CN106058237A - Method for continuously preparing nanoflower lithium ion battery layered anode material and reaction kettle thereof - Google Patents

Method for continuously preparing nanoflower lithium ion battery layered anode material and reaction kettle thereof Download PDF

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CN106058237A
CN106058237A CN201610532087.6A CN201610532087A CN106058237A CN 106058237 A CN106058237 A CN 106058237A CN 201610532087 A CN201610532087 A CN 201610532087A CN 106058237 A CN106058237 A CN 106058237A
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reactor
lithium
anode material
reaction
continuously
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郭孝东
滑纬博
向伟
吴振国
钟本和
刘文元
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CHENGDU XIANGYU TECHNOLOGY Co Ltd
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CHENGDU XIANGYU TECHNOLOGY Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/48—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
    • 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
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    • 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

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Abstract

The invention provides a method for continuously preparing a nanoflower lithium ion battery layered anode material and a reaction kettle realizing the method. The method includes: (1), preparing a: preparing raw materials according to a chemical formula LiNixCoyMn1-x-yO2; (2), co-precipitating: using a co-precipitation method to obtain a reaction product, and subjecting the reaction product to aging, filtering, washing and drying to obtain precursor particles of a nanoflower structure; (3), calcining:calcining the precursor particles at high temperature to obtain the nanoflower lithium ion battery layered anode material. A template agent does not need to be added in the preparation process, and the particles are controllable in size, uniform in distribution and high in uniformity. Three layers of stirring paddles are arranged in the reaction kettle and stir at the same time, so that the materials are quick and uniform in reaction, and the particles are uniform and high in fluidity. By using the method, the lithium ion battery anode material in special nanoflower shape; the method is simple to operate, the reaction kettle is stable and reliable in structure, and industrial production is facilitated.

Description

Prepare method and the reactor thereof of nano flower layered cathode material of lithium ion battery continuously
Technical field
The present invention relates to the preparation method of a kind of layered cathode material, prepare nano flower lithium ion particularly to one continuously Battery laminated ternary positive material (LiNixCoyMn1-x-yO2) method, and provide a kind of novel reaction realizing the method Still, belongs to layered cathode material technical field.
Background technology
The energy be human survival and development important substance basis, the non-renewable energy resources gradually decreased along with the whole world and Increasingly serious environmental problem, the development and application of new forms of energy is very urgent, meets the development strategy of " beautiful China ".Lithium ion Battery receives significant attention because of advantages such as its energy density height, memory-less effect, noise-less pollutions, wherein negative material, barrier film With electrolyte achieved with relatively quantum jump, positive electrode slower development, become the bottleneck of restriction lithium ion battery development.Novel three Unit composite positive pole LiNixCoyMn1-x-yO2There is the features such as tap density is high, specific discharge capacity is high, cost is relatively low, it has also become One important development direction of positive electrode.
LiNi at presentxCoyMn1-x-yO2The preparation method of positive electrode mainly has solid phase method, sol-gal process, coprecipitation Deng.Wherein, solid phase method is easy and simple to handle, but the material granule skewness of preparation, particle diameter is relatively big, and chemical property is poor；Colloidal sol coagulates Though glue method can obtain purity height, the uniform material of composition, but technological process is complicated, and energy consumption is high, is unfavorable for that amplification test is implemented；Altogether The sedimentation method have that stoichiometric proportion is accurate, reproducible and the advantage such as technological process is simple, and beneficially large-scale production.Coprecipitated Shallow lake method is divided into again hydroxide co-precipitation, carbonate coprecipitation and oxalate coprecipitation etc., and wherein hydroxide coprecipitation step is Preparation LiNixCoyMn1-x-yO2A kind of method that material is the most frequently used, what the method obtained material tap density is high, distribution of particles Uniformly, and good processability.But in traditional hydroxide coprecipitation process, little crystal grain has the highest surface can meeting Assembling rapidly, make precursor second particle reunite serious, the high rate performance in turn resulting in final finished is not good enough, it is difficult to meet new one For lithium ion battery to high-energy-density and the demand of high power density.On the other hand, main coprecipitation technology mostly is Intermittent operation, needs to wait for a long time, air speed is slow, and unit cost is high；And intermittently operated easily cause batch stablize poor Disastrous effect.
Summary of the invention
The purpose of the present invention is as overcoming the deficiency in the presence of prior art just, it is provided that a kind of even continuously preparing nano Flower layered cathode material of lithium ion battery (LiNixCoyMn1-x-yO2) new method, and provide a kind of and realize the novel of the method Successive reaction still.When method of the present invention prepares layered cathode material of lithium ion battery, its pilot process need not add Template；Nano-particles size is controlled, even particle distribution, and concordance is good；And simple to operation, be conducive to industry metaplasia Produce.By improving tradition reactor whipped form, the material reaction Quick uniform in reactor can be made；And can continuous effective Prepare the lithium ion battery stratiform tertiary cathode material of nano flower special appearance, and high rate performance is high.
For realizing above-mentioned purpose of the present invention, the present invention is to use the technical scheme being made up of techniques below measure to realize 's.
Of the present invention prepare nano flower layered cathode material of lithium ion battery (LiNi continuouslyxCoyMn1-x-yO2) method, Comprise the following steps that:
(1) solution preparation
According to chemical formula LiNixCoyMn1-x-yO2Proportioning weigh nickel salt, cobalt salt and manganese salt raw material, and they are added together Enter in dissolving tank, be subsequently adding solvent, stir under normal pressure to being completely dissolved the mixing salt solution forming 0.5～3mol/L；With molten Agent and sodium hydroxide prepare 0.5～8mol/L sodium hydroxide solution, with solvent, strong aqua ammonia to be diluted to concentration be 1～12mol/L Ammonia spirit；The mol ratio of described x and y meets: 0.00≤x≤0.80；0.00≤y≤1.00；
(2) co-precipitation
By step (1) gained mixing salt solution, sodium hydroxide solution and ammonia spirit are infused in instead from material inlet respectively Answering in still, the feed rate controlling mixing salt solution is 1～10mL/min, and the charging rate of regulation sodium hydroxide solution is to control The pH value of reaction system is 10～12, regulation ammonia spirit feed rate with ensure reaction system total ammonia content be 0.1～ 1mol/L；
The reaction temperature of described reaction system is 45～60 DEG C, in reactor the stir speed (S.S.) of stirring paddle be 300～ 1000r/min；Protecting gas speed under inert gas shielding is 0～5L/min to react, and obtains product；
Gained product is entered aging reactor by the overfall of reactor, carries out filtering, washing after aged 1～6 hour, It is dried；In drying baker, temperature is 90～120 DEG C, and drying time is 4～20 hours, obtains precursor granule；
(3) calcining
Precursor granule step (2) obtained and lithium source ratio for 1:1.01～1.15 in molar ratio is mixed homogeneously and is obtained Mixture, is uniform mixed-powder by mixture ball milling, in air atmosphere or oxygen atmosphere, in normal pressure, temperature 700～ Calcine 4～20 hours at 1000 DEG C, then naturally cool to room temperature, i.e. obtain the lithium ion battery stratiform ternary of nanometer flower structure Positive electrode.
In such scheme, described nickel salt is NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O or NiCl2·6H2Any one in O.
In such scheme, described cobalt salt is CoSO4·7H2O、Co(NO3)2·6H2O、Co(CH3COO)2·4H2O or CoCl2·6H2Any one in O.
In such scheme, described manganese salt is MnSO4·H2O、Mn(NO3)24H2O、Mn(CH3COO)2·4H2O or MnCl2· 4H2Any one in O.
In such scheme, described lithium source is Li2CO3, LiNO3、LiOH·H2O or LiCH3Any one in COO.
In such scheme, the stirring paddle in described reactor is three kinds of different stirring paddles, under being respectively placed in reactor Layer, intermediate layer and upper strata, reaction mass is stirred by the most respectively.
In such scheme, described noble gas is argon or nitrogen.
In such scheme, described solvent is distilled water or deionized water.
The present invention provides a kind of reactor realizing preparing nano flower layered cathode material of lithium ion battery method continuously, bag Including the first chuck to import and export, flange, baffle plate, motor, speed regulator, material inlet, overfall, the second chuck is imported and exported, reaction Still kettle, reactant bottom exports, air vent；Wherein, material inlet includes the first material inlet, the second material inlet, the 3rd Material inlet and 4 materials import；According to the present invention, also include stirring paddle, deflector and protection gas entry nozzle；Described One chuck is imported and exported and the second chuck is imported and exported and laid respectively at reactor kettle bottom and top；Described flange, motor, speed governing Device and reaction-ure inlet are respectively positioned on above reactor kettle on top cover；Described overfall is positioned at above the second chuck import and export；Institute Stating baffle arrangement in reactor, stirring paddle is connected with motor by reactor gland seal device, protects the setting of gas entry nozzle Bottom reactor, it is used for protecting noble gas and material liquid phase interaction；Described deflector is positioned at inside reactor overfall； The outlet of described reactant bottom is arranged on reactor kettle outer bottom.
In such scheme, described stirring paddle is set to the stirring paddle of three kinds of multi-forms, is respectively and arranges in a kettle. The propeller agitator on upper strata, is arranged on the hinged joint paddle agitator in reactor intermediate layer and is arranged on the turbine of reactor lower floor Formula impeller-agitator, carries out three layers of stirring the most respectively.
In such scheme, lower floor in described reactor, its stir speed (S.S.) of the stirring paddle on intermediate layer and upper strata be 300～ 1000r/min。
In such scheme, the protection gas entry nozzle arranged bottom described reactor, its nipple top is fan-shaped, and surface is equal Even pore is distributed, it is therefore an objective to can be distributed to quickly and evenly with reaction mass after protective gas enters this protection gas entry nozzle In reactant liquor, form bubble and promote the rapid mix homogeneously of reaction mass.
The reactor of the method that nano flower layered cathode material of lithium ion battery is prepared in realization of the present invention continuously has Feature: 1, described reactor is by the improvement to tradition reactor structure, according to the characteristic of reaction mass, is arranged by stirring paddle Being that three kinds of different stirring paddles can carry out three layers of stirring simultaneously to the material in reactor, its reactor upper strata uses push type to stir Mixing oar, intermediate layer uses hinged joint paddle stirring paddle, and lower floor uses turbine type impeller stirring paddle, and stirring makes material more by different level Add uniformly, react more abundant.2, bottom arranges protection gas entry nozzle, its objective is that protective gas enters this protection gas import Can be distributed to quickly and evenly in reactant liquor with reaction mass after nozzle, form bubble and promote that reaction mass mixes rapidly all Even.3, the deflector that top is arranged in a kettle., is to make the flow field of reaction system and distribution of concentration uniform, precipitates granule energy The overflow of continuous uniform goes out reactor.4, the baffle plate arranged in reactor, is the turbulent extent for increasing reacting fluid, will cut Become axially flowing and Radial Flow to flowing, thus the convection current of liquid and diffusion in strengthening reactor, further increase anti- Answer the diffusion of thing, collision, eliminate eddy current, improve mixing effect, make the mixing of reaction system completely.5, Polycondensation Reactor and Esterification Reactor of the present invention Protection noble gas in portion's enters reactor and material liquid phase interaction from protection gas entry nozzle；Shear and axle at each layer stirring paddle Jointly act on its precipitation of lower control to power and form nanometer flower structure；Finally under the guiding of deflector, thing liquid goes out from overfall overflow And enter the ageing stage.
The present invention has following Advantageous Effects compared with prior art:
1, the method for the invention uses coprecipitation, and its simple processing step prepares the precursor of nanometer flower structure Granule, then use high-temperature calcination to prepare nano flower lithium ion battery stratiform tertiary cathode material with this precursor granule and lithium source raw material Material (LiNixCoyMn1-x-yO2), its pilot process need not add template, and nano-particles size is controlled, and distribution of particles is equal Even, concordance is good；And technique is simple.
2, the precursor granule that the method for the invention uses coprecipitation to prepare has micro-nano structure, calcination process profit In heat transfer and mass transfer, therefore required time is shorter when high-temperature process, and energy consumption is low.
3, the method for the invention uses anode material for lithium-ion batteries (LiNi prepared by coprecipitationxCoyMn1-x-yO2) Power density high, good rate capability, under the conditions of 2.7-4.3V, 1C, the specific discharge capacity of material is more than 130mAh/g.
4, realizing the method for the invention uses the reactor improved to prepare precursor granule, by setting in regulation reactor The flow velocity of the protection gas entry nozzle put and the stirring intensity of the stirring paddle of three layers of multi-form, can control bubble in reaction system Quantity and flowing velocity, make crystal grain be in " microreactor ", thus control the nucleation of crystal and growth so as to get front body Body granule has nano flower pattern, and even particle distribution, good fluidity all the time.
5, realizing the method for the invention and use the reactor improved, the deflector arranged in reactor makes reaction system Flow field and distribution of concentration are uniform, and the ground of precipitation granule energy continuous uniform goes out reactor from overfall overflow.
6, the product yield obtained by the reactor of the method for the invention and improvement is up to 99%；The method operation letter Single, reactor Stability Analysis of Structures is reliable；Be conducive to industrialized production.
Accompanying drawing explanation
Fig. 1 is the Ni prepared by embodiment 10.33Co0.33Mn0.33(OH)2The X-ray diffraction spectrogram of precursor；
Fig. 2 is the Ni prepared by embodiment 10.33Co0.33Mn0.33(OH)2Scanning electron microscope (SEM) photograph；
Fig. 3 is the Ni prepared by embodiment 20.5Co0.2Mn0.3(OH)2X-ray diffraction spectrogram；
Fig. 4 is the Ni prepared by embodiment 30.6Co0.2Mn0.2(OH)2Size frequency scattergram；
Fig. 5 is the Ni prepared by embodiment 40.8Co0.1Mn0.1(OH)2X-ray diffraction spectrogram；
Fig. 6 is the LiNi prepared by embodiment 10.33Co0.33Mn0.33O2X-ray diffraction spectrogram；
Fig. 7 is the LiNi prepared by embodiment 10.33Co0.33Mn0.33O2First charge-discharge curve under 0.1C multiplying power；
Fig. 8 is the LiNi prepared by embodiment 10.33Co0.33Mn0.33O2At high rate performance figure；
Fig. 9 is the LiNi prepared by embodiment 20.5Co0.2Mn0.3O2Scanning electron microscope (SEM) photograph；
Figure 10 is the LiNi prepared by embodiment 30.5Mn0.5O2X-ray diffraction spectrogram；
Figure 11 is the LiNi prepared by embodiment 40.6Co0.2Mn0.2O2High rate performance figure；
Figure 12 is the LiNi prepared by embodiment 50.8Co0.1Mn0.1O2X-ray diffraction spectrogram；
Figure 13 is the LiCoO prepared by embodiment 62Scanning electron microscope (SEM) photograph；
Figure 14 is the LiCoO prepared by embodiment 62First charge-discharge curve under 0.1C multiplying power；
Figure 15 is the structural representation realizing the CSTR that the method for the invention uses；Wherein, (a) Front view；(b) top view A；(c) top view B.
In figure, 1-1 turbine type stirring paddle；1-2 hinged joint paddle stirring paddle；1-3 push type stirring paddle；2 first chuck turnover Mouthful；3 baffle plates；4 flanges；5 motor；6 speed regulators；7 material inlets；7-1 the first material inlet；7-2 the second material inlet；7-3 3 material import；7-4 4 materials import；8 deflectors；9 overfalls；10 second chucks are imported and exported；11 reactor kettlies；12 Protection gas entry nozzle；13 reactant bottom outlets；14 air vents.
Detailed description of the invention
To the method for the invention below by accompanying drawing and with specific embodiment and realize the reactor of the method and make into one Step describes in detail, but is not meant to be any restriction to scope.
The present invention realizes the reactor of the described method preparing nano flower layered cathode material of lithium ion battery continuously, its knot Structure as shown in figure 15, including first chuck import and export 2, baffle plate 3, flange 4, motor 5, speed regulator 6, material inlet 7, overfall 9, the second chuck imports and exports 10, and reactor kettle 11, reactant exports 13, air vent 14；Wherein material inlet 7 is divided into the first thing Material import 7-1, the second material inlet 7-2,3 material import 7-3 and 4 materials import 7-4, can be injected simultaneously into four kinds respectively Different material；Also include stirring paddle, deflector 8 and protection gas entry nozzle 12.Wherein, stirring paddle is set to three kinds of multi-forms Stirring paddle, turbine type stirring paddle 1-1 is placed in reactor bottom, and hinged joint paddle stirring paddle 1-2 is placed in reactor intermediate layer, advance Formula stirring paddle 1-3 is placed in reactor bottom, and the material in reactor is sufficiently stirred for by three kinds of stirring paddles the most respectively；Described First chuck import and export 2 and the second chuck are imported and exported 10 and are laid respectively at reactor kettle 11 bottom and top；Described baffle plate 3 decile For the quartering, and it is distributed evenly in left and right sides and front and rear part in reactor；Flange 4, motor 5, speed regulator 6 and material inlet 7 are respectively positioned on above reactor kettle on top cover；Described overfall 9 is positioned at the second chuck and imports and exports above in the of 10；Described deflector 8 In reactor upper end overfall inside and being connected with it, three kinds of stirring paddles are all connected with motor 5 by reactor gland seal device, Protection gas entry nozzle 12 is arranged at bottom reactor, and reactant bottom outlet 13 is arranged on reactor kettle 11 outer bottom.
In the following example, use reactor of the present invention, prepare nano flower continuously according to noted earlier LiNixCoyMn1-x-yO2The processing step of positive electrode method is prepared；Install by Fig. 1 structure and connect each parts of reactor； Reactor volume is 5L.
Embodiment 1
In the present embodiment, by chemical formula LiNi0.33Co0.33Mn0.33O2Dispensing, wherein x=0.33, y=0.33.
(1) solution preparation
It is that 1:1:1 accurately weighs NiSO by nickel, cobalt, manganese mol ratio4·6H2O、CoSO4·7H2O、MnSO4·H2O tri-kinds Three kinds of mixture are added in dissolving tanks by salt, and add and stir to being completely dissolved under distilled water normal pressure, are made into concentration 3mol/L and mix Close saline solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 8mol/L sodium hydroxide solution；Strong aqua ammonia is used Deionized water is diluted to the ammonia spirit of 5mol/L；
(2) co-precipitation
Respectively above-mentioned steps (1) gained mixing salt solution, sodium hydroxide solution and ammonia spirit are added in reactor, control Mixing salt solution feed flow rate processed is 1mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 11.3 ± 0.2, in regulation ammonia spirit inlet amount makes reaction system, ammonia density is in 0.8mol/L；And ensure that whole reaction is at argon Carrying out in gas atmosphere, argon inlet flow is 2L/min, and controlling reaction temperature is 50 ± 2 DEG C, and the stir speed (S.S.) of stirring paddle is 800r/min；Reactant is spilled over to aging reactor from overfall 9, filters, washs after being aged 1 hour, dry in drying baker at 100 DEG C Within dry 12 hours, obtain black precursor granule；
(3) calcining
The black precursor granule that step (2) is obtained and Li2CO3Mixing, the ratio of its integral molar quantity and lithium is 1: 1.09, gained mixture is ball milling uniformly mixed-powder in planetary ball mill, is put into by mixed-powder in tube furnace, Calcine 10 hours in 850 DEG C under air atmosphere, after naturally cooling to room temperature, obtain LiNi0.33Co0.33Mn0.33O2Nano flower ternary Positive electrode
Ni prepared by the present embodiment0.33Co0.33Mn0.33(OH)2The x-ray diffraction pattern of precursor is shown in Fig. 1, and it is nanometer flower-shaped Looks are shown in Fig. 2, the end product LiNi obtained0.33Co0.33Mn0.33O2X-ray diffraction spectrogram see Fig. 6, as can be seen from Figure 6 Grain better crystallinity degree, even particle size distribution, mean diameter is 6 μm.
This example charge-discharge performance is tested: weigh active substance for 80:13:7 in mass ratio, prepared by the present embodiment LiNi0.33Co0.33Mn0.33O2), acetylene black and Kynoar (PVDF), join furnishing slurry in N-Methyl pyrrolidone, Be coated uniformly in aluminium foil, at 100 DEG C, vacuum be-0.094MPa drying baker in be dried 12 hours, then cut out with mould It is cut into pole piece, and under 20MPa pressure, final anode pole piece is made in pole piece compacting；Employing metal lithium sheet is negative pole, Celgard2400 is barrier film, is assembled into the button cell that model is CR2032 in the glove box of full noble gas.Electrical property Testing and be 2.7～4.3V in voltage range, carry out under different electric current density, result shows prepared by this embodiment LiNi0.33Co0.33Mn0.33O2Under under 0.1C multiplying power, discharge capacity is 158mAh/g, 10C multiplying power first, specific discharge capacity reaches 105mAh/g, at the first charge-discharge curve under 0.1C multiplying power, it sees that Fig. 7, high rate performance are shown in Fig. 8.
Embodiment 2
In the present embodiment, by chemical formula LiNi0.5Co0.2Mn0.3O2Dispensing, wherein x=0.5, y=0.2.
(1) solution preparation
It is that 5:2:3 accurately weighs NiCl by nickel, cobalt, manganese mol ratio2·6H2O、CoCl2·6H2O and MnCl2·4H2O tri-kinds Three kinds of mixture are added in dissolving tanks by salt, and add and stir to being completely dissolved under deionized water normal pressure, are made into concentration 1mol/L Mixing salt solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 5mol/L sodium hydroxide solution；By strong aqua ammonia The ammonia spirit of 12mol/L it is diluted to deionized water；
(2) co-precipitation
Respectively above-mentioned mixing salt solution, sodium hydroxide solution and ammonia spirit are added in reactor, control salt-mixture molten Liquid feed flow rate is 10mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 10.5 ± 0.3, adjusts In joint ammonia spirit inlet amount makes reaction system, ammonia density is in 1mol/L；And ensure that whole reaction is carried out in argon gas atmosphere, Argon inlet flow is 3L/min, and controlling reaction temperature is 60 DEG C, and stir speed (S.S.) is 1000r/min；Reactant overflows from overfall 9 Go out to aging reactor, filter after being aged 2 hours, wash, be dried at 120 DEG C and within 4 hours, obtain black precursor granule；
(3) calcining
The black precursor powder that step (2) is obtained and LiOH H2O mixes to obtain mixture, its integral molar quantity and Li's Ratio is 1:1.05, after mixture ball milling uniformly mixed-powder, it is put into tube furnace, forges in 800 DEG C in air atmosphere Burn 20 hours, after naturally cooling to room temperature, obtain final ternary material.
Ni prepared by the present embodiment0.5Co0.2Mn0.3(OH)2The x-ray diffraction pattern of precursor is shown in Fig. 3, and the present embodiment is made Standby LiNi0.5Co0.2Mn0.3O2Pattern is shown in that Fig. 9, granule are nano flower-like, and is evenly distributed.
Charge-discharge performance is tested: method of testing is same as in Example 1, and result shows prepared by the present embodiment LiNi0.5Co0.2Mn0.3O2Discharge capacity first under 0.1C multiplying power be under 166mAh/g, 10C multiplying power specific discharge capacity up to More than 100mAh/g.
Embodiment 3
In the present embodiment, by chemical formula LiNi0.5Mn0.5O2Dispensing, wherein x=0.5, y=0.
(1) solution preparation
It is that 1:1 accurately weighs Ni (NO by nickel, manganese mol ratio3)2·6H2O and Mn (CH3COO)2·4H2Two kinds of raw materials of O, will Mixture adds in dissolving tank, and adds and stir to being completely dissolved under deionized water normal pressure, is made into concentration 0.5mol/L salt-mixture Solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 0.5mol/L sodium hydroxide solution；Strong aqua ammonia is spent Ionized water is diluted to the ammonia spirit of 1mol/L；
(2) co-precipitation
Respectively above-mentioned mixing salt solution, sodium hydroxide solution and ammonia spirit are added in reactor, control salt-mixture molten Liquid feed flow rate is 8mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 10.3 ± 0.3, adjusts In joint ammonia spirit inlet amount makes reaction system, ammonia density is in 0.3mol/L；And ensure that whole reaction is entered in argon gas atmosphere OK, argon inlet flow is 1L/min, and controlling reaction temperature is 45 DEG C, and stir speed (S.S.) is 600r/min；Reactant is from overfall 9 It is spilled over to aging reactor, filters after being aged 3 hours, wash, be dried at 90 DEG C and within 20 hours, obtain black precursor granule；
(3) calcining
The black precursor powder that step (2) is obtained and LiCH3COO mixes to obtain mixture, its integral molar quantity and Li's Ratio is 1:1.15, obtains mixed-powder by uniform for mixture ball milling in planetary ball mill, is existed by the powder after mix homogeneously Air atmosphere is calcined 16 hours in 850 DEG C, after naturally cooling to room temperature, i.e. obtains nanometer flower structure LiNi0.5Mn0.5O2。
LiNi prepared by the present embodiment0.5Mn0.5O2X-ray diffraction spectrogram see Figure 10.
Charge-discharge performance is tested: method of testing is same as in Example 1, and result shows prepared by the present embodiment LiNi0.5Mn0.5O2It is 140mAh/g that discharge capacity first under 0.1C multiplying power reaches specific discharge capacity under 170mAh/g, 1C multiplying power Above.
Embodiment 4
In the present embodiment, by chemical formula LiNi0.6Co0.2Mn0.2O2Dispensing, wherein x=0.6, y=0.2.
(1) solution preparation
It is that 6:2:2 accurately weighs Ni (CH by nickel, cobalt, manganese mol ratio3COO)2·4H2O、Co(CH3COO)2·4H2O and Mn (CH3COO)2·4H2Tri-kinds of slaines of O, feed the mixture in dissolving tank, and add and stir to completely under deionized water normal pressure Dissolve, be made into concentration 2mol/L mixing salt solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 6mol/L hydrogen Sodium hydroxide solution；Strong aqua ammonia deionized water is diluted to the ammonia spirit of 10mol/L；
(2) co-precipitation
Respectively above-mentioned mixing salt solution, sodium hydroxide solution and ammonia spirit are added in reactor, control salt-mixture molten Liquid feed flow rate is 6mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 10.5 ± 0.2, adjusts In joint ammonia spirit inlet amount makes reaction system, ammonia density is in 0.1mol/L；And ensure that whole reaction is entered in nitrogen atmosphere OK, nitrogen charge flow rate is 3L/min, and controlling reaction temperature is 60 DEG C, and stir speed (S.S.) is 300r/min；Reactant is from overfall 9 It is spilled over to aging reactor, filters after being aged 6 hours, wash, be dried at 100 DEG C and within 9 hours, obtain light green color precursor granule；
(3) calcining
The light green color precursor powder that step (2) is obtained and LiNO3Mix to obtain mixture, its integral molar quantity and the ratio of Li Example is 1:1.07, by uniform for mixture ball milling in the planetary ball mill mixed-powder that obtains, by it by mixture ball milling uniformly Put into tube furnace after mixed-powder, calcine 6 hours in 850 DEG C in air atmosphere, finally produced after naturally cooling to room temperature Thing LiNi0.6Co0.2Mn0.2O2。
Ni prepared by the present embodiment0.6Co0.2Mn0.2(OH)2Size frequency scattergram see that Fig. 4, precursor granule-morphology are Nano flower-like.LiNi prepared by the present embodiment0.6Co0.2Mn0.2O2Granule, is evenly distributed, and mean diameter is about 5 μm.
Charge-discharge performance is tested: method of testing is same as in Example 1, and result shows prepared by the present embodiment LiNi0.6Co0.2Mn0.2O2Discharge capacity first under 0.1C multiplying power reaches specific discharge capacity under 170mAh/g, 10C multiplying power 95mAh/g, its high rate performance figure is shown in Figure 11.
Embodiment 5
In the present embodiment, by chemical formula LiNi0.8Co0.1Mn0.1O2Dispensing, wherein x=0.8, y=0.1.
(1) solution preparation
It is that 8:1:1 accurately weighs Ni (NO by nickel, cobalt, manganese mol ratio3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)24H2Tri-kinds of slaines of O, feed the mixture in dissolving tank, and add and stir to being completely dissolved under deionized water normal pressure, are made into dense Degree 3mol/L mixing salt solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 2mol/L sodium hydroxide solution； Strong aqua ammonia deionized water is diluted to the ammonia spirit of 5mol/L；
(2) co-precipitation
Respectively above-mentioned mixing salt solution, sodium hydroxide solution and ammonia spirit are added in reactor, control salt-mixture molten Liquid feed flow rate is 8mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 11.6 ± 0.4, adjusts In joint ammonia spirit inlet amount makes reaction system, ammonia density is in 1mol/L；And ensure that whole reaction is carried out in nitrogen atmosphere, Nitrogen charge flow rate is 1L/min, and controlling reaction temperature is 55 DEG C, and stir speed (S.S.) is 600r/min；Reactant overflows from overfall 9 Go out to aging reactor, filter after being aged 3 hours, wash, be dried at 95 DEG C and within 18 hours, obtain light green color precursor granule；
(3) calcining
The green powder of above-mentioned gained is weighed LiOH H for 1:1.15 in molar ratio2O, obtains mixture, mixes with ball mill Synthesize uniform mixed-powder, it is calcined 20 hours in 750 DEG C in oxygen atmosphere, after naturally cooling to room temperature, i.e. obtains nanometer Floral structure LiNi0.8Co0.1Mn0.1O2。
Ni prepared by the present embodiment0.8Co0.1Mn0.1(OH)2X-ray diffraction spectrogram see Fig. 5.Prepared by the present embodiment LiNi0.8Co0.1Mn0.1O2X-ray diffraction spectrogram see Figure 12.
Charge-discharge performance is tested: method of testing is same as in Example 1, and result shows prepared by the present embodiment LiNi0.8Co0.1Mn0.1O2Discharge capacity first under 0.1C multiplying power reaches specific discharge capacity under 178mAh/g, 1C multiplying power More than 135mAh/g.
Embodiment 6
In the present embodiment, by chemical formula LiCoO2Dispensing, wherein x=0, y=1.
(1) solution preparation
Weigh Co (NO3)2·6H2O slaine, is added in dissolving tank, and it is the completeest to add stirring under deionized water normal pressure CL, is made into concentration 2mol/L saline solution；Weighing sodium hydroxide solid adds deionized water dissolving and is configured to 4mol/L hydrogen-oxygen Change sodium solution；Strong aqua ammonia deionized water is diluted to the ammonia spirit of 8mol/L；
(2) co-precipitation
Respectively above-mentioned saline solution, sodium hydroxide solution and ammonia spirit are added in reactor, control saline solution feed stream Speed is 2mL/min, and the feed rate of regulation sodium hydroxide solution makes pH value of reaction system be in 10.8 ± 0.3, and regulation ammonia is molten In liquid inlet amount makes reaction system, ammonia density is in 0.8mol/L；Controlling reaction temperature is 55 DEG C, and stir speed (S.S.) is 500r/min； This reaction need not protective gas, i.e. protection gas charge flow rate is 0L/min；Reactant is spilled over to aging reactor from overfall 9, old Filter after changing 6 hours, wash, be dried at 100 DEG C and within 12 hours, obtain rufous precursor granule；
(3) calcining
The rufous precursor granule of above-mentioned gained is weighed Li for 1:1.08 in molar ratio2CO3, mixture is in ball mill After middle mix homogeneously mixed-powder, it is calcined 8 hours in 1000 DEG C in air atmosphere, after naturally cooling to room temperature and get final product Nanometer flower structure LiCoO2。
LiCoO prepared by the present embodiment2Scanning electron microscope (SEM) photograph see Figure 13.
Charge-discharge performance is tested: method of testing is same as in Example 1, and result shows the LiCoO prepared by the present embodiment2? Discharge capacity first under 0.1C multiplying power reaches 162mAh/g, sees that under Figure 14,1C multiplying power, specific discharge capacity is more than 145mAh/g.

Claims (10)

1. the method preparing nano flower anode material for lithium-ion batteries continuously, it is characterised in that comprise the following steps that:
(1) solution preparation
According to chemical formula LiNixCoyMn1-x-yO2Proportioning weigh nickel salt, cobalt salt and manganese salt raw material, and they are added together molten Solve in groove, be subsequently adding solvent, stir under normal pressure to being completely dissolved the mixing salt solution forming 0.5～3mol/L；With solvent and Sodium hydroxide prepares 0.5～8mol/L sodium hydroxide solution, with solvent, strong aqua ammonia to be diluted to concentration be 1～12mol/L ammonia Solution；The mol ratio of described x and y meets: 0.00≤x≤0.80；0.00≤y≤1.00；
(2) co-precipitation
By step (1) gained mixing salt solution, sodium hydroxide solution and ammonia spirit are infused in reactor from material inlet respectively In, the feed rate controlling mixing salt solution is 1～10mL/min, and the charging rate of regulation sodium hydroxide solution is to control reaction The pH value of system is 10～12, and the feed rate of regulation ammonia spirit is 0.1～1mol/ to ensure total ammonia content of reaction system L；
The reaction temperature of described reaction system is 45～60 DEG C, and in reactor, the stir speed (S.S.) of stirring paddle is 300～1000r/ min；Protecting gas speed under inert gas shielding is 0～5L/min to react, and obtains product；
Gained product is entered aging reactor by the overfall of reactor, carries out filtering, washing after aged 1～6 hour, dry Dry；In drying baker, temperature is 90～120 DEG C, and drying time is 4～20 hours, obtains precursor granule；
(3) calcining
Precursor granule step (2) obtained is that the ratio of 1:1.01～1.15 is mixed homogeneously and must be mixed in molar ratio with lithium source Thing, is uniform mixed-powder by mixture ball milling, in air atmosphere or oxygen atmosphere, in normal pressure, temperature 700～1000 Calcine 4～20 hours at DEG C, then naturally cool to room temperature, i.e. obtain the lithium ion battery stratiform positive pole material of nanometer flower structure Material.
The method preparing nano flower anode material for lithium-ion batteries the most continuously, it is characterised in that described Nickel salt is NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O or NiCl2·6H2Any one in O.
The method preparing nano flower anode material for lithium-ion batteries the most continuously, it is characterised in that described Cobalt salt is CoSO4·7H2O、Co(NO3)2·6H2O、Co(CH3COO)2·4H2O or CoCl2·6H2Any one in O.
The method preparing nano flower anode material for lithium-ion batteries the most continuously, it is characterised in that described Manganese salt is MnSO4·H2O、Mn(NO3)24H2O、Mn(CH3COO)2·4H2O or MnCl2·4H2Any one in O.
The method preparing nano flower anode material for lithium-ion batteries the most continuously, it is characterised in that described Lithium source is Li2CO3, LiNO3、LiOH·H2O or LiCH3Any one in COO.
6. according to the method preparing nano flower anode material for lithium-ion batteries described in claim 1-5 continuously, it is characterised in that institute State the stirring paddle that the stirring paddle in reactor is three kinds of multi-forms, be respectively placed in lower floor in reactor, intermediate layer and upper strata, right Reaction mass is stirred the most respectively.
7. according to the method preparing nano flower anode material for lithium-ion batteries described in claim 1-5 continuously, it is characterised in that institute Stating solvent is distilled water or deionized water；Described noble gas is argon or nitrogen.
8. one kind realizes preparing nano flower layered cathode material of lithium ion battery method described in any one of claim 1-7 continuously Reactor, imports and exports (2) including the first chuck, baffle plate (3), flange (4), motor (5), speed regulator (6), material inlet (7), Overfall (9), the second chuck import and export (10), reactor kettle (11), reactant outlet (13), air vent (14)；Its feature It is also to include stirring paddle, deflector (8) and protection gas entry nozzle (12)；Described first chuck imports and exports and the second chuck enters Outlet lays respectively at reactor kettle bottom and top；Described flange, motor, speed regulator and reaction-ure inlet are respectively positioned on reaction Above still kettle on top cover；Described overfall is positioned at above the second chuck import and export；Described baffle arrangement, in reactor, stirs Oar is connected with motor by reactor gland seal device, and protection gas entry nozzle is arranged at bottom reactor, described deflector position In reactor overfall；The outlet of described reactant is arranged on reactor kettle outer bottom.
Reactor the most according to claim 8, it is characterised in that described stirring paddle is set to the stirring of three kinds of multi-forms Oar, is respectively arranged on reactor propeller agitator (1-1) at the middle and upper levels, and the hinged joint paddle being arranged on reactor intermediate layer is stirred Mix device (1-2) and be arranged on the turbine type impeller-agitator (1-3) of reactor lower floor, reactant being carried out three layers the most respectively and stirs Mix；The stir speed (S.S.) of described three layers of stirring paddle is 300～1000r/min.
Reactor the most according to claim 1, it is characterised in that the protection gas entry nozzle arranged bottom described reactor (12), its nipple top is fan-shaped, and surface is evenly distributed with pore.
CN201610532087.6A 2016-07-07 2016-07-07 Method for continuously preparing nanoflower lithium ion battery layered anode material and reaction kettle thereof Pending CN106058237A (en)

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Application publication date: 20161026