CN108520959A - Waterborne polymeric-isocyanate group electrode composite material and preparation method thereof - Google Patents
Waterborne polymeric-isocyanate group electrode composite material and preparation method thereof Download PDFInfo
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- CN108520959A CN108520959A CN201810229403.1A CN201810229403A CN108520959A CN 108520959 A CN108520959 A CN 108520959A CN 201810229403 A CN201810229403 A CN 201810229403A CN 108520959 A CN108520959 A CN 108520959A
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Abstract
The invention discloses a kind of waterborne polymeric-isocyanate group electrode composite materials and preparation method thereof, it can apply to electrode for secondary battery composite material and its molding, the present invention is based on waterborne polymeric isocyanates bondings and crosslinking electrode activity particle and conductive auxiliary agent, and the technique coated on metal collector, belong to lithium, sodium-ion battery technical field.Its main feature is that based on aqueous solution mixing and rubbing method, composite material is prepared using 3.0% 15.0% waterborne polymerics, 80.5% 95.7% electrode activity particle, 2.0%~8.0% conductive auxiliary agent and 0.5% 1.5% water emulsification polymeric isocyanate crosslinking agents, then coating obtains cathode in collector.There is excellent electrochemical behavior and mechanical property using the made electrode composite material of this method, moulding process is simple, production efficiency is high and meets environment protection requirement.
Description
Technical field
The present invention relates to a kind of electrode composite material and preparation method thereof, especially a kind of waterborne polymeric base cathode is compound
Material and preparation method thereof is applied to lithium, sodium rechargeable battery technical field and new energy materials and molding technology thereof field.
Background technology
Although the main energy sources of Present Global still are based on the fossil fuel such as oil, coal and natural gas, it has not
Reproducible feature, and the gases such as carbon dioxide, nitrous oxide and sulfur dioxide discharged in combustion process cause air dirty
Therefore the development and utilization of dye, wind energy, solar energy and geothermal energy etc. becomes three emphasis that energy field gives more sustained attention during the last ten years.
However, these renewable and clean energy resources because being restricted by environmental factor, can not be stablized, persistently energize, the energy for developing high power capacity is needed
Amount storage reforming unit is effectively stored and is distributed to realize, i.e., energy storage technology is that the transformation of future source of energy structure and power generation disappear
The strategic support that expense mode is changed.Although the electrochemical energies such as lithium, sodium rechargeable battery, fuel cell and ultracapacitor store
System is rapidly developed in recent years, and wherein graphite-based lithium ion battery is widely used to mobile communication, portable computer
With the consumer-elcetronics devices such as video camera, be also acknowledged as the first choice of the storage of electrical source of power and regenerative resource, but its capacity and
Power still cannot be satisfied engineering actual demand.For relative theory capacity only has the graphite of 372mAh/g, although silicon, germanium, tin
There is higher energy density with novel anode materials such as ternary transition metal oxides, but this kind of electrode activity particle is in electrode
It is resulting larger to answer since deformation is constrained by surrounding matrix along with violent volume change in charge and discharge cycle
Power easily leads to electrode breakages, and the cycle life of battery is significantly lower than existing commercial product.How high-capacity secondary battery is improved
Military service performance be in recent years chemistry, mechanics and material educational circles facing challenge.
Lithium, the composite material that the electrode of sode cell is prepared by active particle, conductive auxiliary agent, adhesives are coated in metal collection
Flow surface forms.Polymer bonding agent is key component therein, it is intended to by active particle and conductive material (carbon black, acetylene
Black and nickel powder etc.) with the close connection of collector, keep the integrality of conductive path.The poly- of bonding agent is often used as graphite cathode
Vinylidene (PVdF), the mechanical performance in electrolyte environment are difficult to reach the service demand of high-capacity electrode material.No
Only adhesive polymer ontology easily destroys, and it is notable with the unsticking phenomenon of active particle and current collector, leads to not tie up
Complete electron motion channel is held, one of the principal element of battery capacity decaying is thus become.In addition, PVdF electrodes had been molded
It needs to use a large amount of N-Methyl pyrrolidone (NMP) in journey, the organic solvent is not only expensive, toxic, but also evaporates
Slowly, cause slurry drying time long, electrode production is less efficient.And aqueous bonding system has at low cost, pollution-free and nothing
Need to pre-process control humidity many advantages, carboxymethyl cellulose (CMC), carboxyl styrene emulsion (SBR), polyvinyl alcohol (PVA),
The waterborne polymeric of the hydroxyls such as polyacrylic acid (PAA) and extra large bath acid sodium or carboxyl has gradually replaced PVdF in recent years, becomes
The primary bond agent of lithium, sodium rechargeable battery negative material.Although the cycle energy based on high power battery prepared by waterborne polymeric
Power, coulombic efficiency and high rate performance are significantly improved, but it is still remained at a distance from larger with engineering demand.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Waterborne polymeric-isocyanate group electrode composite material and preparation method thereof, made composite material have excellent mechanics and
Chemical property, electrode moulding rate of drying is fast, and simple for process and meet environment protection requirement.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of waterborne polymeric-isocyanate group electrode composite material, by the waterborne polymeric of hydroxyl or carboxyl, electricity
Pole active particle, conductive auxiliary agent and water emulsification polymeric isocyanate are composed as material component, and each material component is according to group
Part dry mass percentage proportioning is as follows：
Waterborne polymeric 3.0-15.0wt%；
Active particle 80.5-95.7wt%；
Conductive auxiliary agent 1.0-3.0wt%；
Water emulsification polymeric isocyanate 0.3-1.5wt%.
Above-mentioned waterborne polymeric preferably uses carboxymethyl cellulose, carboxyethyl cellulose, carboxyl styrene emulsion, polyethylene
Alcohol, polyacrylic acid, extra large bath acid sodium, vinyl acetate homopolymerization and copolymer emulsion in any one polymer or arbitrary several poly-
Close the mixture of object.
Above-mentioned electrode activity particle preferably uses appointing for graphite, silicon, germanium, tin, transition metal oxide and nanometer zinc ferrite
It anticipates a kind of material or arbitrary several mixture is made.
Above-mentioned conductive auxiliary agent preferably use carbon black, acetylene black, carbon fiber, carbon nanosheet and nickel powder any one material or
The mixture of arbitrary different materials.
Above-mentioned water emulsification polymeric isocyanate preferably uses the polymeric multi isocyanate that nonionic surfactant is modified.
Make waterborne polymeric and water and milk by waterborne polymeric as adhesives as currently preferred technical solution
The crosslinking for changing polymeric isocyanate is bonded system, and is formed by water emulsification polymeric isocyanate crosslinking electrode particle and conductive auxiliary agent
Firm chemistry coupling structure, makes waterborne polymeric, electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate be formed
Waterborne polymeric with three-dimensional net structure-isocyanate group electrode composite material.
A kind of preparation method of electrode composite material is mixed and is coated with using aqueous solution casting method or using aqueous solution
Method, each material component according to component dry mass percentage match, using the waterborne polymeric of 3.0~15wt%, 80.5~
The water emulsification of the electrode activity particle of 95.7wt%, the conductive auxiliary agent of 1.0~3.0wt% and 0.3~1.5wt% polymerize isocyanic acid
Ester prepares waterborne polymeric-isocyanate group electrode composite material, includes the following steps as raw material：
A. by waterborne polymeric and deionized water according to 2:100 quality proportioning is added in reaction kettle, is to slowly warm up to 60-
90 DEG C, mechanical agitation 1-2 hours, so that it becomes the aqueous polymer solution being evenly distributed；
B. 50 DEG C are cooled to, and conductive auxiliary agent is slowly added into the aqueous polymer solution prepared in the step a,
Under ultrasonic wave and churned mechanically collective effect, mixing 2-3 hours is carried out, it is made to be dispersed in aqueous polymer solution
In；
C. continue to be cooled to 30-40 DEG C, electrode activity particle is gradually added into the polymerizable aqueous prepared in the step b
In the mixed solution of object and conductive agent, mechanical agitation is carried out 1-2 hours, active particle is made to be scattered in mixed liquor；As this hair
Bright preferred technical solution, continues to be cooled to 30-35 DEG C, and electrode activity particle is gradually added into waterborne polymeric and conductive agent
In mixed solution, mechanical agitation is carried out, active particle is made to be scattered in mixed liquor；
D. water emulsification polymeric isocyanate is added dropwise in the mixed liquor prepared to the step c, and stirs 15-30 minutes, obtains
To slurry；
E. the step d is prepared slurry to be coated in the metal collector not less than 8 μ m-thicks, then carries out three sections of dryings
Moulding process：
Carry out initial segment drying process within first dry 30-60 minutes at 40-60 DEG C；Then the dry 20- at 110-140 DEG C
Carry out intermediate stage drying process within 50 minutes；It is dried in vacuo at 30-60 DEG C again and carries out within 60-120 minutes last drying process, obtained
Negative electricity pole piece composite material.
As currently preferred technical solution, three sections of drying technologies are carried out：
Carry out initial segment drying process within first dry 45-60 minutes at 50-60 DEG C；Then the dry 30- at 110-140 DEG C
Carry out intermediate stage drying process within 50 minutes；It is dried in vacuo at 30-60 DEG C again and carries out within 60-120 minutes last drying process, obtained
Negative electricity pole piece composite material.
As currently preferred technical solution, the preparation method of electrode composite material, using material component polymerizable aqueous
Object, electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate are (3-6) according to the ratio that component dry mass matches:
90:3:1。
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. electrode composite material matrix prepared by the present invention is waterborne polymeric system Nian Jie with the crosslinking of polyisocyanates,
Wherein there are Hyarogen-bondings between polymerizable aqueous owner glue and electrode activity particle, and excellent toughness is provided for composite material
And self-repair function；And isocyanate groups-the NCO in water emulsification polymeric isocyanate not only with the hydroxyl in waterborne polymeric
Or carboxyl formed chemical bond, and electrode particle can be crosslinked, the free hydroxyl group on conductive auxiliary agent surface reacts to form firmization
Student's federation connects, and effective three-dimensional net structure is formd between composite material each component, therefore macro-mechanical property is obtained and significantly carried
It is high；
2. composite material sizing agent prepared by the present invention, during coating molding, collector metal surface is existing to adsorb water
Or metal oxide hydrate ,-NCO is reacted with water to be chelated due to hydrogen bond between the urea bond generated and metal oxide and to be formed acyl
Urea, i.e. metallic oxide complex object；The answering in addition, group can also form covalent bond etc. with metal hydrate, therefore after drying
Condensation material has excellent adhesive strength with collector；
3.-the NCO of bonding system of the present invention can be discharged when being chemically crosslinked with carboxyl contained by solvent and component
A certain amount of carbon dioxide, gas escape a small amount of micropore for generating in the process, can not only buffer electrode active particle removal lithium embedded/
The volume change that sodium generates reduces internal stress, and contributes to the diffusion of electrolyte in the composite, to reduce internal resistance, and
Improve the high rate performance of battery；
4. in the prior art, to improve the production efficiency of electrode slice, common solution is raising drying temperature, but
Capillary effect causes polymer content in composite material that gradient distribution, the i.e. bonding close to afflux side is presented along coating layer thickness
Agent is less, and active layer surface is enriched with, and has thus not only easy tod produce delamination failure, but also increase the fortune of active ion in electrolyte
Dynamic resistance, when being based on electrode moulding, the non-linear behavior of solvent evaporation process in composite material, and its mechanics with cured film
Performance strong correlation；And the present invention devises three sections of dryings and relents the moulding process of time, realization is segmented into trip temperature
And time control, initial and end temperature is controlled in 40-60 DEG C and 30-60 DEG C of lower temperature section, only by scala media
The drying temperature of section rises to 110-140 DEG C, not only increases shaping efficiency accordingly, and increase the crosslinking degree of composite material,
Also the inhomogeneities of wherein polymer bonding agent distribution is preferably solved；
5. waterborne polymeric made from the method for the present invention-isocyanate group electrode composite material has excellent electrochemistry
And mechanical property；
6. the method for the present invention is compared with existing lithium secondary battery anode preparation method, not only the performance of product is more excellent
More, production efficiency is higher, and avoids the release of organic solvent.
Description of the drawings
Fig. 1 is made of one waterborne polymeric of the embodiment of the present invention-isocyanate group electrode composite material as negative material
Battery specific capacity performance chart.
Specific implementation mode
Said program is described further below in conjunction with specific examples of the implementation, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one：
In the present embodiment, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, using material component sodium carboxymethylcellulose, SBR emulsion, electrode ferrous acid zinc nanoparticles, leads
The polymeric multi isocyanate that electric carbon black and nonionic surfactant are modified is 3 according to the ratio that component dry mass number matches:
3:90:3:1, include the following steps：
A. by sodium carboxymethylcellulose and deionized water according to 2:100 quality proportioning is added in reaction kettle, with 10 DEG C/
The heating rate of min is to slowly warm up to 80 DEG C, mechanical agitation 1 hour, so that it becomes the sodium carboxymethylcellulose being evenly distributed is molten
Liquid；
B. 50 DEG C, and the carboxymethylcellulose sodium solution for being 30 parts to the dry mass prepared in the step a are cooled to
In to be slowly added into dry mass be 30 parts of conductive black, under ultrasonic wave and churned mechanically collective effect, it is small to carry out mixing 2
When, so that it is dispersed in carboxymethylcellulose sodium solution；
C. continue to be cooled to 35 DEG C, the electrode ferrous acid zinc nanoparticles that dry mass is 900 parts are gradually added into the step
In the mixed solution of the sodium carboxymethylcellulose and conductive black that are prepared in rapid b, mechanical agitation is carried out 1 hour, make active particle
It is scattered in mixed liquor；
D. it is gradually added into the SBR emulsion of 30 parts of dry content in the mixed liquor prepared into step c, and is added 30 parts
Deionized water, mechanical agitation makes it be scattered in mixed liquor in 30 minutes；
E. 25 DEG C are cooled to, the non-ionic surface that dry mass is 10 parts is added dropwise in the mixed liquor prepared to the step c and lives
Property agent be modified polymeric multi isocyanate, and stir 15 minutes, obtain slurry；
F. the step e is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：Carry out initial segment drying process within first dry 45 minutes at 50 DEG C；Then it carries out within dry 30 minutes at 110 DEG C intermediate
Stage is dried；It is dried in vacuo at 30 DEG C again and carries out within 60 minutes last drying process, obtain negative electricity pole piece composite material.
Experimental test and analysis：
Using waterborne polymeric manufactured in the present embodiment-isocyanate group electrode composite material as negative electricity pole piece, carry out
Experiment detection, surface density 12.5mg/cm2, tensile strength 5.46MPa, adhesive strength 0.81N/cm, referring to table 1.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, is changed using material component polyvinyl alcohol, electrode graphite particle, conductive black and nonionic surfactant
Property the ratio that matches according to component dry mass number of polymeric multi isocyanate be 6:90:3:1, include the following steps：
A. by polyvinyl alcohol and deionized water according to 2:100 quality proportioning is added in reaction kettle, with the liter of 10 DEG C/min
Warm speed is to slowly warm up to 80 DEG C, mechanical agitation 1 hour, so that it becomes the poly-vinyl alcohol solution being evenly distributed；
B. 50 DEG C are cooled to, and in the poly-vinyl alcohol solution for being 60 parts to the dry mass prepared in the step a slowly
The conductive black that dry mass is 30 parts is added, under ultrasonic wave and churned mechanically collective effect, carries out mixing 2 hours, makes it
It is dispersed in poly-vinyl alcohol solution；
C. continue to be cooled to 30 DEG C, the electrode graphite particle that dry mass is 900 parts is gradually added into and is made in the step b
In the mixed solution of standby polyvinyl alcohol and conductive black, mechanical agitation is carried out 1 hour, active particle is made to be scattered in mixed liquor
In；
D. 25 DEG C are cooled to, the non-ionic surface that dry mass is 10 parts is added dropwise in the mixed liquor prepared to the step c and lives
Property agent be modified polymeric multi isocyanate, and stir 15 minutes, obtain slurry；
E. the step d is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：Carry out initial segment drying process within first dry 45 minutes at 50 DEG C；Then it carries out within dry 30 minutes at 110 DEG C intermediate
Stage is dried；It is dried in vacuo at 30 DEG C again and carries out within 60 minutes last drying process, obtain negative electricity pole piece composite material.
Experimental test and analysis：
Using waterborne polymeric manufactured in the present embodiment-isocyanate group electrode composite material as negative electricity pole piece, carry out
Experiment detection, surface density 13.8mg/cm2, tensile strength 4.50MPa, adhesive strength 0.80N/cm.The present embodiment system
Although standby waterborne polymeric-isocyanate group electrode composite material is than waterborne polymeric-isocyanic acid prepared by embodiment one
The tensile strength of ester group electrode composite material is slightly lower, but surface density higher, and composite material and collector have excellent bonding strong
Degree is suitable with embodiment one, referring to table 1.
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, is changed using material component polyvinyl alcohol, electrode graphite particle, conductive black and nonionic surfactant
Property the ratio that matches according to component dry mass number of polymeric multi isocyanate be 6:90:3:1, include the following steps：
A. by polyvinyl alcohol and deionized water according to 2:100 quality proportioning is added in reaction kettle, with the liter of 10 DEG C/min
Warm speed is to slowly warm up to 60 DEG C, mechanical agitation 2 hours, so that it becomes the poly-vinyl alcohol solution being evenly distributed；
B. 50 DEG C are cooled to, and in the poly-vinyl alcohol solution for being 60 parts to the dry mass prepared in the step a slowly
The conductive black that dry mass is 30 parts is added, under ultrasonic wave and churned mechanically collective effect, carries out mixing 3 hours, makes it
It is dispersed in poly-vinyl alcohol solution；
C. continue to be cooled to 40 DEG C, the electrode graphite particle that dry mass is 900 parts is gradually added into and is made in the step b
In the mixed solution of standby polyvinyl alcohol and conductive black, mechanical agitation is carried out 3 hours, active particle is made to be scattered in mixed liquor
In；
D. 30 DEG C are cooled to, the non-ionic surface that dry mass is 10 parts is added dropwise in the mixed liquor prepared to the step c and lives
Property agent be modified polymeric multi isocyanate, and stir 30 minutes, obtain slurry；
E. the step d is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：
Carry out initial segment drying process within first dry 60 minutes at 40 DEG C；Then in carrying out within dry 20 minutes at 140 DEG C
Between the stage be dried；It is dried in vacuo at 60 DEG C again and carries out within 60 minutes last drying process, obtain negative electricity pole piece composite material.
Experimental test and analysis：
Using waterborne polymeric manufactured in the present embodiment-isocyanate group electrode composite material as negative electricity pole piece, carry out
Experiment detection, surface density 13.7mg/cm2, tensile strength 4.48MPa, adhesive strength 0.82N/cm.The present embodiment system
Although standby waterborne polymeric-isocyanate group electrode composite material is than waterborne polymeric-isocyanic acid prepared by embodiment two
The surface density of ester group electrode composite material is slightly lower, but with the comparable excellent tensile strength of embodiment two and it is Nian Jie by force
Degree, referring to table 1.
Example IV：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, is modified using material component polyvinyl alcohol, graphite particle, conductive black and nonionic surfactant
Polymeric multi isocyanate is 6 according to the ratio that component dry mass number matches:90:3:1, include the following steps：
A. by polyvinyl alcohol and deionized water according to 2:100 quality proportioning is added in reaction kettle, with the liter of 15 DEG C/min
Warm speed is to slowly warm up to 90 DEG C, mechanical agitation 1 hour, so that it becomes the poly-vinyl alcohol solution being evenly distributed；
B. 50 DEG C are cooled to, and in the poly-vinyl alcohol solution for being 60 parts to the dry mass prepared in the step a slowly
The conductive black that dry mass is 30 parts is added, under ultrasonic wave and churned mechanically collective effect, carries out mixing 2 hours, makes it
It is dispersed in poly-vinyl alcohol solution；
C. continue to be cooled to 40 DEG C, the electrode graphite particle that dry mass is 900 parts is gradually added into and is made in the step b
In the mixed solution of standby polyvinyl alcohol and conductive black, mechanical agitation is carried out 2 hours, active particle is made to be scattered in mixed liquor
In；
D. 30 DEG C are cooled to, the non-ionic surface that dry mass is 10 parts is added dropwise in the mixed liquor prepared to the step c and lives
Property agent be modified polymeric multi isocyanate, and stir 30 minutes, obtain slurry；
E. the step d is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：
Carry out initial segment drying process within first dry 30 minutes at 60 DEG C；Then in carrying out within dry 50 minutes at 110 DEG C
Between the stage be dried；It is dried in vacuo at 120 DEG C again and carries out within 30 minutes last drying process, obtain negative electricity pole piece composite wood
Material.
Experimental test and analysis：
Using waterborne polymeric manufactured in the present embodiment-isocyanate group electrode composite material as negative electricity pole piece, carry out
Experiment detection, surface density 13.5mg/cm2, tensile strength 4.51MPa, adhesive strength 0.79N/cm.The present embodiment system
The polymerizable aqueous that standby waterborne polymeric-isocyanate group electrode composite material is prepared with above-described embodiment two and embodiment three
Although object-isocyanate group electrode composite material is slightly lower compared to surface density, there is same excellent tensile strength and and afflux
The adhesive strength of body.
Comparative example one：
In this comparative example, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, using material component sodium carboxymethylcellulose, SBR emulsion, electrode ferrous acid zinc nanoparticles, leads
Electric carbon black is 3.5 according to the ratio that component dry mass number matches:3.5:90:3, include the following steps：
A. by sodium carboxymethylcellulose and deionized water according to 2:100 quality proportioning is added in reaction kettle, with 10 DEG C/
The heating rate of min is to slowly warm up to 80 DEG C, mechanical agitation 1 hour, so that it becomes the sodium carboxymethylcellulose being evenly distributed is molten
Liquid；
B. 50 DEG C, and the carboxymethylcellulose sodium solution for being 35 parts to the dry mass prepared in the step a are cooled to
In to be slowly added into dry mass be 30 parts of conductive black, under ultrasonic wave and churned mechanically collective effect, it is small to carry out mixing 2
When, so that it is dispersed in carboxymethylcellulose sodium solution；
C. continue to be cooled to 35 DEG C, the electrode ferrous acid zinc nanoparticles that dry mass is 900 parts are gradually added into the step
In the mixed solution of the sodium carboxymethylcellulose and conductive black that are prepared in rapid b, mechanical agitation is carried out 1 hour, make active particle
It is scattered in mixed liquor；
D. 25 DEG C are cooled to, the SBR emulsion that dry mass is 35 parts is added dropwise in the mixed liquor prepared to the step d,
And the deionized water of 30 parts of addition, mechanical agitation 30 minutes obtain slurry；
E. the step d is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：Carry out initial segment drying process within first dry 45 minutes at 50 DEG C；Then it carries out within dry 30 minutes at 110 DEG C intermediate
Stage is dried；It is dried in vacuo at 30 DEG C again and carries out within 60 minutes last drying process, obtain negative electricity pole piece composite material.
Experimental test and analysis：
Electrode composite material prepared by this comparative example carries out experiment detection as negative electricity pole piece, and surface density is
10.5mg/cm2, tensile strength 3.45MPa, adhesive strength 0.51N/cm.Waterborne polymeric-prepared by embodiment one is different
Cyanate base electrode composite material is compared with waterborne polymeric base electrode composite material prepared by this comparative example, surface density, tension
Intensity and adhesive strength are significantly improved.
Comparative example two：
In this comparative example, a kind of preparation method of electrode composite material, using aqueous solution casting method or using water-soluble
Liquid mixes and rubbing method, using material component polyvinyl alcohol, electrode ferrous acid zinc nanoparticles, conductive black according to component dry mass
The ratio of number proportioning is 7:90:3, include the following steps：
A. by polyvinyl alcohol and deionized water according to 2:100 quality proportioning is added in reaction kettle, with the liter of 10 DEG C/min
Warm speed is to slowly warm up to 80 DEG C, mechanical agitation 1 hour, so that it becomes the poly-vinyl alcohol solution being evenly distributed；
B. 50 DEG C are cooled to, and in the poly-vinyl alcohol solution for being 60 parts to the dry mass prepared in the step a slowly
The conductive black that dry mass is 30 parts is added, under ultrasonic wave and churned mechanically collective effect, carries out mixing 2 hours, makes it
It is dispersed in poly-vinyl alcohol solution；
C. continue to be cooled to 30 DEG C, the electrode ferrous acid zinc nanoparticles that dry mass is 900 parts are gradually added into the step
In the mixed solution of the polyvinyl alcohol and conductive black that are prepared in rapid b, mechanical agitation is carried out 1 hour, active particle is made to be scattered in
In mixed liquor；
D. 25 DEG C are cooled to, and is added 30 parts
Deionized water, mechanical agitation 30 minutes obtains slurry；
E. the step d is prepared slurry to be coated in the copper foil metal collector of 8 μ m-thicks, then carrying out three sections is dried to
Type technique：Carry out initial segment drying process within first dry 45 minutes at 50 DEG C；Then it carries out within dry 30 minutes at 110 DEG C intermediate
Stage is dried；It is dried in vacuo at 30 DEG C again and carries out within 60 minutes last drying process, obtain negative electricity pole piece composite material.
Experimental test and analysis：
Using waterborne polymeric manufactured in the present embodiment-isocyanate group electrode composite material as negative electricity pole piece, carry out
Experiment detection, surface density 13.0mg/cm2, tensile strength 3.21MPa, adhesive strength 0.55N/cm, referring to table 1.It is real
Apply waterborne polymeric-isocyanate group electrode composite material and this comparative example system prepared by example two, embodiment three and example IV
Standby waterborne polymeric base electrode composite material is compared, and surface density, tensile strength and adhesive strength are significantly improved.
The main physico-mechanical performance comparison table of electrode composite material prepared by 1. embodiment of the present invention of table and comparative example
By table 1 and Fig. 1 as it can be seen that the above embodiment of the present invention, which is based on waterborne polymeric-isocyanates, is bonded system, prepare
Composite material have good electrochemical behavior and excellent mechanical property, can be widely applied to lithium ion or sodium ion be secondary
Battery industry field.Waterborne polymeric-isocyanate group electrode composite material prepared by embodiment one is prepared with comparative example one
Electrode composite material is made battery and compares as negative material, waterborne polymeric prepared by embodiment one-isocyanate group electricity
Battery made of the composite material of pole for the first time imitate and battery capacity higher by coulomb.Waterborne polymeric-isocyanic acid prepared by embodiment two
Ester group electrode composite material has same outstanding electricity compared with battery is made in electrode composite material prepared by embodiment three, four
Battery phase is made as negative material in coulombic efficiency and battery capacity, the electrode composite material prepared with comparative example two for the first time in pond
Battery made of the waterborne polymeric-isocyanate group electrode composite material prepared than, embodiment two coulombic efficiency and electricity for the first time
Tankage higher.And embodiment two compares the electrode composite material of the preparation of embodiment one as negative material, and battery phase is made
Than, battery capacity improves twice or more.The above embodiment of the present invention prepare based on waterborne polymeric-isocyanates convered structure
The composite material of system, preparation has good electrochemical behavior and excellent mechanical property, can be widely applied to lithium ion or sodium
Ion secondary battery industrial circle.
In short, electrode composite material matrix prepared by the above embodiment of the present invention is waterborne polymeric and polyisocyanates
It is crosslinked bonding system, wherein there are Hyarogen-bondings between polymerizable aqueous owner glue and electrode activity particle, are carried for composite material
Excellent toughness and self-repair function are supplied；And isocyanate groups-the NCO in water emulsification polymeric isocyanate not only with it is aqueous
Hydroxyl or carboxyl in polymer form chemical bond, and it is anti-to be crosslinked electrode particle, the free hydroxyl group on conductive auxiliary agent surface
Firm chemistry connection should be formed, effective three-dimensional net structure, macro-mechanical property are formd between composite material each component
Therefore it is significantly improved；Composite material sizing agent manufactured in the present embodiment during coating molding, deposit by collector metal surface
Absorption water or metal oxide hydrate ,-NCO reacted with water generate urea bond and metal oxide between due to hydrogen bond and
Chelating forms uride, i.e. metallic oxide complex object；In addition, the group can also form covalent bond etc. with metal hydrate, therefore
Composite material after drying has excellent adhesive strength with collector；The above embodiment of the present invention be bonded system-NCO with
When carboxyl contained by solvent and component is chemically crosslinked, a certain amount of carbon dioxide can be discharged, is produced during gas effusion
Raw a small amount of micropore, can not only the volume change that generates of buffer electrode active particle removal lithium embedded/sodium, reduce internal stress, and have
Help the diffusion of electrolyte in the composite, to reduce internal resistance, and improves the high rate performance of battery.
In the prior art, it is the production efficiency for improving electrode slice, common solution is to improve drying temperature, but hair
Tubule effect causes polymer content in composite material that gradient distribution, the i.e. bonding agent close to afflux side is presented along coating layer thickness
It is less, and active layer surface is enriched with, and has thus not only easy tod produce delamination failure, but also increase the movement of active ion in electrolyte
Resistance, when being based on electrode moulding, the non-linear behavior of solvent evaporation process in composite material, and its mechanical property with cured film
It can strong correlation；And it is that embodiment uses three sections of dryings and relents the moulding process of time that the present invention is above-mentioned, realizes and divides
Duan Jinhang temperature and times control, and initial and end temperature is controlled in 40-60 DEG C and 30-60 DEG C of lower temperature section,
The drying temperature in intermediate stage is only risen to 110-140 DEG C, not only increases shaping efficiency accordingly, and increase composite material
Crosslinking degree also preferably solves the inhomogeneities of wherein polymer bonding agent distribution；The above embodiment of the present invention method system
Waterborne polymeric-isocyanate group the electrode composite material obtained has excellent electrochemistry and mechanical property；The above-mentioned reality of the present invention
A method is applied to compare with existing lithium secondary battery anode preparation method, not only the performance of product is more superior, production efficiency compared with
Height, and avoid the release of organic solvent.The above embodiment of the present invention is mixed using aqueous solution and rubbing method, by polymerizable aqueous
Object, electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate crosslinking agent prepare composite material, and then coating is in afflux
Body obtains cathode.There is excellent electrochemical behavior and power using the made electrode composite material of the above embodiment of the present invention method
Performance is learned, moulding process is simple, production efficiency is high and meets environment protection requirement.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from the technical principle and hair of waterborne polymeric of the present invention-isocyanate group electrode composite material and preparation method thereof
Bright design, belongs to protection scope of the present invention.
Claims (10)
1. a kind of waterborne polymeric-isocyanate group electrode composite material, which is characterized in that by the aqueous of hydroxyl or carboxyl
Polymer, electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate are composed as material component, each raw material group
Part matches as follows according to component dry mass percentage：
2. waterborne polymeric-isocyanate group electrode composite material according to claim 1, it is characterised in that：It is described aqueous
Polymer is carboxymethyl cellulose, carboxyethyl cellulose, carboxyl styrene emulsion, polyvinyl alcohol, polyacrylic acid, extra large bath acid sodium, second
The mixture of any one polymer or arbitrary several polymer in the homopolymerization and copolymer emulsion of vinyl acetate.
3. waterborne polymeric-isocyanate group electrode composite material according to claim 1, it is characterised in that：The electrode
Active particle uses any one material or arbitrary several of graphite, silicon, germanium, tin, transition metal oxide and nanometer zinc ferrite
Mixture be made.
4. waterborne polymeric-isocyanate group electrode composite material according to claim 1, it is characterised in that：The conduction
Auxiliary agent is any one material of carbon black, acetylene black, carbon fiber, carbon nanosheet and nickel powder or the mixture of arbitrary different materials.
5. waterborne polymeric-isocyanate group electrode composite material according to claim 1, it is characterised in that：The water and milk
Change the polymeric multi isocyanate that polymeric isocyanate uses nonionic surfactant to be modified.
6. according to any one of Claims 1 to 5 waterborne polymeric-isocyanate group electrode composite material, feature
It is：By waterborne polymeric as adhesives, make waterborne polymeric system Nian Jie with the crosslinking of water emulsification polymeric isocyanate,
And firm chemical coupling structure is formed by water emulsification polymeric isocyanate crosslinking electrode particle and conductive auxiliary agent, make polymerizable aqueous
Object, electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate form the polymerizable aqueous with three-dimensional net structure
Object-isocyanate group electrode composite material.
7. a kind of preparation method of electrode composite material, which is characterized in that mixed using aqueous solution casting method or using aqueous solution
Close and rubbing method, each material component according to component dry mass percentage match, using the waterborne polymeric of 3.0~15wt%,
The water emulsification of the electrode activity particle of 80.5~95.7wt%, the conductive auxiliary agent of 1.0~3.0wt% and 0.3~1.5wt% polymerize
Isocyanates prepares waterborne polymeric-isocyanate group electrode composite material, includes the following steps as raw material：
A. by waterborne polymeric and deionized water according to 2:100 quality proportioning is added in reaction kettle, is to slowly warm up to 60-90
DEG C, mechanical agitation 1-2 hours, so that it becomes the aqueous polymer solution being evenly distributed；
B. 50 DEG C are cooled to, and conductive auxiliary agent is slowly added into the aqueous polymer solution prepared in the step a, super
Sound wave carries out mixing 2-3 hours, it is made to be dispersed in aqueous polymer solution under churned mechanically collective effect；
C. continue to be cooled to 30-40 DEG C, electrode activity particle is gradually added into the waterborne polymeric that is prepared in the step b with
In the mixed solution of conductive agent, mechanical agitation is carried out 1-2 hours, active particle is made to be scattered in mixed liquor；
D. it is cooled in the mixed liquor not higher than 30 DEG C, prepared to the step c and water emulsification polymeric isocyanate is added dropwise, and stir
15-30 minutes, obtain slurry；
E. the step d is prepared slurry to be coated in the metal collector not less than 8 μ m-thicks, then carries out three sections of drying and mouldings
Technique：
Carry out initial segment drying process within first dry 30-60 minutes at 40-60 DEG C；Then dry 20-50 points at 110-140 DEG C
Clock carries out intermediate stage drying process；It is dried in vacuo at 30-60 DEG C again and carries out within 60-120 minutes last drying process, obtain cathode
Electrode slice composite material.
8. the preparation method of electrode composite material according to claim 7, it is characterised in that：Material component waterborne polymeric,
Electrode activity particle, conductive auxiliary agent and water emulsification polymeric isocyanate are (3-6) according to the ratio that component dry mass matches:90:
3:1。
9. the preparation method of electrode composite material according to claim 7, it is characterised in that：In the step c, continue to drop
Electrode activity particle is gradually added into 30-35 DEG C in the mixed solution of waterborne polymeric and conductive agent by temperature, is carried out machinery and is stirred
It mixes, active particle is made to be scattered in mixed liquor.
10. the preparation method of electrode composite material according to claim 7, it is characterised in that：In the step e, carry out
Three sections of drying technologies：
Carry out initial segment drying process within first dry 45-60 minutes at 50-60 DEG C；Then dry 30-50 points at 110-140 DEG C
Clock carries out intermediate stage drying process；It is dried in vacuo at 30-60 DEG C again and carries out within 60-120 minutes last drying process, obtain cathode
Electrode slice composite material.
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| CN112802986A (en) * | 2020-12-30 | 2021-05-14 | 上海大学 | Rapid drying and forming method of electrode composite material |
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| EP3951955A4 (en) * | 2019-12-27 | 2022-08-17 | LG Energy Solution, Ltd. | Binder composition for anode, anode, and secondary battery |
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