CN109290155A - A kind of coating method of graphene lithium battery pole slice - Google Patents
A kind of coating method of graphene lithium battery pole slice Download PDFInfo
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- CN109290155A CN109290155A CN201810875183.XA CN201810875183A CN109290155A CN 109290155 A CN109290155 A CN 109290155A CN 201810875183 A CN201810875183 A CN 201810875183A CN 109290155 A CN109290155 A CN 109290155A
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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Abstract
The invention belongs to technical field of lithium ion, a kind of coating method of graphene lithium battery pole slice is specifically disclosed, including positive active material, water-soluble binder and plasticizer are add to deionized water and are stirred under vacuum to obtain positive-active slurry；Graphene, carbon nanotube and dispersing agent are add to deionized water ultrasonic treatment and obtain conductive agent slurry；Two kinds of slurries are mixed and obtain water-soluble anode sizing agent after ultrasound, stir process；It is coated on collector and dries again.The pole piece slurry that the present invention is prepared is uniformly dispersed, adhesion-tight, no cracking obscission.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of coating process of graphene lithium battery pole slice.
Background technique
Lithium ion battery is a kind of secondary cell, it relies primarily on lithium ion, and movement carrys out work between a positive electrode and a negative electrode.
In charge and discharge process, Li+ insertion and deintercalation back and forth between two electrodes: when charging, Li+ is from positive deintercalation, by electrolysis
Matter is embedded in cathode, and cathode is in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery as current classic electrochmical power source it
One, it is widely used in energy storage and conversion field.
Coating is one of most important process flow of lithium ion battery, and coating is exactly required for manufacturing lithium ion battery
Anode sizing agent or negative electrode slurry be equably coated on matrix, then dried.Studying at present more is to improve to apply to lay
It is standby, and the control of coating process, especially coating process is studied less.
Graphene is Novel Carbon Nanomaterials, has the specific surface area much larger than traditional material, and carrier mobility reaches
1.5 × 104cm2/ (Vs), can effectively reduce the migration path of lithium ion, improve the high rate performance of battery.However graphite
Alkene composite material is easily mutually reunited in the application, and bulk density is lower and is difficult to disperse, and leads to the volume energy density of battery
It reduces, the coating process difficulty of pole piece increases.
Prior art CN106025185A discloses a kind of coating electrode piece method, comprising the following steps: according to battery
Applying area is respectively set in the two sides of coating machine in the width of pole piece, and the gap between two applying areas is to be left white area, S2, opens painting
Cloth machine, two applying areas are continuously coated with two lateral edge substrate transport direction of substrate.Above-mentioned coating method waste material is few, resource utilization
It is high.But the pole piece of this method coating haves the defects that poor dispersion.Prior art CN106953066A discloses one kind
The coating process of anode sizing agent, comprising the following steps: (1) stirred after adhesive, conductive agent being added into N-Methyl pyrrolidone
Obtain level-one slurry；(2) positive active material, conductive agent, Gemini surface active agent are added into N-Methyl pyrrolidone to mix
Second level slurry；(3) level-one slurry is mixed with second level slurry；(4) it is coated with.Above-mentioned technique can make final lithium battery obtained
Forthright again, capacity has greatly improved.However, the anode sizing agent prepared with this method is due to using organic solvent to make
For solvent, a large amount of industrial wastewater can be generated in production process, can not only pollution be generated to environment, to the body of production operation personnel
Body can also be influenced；In addition, that in coating, there is also smoothness is low for slurry obtained in this way, pole piece dries that difficulty is big to be lacked
It falls into.
Summary of the invention
In view of this, technical problem to be solved by the invention is to provide a kind of coating sides of graphene lithium battery pole slice
Method.Anode sizing agent good dispersion that this method obtains, electric conductivity are high；The anode pole piece being coated with is less prone to cracking, falls off
Phenomenon.Greatly reduce production cost and environmentally protective.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of coating method of graphene lithium battery pole slice, comprising the following steps:
(1) positive active material, water-soluble binder, plasticizer and deionized water a are mixed, is stirred under vacuum 3-6h and obtains
To positive-active slurry A；
(2) by graphene, carbon nanotube, dispersing agent and deionized water b mix, ultrasonic disperse 1-3h obtain graphene/
Carbon nanotube composite conductive agent slurry B；
(3) gained A is mixed with B, is ultrasonically treated 2-4h, after being stirred under vacuum 2-4h, obtain slurry C, adjust the viscous of slurry C
It spends to 2500~3500mPa.s and obtains water-soluble anode sizing agent；
(4) on a current collector by the resulting water-soluble anode sizing agent coating of step 3, it is adjustable to be put into heating cooling rate
Baking oven, drying and processing.
It is understood that above-mentioned deionized water a and deionized water b, is for convenience of description, to distinguish described in preparation
Deionized water used in the different step of the positive-active slurry A and graphene/carbon nano-tube combined conductive agent slurry B,
It is not the restriction to deionized water ingredient.
The lithium ion battery of existing market mostly uses greatly the anode of oiliness organic system, i.e., is dissolved in anode sizing agent organic
Solvent, the binder of selection are also mostly oiliness binder such as PVDF, the anode sizing agent of organic system exist be coated with smooth performance it is low,
The defect that equipment investment is big, recovery difficult is big is unfavorable for the clean manufacturing of battery.The present invention selects deionized water as molten
Positive-active slurry, while the ultrasonic disperse under dispersing agent effect are made with water-soluble binder under the conditions of vacuum stirring for agent
Composite graphite alkene/carbon nanotube conducting agent slurry is obtained, the use of organic solvent is avoided, reduces production cost, to ecology
It is environmental-friendly pollution-free.
Positive-active slurry is mixed with conductive agent slurry, slurry dispersion that is sonicated, obtaining after vacuum stirring is equal
It is even.By deionized water, slurry temperature adjust viscosity to 2500~3500mPa.s, many experimental phenomenas show be when viscosity
Water-soluble anode sizing agent when 2500~3500mPa.s, when coating, can be with the progress of continuous-stable, and Painting effect is good.
The heating adjustable baking oven of cooling rate, drying and processing are put into described in step (4).Pole coating drying course
In, particularly important for the adjusting of temperature, if drying temperature raising is too fast, evaporation rate of solvent is too fast, and pole piece slurry holds
Easily there is phenomena such as cracking, fall off；If oven temperature reduces rapidly, the phenomenon that coating layer of pole piece is cracked is also resulted in,
To influence the performance of pole piece.The present invention passes through the warming and cooling rate of control baking oven, so that the deionized water in pole piece is uniform
Volatilization, hence it is evident that improve the abnormal appearance phenomenon of anode pole piece.
As a preference, the positive active material includes LiCoO2、LiNiO2, spinel-type LiMn2O4、LiFePO4
Or LiNixMnyCo1-x-yO2One of or it is a variety of, wherein 0.1≤x≤0.3,0.1≤y≤0.2.
LiCoO2It is the positive electrode for being used for commercial lithium-ion batteries earliest, as a positive electrode active material, invertibity,
The chemical properties such as discharge capacity, stability and efficiency for charge-discharge are all very excellent.LiNiO2Pair theoretical specific capacity be
274mAh/g, actual capacity is also up to 190~210mAh/g, and its requirement to electrolyte is lower.Spinel-type LiMn2O4Tool
There are wide raw material sources, resourceful, the low overcharge resistance performance of preparation cost and the good advantage of safety.LiFePO4With olivine-type
Structure, cycle performance is excellent, and the small advantage of the structure change of electrode in charge and discharge process.The LiNixMnyCo1-x-yO2
The advantages of (0.1≤x≤0.3,0.1≤y≤0.2) combines three classes material, function admirable.
The addition of water soluble adhesive makes active material, conduction for connecting positive active material, conductive agent and collector
There is whole connectivity between agent and collector, to reduce the internal resistance of battery, while making pole piece that there is good mechanicalness
Energy and processability, meet the needs of actual production.As a preference, water-soluble binder of the present invention be CMC,
One of SBR, F103, F105, W812, W811, LA132 and LA133 are a variety of.
As a preference, the plasticizer is selected from one of acrylate, ethylene carbonate or methyl ethyl carbonate；Institute
It states dispersing agent and is selected from one of polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol or sodium carboxymethylcellulose.
Further, on the basis of the total weight of slurry C, the positive active material accounts for 30~40%, water solubility
Binder account for 3~7%, the plasticizer account for 0.8~4%, the deionized water a account for 20~30%, graphene account for 1~
5%, the carbon nanotube, which accounts for 5~10%, dispersing agent and accounts for 0.2~2%, the deionized water b, accounts for 30~40%.According to conjunction
The anode sizing agent that suitable component is prepared, good dispersion, electric conductivity are high.
As a preference, vacuum stirring described in step (1), mixing speed is 300~700r/min, and vacuum degree is
0.085~0.098MPa；Vacuum stirring described in step (3), mixing speed are 1200~1500r/min, and vacuum degree is
0.07~0.09MPa.The degree of scatter that slurry equally can be improved is sufficiently stirred, prevents slurry from depositional phenomenon occur.
As a preference, the power of step (2) ultrasound is 400~800W, frequency is 40~60kHz；Step (3)
The power of the ultrasound is 1000~1500W, and frequency is 50~70kHz.Ultrasonic treatment can make graphene, carbon nanotube dispersion
Uniformly, its agglomeration is effectively inhibited to occur, to improve the electric conductivity and cycle performance of pole piece.
If slurry coating thickness it is too thin or it is too thick subsequent pole piece rolling mill practice can be had an impact, it cannot be guaranteed that
The consistency of pole piece；If the surface density of coating is too small, then the capacity of battery is possible to that nominal capacity is not achieved, if coating
Surface density is too big, then be easy to cause the waste of ingredient, if positive electrode capacity is excessive when serious, since the precipitation of lithium forms Li dendrite
Battery diaphragm short circuit is pierced through, to cause security risk.Therefore, as a preference, collector of the present invention be with a thickness of
10~20 μm of aluminium foils, slurry coating with a thickness of 15~20 μm, coated face density is 22~25mg/cm2。
As a preference, the stoving process, sets baking oven heating rate as 0.2~3 DEG C/min, when temperature reaches 80
~90 DEG C, after 1~3h of constant temperature, cooling processing sets cooling rate as 0.2~4 DEG C/min.The heating of uniform speed slow can make to apply
Solvent of the cloth in aluminium foil spreading mass uniformly volatilizees, and effectively reduces coating layer and phenomena such as cracking, fall off occurs.Constant temperature processing
A period of time can guarantee that the slurry of coating is completely dried, the cooling of uniform speed slow when cooling, equally can be to avoid slurry
The break-off of material.
Further, baking oven heating rate is set as 1~2 DEG C/min, and when temperature reaches 60~70 DEG C, setting heating is fast
Degree is 0.2~1 DEG C/min, is slowly warming up to 85~90 DEG C, after 2~3h of freeze-day with constant temperature, is cooled down with the speed of 0.2~1 DEG C/min,
When temperature is down to 50~60 DEG C/min, cooling rate is set as 1~2 DEG C/min, is down to room temperature to get adhesion-tight, nothing is arrived
The anode pole piece for the obscission that is cracked.
The beneficial effects of the present invention are:
1) by the way that the improvement of dispersing agent, water-soluble binder and mixing procedure is added, obtained anode sizing agent dispersion is equal
It is even, electric conductivity is high.
2) water-soluble binder is selected, organic system is substituted with water-based system, reduces the production cost of lithium battery, and green
Colour circle is protected.
3) the volatilization speed of solvent is controlled by controlling the heating rate of temperature, keeps slurry coating drying course more equal
It is even, improve cracking, the obscission of collection liquid surface slurry.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
Embodiment one
1. preparing water-soluble anode sizing agent
The deionized water a of 30 parts by weight is added in blender, adds the positive active material LiCoO of 30 parts by weight2、
The plasticizer acrylate of the water-soluble binder SBR of 3 parts by weight, 0.8 parts by weight, are evacuated to 0.085MPa, with 300r/
The mixing speed stirring 6h of min obtains positive-active slurry A；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 5 parts by weight of 1 parts by weight
Carbon nanotube and 0.2 parts by weight polyethylene of dispersing agent pyrrolidones, be 400W with ultrasonic power, frequency is 40kHz's
Ultrasonic wave decentralized processing 1h obtains graphene/carbon nano-tube combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 2h of 70kHz, power selection 1000W；It is stirred under vacuum 2h, vacuum degree again
It is set as 0.09MPa, mixing speed 1200r/min, the viscosity of mixed slurry is adjusted to 2500mPa.s and obtains water-soluble anode
Slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 10 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 15 μm, coated face density 22mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, set heating rate as 3 DEG C/
Min stops heating up, after constant temperature 1h, being cooled to room temperature with the speed of 4 DEG C/min can be obtained anode when temperature reaches 80 DEG C
Pole piece.
Embodiment two
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material LiNiO of 30 parts by weight2、
The plasticizer ethylene carbonate of the water-soluble binder LA-132 of 7 parts by weight, 4 parts by weight, are evacuated to 0.098MPa, with
The mixing speed stirring 3h of 700r/min obtains positive-active slurry A；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 6 parts by weight of 2 parts by weight
Carbon nanotube and 1 parts by weight dispersing agent polyacrylamide, be 800W with ultrasonic power, frequency is the ultrasonic wave of 60kHz
Decentralized processing 3h obtains graphene/carbon nano-tube combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 4h of 50kHz, power selection 1500W；It is stirred under vacuum 4h, vacuum degree again
It is set as 0.07MPa, mixing speed 1500r/min, the viscosity of mixed slurry is adjusted to 3500mPa.s and obtains water-soluble anode
Slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 20 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 20 μm, coated face density 25mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, set heating rate as 2 DEG C/
Min stops heating up, after constant temperature 3h, is cooled to room temperature with the speed of 2 DEG C/min and obtains anode pole piece when temperature reaches 90 DEG C.
Embodiment three
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material of 33 parts by weight
LiFePO4, the water-soluble binder LA-133 of 4 parts by weight, 1 parts by weight plasticizer methyl ethyl carbonate, be evacuated to
0.09MPa obtains positive-active slurry A with the mixing speed stirring 5h of 500r/min；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 5 parts by weight of 5 parts by weight
Carbon nanotube and 2 parts by weight polyethylene of dispersing agent alcohol, be 600W with ultrasonic power, frequency is the ultrasonic wavelength-division of 50kHz
Processing 2h is dissipated, graphene/carbon nano-tube combined conductive agent slurry B is obtained；
After A is mixed with B, with the ultrasonication 3h of 60kHz, power selection 1300W；It is stirred under vacuum 3h, vacuum degree again
It is set as 0.08MPa, mixing speed 1400r/min, the viscosity of mixed slurry is adjusted to 3000mPa.s and obtains water-soluble anode
Slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 15 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 17 μm, coated face density 24mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, sets heating rate as 0.2
DEG C/min, when temperature reaches 85 DEG C, stopping heats up, and after constant temperature 2h, being cooled to room temperature with the speed of 0.2 DEG C/min be can be obtained
Anode pole piece.
Example IV
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material of 30 parts by weight
LiNi0.1Mn0.2Co0.7O2, W811 the and LA-132 mixing water-soluble binders of 3 parts by weight, 0.8 parts by weight plasticizer propylene
Acid esters is evacuated to 0.095MPa, obtains positive-active slurry A with the mixing speed stirring 5h of 500r/min；
It takes the deionized water b of 35 parts by weight to be added in ultrasonic reactor, adds graphene, 10 weight of 1 parts by weight
The carbon nanotube of part and the dispersing agent sodium carboxymethylcellulose of 0.2 parts by weight, are 700W, frequency 60kHz with ultrasonic power
Ultrasonic wave decentralized processing 2h, obtain graphene/carbon nano-tube combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 3h of 60kHz, power selection 1200W；It is stirred under vacuum 2h, vacuum degree again
Be set as 0.085MPa, mixing speed 1400r/min, adjust the viscosity of mixed slurry to 3300mPa.s obtaining it is water-soluble just
Pole slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 16 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 18 μm, coated face density 23mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, set heating rate as 2 DEG C/
Min, when temperature reaches 65 DEG C, adjusting heating rate is 0.2 DEG C/min, is to slowly warm up to 90 DEG C, stops heating, freeze-day with constant temperature
After 2h, 60 DEG C are cooled to the speed of 0.5 DEG C/min, adjusting cooling rate again is 1 DEG C/min, and being down to room temperature can be obtained just
Pole pole piece.
Embodiment five
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material of 40 parts by weight
LiNi0.3Mn0.1Co0.6O2, F103 and LA-133 the mixing water-soluble binders of 3 parts by weight, 0.8 parts by weight plasticizer carbonic acid
Methyl ethyl ester is evacuated to 0.09MPa, obtains positive-active slurry A with the mixing speed stirring 3h of 500r/min；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 5 parts by weight of 1 parts by weight
Carbon nanotube and 0.2 parts by weight dispersing agent polyacrylamide, be 800W with ultrasonic power, frequency is the ultrasound of 50kHz
Wave decentralized processing 3h obtains graphene/carbon nano-tube combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 3h of 50kHz, power selection 1500W；It is stirred under vacuum 3h, vacuum degree again
Be set as 0.088MPa, mixing speed 1200r/min, adjust the viscosity of mixed slurry to 3500mPa.s obtaining it is water-soluble just
Pole slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 20 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 19 μm, coated face density 24mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, set heating rate as 1 DEG C/
Min, when temperature reaches 70 DEG C, adjusting heating rate is 0.5 DEG C/min, is to slowly warm up to 90 DEG C, stops heating, freeze-day with constant temperature
After 2.5h, 50 DEG C are cooled to the speed of 0.2 DEG C/min, adjusting cooling rate again is 2 DEG C/min, and being down to room temperature can be obtained
Anode pole piece.
Six comparative example of embodiment
The deionized water a of 30.8 parts by weight is added in blender, adds the positive active material of 30 parts by weight
LiCoO2, 3 parts by weight water-soluble binder SBR, be evacuated to 0.085MPa, obtained with the mixing speed of 300r/min stirring 6h
To positive-active slurry A；
It takes the deionized water b of 30.2 parts by weight to be added in ultrasonic reactor, adds graphene, 5 weight of 1 parts by weight
The carbon nanotube of part is 400W with ultrasonic power, and frequency is the ultrasonic wave decentralized processing 1h of 40kHz, obtains graphene/carbon nanometer
Pipe combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 2h of 70kHz, power selection 1000W；It is stirred under vacuum 2h, vacuum degree again
It is set as 0.09MPa, mixing speed 1200r/min, the viscosity of mixed slurry is adjusted to 2500mPa.s and obtains water-soluble anode
Slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 10 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 15 μm, coated face density 22mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, sets oven temperature as 80
DEG C, being cooled to room temperature after dry 1.5h can be obtained anode pole piece.
Seven comparative example of embodiment
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material LiNiO of 30 parts by weight2、
The plasticizer ethylene carbonate of the water-soluble binder LA-132 of 7 parts by weight, 4 parts by weight, under condition of normal pressure, with 700r/min's
Mixing speed stirring 3h obtains positive-active slurry A；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 6 parts by weight of 2 parts by weight
Carbon nanotube and 1 parts by weight dispersing agent polyacrylamide, be 800W with ultrasonic power, frequency is the ultrasonic wave of 60kHz
Decentralized processing 3h obtains graphene/carbon nano-tube combined conductive agent slurry B；
After A is mixed with B, with the ultrasonication 4h of 50kHz, power selection 1500W；Atmospheric agitation 4h again, stirring speed
Degree is 1500r/min, adjusts the viscosity of mixed slurry to 3500mPa.s and obtains water-soluble anode sizing agent.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 20 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 20 μm, coated face density 25mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, directly set drying temperature as
90 DEG C, room temperature is down to after dry 3h and obtains anode pole piece.
Eight comparative example of embodiment
1. preparing water-soluble anode sizing agent
The deionized water a of 20 parts by weight is added in blender, adds the positive active material of 33 parts by weight
LiFePO4, the water-soluble binder LA-133 of 4 parts by weight, 1 parts by weight plasticizer methyl ethyl carbonate, be evacuated to
0.09MPa obtains positive-active slurry A with the mixing speed stirring 5h of 500r/min；
It takes the deionized water b of 30 parts by weight to be added in ultrasonic reactor, adds graphene, 5 parts by weight of 5 parts by weight
Carbon nanotube and 2 parts by weight polyethylene of dispersing agent alcohol, be 600W with ultrasonic power, frequency is the ultrasonic wavelength-division of 50kHz
Processing 2h is dissipated, graphene/carbon nano-tube combined conductive agent slurry B is obtained；
After A is mixed with B, with the ultrasonication 3h of 60kHz, power selection 1300W；It is stirred under vacuum 3h, vacuum degree again
It is set as 0.08MPa, mixing speed 1400r/min, the viscosity of mixed slurry is adjusted to 5000mPa.s and obtains water-soluble anode
Slurry.
2. coating
The water-soluble anode sizing agent prepared is coated on the aluminium foil with a thickness of 15 μm, adjusting coating machine makes the painting of slurry
Cloth is with a thickness of 17 μm, coated face density 24mg/cm2, the aluminium foil of coating sizing-agent is put into baking oven, directly set drying temperature as
85 DEG C, room temperature is down to after dry 2h and obtains anode pole piece.
One to eight analysis of experimental results of embodiment statistics
| Slurry dispersibility | Slurry and aluminium foil adhesion property | |
| Embodiment one | It is uniformly dispersed | Adhesion-tight, no cracking, nothing fall off |
| Embodiment two | It is uniformly dispersed | Adhesion-tight, no cracking, nothing fall off |
| Embodiment three | It is uniformly dispersed | Adhesion-tight, no cracking, nothing fall off |
| Example IV | It is uniformly dispersed | Adhesion-tight, no cracking, nothing fall off |
| Embodiment five | It is uniformly dispersed | Adhesion-tight, no cracking, nothing fall off |
| Embodiment six | There is part deposition | Adhesion is poor, has part cracking and falls off |
| Embodiment seven | There is partly precipitated | Adhesion is poor, has part cracking and falls off |
| Embodiment eight | There is partly precipitated | Adhesion is poor, has part cracking and falls off |
In the description of this specification, reference term " embodiment ", " another embodiment ", " other embodiments " or "
The description of one embodiment~X embodiment " etc. mean specific features described in conjunction with this embodiment or example, structure, material or
Person's feature is included at least one embodiment or example of the invention.In the present specification, to the schematic table of above-mentioned term
Stating may not refer to the same embodiment or example.Moreover, specific features, structure, material, method and step or the spy of description
Point can be combined in any suitable manner in any one or more of the embodiments or examples.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or the device that include a series of elements not only include those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or device institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including being somebody's turn to do
There is also other identical elements in the process, method of element, article or device.
The serial number of the above embodiments of the invention is only for description, does not represent the advantages or disadvantages of the embodiments.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.
Claims (10)
1. a kind of coating method of graphene lithium battery pole slice, which comprises the following steps:
(1) positive active material, water-soluble binder, plasticizer and deionized water a are mixed, is stirred under vacuum 3-6h and obtains just
Pole active slurry A；
(2) graphene, carbon nanotube, dispersing agent and deionized water b are mixed, ultrasonic disperse 1-3h obtains graphene/carbon and receives
Mitron combined conductive agent slurry B；
(3) gained A is mixed with B, is ultrasonically treated 2-4h, after being stirred under vacuum 2-4h, obtain slurry C, adjust the viscosity of slurry C to
2500~3500mPa.s obtains water-soluble anode sizing agent；
(4) on a current collector by the resulting water-soluble anode sizing agent coating of step 3, it is put into the heating adjustable baking of cooling rate
Case, drying and processing.
2. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that the anode is living
Property substance includes LiCoO2、LiNiO2, spinel-type LiMn2O4、LiFePO4Or LiNixMnyCo1-x-yO2One of or it is a variety of,
Wherein, 0.1≤x≤0.3,0.1≤y≤0.2.
3. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that the water solubility
Binder is one of CMC, SBR, F103, F105, W812, W811, LA-132 and LA-133 or a variety of.
4. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that the plasticizer
Selected from one of acrylate, ethylene carbonate or methyl ethyl carbonate；The dispersing agent is selected from polyvinylpyrrolidone, poly- third
One of acrylamide, polyvinyl alcohol or sodium carboxymethylcellulose.
5. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that with slurry C
On the basis of total weight, the positive active material accounts for 30~40%, water-soluble binder and accounts for 3~7%, the plasticizer and account for
0.8~4%, the deionized water a, which accounts for 20~30%, graphene and accounts for 1~5%, carbon nanotube, accounts for 5~10%, institute
It states dispersing agent and accounts for 0.2~2%, the deionized water b and account for 30~40%.
6. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that in step (1)
The vacuum stirring, mixing speed are 300~700r/min, and vacuum degree is 0.085~0.098MPa；Described in step (3)
It is stirred under vacuum, mixing speed is 1200~1500r/min, and vacuum degree is 0.07~0.09MPa.
7. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that step (2) institute
The power for stating ultrasound is 400~800W, and frequency is 40~60kHz；The power of step (3) ultrasound is 1000~1500W, frequency
Rate is 50~70kHz.
8. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that the collector
It is with a thickness of 10~20 μm of aluminium foils.
9. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that slurry coating
With a thickness of 15~20 μm, coated face density is 22~25mg/cm2。
10. a kind of coating method of graphene lithium battery pole slice according to claim 1, which is characterized in that the drying
Technique, sets baking oven heating rate as 0.2-3 DEG C/min, when temperature reaches 80~90 DEG C, after constant temperature 1-3h, and cooling processing, if
Determining cooling rate is 0.2-4 DEG C/min.
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| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
| CN110148705A (en) * | 2019-05-29 | 2019-08-20 | 珠海冠宇电池有限公司 | A kind of method and device for improving pole piece baking and splitting |
| CN110465442A (en) * | 2019-09-12 | 2019-11-19 | 邹娥贞 | A kind of coating operations system manufactured for lithium battery |
| CN112467143A (en) * | 2020-12-01 | 2021-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion battery cathode slurry |
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| CN117995998A (en) * | 2024-02-21 | 2024-05-07 | 赣州旭航诚新能源有限公司 | Preparation method of nickel cobalt lithium manganate water-based positive plate of lithium ion battery |
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