CN110379999A - A kind of combination electrode, electrode coating unit and electrode preparation method - Google Patents
A kind of combination electrode, electrode coating unit and electrode preparation method Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present invention provides a kind of combination electrodes, and including adjacent surface layer, transition zone and bottom, the skin depth is 0.5-30 μm, and the underlayer thickness is 50-150 μm, and the transition region thickness is 2-20 μm.The present invention also provides a kind of electrode coating unit and the method for preparing combination electrode using the device, which includes transmission device, spray equipment and drying unit；The transmission device is for transmitting collector.The combination electrode that the present invention is prepared by the way of the synchronous coating of wet process has excellent dynamic performance, and the lithium ion battery of combination electrode assembly, interfacial reaction concentration polarization is small, has outstanding power-performance, rate charge-discharge temperature rise is low, and dynamic performance is excellent.This method is easy to operate, at low cost, and the combination electrode containing transition zone of production has excellent dynamic performance, can greatly promote the comprehensive technical indexes of lithium-ions battery.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of lithium ion battery combination electrode and the compound electric
The method of the coating unit and application electrode coating unit progress combination electrode preparation of pole.
Background technique
With economic and science and technology rapid development, the consumption of fossil resource is growing day by day, caused environmental problem and energy
Source crisis has become the foreseeable problem of modern social development.Under the premise of herein, the exploitation of new energy has become the whole world
The main trend of change, as one kind of new energy, it is powerful that lithium ion battery in fields such as electric car, intelligent energy storage has embodied its
Function.Lithium ion battery is a kind of with clear superiorities such as high operating voltage, high-energy-density, long circulation lifes, also it is positive because
For with above-mentioned irreplaceable advantage, lithium ion battery is widely used.
With the development of science and technology, more stringent requirements are proposed to lithium ion battery for market and application demand, in recent years
Come, the concept of combination electrode causes extensive concern.Combination electrode refers to electrode on a current collector, and there are two coatings, pass through
Composite coating can improve the chemical property and dynamic performance of electrode surface, to the capacity, power-performance, cyclicity of battery
There can be biggish promotion with security performance.Currently, be often used be method be first on a current collector apply one layer of base pastes, drying
Continue to apply one layer of surface layer slurry again on the surface of base pastes afterwards, then surface layer slurry is dried.But be in this way by
Top coat is coated in relative coarseness and has on the priming coat of porosity, and the interfacial bonding effect between two layers is poor, easily peelable, top coat
Appearance it is also defective, greatly affected the performance of this kind of combination electrode.
Application No. is in 201611071066.5 entitled " a kind of method of dry process battery capacitor combination electrode "
A kind of technique of dry process combination electrode is provided in state's patent, specifically: electrode material is weighed, by squeezing raw material system
At dry state electrode film, the electrode film is pasted on conductive coating using conducting resinl then, then rolls to obtain composite coating.On
Technical solution is stated although feasible, dry state film is easy to happen cracking, and conducting resinl can generate nothing to combination electrode after stickup
The influence that method is estimated.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of compound electrics with multilayer active material layer
Pole, the combination electrode have excellent dynamic performance, can reply the comprehensive technical indexes for promoting lithium ion battery.Meanwhile it mentioning
A kind of coating unit of combination electrode, and the preparation method coated using the device are supplied.
Present invention technical effect to be achieved is realized by following scheme:
Combination electrode provided in the present invention includes adjacent surface layer, transition zone and bottom, and the skin depth is
0.5-30 μm, the underlayer thickness is 50-150 μm, and the transition region thickness is 2-20 μm.
Further, the top layer raw material is to include amorphous carbon, lithium titanate, carbonaceous mesophase spherules, graphene, carbon nanometer
One or more kinds of electrocondution slurry in pipe, fullerene；The bottom raw material is to include artificial graphite, natural graphite, interphase
One or more kinds of active material slurry in carbosphere, silicon-carbon cathode material.
In combination electrode of the present invention, surface layer is anti-come the interface for improving electrode surface by the ionic conduction function of providing superelevation
Dynamics is answered, bottom is main active material layer, provides the ability of removal lithium embedded.Likewise it is preferred that used primary coat slurry and table
Apply slurry bonding agent it is identical, bonding agent has stronger intermolecular force after the drying, it is ensured that combination electrode top coat with
Good adhesive effect between priming coat.Simultaneously because the synchronous coating of wet process, gradually volatilizees and pole piece drying process in solvent
In, the slurry between priming coat and top coat has certain diffusion and convection current, generates a transition zone, transition zone utilizes after drying
Its diffusion effect can also improve the interface ion diffusion between top coat and priming coat.Obtained combination electrode, table
Interfacial bonding effect is good between coating and priming coat, does not generate removing；Simultaneously because there is transition zone in centre, in charge and discharge process
Ion diffusion there will not be concentration polarization caused by apparent interfacial concentration difference, dynamic performance is excellent.The present invention pass through by
Top coat and priming coat slurry are produced transition zone, and carry out first drying, are greatly changed using the double-deck squash type wet coating
It has been apt to the interfacial bonding effect of two coatings.This method is easy to operate, technical maturity, and the compound electric containing transition zone of production is great
There is excellent dynamic performance, can greatly promote the comprehensive technical indexes of lithium-ions battery.
A kind of coating unit, including transmission device, spray equipment and drying unit are additionally provided in the present invention；
The transmission device is for transmitting collector；
The spray equipment includes the first spray module and the second spray module, and first spray module is located at described the
The lower section of two spray modules, first spray module are used for sprayed layer undercoat slurry, and second spray module is for spraying table
Layer slurry, the discharge port of the discharge port of first spray module and second spray module towards the transmission device,
To spray the base pastes and the surface layer slurry simultaneously；
The drying unit is located at the downstream of the spray equipment, and is located at the discharging side of the transmission device.
As a result, by setting spray equipment and drying unit, can the surface of collector coat simultaneously base pastes and
Surface layer slurry, then property is dried again, can simplify coating method in this way, and the compound electric containing transition zone made is great
There is excellent dynamic performance, can greatly promote the comprehensive technical indexes of lithium-ions battery.
Further, the discharge port of first spray module and the discharge port of second module are located at same level position
It sets.
Further, the spray equipment includes upper mold, middle mould and lower die, the top split-phase of the upper mold and the middle mould
To being arranged and constituting second spray module, the lower part point of the lower die and the middle mould is oppositely arranged and constitutes described first
Spray module.
Further, the clearance distance point between the top of the upper mold and the middle mould is h1, the lower die and described
Clearance distance between the lower part of middle mould point is h2, wherein h2 > h1.
Further, the spray equipment is located at the feed side of the transmission device.
It further, further include first pump housing and second pump housing, first pump housing connects first spray module, institute
It states second pump housing and connects second spray module, first pump housing and second pump housing are metering pump.
The above-mentioned method for carrying out electrode preparation using above-mentioned coating unit is additionally provided in the present invention, specifically includes following step
It is rapid:
S01, the transmission device transmit the collector；
S02, the spray equipment are starched using first spray module to the first surface sprayed layer undercoat of the collector
Material, and also while using second spray module to the base pastes spray surface layer slurry；
S03, the drying unit dry the base pastes and the surface layer slurry on the collector first surface.
As a result, due to gradually volatilizing and doing in the solvent of base pastes and surface layer slurry using the synchronous coating method of wet process
During dry, the slurry between priming coat and top coat has certain diffusion and convection current, generates a transition zone, transition after drying
Layer utilizes its diffusion effect, can also improve the interface ion diffusion between top coat and priming coat.Obtained is compound
Electrode, interfacial bonding effect is good between top coat and priming coat, is not likely to produce removing；Simultaneously because there is transition zone in centre, filling
Ion diffusion in discharge process there will not be concentration polarization caused by apparent interfacial concentration difference, and dynamic performance is excellent.And
And this method is easy to operate, technical maturity, the combination electrode containing transition zone of production has excellent dynamic performance, can be compared with
Significantly promote the comprehensive technical indexes of lithium-ions battery.
Further, after the completion of S03, further includes:
Overturn the collector；
The transmission device transmits the collector；
The spray equipment utilizes second surface sprayed layer undercoat slurry of first spray module to the collector, and
Also surface layer slurry is sprayed to the base pastes using second spray module simultaneously；
The drying unit dries the base pastes and the surface layer slurry on the collector second surface.
Technical solution of the present invention has the advantages that
1, the combination electrode that the present invention is prepared by the way of the synchronous coating of wet process has excellent dynamic performance, multiple
The lithium ion battery of composite electrode assembly, interfacial reaction concentration polarization is small, there is outstanding power-performance, and rate charge-discharge temperature rise is low,
Dynamic performance is excellent.This method is easy to operate, at low cost, and the combination electrode containing transition zone of production has excellent dynamics
Performance can greatly promote the comprehensive technical indexes of lithium-ions battery；
2, the electrode coating unit in the present invention can coat base pastes and surface layer slurry simultaneously on the surface of collector,
Then property is dried again, can simplify coating method in this way, and the combination electrode containing transition zone made is with excellent
Dynamic performance can greatly promote the comprehensive technical indexes of lithium-ions battery；
3, the electrode coating method in the present invention is simple and easy, and large scale quantities metaplasia is suitble to produce.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of combination electrode coating equipment provided in the present invention；
Fig. 2 is the structural schematic diagram of preparation-obtained combination electrode in the present invention；
Fig. 3 is to be somebody's turn to do using the preparation-obtained combination electrode of method for preparing composite electrode of the embodiment of the present invention with unused
The resistivity value comparison diagram of the preparation-obtained combination electrode of method；
Fig. 4 is to be somebody's turn to do using the preparation-obtained combination electrode of method for preparing composite electrode of the embodiment of the present invention with unused
The preparation-obtained combination electrode of method is applied to the battery direct current resistance value comparison diagram carried out after battery；
The reference numerals are as follows:
Coating apparatus 100；
Transmission device 10；
Spray equipment 20；First spray module 21；Second spray module 22；First discharge port 23；Upper mold 24；Middle mould 25；
Lower die 26；Second discharge port 27；
First pump housing 30；Second pump housing 40；Drying unit 50；Base pastes 60；Surface layer slurry 70；
Combination electrode 200；Collector 210；Priming coat 220；Top coat 230；Transition zone 240.
Specific embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
It is as shown in Fig. 1 the coating apparatus 100 for carrying out combination electrode preparation in embodiment provided by the invention, changes coating
Equipment 100 is used to carry out the coating of active slurry on 210 surface of collector.
Combined electrode structure provided in the embodiment of the present invention is as shown in Fig. 2, including adjacent top coat 230,
Transition zone 240 and priming coat 220, top coat is with a thickness of 0.5-30 μm, and primer thickness is 50-150 μm, transition region thickness 2-
20μm.Top layer raw material is comprising a kind of in amorphous carbon, lithium titanate, carbonaceous mesophase spherules, graphene, carbon nanotube, fullerene
Or a variety of electrocondution slurry；Bottom raw material is to include artificial graphite, natural graphite, carbonaceous mesophase spherules, silicon-carbon cathode material
The active material slurry of middle one or more.
As shown in Fig. 1, coating apparatus 100 according to an embodiment of the present invention includes: transmission device 10,20 and of spray equipment
Drying unit 50, transmission device 10 is for transmitting collector 210, wherein and transmission device 10 may include actuator and transfer roller,
Actuator drives transfer roller rotation, and actuator can be motor, and transfer roller draws collector 210, afflux under the action of motor
The surface of body 210 can be sticked on the surface of transfer roller, for example, the first surface of collector 210 upward when, collector 210
Second surface can be sticked on the surface of transfer roller.
Spray equipment 20 includes the first spray module 21 and the second spray module 22, and the first spray module 21 is located at the second spray
The lower section of module 22 is applied, the first spray module 21 is used for sprayed layer undercoat slurry 60, and the second spray module 22 is for spraying surface layer slurry
Material 70, the first discharge port 23 of the first spray module 21 and the second discharge port 27 of the second spray module 22 are towards transmission device
10, with sprayed layer undercoat slurry 60 and surface layer slurry 70 simultaneously.That is, the first discharge port 23 of the first spray module 21 and the second spraying
The collector 210 that second discharge port 27 of module 22 is sent out towards transmission device 10, so as to which sprayed layer undercoat is starched simultaneously
Material 60 and surface layer slurry 70.It should be noted that base pastes 60 refer to that the first layer coated in 210 surface of collector is starched
Material, on this basis, the slurry coated again are surface layer slurry 70, and surface layer slurry 70 can be one layer, or multilayer.It is logical
The lower section that the first spray module 21 is arranged in the second spray module 22 is crossed, so as to 21 sprayed layer undercoat slurry of the first spray module
60, and so that the second spray module 22 sprays surface layer slurry 70.
Drying unit 50 is located at the downstream of spray equipment 20, and drying unit 50 is located at the discharging one of transmission device 10
Side.That is, spray equipment 20 is located at the upstream of drying unit 50, base pastes 60 and surface layer slurry have been sprayed on such collector 210
Expect 70 and then utilize 50 first drying of drying unit, obtains the priming coat 220 and top coat 230 on collector 210.Transmission
Device 10 divides to feed side and discharging side, and specifically, as shown in Figure 1, transfer roller rotates clockwise, the left side of roller is
Side is fed, the right side of roller is the side that discharges, by the way that the setting of drying unit 50 in discharging side, can be convenient drying dress
Set 50 carry out drying operations, and facilitate the arrangement of spray equipment 20, for example, spray equipment 20 can be set roller into
Expect side.
Base pastes 60 and surface layer slurry 70 gradually volatilize and drying process in, 70 meeting of base pastes 60 and surface layer slurry
There are certain diffusion and convection current, generate a transition zone 240, i.e., transition zone 240 shown in Fig. 2, transition zone 240 utilizes it after drying
Diffusion effect, the interface ion that can also improve between top coat 230 and priming coat 220 is spread, between two layers of slurry
Bonding agent can also occur intermolecular force and be combined together, so obtained combination electrode 200, top coat 230 and bottom
Interfacial bonding effect is good between coating 220, is not likely to produce removing.
Since there is transition zone 240 in centre, it is poor that the ion diffusion in charge and discharge process there will not be apparent interfacial concentration
Caused concentration polarization, dynamic performance are excellent.The lithium ion battery that combination electrode 200 assembles as a result, interfacial reaction concentration polarization
Change small, has outstanding power-performance, rate charge-discharge temperature rise is low, and dynamic performance is excellent.Moreover, made using above equipment
The resistance of combination electrode 200 is low.
As a result, by setting spray equipment 20 and drying unit 50, bottom can be coated simultaneously on the surface of collector 210
Slurry 60 and surface layer slurry 70, then property is dried again, can simplify coating method in this way, and what is made contains transition zone
240 combination electrode 200 has excellent dynamic performance, can greatly promote the complex art of lithium-ions battery
Index.
An alternative embodiment according to the present invention, as shown in Fig. 1,23 He of the first discharge port of the first spray module 21
Second discharge port 27 of the second spray module 22 is located at same horizontal line.The first spray module 21 being arranged such and the second spray
Applying module 22 can be convenient its sprayed layer undercoat slurry 60 and surface layer slurry 70 simultaneously, so as to further be conducive in slurry
Solvent volatilization and diffusion, and then enable to top coat 230 and 220 adhesive effect of priming coat good, be not likely to produce removing.
Specifically, as shown in Figure 1, spray equipment 20 includes: upper mold 24, middle mould 25 and lower die 26, upper mold 24 and middle mould 25
Upper part be oppositely arranged and constitute the second spray module 22, the lower part point of lower die 26 and middle mould 25 is oppositely arranged and constitutes first
Spray module 21.That is, spray equipment 20 at least needs to include three parts, i.e. upper mold 24, middle mould 25 and lower die 26, three
A part respectively corresponds to form two spray modules again, i.e. the first spray module 21 and the second spray module 22, such setting
First spray module 21 and the second spray module 22 can be reasonably combined together by spray equipment 20, so that spray
Coating device 20 is simple and reliable for structure, can spray two different slurries simultaneously, and two kinds of slurries can be made more preferably to collect
210 surface of fluid forms coating.
Optionally, the clearance distance between the top of upper mold 24 and middle mould 25 point is h1, the lower part of lower die 26 and middle mould 25
/ clearance distance be h2, wherein h2 > h1.It should be noted that the coating thickness of base pastes 60 is much larger than surface layer
The coating thickness of slurry 70 can be so as to by the way that the clearance distance of the first spray module 21 and the second spray module 22 is rationally arranged
More base pastes 60 are sprayed out within the same time in the first spray module 21, to form the coating of corresponding thickness.
The spray equipment 20 of such setting can be conducive to the molding of combination electrode 200, and can promote the structure of combination electrode 200
Stability.
Wherein, as shown in Figure 1, coating apparatus 100 can also include first pump housing 30 and second pump housing 40, first pump housing 30
The first spray module 21 is connected, second pump housing 40 connects the second spray module 22, and first pump housing 30 and second pump housing 40 are meter
Amount pump.Metering pump be it is a kind of can satisfy various stringent process flow needs, flow can within the scope of 0-100% stepless-adjustment
Section, for conveying a kind of special positive displacement pump of liquid (especially corrosive liquids).By the way that first pump housing 30 and is respectively set
Two pump housings 40 can convey slurry to the first spray module 21 and the second spray module 22 at different rates respectively, for example,
When work, the speed of the conveying slurry of first pump housing 30 can be greater than the conveying speed of second pump housing 40, can expire simultaneously in this way
The conveying capacity of sufficient base pastes 60 requires and the requirement of the conveying capacity of surface layer slurry 70, satisfactory compound so as to produce
Electrode 200.First pump housing 30 can be correspondingly connected with the first feeding mechanism (not shown go out), the first feeding mechanism for storing and
Base pastes 60 are supplied, second pump housing 40 can be correspondingly connected with the second feeding mechanism (not shown go out), and the second feeding mechanism is used
In storage and supply surface layer slurry 70.
Mainly included the following steps: using the method that above-mentioned electrode coating unit carries out combination electrode preparation
S01, transmission device 10 transmit collector 210, and transfer roller draws collector 210, and transfer roller can guarantee collector
210 transmission ride comfort.
The first surface of S02, collector 210 of the spray equipment 20 using the first spray module 21 on transmission device 10 spray
Priming operation slurry 60, and also while using the second spray module 22 to base pastes 60 spray surface layer slurry 70.That is, spray
Coating device 20 is using two spray modules while to 210 sprayed layer undercoat slurry 60 of collector and surface layer slurry 70, then in afflux
210 surface of body forms priming coat 220 and top coat 230, can effectively simplify spraying process in this way, and two spray modules it
Between without increasing drying unit 50.
In this step, the base pastes 60 that the first spray module 21 sprays out with a thickness of d1, the spray of the second spray module 22
Thickness is applied out to be less than d1 and be the surface layer slurry 70 of d2.It should be noted that the coating thickness of base pastes 60 is much larger than surface layer
The coating thickness of slurry 70,200 stable structure of combination electrode being thusly-formed, dynamic performance are excellent.
Further, the spraying rate for setting the first spray module 21 is greater than the spraying rate of the second spray module 22.Its
In, first pump housing 30 is connected with the first spray module 21, and second pump housing 40 is connected with the second spray module 22, first pump housing
The speed of 30 conveying slurry can be greater than the conveying speed of second pump housing 40, can meet the defeated of base pastes 60 simultaneously in this way
The amount of sending requires and the requirement of the conveying capacity of surface layer slurry 70,60 coating thickness of base pastes can be made big, and surface layer is starched
Expect that 70 coating thickness are small, so as to produce satisfactory combination electrode 200.
Wherein, the base pastes 60 that the first spray module 21 sprays out with a thickness of 50-150 μm, the spray of the second spray module 22
Apply out the surface layer slurry 70 with a thickness of 0.5-30 μm.For example, the first spray module 21 can spray out the bottom with a thickness of 60-63 μm
Layer slurry 60, the surface layer slurry 70 that the second spray module 22 can spray out with a thickness of 4-7 μm；For another example, the first spray module 21
The base pastes 60 with a thickness of 65-68 μm can be sprayed out, the second spray module 22 can spray out the surface layer with a thickness of 5-7 μm
Slurry 70.By spraying out the base pastes 60 and surface layer slurry 70 of Rational Thickness, the combination electrode 200 produced can be made
Stable structure, dynamic performance are excellent.
Further, base pastes 60 and the preferably bonding agent having the same of surface layer slurry 70.For example, 60 He of base pastes
Surface layer slurry 70 may each comprise: CMC (Carboxymethyl, Cellulose Sodium, Sodium salt of Caboxy
Methyl Cellulose- sodium carboxymethylcellulose) and SBR (Styrene Butadiene Rubber- butadiene-styrene rubber).Due to
The bonding agent having the same of base pastes 60 and surface layer slurry 70 can further promote priming coat 220 and top coat 230
Adhesive effect, two coatings can be made more to be not likely to produce removing.
S03, drying unit 50 dry the base pastes 60 and surface layer slurry 70 on 210 first surface of collector.It is drying
In the process, base pastes 60 and surface layer slurry 70 have certain diffusion and convection current, generate a transition zone 240, mistake after drying
It crosses layer 240 and utilizes its diffusion effect, the interface ion diffusion between top coat 230 and priming coat 220 can also be improved.
As a result, due to gradually being volatilized in the solvent of base pastes 60 and surface layer slurry 70 using the synchronous coating method of wet process
In drying process, the slurry between priming coat 220 and top coat 230 has certain diffusion and convection current, generates a transition zone
240, transition zone 240 utilizes its diffusion effect after drying, can also improve the boundary between top coat 230 and priming coat 220
The diffusion of face ion.Obtained combination electrode 200, interfacial bonding effect is good between top coat 230 and priming coat 220, is not easy to produce
Raw removing；Simultaneously because there is transition zone 240 in centre, the ion diffusion in charge and discharge process there will not be apparent interfacial concentration
Concentration polarization caused by difference, dynamic performance are excellent.And this method is easy to operate, technical maturity, and production contains transition zone 240
Combination electrode 200 there is excellent dynamic performance, the complex art that can greatly promote lithium-ions battery refers to
Mark.
As shown in figure 3, using the combination electrode 200 of the synchronous coating method of above-mentioned wet process and using asynchronous painting by comparison
The combination electrode covered, it is found that be far below using the resistance value of the combination electrode 200 of the above method and do not use asynchronous coating
Combination electrode resistance value, that is to say, that using the synchronous coating method of above-mentioned wet process combination electrode 200 resistance value compared with
It is low, so that combination electrode 200 has excellent properties.
As shown in figure 4, using the combination electrode 200 of the synchronous coating method of above-mentioned wet process and using asynchronous painting by comparison
The combination electrode covered, it is found that during battery charging and discharging, using the combination electrode of the synchronous coating method of above-mentioned wet process
200 DC resistance is less than the DC resistance of the combination electrode using asynchronous coating, can promote the charge and discharge of battery
Electrical property.
Further, coating preparation process can with the following steps are included:
S4 overturns collector 210, i.e., by the whole turn-over of collector 210, for example, in the first surface direction of collector 210
After spray equipment 20 and sprayed layer undercoat slurry 60 and surface layer slurry 70, by the second surface of collector 210 towards spray equipment
20, it can be convenient spray equipment 20 in this way and the second surface of collector 210 sprayed.The first surface of collector 210 and
Second surface is two opposite surfaces.
S5, transmission device 10 transmit collector 210, and the step is identical with above-mentioned step S1, the roller in transmission device 10
Son traction collector 210.
The second surface of S6, collector 210 of the spray equipment 20 using the first spray module 21 on transmission device 10 spray
Priming operation slurry 60, and also while using the second spray module 22 to base pastes 60 spray surface layer slurry 70.The step is same as above
The step S2 stated is identical, is only that sprayed surface by first surface has changed second surface into, other requirements can keep identical.It should
Step can make the second surface of collector 210 be coated with base pastes 60 and surface layer slurry 70, and 60 He of base pastes
Surface layer slurry 70 can generate diffusion and convection current, form transition zone 240, promote the dynamic performance of combination electrode 200.
S7, drying unit 50 dry the base pastes 60 and surface layer slurry 70 on 210 second surface of collector.The step is same
Above-mentioned step S3 is identical, which can to generate a transition zone 240 between base pastes 60 and surface layer slurry 70, does
Transition zone 240 utilizes its diffusion effect after dry, can also improve the interface ion between top coat 230 and priming coat 220
Diffusion.Coating apparatus 100 can spray the of collector 210 after the first surface for having sprayed collector 210 again as a result,
Two surfaces, after completing 210 double spread of collector by same coating method in this way, the electricity of obtained combination electrode 200
Resistance, much smaller than the electrode that table applies again after original difference primary coat drying, with excellent charge-discharge performance.
Two specific embodiments are provided again below to be described.
An alternative embodiment according to the present invention, top coat 230 use soft carbon slurry, and priming coat 220 uses artificial stone
Ink is mainly used for improving the rapid charging performance of lithium ion battery.Taking average partial size is 4 μm of soft carbon material, and prescription quality ratio is as follows:
Soft carbon: conductive carbon black: VGCF (Vapor-grown carbon fiber- vapor-grown carbon fibers): CMC:SBR=94.3%:
The soft carbon surface layer slurry 70 that solid content is 42% is made in 2.0%:0.5%:1.2%:2.0%.Taking average partial size is the people of 10um
Graphite is made, prescription quality ratio is as follows: artificial graphite: conductive carbon black: CMC:SBR=95.5%:1.0%:1.5%:2.0%, system
Obtain the artificial graphite base pastes 60 that solid content is 46%.Surface layer slurry 70 squeezes into the second spray module 22 by second pump housing 40
In, base pastes 60 squeeze into the first spray module 21 by first pump housing 30.
By the spraying of the first spray module 21 and the second spray module 22, artificial graphite base pastes 60 and soft carbon surface layer
Slurry 70 is transferred on collector 210 simultaneously, the solvent being re-fed into the removal slurry of drying unit 50.The face of top coat 230 is close
Degree is 5g/m2, the surface density of priming coat 220 is 102g/m2.Due to being the synchronous coating of wet process, solvent gradually volatilize with it is dried
Cheng Zhong, the slurry between base pastes 60 and surface layer slurry 70 have certain diffusion and convection current, generate a transition zone 240, do
Transition zone 240 utilizes its diffusion effect after dry, when can also improve charge and discharge between top coat 230 and priming coat 220
Interface ion diffusion.Obtained combination electrode 200, interfacial bonding effect is good between top coat 230 and priming coat 220, is not easy
Removing is generated, 230 thickness of top coat is in 4-7um, and 220 thickness of priming coat is at 60-63 μm.Simultaneously because there is transition zone 240 in centre,
Thickness is about 3 μm, and due to the presence of transition zone 240, it is dense that the ion diffusion in charge and discharge process there will not be apparent interface
Concentration polarization caused by degree difference, dynamic performance are excellent.After completing 210 double spread of collector by same coating method,
The resistance of obtained combination electrode 200, much smaller than the combination electrode resistance that table applies again after original difference primary coat drying；Have
Excellent charge-discharge performance.
According to another alternative embodiment of the present invention, the present embodiment top coat 230 uses carbonaceous mesophase spherules slurry, bottom
Coating 220 uses silicon-carbon, is mainly used for improving the cycle performance of lithium ion battery.Taking average partial size is 8 μm of carbosphere material,
Prescription quality ratio is as follows: carbosphere: conductive carbon black: CMC:SBR=96.0%:1.0%:1.2%:1.8%, obtained solid content are
45% carbosphere surface layer slurry 70.Taking average partial size is the Si-C composite material of 16um, in active material containing 10% silicon
Carbon, prescription quality is than as follows: compound silicon-carbon: conductive carbon black: CMC:SBR=95.0%:1.0%:1.5%:2.5%, is made solid
The compound silicon-carbon base pastes 60 that content is 44%.Surface layer slurry 70 is squeezed into the second spray module 22 by second pump housing 40,
Base pastes 60 squeeze into the first spray module 21 by first pump housing 30.
By the spraying of the first spray module 21 and the second spray module 22, artificial graphite base pastes 60 and soft carbon surface layer
Slurry 70 is transferred on collector 210 simultaneously, the solvent being re-fed into the removal slurry of drying unit 50.The face of top coat 230 is close
Degree is 5g/m2, the surface density of priming coat 220 is 96g/m2.Due to being the synchronous coating of wet process, solvent gradually volatilize with it is dried
Cheng Zhong, the slurry between base pastes 60 and surface layer slurry 70 have certain diffusion and convection current, generate a transition zone 240, do
Transition zone 240 utilizes its diffusion effect after dry, when can also improve charge and discharge between top coat 230 and priming coat 220
Interface ion diffusion, and can preferably absorb the expansion of the generation of priming coat 220.Obtained combination electrode 200, top coat
Interfacial bonding effect is good between 230 and priming coat 220, is not likely to produce removing, and 230 thickness of top coat is at 5-7 μm, priming coat 220
Thickness is at 65-68 μm.Simultaneously because there is transition zone 240 in centre, thickness is about 3 μm, due to the presence of transition zone 240, in charge and discharge
Ion diffusion in electric process there will not be concentration polarization caused by apparent interfacial concentration difference, and dynamic performance is excellent.Pass through
After same coating method completes 210 double spread of collector, the resistance of obtained combination electrode 200, much smaller than original
The electrode that table applies again after primary coat drying respectively；With excellent charge-discharge performance.Carbosphere top coat 230 possesses lesser expansion
And the presence of transition zone 240, the expansion of priming coat 220 can be preferably absorbed, the cycle performance of battery is improved.
Finally, it should be noted that above embodiments be only to illustrate the technical solution of the embodiment of the present invention rather than to its into
Row limitation, although the embodiment of the present invention is described in detail referring to preferred embodiment, those skilled in the art
It should be understood that the technical solution of the embodiment of the present invention can be still modified or replaced equivalently, and these are modified or wait
The range of modified technical solution disengaging technical solution of the embodiment of the present invention cannot also be made with replacement.
Claims (10)
1. a kind of combination electrode, it is characterised in that:
Including adjacent surface layer, transition zone and bottom, the skin depth is 0.5-30 μm, and the underlayer thickness is 50-150
μm, the transition region thickness is 2-20 μm.
2. combination electrode as described in claim 1, it is characterised in that: the top layer raw material be comprising amorphous carbon, lithium titanate, in
Between phase carbosphere, graphene, carbon nanotube, electrocondution slurry one or more kinds of in fullerene；The bottom raw material be comprising
Artificial graphite, natural graphite, carbonaceous mesophase spherules, active material slurry one or more kinds of in silicon-carbon cathode material.
3. a kind of electrode coating unit, it is characterised in that:
Including transmission device, spray equipment and drying unit；
The transmission device is for transmitting collector；
The spray equipment includes the first spray module and the second spray module, and first spray module is located at second spray
The lower section of module is applied, first spray module is used for sprayed layer undercoat slurry, and second spray module is for spraying surface layer slurry
The discharge port of material, the discharge port of first spray module and second spray module is towards the transmission device, with same
When spray the base pastes and the surface layer slurry；
The drying unit is located at the downstream of the spray equipment, and is located at the discharging side of the transmission device.
4. electrode coating unit as claimed in claim 3, it is characterised in that: the discharge port of first spray module and described
The discharge port of two modules is located at the same horizontal position.
5. electrode coating unit as claimed in claim 3, it is characterised in that: the spray equipment includes upper mold, middle mould and lower die,
The upper part of the upper mold and the middle mould is oppositely arranged and constitutes second spray module, the lower die and the middle mould
Lower part point is oppositely arranged and constitutes first spray module.
6. electrode coating unit as claimed in claim 5, it is characterised in that: between the top of the upper mold and the middle mould point
Clearance distance is h1, and the clearance distance between the lower part point of the lower die and the middle mould is h2, wherein h2 > h1.
7. electrode coating unit as claimed in claim 3, it is characterised in that: the spray equipment be located at the transmission device into
Expect side.
8. electrode coating unit as claimed in claim 3, it is characterised in that: it further include first pump housing and second pump housing, described
One pump housing connects first spray module, and second pump housing connects second spray module, first pump housing and institute
Stating second pump housing is metering pump.
9. a kind of method for carrying out combination electrode preparation using the electrode coating unit as described in claim 3-8 is any, feature
It is to comprise the following steps:
S01, the transmission device transmit the collector；
S02, the spray equipment utilize first surface sprayed layer undercoat slurry of first spray module to the collector, and
Also surface layer slurry is sprayed to the base pastes using second spray module simultaneously；
S03, the drying unit dry the base pastes and the surface layer slurry on the collector first surface.
10. carrying out the method for combination electrode preparation as claimed in claim 9, it is characterised in that: after the completion of S03, further includes:
Overturn the collector；
The transmission device transmits the collector；
The spray equipment utilizes second surface sprayed layer undercoat slurry of first spray module to the collector, and also same
Second spray module described in Shi Liyong sprays surface layer slurry to the base pastes；
The drying unit dries the base pastes and the surface layer slurry on the collector second surface.
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Application publication date: 20191025 |