimed in claim 1, is characterized in that, the positive electrode obtained is the controlled gradient anode material of a kind of surface and body phase Co and Al concentration.
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| CN106207138A (en) * | 2016-09-20 | 2016-12-07 | 中国科学院化学研究所 | A kind of method for preparing anode material of lithium-ion battery and application thereof |
| CN106315694A (en) * | 2016-07-28 | 2017-01-11 | 天津巴莫科技股份有限公司 | Preparation method of doped lithium nickel cobalt oxide precursor |
| CN106532029A (en) * | 2016-12-28 | 2017-03-22 | 四川富骅新能源科技有限公司 | High-voltage ternary positive electrode material for lithium-ion battery and preparation method of high-voltage ternary positive electrode material |
| CN108598379A (en) * | 2018-02-08 | 2018-09-28 | 中南大学 | A kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material and its preparation method and application |
| CN109119711A (en) * | 2018-07-16 | 2019-01-01 | 昆明理工大学 | A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery |
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| CN109119711A (en) * | 2018-07-16 | 2019-01-01 | 昆明理工大学 | A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery |
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