CN107482214A - The mixed lithium method and device of lithium ion cell positive ternary material - Google Patents
The mixed lithium method and device of lithium ion cell positive ternary material Download PDFInfo
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- CN107482214A CN107482214A CN201710646171.5A CN201710646171A CN107482214A CN 107482214 A CN107482214 A CN 107482214A CN 201710646171 A CN201710646171 A CN 201710646171A CN 107482214 A CN107482214 A CN 107482214A
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- ternary material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of lithium ion, it is related to the mixed lithium method and device of a kind of lithium ion cell positive ternary material.The mixed lithium method of lithium ion cell positive ternary material provided by the invention, comprises the following steps：(a) weigh：Ternary material precursor, lithium source and deionized water are weighed in proportion；(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source all to dissolve, ternary material precursor is added and is mixed together stirring, the suspension being uniformly mixed；(c) it is spray-dried：Obtained suspension is spray-dried, obtains matching somebody with somebody lithium mixture.The present invention can improve the mixing efficiency of ternary material precursor and lithium source, and the uniformity of mixing particle diameter, while can prevent dust pollution, safety and environmental protection.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of mixed lithium of lithium ion cell positive ternary material
Method and device.
Background technology
In existing secondary cell system, no matter from development space, or from the life-span, than energy, operating voltage and from
From the point of view of the technical indicators such as discharge rate, lithium ion battery is all current most competitive secondary cell.And the pass of lithium ion battery
Key material is positive electrode, accounts for the 30%-40% or so of lithium ion battery cost.Lithium ion battery uses in the market
Positive electrode mainly have cobalt acid lithium, LiFePO4, LiMn2O4 and ternary nickle cobalt lithium manganate etc..Ternary nickle cobalt lithium manganate positive pole material
Expect that (abbreviation ternary material) is a kind of new cell positive material, compared with the other materials such as cobalt acid lithium, there is quality specific volume
Amount is high, heat endurance is good, good cycle, the advantages that operating temperature range is wide, energy density is big.Good combination property, makes
Obtaining ternary nickel-cobalt lithium manganate cathode material turns into the main flow of existing market, and a kind of most potential cell positive material,
The fields such as digital electronic goods, electric bicycle, electric tool have good application scenarios.
At present, the preparation method of ternary material mainly using ternary material precursor and lithium source dry method batch mixing, high temperature sintering,
Broken, iron removaling, sieving, the mode of packaging, are prepared ternary material.Wherein, what ternary material precursor mixed with lithium source is equal
Even degree, sintering finished particle diameter distribution, spheric granules size, crystalline structure and spherical surface microscopic appearance are directly affected,
And then influence the property indices of material.Because the proportion and particle diameter of lithium source and presoma have very big difference, current is this
Dry method mixes the mode of lithium on the one hand there is problem of environmental pollution, and on the other hand inevitably there is lithium source and presoma material
The problem of material mixing is uneven, and then cause the product after sintering rich lithium or scarce lithium occur, stability is poor between batch, product
Electrochemistry can be guaranteed, and have a strong impact on the quality of product.In addition, existing mixed lithium technology, the work of degree of mixing is influenceed
Skill parameter is more, for example, the rotating speed of the mobility of presoma and lithium source, powder tack, the dew point of environment, mixer, when mixing
Between etc., these all affect the mixing efficiency of precursor and lithium source, and then affect production efficiency.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is a kind of mixed lithium method for providing lithium ion cell positive ternary material, this method energy
The mixing efficiency of ternary material precursor and lithium source, and the uniformity of mixing particle diameter are enough improved, while can prevent that dust is dirty
Dye, safety and environmental protection.
The second object of the present invention is the mixed lithium device for providing a kind of lithium ion cell positive ternary material, the device energy
Enough so that ternary material precursor is well mixed with lithium source, and it is simple to operate, it is easily controlled, operating efficiency is high, it is easy to accomplish
Industrial-scale production.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of mixed lithium method of lithium ion cell positive ternary material,
Comprise the following steps：
(a) weigh：Ternary material precursor, lithium source and deionized water are weighed in proportion；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source all to dissolve, before adding ternary material
Drive body and be mixed together stirring, the suspension being uniformly mixed；
(c) it is spray-dried：Obtained suspension is spray-dried, obtains matching somebody with somebody lithium mixture.
As further preferred technical scheme, the chemical formula of the ternary material precursor is NixCoyMnz(OH)2, wherein
x：y：Z=1：1：1、4：2：4、5：2：3、6：2：2 or 8：1：1.
As further preferred technical scheme, the lithium source is monohydrate lithium hydroxide.
As further preferred technical scheme, the ternary material precursor and Li in lithium source mol ratio are 1：1~
1.20；
Preferably, the quality of the ternary material precursor is 1~3 times of quality of the lithium source, preferably 1.8~
2.2 again；
Preferably, the quality of the deionized water is 1~5 times of ternary material precursor and lithium source gross mass, preferably 2
~3 times.
As further preferred technical scheme, in the step (b), using agitator to lithium source, deionized water and three
First material precursor is mixed, and the rotating speed of mixing is 2000~4000rpm, and the time is 40~90min.
As further preferred technical scheme, in the step (c), it is spray-dried using pressure spray dryer device,
Atomizing pressure is 0.05Mpa~0.75MPa, and EAT is 200 DEG C~350 DEG C, and leaving air temp is 90 DEG C~120 DEG C.
As further preferred technical scheme, peristaltic pump is provided between the agitator and spray dryer, by described in
The suspension obtained in agitator is delivered in spray dryer by the peristaltic pump and is spray-dried.
According to another aspect of the present invention, the present invention is also providing a kind of lithium ion battery for realizing approach described above just
The mixed lithium device of pole ternary material, including agitator, spray dryer, collecting mechanism and the air-introduced machine being sequentially connected.
As further preferred technical scheme, the collecting mechanism includes cyclone separator and the first collector, and described
One collector is located at the lower section of the cyclone separator；
Preferably, the collecting mechanism also includes the second collector, and second collector is located at the spray dryer
Lower section；
Preferably, the collecting mechanism also includes dust collector, and the dust collector passes through air-introduced machine and whirlwind point
Connected from device.
As further preferred technical scheme, peristaltic pump is provided between the agitator and spray dryer；
Preferably, the agitator is double spiral agitator；
Preferably, the spray dryer is pressure spray dryer device.
Compared with prior art, the beneficial effects of the present invention are：
The mixed lithium method of lithium ion cell positive ternary material provided by the invention, by the way of material by wet type mixing, solve
Dry method batch mixing presoma mixes the problem of uneven with lithium source, then by spray drying by ternary material precursor and lithium source
It is granulated, lithium ion is evenly embedded into presoma when can guarantee that follow-up sintering, it is ensured that final obtained ternary material tool
There is excellent chemical property, improve product quality.Further speaking：
(1) mixing uniformity is good：By way of lithium source and deionized water are mixed, mixed again with presoma,
So that the presoma and the mixture of lithium source that obtain are the uniformity for having height with lithium mixture, product matter is favorably improved
Amount so that the uniformity of product is guaranteed in large-scale production.
(2) mixing efficiency is high：It can realize and carry out quick combination drying, simplify production technology, shorten the production time, improve
Production efficiency, reduces production cost.
(3) safety and environmental protection：Dusting problem can be avoided and had no irritating odor, maintenance work environment, securely and reliably,
It is environment-friendly.
(4) cost is low：The solvent cost that this method is related to is low, and efficiently, it is environmental protection, economical, production efficiency is high, produces energy
Consume it is low, it is simple to operate, be easy to industrialized production.
The mixed lithium device of lithium ion cell positive ternary material provided by the invention, it is simple to operate, it is easily controlled, can makes
Presoma is obtained to be well mixed with lithium source, and production efficiency is high, and environmental benefit is good, it is easy to accomplish industrialization large-scale production, tool
There is industrial applicibility.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the mixed lithium apparatus structure schematic diagram of lithium ion cell positive ternary material provided in an embodiment of the present invention；
Fig. 2 is LiNi provided in an embodiment of the present invention1/3Co1/3Mn1/3O2Cycle-index-specific discharge capacity of positive electrode
Figure, abscissa is cycle-index, and ordinate is specific discharge capacity (mAh/g)；
Fig. 3 is LiNi provided in an embodiment of the present invention1/3Co1/3Mn1/3O2SEM figures (the Scanning of positive electrode
Electron Microscope scanning electron microscope (SEM) photographs)；
Fig. 4 is the LiNi that comparative example of the present invention provides1/3Co1/3Mn1/3O2SEM figures (the Scanning of positive electrode
Electron Microscope scanning electron microscope (SEM) photographs).
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
Enclose.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is suggested according to normal condition or manufacturer
Condition carry out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a kind of mixed lithium method of lithium ion cell positive ternary material, including it is following
Step：
(a) weigh：Ternary material precursor, lithium source and deionized water are weighed in proportion；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source all to dissolve, before adding ternary material
Drive body and be mixed together stirring, the suspension being uniformly mixed；
(c) it is spray-dried：Obtained suspension is spray-dried, obtains matching somebody with somebody lithium mixture.
In view of ternary material in the prior art in preparation process, the mixing of ternary material precursor and lithium source is also present
That mixing is uneven, and influence factor is more, cause the problem of mixing efficiency is low, cost is high, the present invention provides one kind can be effective
Alleviate the mixed lithium method of the lithium ion cell positive ternary material of above-mentioned technical problem.
The present invention using weigh, material by wet type mixing, spray drying mode of operation, on the one hand with the behaviour of existing dry method batch mixing
Compared as mode, there is the well mixed, consistent performance of product to access guarantee, safety and environmental protection, dust from flying etc. can be avoided existing
The advantage of elephant；On the other hand compared with the mode of operation of existing material by wet type mixing, without use other organic solvents, dispersant,
Complicated operation equipment etc., simply carries out dissolving mixing using deionized water, and cost is cheap, simple to operate, and production efficiency is high.This
Outside, mix to lithium source using lithium source and deionized water all to dissolve, add ternary material precursor and be mixed together stirring
Mode of operation, be not only easy to operate, efficiency high, and can further improve being well mixed for ternary material precursor and lithium source
Degree, it is ensured that product cut size is evenly distributed.
It should be noted that the solvent in the present invention is preferably deionized water, or distilled water or pure water.
In a kind of optional embodiment, the chemical formula of the ternary material precursor is NixCoyMnz(OH)2, wherein
x：y：Z=1：1：1、4：2：4、5：2：3、6：2：2 or 8：1：1.
In a kind of optional embodiment, the lithium source is monohydrate lithium hydroxide.
In three kinds of nickel (Ni) of ternary material, cobalt (Co), manganese (Mn) components, influence of each element to material is different, typically
For, the content of nickel element is related to the capacity of material, and Ni constituent contents are higher, the gram volume of whole multi-element composite material system
It is higher, but the cycle performance of the whole material of Ni too high levels and heat endurance will decline.The layer of cobalt element content and material
Shape structural development is related to electrical conductivity, and Co constituent contents are higher, and whole positive electrode system electrical conductivity is higher, the stratiform knot of material
Under structure is better, but Co too high levels will increase the preparation cost of polynary positive pole material, while the heat endurance of material is also understood
Drop.The content of manganese element is related to the heat endurance of material, and Mn contents are higher, and the cycle performance of material is better, and heat endurance is got over
Height, but Mn elements are too high, and material capacity will be caused to reduce, and eventually it is converted into instable Mn3+, influence the circulation of material
Performance.Case above is considered, present invention defines above-mentioned Ni, Co, Mn ratio, using above-mentioned several ternary material forerunners
Body, by using the mixed lithium mode of the present invention, Ni, Co, Mn, Li in final product is enabled to be well mixed, and give full play to
Respective effect, the ternary material being finally prepared have good chemical property.
The lithium source of the present invention is preferably monohydrate lithium hydroxide, can extend making for lithium ion battery using monohydrate lithium hydroxide
With the life-span, increase charge capacity.Also, monohydrate lithium hydroxide water solubility preferably, can preferably in deionized water with ternary
Material precursor is well mixed, and raw material is easy to get, and price is relatively low.
In a kind of optional embodiment, the ternary material precursor and Li in lithium source mol ratio are 1：1~
1.20；
Preferably, the quality of the ternary material precursor is 1~3 times of quality of the lithium source, preferably 1.8~
2.2 again；
Preferably, the quality of the deionized water is 1~5 times of ternary material precursor and lithium source gross mass, preferably 2
~3 times.
Using above-mentioned ternary material precursor and lithium source, under conditions of above-mentioned mol ratio, mass ratio, mixing behaviour is carried out
Make, it is not only economical, efficient, economize on resources, and obtained ternary material uniformity is good, electrochemical performance, preparation process
Simply, it is not necessary to harsh process conditions, easily-controlled operation.
In a detailed embodiment, optionally, the ternary material precursor and the mol ratio of Li in lithium source are 1：
1、1：1.01、1：1.02、1：1.03、1：1.04、1：1.05、1：1.06、1：1.07、1：1.08、1：1.09、1：1.10、1：
1.11、1：1.12、1：1.13、1：1.14、1：1.15、1：1.16、1：1.17、1：1.18、1：1.19 or 1.20.
In a detailed embodiment, optionally, the quality of the ternary material precursor is the quality of the lithium source
1 times, 1.2 times, 1.4 times, 1.5 times, 1.6 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times, 2.4 times, 2.5 times, 2.6
Again, 2.8 times or 3 times.
In a detailed embodiment, optionally, the quality of the deionized water is ternary material precursor and lithium source
1 times of gross mass, 1.5 times, 1.8 times, 2 times, 2.2 times, 2.5 times, 2.8 times, 3 times, 3.2 times, 3.5 times, 3.8 times, 4 times, 4.2
Again, 4.5 times, 4.8 times or 5 times.
In a kind of optional embodiment, in the step (b), using agitator to lithium source, deionized water and three
First material precursor is mixed, and the rotating speed of mixing is 2000~4000rpm, and the time is 40~90min.
It should be noted that in whipping process, a certain amount of lithium source is first added, adds portions of de-ionized water, is carried out molten
Solution stirring is all dissolved to lithium source, then adds a certain amount of ternary material precursor and remainder deionized water, is carried out
Mix.Lithium source is so enabled to preferably to be well mixed with ternary material precursor.
In a detailed embodiment, optionally, the rotating speed of mixing be 2000rpm, 2200rpm, 2500rpm,
2800rpm, 3000rpm, 3200rpm, 3500rpm, 3800rpm or 4000rpm；Total mixing time be 40min, 45min,
50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min.
In a kind of optional embodiment, in the step (c), it is spray-dried using pressure spray dryer device,
Atomizing pressure is 0.05Mpa~0.75MPa, and EAT is 200 DEG C~350 DEG C, and leaving air temp is 90 DEG C~120 DEG C.
It is spray-dried, the grain size size and particle diameter distribution of mixture can be carried out by pressure spray dryer device
Adjustment so that the particle diameter distribution of material is homogeneous, has the good uniformity.Charging rate, atomizing pressure etc. can be according to product institutes
The granularity difference needed is adjusted.
In a detailed embodiment, optionally, atomizing pressure 0.05Mpa, 0.10Mpa, 0.15Mpa,
0.20Mpa、0.25Mpa、0.30Mpa、0.35Mpa、0.40Mpa、0.45Mpa、0.50Mpa、0.55Mpa、0.60Mpa、
0.65Mpa, 0.70Mpa or 0.75MPa.
In a detailed embodiment, optionally, EAT be 200 DEG C, 220 DEG C, 240 DEG C, 250 DEG C, 260 DEG C,
280 DEG C, 300 DEG C, 320 DEG C, 340 DEG C or 350 DEG C；Leaving air temp be 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or
120℃。
In a kind of optional embodiment, peristaltic pump is provided between the agitator and spray dryer, by described in
The suspension obtained in agitator is delivered in spray dryer by the peristaltic pump and is spray-dried.
Easy to operate by way of peristaltic pump conveying, easily controllable, operating efficiency is high, it is easy to accomplish serialization scale
Production.
Second aspect, present embodiment provide a kind of lithium ion cell positive ternary material for realizing approach described above
Mixed lithium device, including agitator, spray dryer, collecting mechanism and the air-introduced machine being sequentially connected.
The mixed lithium device of lithium ion cell positive ternary material provided by the invention, agitator pass through pipeline and spray drying
Device is connected, and spray dryer is connected by pipeline with collecting mechanism, and collecting mechanism is connected by pipeline with air-introduced machine.
Ternary material precursor is stirred with lithium source and deionized water in agitator, after being well mixed, is delivered to spray
It is spray-dried in mist drier, and is collected by collecting mechanism, is blowed by air-introduced machine.
By the setting of said apparatus, it is well mixed, the homogeneity of product is good, and rate of drying is fast, simple to operate, controlling party
Just, energy consumption is low, and production efficiency is high, it is easy to accomplish serialization large-scale production.
In a kind of optional embodiment, the collecting mechanism includes cyclone separator and the first collector, and described the
One collector is located at the lower section of the cyclone separator；
Preferably, the collecting mechanism also includes the second collector, and second collector is located at the spray dryer
Lower section；
Preferably, the collecting mechanism also includes dust collector, and the dust collector passes through air-introduced machine and whirlwind point
Connected from device.
In the present invention, spray dryer is connected with cyclone separator, and cyclone separator passes through air-introduced machine and dust collection
Device is connected, and sets the second collector in the lower section of spray dryer, and the first collector is set in the lower section of cyclone separator.
So by the connection and setting of said apparatus, not only mixture is caused to lose reduction in spray-drying process,
Product yield is high, and energy consumption is low, and manipulation is convenient, and the quality of product is good, and environmental benefit is good, application easy to spread.
In a kind of optional embodiment, peristaltic pump is provided between the agitator and spray dryer；
Preferably, the agitator is double spiral agitator；
Preferably, the spray dryer is pressure spray dryer device.
Suspension is conveyed by peristaltic pump, convenient operation, is easily controlled, operating efficiency is high.Using double spiral agitator energy
Enough further to improve mixed effect, mixed-precision is high, and precursor spherical granule-morphology can remain intact, through press atomization after
The ternary material electrochemical performance dry, sintered out, improves product quality.
With reference to specific embodiment, comparative example and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of mixed lithium method of lithium ion cell positive ternary material, comprises the following steps：
(a) weigh：Ternary material precursor Ni is weighed respectively1/3Co1/3Mn1/3(OH)2, lithium source monohydrate lithium hydroxide and go
Ionized water；
Wherein, ternary material precursor and the mol ratio of Li in lithium source are 1：1, the quality of ternary material precursor is lithium source
2.2 times of quality, 2.08 times for ternary material precursor with lithium source gross mass of the quality of deionized water；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source using agitator all to dissolve, added
Ternary material precursor is mixed together stirring, the suspension being uniformly mixed；
Wherein, the rotating speed of mixing is 2500rpm, time 60min；
(c) it is spray-dried：Obtained suspension is spray-dried using pressure spray dryer device, obtains mixing with lithium
Thing, should be black powder with the mixture that lithium mixture is ternary material precursor and lithium source；
Wherein, atomizing pressure 0.15Mpa, EAT are 250 DEG C, and leaving air temp is 90 DEG C.
Embodiment 2
A kind of mixed lithium method of lithium ion cell positive ternary material, comprises the following steps：
(a) weigh：Ternary material precursor Ni is weighed respectively1/3Co1/3Mn1/3(OH)2, lithium source monohydrate lithium hydroxide and go
Ionized water；
Wherein, ternary material precursor and the mol ratio of Li in lithium source are 1：1.2, the quality of ternary material precursor is lithium
2.5 times of the quality in source, the quality of deionized water are 3.5 times of ternary material precursor and lithium source gross mass；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source using agitator all to dissolve, added
Ternary material precursor is mixed together stirring, the suspension being uniformly mixed；
Wherein, the rotating speed of mixing is 4000rpm, time 40min；
(c) it is spray-dried：Obtained suspension is spray-dried using pressure spray dryer device, obtains mixing with lithium
Thing, should be black powder with the mixture that lithium mixture is ternary material precursor and lithium source；
Wherein, atomizing pressure 0.75Mpa, EAT are 350 DEG C, and leaving air temp is 120 DEG C.
Embodiment 3
A kind of mixed lithium method of lithium ion cell positive ternary material, comprises the following steps：
(a) weigh：Ternary material precursor Ni is weighed respectively0.8Co0.1Mn0.1(OH)2, lithium source monohydrate lithium hydroxide and go
Ionized water；
Wherein, ternary material precursor and the mol ratio of Li in lithium source are 1：1.07, the quality of ternary material precursor is
2.8 times of the quality of lithium source, the quality of deionized water are 2 times of ternary material precursor and lithium source gross mass；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source using agitator all to dissolve, added
Ternary material precursor is mixed together stirring, the suspension being uniformly mixed；
Wherein, the rotating speed of mixing is 2000rpm, time 90min；
(c) it is spray-dried：Obtained suspension is spray-dried using pressure spray dryer device, obtains mixing with lithium
Thing, should be black powder with the mixture that lithium mixture is ternary material precursor and lithium source；
Wherein, atomizing pressure 0.05Mpa, EAT are 250 DEG C, and leaving air temp is 100 DEG C.
Embodiment 4
A kind of mixed lithium method of lithium ion cell positive ternary material, comprises the following steps：
(a) weigh：Ternary material precursor Ni is weighed respectively0.5Co0.2Mn0.3(OH)2, lithium source monohydrate lithium hydroxide and go
Ionized water；
Wherein, ternary material precursor and the mol ratio of Li in lithium source are 1：1, the quality of ternary material precursor is lithium source
2.1 times of quality, 2.6 times for ternary material precursor with lithium source gross mass of the quality of deionized water；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source using agitator all to dissolve, added
Ternary material precursor is mixed together stirring, the suspension being uniformly mixed；
Wherein, the rotating speed of mixing is 3000rpm, time 55min；
(c) it is spray-dried：Obtained suspension is spray-dried using pressure spray dryer device, obtains mixing with lithium
Thing, should be black powder with the mixture that lithium mixture is ternary material precursor and lithium source；
Wherein, atomizing pressure 0.50Mpa, EAT are 280 DEG C, and leaving air temp is 110 DEG C.
Embodiment 5
As shown in figure 1, the present embodiment provides a kind of mixed lithium device of lithium ion cell positive ternary material, including connect successively
Agitator 1, spray dryer 3, collecting mechanism 4 and the air-introduced machine 5 connect.
Wherein, agitator 1 is connected by pipeline with spray dryer 3, and spray dryer 3 passes through pipeline and collecting mechanism 4
Connection, collecting mechanism 4 are connected by pipeline with air-introduced machine 5.
Further, collecting mechanism 4 includes cyclone separator and the first collector, and the first collector is located at cyclone separator
Lower section.Collecting mechanism also includes the second collector, and the second collector is located at the lower section of the spray dryer.Collecting mechanism is also
Including dust collector, dust collector is connected by air-introduced machine with cyclone separator.
Further, peristaltic pump 2 is provided between agitator 1 and spray dryer 3.
Further, the agitator 1 is double spiral agitator.Spray dryer 3 is pressure spray dryer device.
The mixed lithium device for the lithium ion cell positive ternary material that the present embodiment provides, can be realized described in embodiment 1~4
Lithium ion cell positive ternary material mixed lithium method.
Embodiment 6
It is placed in what embodiment 1 obtained with lithium mixture in high-temperature roller kiln, under oxygen-enriched state, with 2 DEG C/min liter
Warm speed rises to 550 DEG C and fired 6 hours, then rises to 880 DEG C with 2 DEG C/min programming rate and fire 11 hours, naturally cools to
Room temperature, obtain LiNi1/3Co1/3Mn1/3O2Powder.By LiNi1/3Co1/3Mn1/3O2Used as anode material for lithium-ion batteries.It is right
Electrochemical property test should be carried out with lithium mixture and positive electrode, and be assembled into lithium ion battery and carry out electrochemistry
Can test.
Test result is as follows：Tap density with lithium mixture is 0.97g/cm3, specific surface area 42.83m2/g。
LiNi1/3Co1/3Mn1/3O2The tap density of positive electrode is 2.14g/cm3, specific surface area 0.58m2/g。
As shown in Fig. 2 under conditions of 0.2C electric discharges, material initial discharge capacity reaches 157.73mAh/g, 30 circulations
Conservation rate is 99.33% afterwards, the LiNi that will be obtained1/3Co1/3Mn1/3O2Powder is scanned Electronic Speculum test, test result such as Fig. 3
It is shown.As seen from Figure 3, the material is spherical morphology, and granular size is homogeneous, and uniformity is preferable.
Comparative example 1
A kind of mixed lithium method of lithium ion cell positive ternary material, is carried out by the way of existing dry method batch mixing.And
To resulting performance test is carried out with lithium mixture and positive electrode.
Test result shows that the tap density with lithium mixture is 0.65g/cm3, specific surface area 38.75m2/g。
LiNi1/3Co1/3Mn1/3O2The tap density of positive electrode is 1.68g/cm3, specific surface area 0.38m2/g。
Under conditions of 0.2C electric discharges, material initial discharge capacity reaches 148.62mAh/g, and conservation rate is after 30 circulations
98.22%.As shown in figure 4, the spherical morphology of the material of scanned Electronic Speculum test analysis comparative example 1 is destroyed, size distribution
Uniformity is poor, and has more chip and foreign particle to be mixed between particle.
Comparative example 2
A kind of mixed lithium method of lithium ion cell positive ternary material, as different from Example 1, the quality of deionized water
For 5.5 times of ternary material precursor and lithium source gross mass, lithium source and ternary material precursor are mixed together with simultaneously with deionized water
Stirring is closed, remaining uniform embodiment 1 is identical.And carry out performance test with lithium mixture and positive electrode to resulting.
Test result shows that the tap density with lithium mixture is 0.71g/cm3, specific surface area 34.06m2/g。
LiNi1/3Co1/3Mn1/3O2The tap density of positive electrode is 1.75g/cm3, specific surface area 0.46m2/g。
Under conditions of 0.2C electric discharges, material initial discharge capacity reaches 147.35mAh/g, and conservation rate is after 30 circulations
97.25%.The spherical morphology of the material of scanned Electronic Speculum test analysis comparative example 2 is destroyed, and size distribution uniformity is poor.
Pass through the above embodiments and the analysis test result of comparative example, lithium ion cell positive provided by the invention
The mixed lithium method of ternary material, higher with tap density, even particle distribution, the uniformity of particle diameter is good, and chemical property is excellent
The advantages of different.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of mixed lithium method of lithium ion cell positive ternary material, it is characterised in that comprise the following steps：
(a) weigh：Ternary material precursor, lithium source and deionized water are weighed in proportion；
(b) material by wet type mixing：Lithium source and deionized water first are mixed into lithium source all to dissolve, add ternary material precursor
Stirring is mixed together, the suspension being uniformly mixed；
(c) it is spray-dried：Obtained suspension is spray-dried, obtains matching somebody with somebody lithium mixture.
2. the mixed lithium method of lithium ion cell positive ternary material according to claim 1, it is characterised in that the ternary
The chemical formula of material precursor is NixCoyMnz(OH)2, wherein x：y：Z=1：1：1、4：2：4、5：2：3、6：2：2 or 8：1：1.
3. the mixed lithium method of lithium ion cell positive ternary material according to claim 1, it is characterised in that the lithium source
For monohydrate lithium hydroxide.
4. the mixed lithium method of the lithium ion cell positive ternary material according to any one of claims 1 to 3, its feature exist
In the ternary material precursor and Li in lithium source mol ratio are 1：1~1.20；
Preferably, the quality of the ternary material precursor is 1~3 times, preferably 1.8~2.2 times of quality of the lithium source；
Preferably, the quality of the deionized water is 1~5 times of ternary material precursor and lithium source gross mass, preferably 2~3
Times.
5. the mixed lithium method of lithium ion cell positive ternary material according to claim 1, it is characterised in that the step
(b) in, lithium source, deionized water and ternary material precursor are mixed using agitator, the rotating speed of mixing
For 2000~4000rpm, the time is 40~90min.
6. the mixed lithium method of lithium ion cell positive ternary material according to claim 5, it is characterised in that the step
(c) in, it is spray-dried using pressure spray dryer device, atomizing pressure is 0.05Mpa~0.75MPa, EAT 200
DEG C~350 DEG C, leaving air temp is 90 DEG C~120 DEG C.
7. the mixed lithium method of the lithium ion cell positive ternary material according to claim 5 or 6, it is characterised in that described
Peristaltic pump is provided between agitator and spray dryer, the suspension obtained in the agitator is defeated by the peristaltic pump
Deliver in spray dryer and be spray-dried.
8. a kind of mixed lithium device for the lithium ion cell positive ternary material for realizing any one of claim 1~7 methods described, its
It is characterised by, including agitator, spray dryer, collecting mechanism and the air-introduced machine being sequentially connected.
9. the mixed lithium device of lithium ion cell positive ternary material according to claim 8, it is characterised in that the collection
Mechanism includes cyclone separator and the first collector, and first collector is located at the lower section of the cyclone separator；
Preferably, the collecting mechanism also includes the second collector, and second collector is located under the spray dryer
Side；
Preferably, the collecting mechanism also includes dust collector, and the dust collector passes through air-introduced machine and cyclone separator
Connection.
10. the mixed lithium device of lithium ion cell positive ternary material according to claim 8 or claim 9, it is characterised in that described
Peristaltic pump is provided between agitator and spray dryer；
Preferably, the agitator is double spiral agitator；
Preferably, the spray dryer is pressure spray dryer device.
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