CN105529432B - A kind of anode material for lithium-ion batteries liquid phase coating method and its coating unit - Google Patents
A kind of anode material for lithium-ion batteries liquid phase coating method and its coating unit Download PDFInfo
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- CN105529432B CN105529432B CN201610075092.9A CN201610075092A CN105529432B CN 105529432 B CN105529432 B CN 105529432B CN 201610075092 A CN201610075092 A CN 201610075092A CN 105529432 B CN105529432 B CN 105529432B
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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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
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- H01M4/366—Composites as layered products
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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
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Abstract
The present invention relates to anode material for lithium-ion batteries surface coating technology fields, traditional anode material for lithium-ion batteries liquid phase coating method tedious process, use the organic solvents such as ethyl alcohol more, have to pass through liquid processed, cladding, solvent recovery, it is dry, the processes such as calcining, there are manufacturing cost height, yield rate is low, low production efficiency, the problems such as dangerous, regarding to the issue above, the present invention provides a kind of liquid phase coating method that element compound aqueous solution to be covered is sprayed to anode material for lithium-ion batteries powder surface using specially designed device, this method needs not move through liquid processed, solvent recovery, the processes such as dry, positive electrode powder after cladding obtained can be directly entered subsequent heat treatment procedure, this method has safety, process is easy, manufacturing cost is low, high yield rate, the advantages that production efficiency is high.The present invention also provides a kind of anode material for lithium-ion batteries liquid phase coating device, which is applied in large-scale production, and simple in structure, safety, covered effect are good.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries surface coating technology field, specially a kind of lithium ion cell positive
Material liquid phase method for coating and its coating unit.
Background technology
Since lithium ion battery has, memory-less effect, self discharge is small, operating temperature range is wide, energy density is high and environmentally friendly
The advantages that, it is widely used in the every field of production and life, such as mobile electronic device, electric tool, electric environment protecting vapour
The fields such as vehicle, ups power.
The positive electrode of lithium ion battery has great influence as its core component to the performance of battery.Common anode
Material includes mainly LiCoO2、LiNiXCoYMn1-X-YO2、LiMn2O4、LiFePO4Deng.3C equipment (laptop, mobile phone etc.)
Field requires very high, LiCoO to material volume energy density2、LiNiXCoYMn1-X-YO2Because having higher volume energy density,
Thus it is widely used as main positive electrode.
As the function of 3C equipment is gradually become strong, the requirement to lithium ion battery energy density is also higher and higher.To improve
Battery charge cutoff voltage is increased to 4.35V or 4.4V by 4.2V, can make same system by the energy density of lithium ion battery
Capacity of lithium ion battery improve 10~15%, such method be improve lithium ion battery energy density effective way.But work as
When charge cutoff voltage is increased to 4.35V or 4.4V, anode material for lithium-ion batteries has higher oxidisability, violent with electrolyte
Reaction, cycle performance drastically deteriorate, and security performance also decreases.Therefore, we will carry out anode material for lithium-ion batteries
Surface coating modification, inhibitory activity material is reacted with electrolyte, to improve high temperature cyclic performance.
The patent of invention of China Patent Publication No. CN102956895A discloses a kind of lithium-ion electric of surface recombination cladding
Pond positive electrode and preparation method and lithium ion battery.The preparation method does dispersant using absolute ethyl alcohol, not only makes
There are security risks for industrial production, and manufacturing cost is high.The patent of invention of China Patent Publication No. CN101150190A discloses
A kind of lithium ion secondary battery anode material zirconium, phosphor adulterated cobalt acid lithium and preparation method thereof, which is done using water
Dispersant, although the problem of there is no security risks, must there is one of drying process, complex procedures, manufacturing cost is higher.
Invention content
For the problems of the prior art, the present invention provide a kind of cladding process simplicity, high yield rate, production efficiency height,
Low, the safe anode material for lithium-ion batteries liquid phase coating method of manufacturing cost.
To realize the above technical purpose, the technical scheme is that：A kind of anode material for lithium-ion batteries liquid phase coating
Method, specific steps include：
A. anode material for lithium-ion batteries powder is added in cladding tank, starts cladding tank and rotates, in mixing cladding tank
Anode material for lithium-ion batteries powder；
B. tap water obtains pure water after ultrapure water machine purifies, and element compound to be covered is dissolved in pure water,
Obtain cladding solution；
C. the lithium ion battery in the cladding tank of rotation is sprayed after the cladding solution of acquisition being atomized by atomising device
Positive electrode powder surface, after the completion of spraying, cladding tank continues to rotate, the anode material for lithium-ion batteries powder in mixing cladding tank
Body, covering liquid are evenly coated at anode material for lithium-ion batteries powder surface；
D. after being covered to complete, stop cladding tank operation, material is drawn off, into subsequent heat treatment process.
From the above, it can be seen that the present invention has following advantages：
1. cladding solution is aqueous solution rather than organic solution, safe, not volatile, environmental pollution is small；
2. element compound aqueous solution to be covered is sprayed in anode material for lithium-ion batteries powder surface by atomizer,
It is easy to be evenly coated, modified effect is good, high yield rate；
3. the modified positive electrode sprayed using atomizer, water content is extremely low, no longer needs to be dried
Processing can be directly entered subsequent heat treatment procedure, save process, reduce manufacturing cost；
4. carry out cladding process compared with traditional method for coating using method of the present invention, need not move through liquid processed,
Solvent recovery, drying process, process is easy, and production efficiency is high, and manufacturing cost is low, is easy to industrialization.
Preferably, the cladding tank rotational time described in step A is 30-120 minutes.
Preferably, the cladding tank rotational time described in step C is 30-120 minutes.
In order to realize that above-mentioned method for coating, the present invention provide a kind of anode material for lithium-ion batteries liquid phase coating device, packet
Ultrapure water machine, agitator tank, agitating paddle, agitating paddle motor, atomizer and rotatable cladding tank are included, the agitator tank is equipped with water inlet
The water outlet of mouth, liquid outlet and charge door, the water inlet and ultrapure water machine connects, the inlet of the liquid outlet and atomizer
Connection, the agitating paddle are set in agitator tank and are driven by agitating paddle motor, and the atomizer includes multiple spray outlets, described
It is horizontally disposed to coat tank, the spray outlet is set in cladding tank, and the cladding tank is equipped with feed inlet.
The course of work of the device is：
1. anode material for lithium-ion batteries powder is added in cladding tank, starts cladding tank and rotate, in mixing cladding tank
Anode material for lithium-ion batteries powder.
2. tap water through ultra-pure water and is cleaned into water inlet addition agitator tank of the pure water by agitator tank.
3. agitator tank is added in the charge door of the agitated tank of element compound to be covered, element compound to be covered is dissolved in
In pure water in agitator tank, cladding solution is formed.
4. the liquid outlet of the agitated tank of cladding solution enters atomizer, atomizer is atomized cladding solution, after atomization
Cladding solution sprayed on the surface of anode material for lithium-ion batteries powder by spray outlet.
5. after the completion of spraying, cladding tank continues to rotate, the anode material for lithium-ion batteries powder in mixing cladding tank, cladding
Liquid is evenly coated at anode material for lithium-ion batteries powder surface, is covered to complete.
From the above, it can be seen that the present invention has following advantages：The coating unit overall structure is simple, covered effect
Good, process simplicity, safety.
Preferably, the spray outlet is axial uniform in cladding tank along cladding tank；Spray outlet is along cladding tank axis
To being uniformly arranged, most preferably effect is sprayed to reach.
As an improvement, further include air compressor machine, be additionally provided with air inlet on the agitator tank, the gas outlet of the air compressor machine with stir
Mix the air inlet connection of tank；When the insufficient pressure in agitator tank so as to when solution normally enters atomizer in tank or need to adjust
When going out liquid speed and spending of agitator tank liquid outlet, using air compressor machine into agitator tank injecting compressed air, compressed air is to pot liquid
It is pressurized.
As an improvement, the agitator tank is additionally provided with exhaust outlet；When stirring pressure inside the tank is excessive, by exhaust outlet to stirring
Tank pressure release.
As an improvement, being additionally provided with the first pressure gauge for monitoring pressure inside the tank on the agitator tank；Use pressure gauge pair
Pressure in agitator tank is monitored, and according to monitoring data, adjusts the working condition of air compressor machine and exhaust outlet, in timely adjustment tank
Pressure.
As an improvement, the liquid outlet of the agitator tank and the inlet of atomizer are connected by pipeline, set on the pipeline
There is second pressure gauge；For monitoring agitator tank and the pressure condition on atomizer connecting line.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention；
Fig. 2 is the spray outlet structural schematic diagram of atomizer of the present invention；
Reference numeral：1. ultrapure water machine, 2. agitator tanks, 2.1. water inlets, 2.2. liquid outlets, 2.3. charge doors, 2.4. into
Gas port, 2.5. exhaust outlets, 3. agitating paddles, 4. agitating paddle motors, 5. atomizers, 5.1. inlets, 5.2. spray outlets, 6. can revolve
Turn cladding tank, 6.1. feed inlets, 7. air compressor machines, the gas outlets 7.1., 8. first pressure gauges, 9. second pressure gauges.
Specific implementation mode
In conjunction with Fig. 1, the specific embodiment that the present invention will be described in detail, but any limit is not done to the claim of the present invention
It is fixed.
As shown in Figure 1, a kind of anode material for lithium-ion batteries liquid phase coating device, including ultrapure water machine 1, agitator tank 2, stir
Paddle 3, agitating paddle motor 4, atomizer 5 and rotatable cladding tank 6 are mixed, agitator tank 2 is equipped with water inlet 2.1, liquid outlet 2.2 and adds
Material mouth 2.3, water inlet 2.1 are connect with the water outlet of ultrapure water machine 1, and liquid outlet 2.2 is connect with the inlet 5.1 of atomizer 5, is stirred
It mixes paddle 3 to drive in agitator tank 2 and by agitating paddle motor 4, atomizer 5 includes multiple spray outlets 5.2, and cladding tank level is set
It sets, spray outlet 5.2 is set in cladding tank, and cladding tank 6 is equipped with feed inlet 6.1.
Using above-mentioned apparatus, using 2000Kg cobalt acid lithiums as anode material for lithium-ion batteries, the process of liquid phase coating is carried out
It is as follows：
1. the cobalt acid lithium of the 6 addition 2000Kg into cladding tank of feed inlet 6.1 by coating tank 6, starts cladding tank 6 and rotates
30-120 minutes, coat tank in 6 cobalt acid lithium be uniformly mixed.
2. the tap water of constant weight is pure water through the purification of ultrapure water machine 1, then pass through the water inlet 2.1 of agitator tank 2
It is added in agitator tank 2.
3. the element compound to be covered of constant weight is added by the charge door 2.3 of agitator tank 2 in agitator tank 2, wait wrapping
The weight of element compound is covered with the pure water weight in step 2 to match.
It drives agitating paddle 3 to be stirred 4. opening agitating paddle motor 4, element compound to be covered is made to be dissolved in agitator tank 2
Interior pure water obtains qualified cladding solution.
5. opening the inlet 5.1 of atomizer 5, atomizer 5, which is added, in the qualified cladding solution in agitator tank 2 is atomized
Processing, spray outlet 5.2 of the qualified cladding solution through atomizer 5 after atomization spray the cobalt acid lithium in the cladding tank 6 of rotation
Powder surface, after the completion of spraying, cladding tank 6 continues rotation 30-120 minutes, and mixing coats in tank 6 cobalt acid lithium powder, cladding
Liquid is evenly coated at surface of material.
6. after being covered to complete, stopping cladding operation, material being drawn off, into subsequent processing process.
It is noticeable to have in the above process：
1. the Best Times of the embodiment thus of cladding tank 6 rotational time of step 1 30-120 minutes, are not particularly suited for owning
Cladding process, rotational time the step for when specific cladding are set according to the actual situation that feeds intake, are uniformly mixed；
2. the Best Times of the embodiment thus of cladding tank 6 rotational time of step 5 30-120 minutes, are not particularly suited for owning
Cladding process, rotational time the step for when specific cladding are set according to actual conditions, and covering liquid is evenly coated at object
Expect surface；
3. in step 2 and step 3, the weight proportion of pure water and element compound to be covered is according to cladding standard division
What be calculated, cladding standard is then formulated according to practical cladding demand；
4. the surface for drawing off material in step 6 is the cladding moisture film formed by covering liquid, the water content for coating moisture film meets
Subsequent heat treatment procedure calls in industry technique, the material drawn off, which no longer needs to be dried processing, can enter heat treatment work
Sequence.
In order to further strengthen the function of the device, following corrective measure can be carried out：
1. spray outlet 5.2 is coated along axial be uniformly set to of cladding tank 6 in tank 6, most preferably effect is sprayed to reach.
2. adding air compressor machine 7, air inlet 2.4 is correspondingly added on agitator tank 2, by the gas outlet 7.1 of air compressor machine with stir
The air inlet 2.4 for mixing tank 2 connects, and the compressed air that air compressor machine 7 generates can enter through air inlet 2.4 in agitator tank 2, compressed air
There are two types of functions for tool:(1) when the insufficient pressure in agitator tank 2 so that the cladding solution in tank normally enters mist from liquid outlet 2.2
When changing device 5, under the action of compressed air pressure, cladding solution is pressed into atomizer 5；(2) when 2 liquid outlet of agitator tank, 2.2 energy
Enough normally to go out liquid but need to adjust out liquid speed when spending, compressed air is pressurized the cladding solution in tank, improves out liquid speed degree.
3. exhaust outlet 2.5 is added on agitator tank 2, when pressure is excessive in agitator tank 2, by exhaust outlet 2.5 to stirring
Tank 2 carries out pressure release processing.
4. the first pressure gauge 8 for monitoring pressure inside the tank is added on agitator tank 2, using pressure gauge 8 in agitator tank 2
Pressure be monitored, according to monitoring data, adjust the working condition of air compressor machine 7 and exhaust outlet 2.5, timely adjustment tank internal pressure
Power.
5. the liquid outlet 2.2 of agitator tank 2 is connect with the inlet 5.1 of atomizer 5 by pipeline, pipeline is equipped with the second pressure
Power table 9, for monitoring agitator tank 2 and the pressure condition on 5 connecting line of atomizer.
In conclusion the present invention has the following advantages：
1. cladding solution is aqueous solution rather than organic solution, safe, not volatile, environmental pollution is small.
2. element compound aqueous solution to be covered is sprayed in anode material for lithium-ion batteries powder table by atomizer 5
Face is easy to be evenly coated, and modified effect is good, high yield rate.
3. the modified positive electrode sprayed using atomizer 5, water content is extremely low, no longer needs to be dried
Processing can be directly entered subsequent heat treatment procedure, save process, reduce manufacturing cost.
4. carry out cladding process compared with traditional method for coating using method of the present invention, need not move through liquid processed,
Solvent recovery, drying process, process is easy, and production efficiency is high, and manufacturing cost is low, is easy to industrialization.
5. coating unit of the present invention, overall structure is simple, covered effect is good, process is easy, safety.
It is understood that above with respect to the specific descriptions of the present invention, it is merely to illustrate the present invention and is not limited to this
Technical solution described in inventive embodiments.It will be understood by those of ordinary skill in the art that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technique effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (5)
1. a kind of anode material for lithium-ion batteries liquid phase coating method, it is characterised in that：
It is coated using liquid phase coating device, the liquid phase coating device includes ultrapure water machine (1), agitator tank (2), agitating paddle
(3), agitating paddle motor (4), atomizer (5) and rotatable cladding tank (6), the agitator tank (2) be equipped with water inlet (2.1),
Liquid outlet (2.2) and charge door (2.3), the water inlet (2.1) connect with the water outlet of ultrapure water machine (1), the liquid outlet
(2.2) it is connect with the inlet of atomizer (5) (5.1), the agitating paddle (3) is set in agitator tank (2) and by agitating paddle motor
(4) it drives, the atomizer (5) includes multiple spray outlets (5.2), and the cladding tank (6) is horizontally disposed, the spray outlet
(5.2) axial uniform in cladding tank (6) along cladding tank (6), the cladding tank (6) is equipped with feed inlet (6.1)；
The specific steps of liquid phase coating method include：
A. by anode material for lithium-ion batteries powder be added cladding tank in, start cladding tank rotation, mixing cladding tank in lithium from
Sub- cell positive material powder, cladding tank rotational time are 30-120 minutes；
B. tap water obtains pure water after ultrapure water machine purifies, and element compound to be covered is dissolved in pure water, is obtained
Cladding solution, the cladding solution are aqueous solution rather than organic solution；
C. the lithium ion cell positive material in the cladding tank of rotation is sprayed after the cladding solution of acquisition being atomized by atomizer
Expect powder surface, after the completion of spraying, cladding tank continues to rotate, the anode material for lithium-ion batteries powder in mixing cladding tank, packet
Covering liquid is evenly coated at anode material for lithium-ion batteries powder surface, and cladding tank rotational time is 30-120 minutes；
D. after being covered to complete, stop cladding tank operation, material is drawn off, into subsequent heat treatment process.
2. anode material for lithium-ion batteries liquid phase coating method as described in claim 1, it is characterised in that：The liquid phase coating
Device further includes air compressor machine (7), and air inlet (2.4), the gas outlet of the air compressor machine (7) are additionally provided on the agitator tank (2)
(7.1) it is connect with the air inlet of agitator tank (2.4).
3. anode material for lithium-ion batteries liquid phase coating method as described in claim 1, it is characterised in that：The agitator tank
(2) it is additionally provided with exhaust outlet (2.5).
4. anode material for lithium-ion batteries liquid phase coating method as described in claim 1, it is characterised in that：The agitator tank
(2) first pressure gauge (8) for monitoring pressure inside the tank is additionally provided on.
5. anode material for lithium-ion batteries liquid phase coating method as described in claim 1, it is characterised in that：The agitator tank
(2) liquid outlet (2.2) is connect with the inlet (5.1) of atomizer (5) by pipeline, and the pipeline is equipped with second pressure gauge
(9)。
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| CN109671917A (en) * | 2017-10-17 | 2019-04-23 | 赣州市瑞富特科技有限公司 | A kind of lithium ion battery negative material high speed atomisation coating machine and its application |
| CN108448094A (en) * | 2018-03-21 | 2018-08-24 | 深圳新恒业电池科技有限公司 | A kind of surface modification device of positive electrode and a kind of preparation method of positive electrode |
| CN110270251A (en) * | 2019-08-05 | 2019-09-24 | 安徽科达新材料有限公司 | A kind of liquid phase coating device of silicon monoxide composite cathode material |
| CN111146426A (en) * | 2019-12-31 | 2020-05-12 | 无锡晶石新型能源股份有限公司 | Compounding method of lithium ion battery electrode active material |
| CN115634618B (en) * | 2022-11-07 | 2023-09-08 | 承德石油高等专科学校 | Intelligent coating device for preparing lithium battery anode material |
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| CN102637877B (en) * | 2012-05-07 | 2015-01-28 | 昆明理工大学 | Lithium ion battery anode material and manufacturing method thereof |
| CN202977594U (en) * | 2012-11-27 | 2013-06-05 | 天津市贝特瑞新能源科技有限公司 | Coating device applied to coating preparation of negative electrode material of lithium ion battery |
| CN103396242A (en) * | 2013-08-08 | 2013-11-20 | 徐庆海 | Production process and device for organization of inorganic fertilizers |
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