CN110350196A - A kind of compound binding agent, silicon-based anode piece and preparation method thereof - Google Patents
A kind of compound binding agent, silicon-based anode piece and preparation method thereof Download PDFInfo
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- CN110350196A CN110350196A CN201910566917.0A CN201910566917A CN110350196A CN 110350196 A CN110350196 A CN 110350196A CN 201910566917 A CN201910566917 A CN 201910566917A CN 110350196 A CN110350196 A CN 110350196A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of compound binding agents, silicon-based anode piece and preparation method thereof.The preparation method of the silicon-based anode piece includes: that the Kynoar of different molecular weight is obtained compound binding agent by ball mill mixing；Compound binding agent is dissolved in organic solvent, obtains adhesive gelatin；It disperses conductive agent in adhesive gelatin, obtains conductive gelatin；Si-C composite material powder and organic solvent are added in conductive gelatin, electrode slurry is made；Electrode slurry is coated on negative current collector, the collector that gained is coated with electrode slurry is subjected to vacuum high-temperature, solvent is gone to handle；Roll-in is carried out to resulting cathode pole piece, obtains silicon-based anode piece.Prepared silicon-based anode piece can be effectively improved electrode material of lithium battery performance, improve the high rate performance and cycle life of battery.
Description
Technical field
The present invention relates to a kind of high-performance compound binding agent, the silicon-based anode piece based on this binder and preparation method thereof,
Belong to energy-storage battery technical field.
Background technique
Lithium ion battery energy density is high, operating voltage height, memory-less effect, has extended cycle life, and is widely used in intelligence
The fields such as wearable device and new-energy automobile.However, people are close to its energy since lithium ion battery applications operating condition is complicated
More stringent requirements are proposed for degree, cycle life, security performance etc..Research and develop high-energy density silicium cathode (theoretical specific capacity
4200mAh·g-1) to replace current graphite cathode (theoretical specific capacity 372mAhg-1) it is improve performance of lithium ion battery one
A important channel.However, silicon materials volume change is huge (being much higher than graphite) in charge and discharge process, causes itself dusting, make
Viability substance falls off from collector, causes the cyclical stability of battery poor.It is to solve using the bonding agent for inhibiting electrode expansion
The important method of silicon volume expansion problem.Binder can exist Si-C composite material, conductive agent and collector tight bond
Together, to stablize electrode structure, silicon volume expansion is solved.
Currently used lithium ion battery binder includes the multi-component copolymer of SBR styrene butadiene rubbers (SBR), acrylonitrile
Object (LA series polymer) and Kynoar (PVDF) class.The compatibility of SBR and polarity electrolyte are poor, lead to charge and discharge
Lithium ion conducts difficulty in a binder in the process, and the internal resistance of cell increases, it is difficult to meet lithium battery especially power battery to big
The demand of rate charge-discharge.LA series polymer glass transition temperature is excessively high, and pole piece mutability cirrhosis is crisp, causes its processing performance
Difference.For example, it is easy to crack in coating process, striped is also easy to produce after roll-in, it is especially dynamic in lithium battery that these all constrain it
Application in power battery.For traditional PVDF (molecular weight is about 1,000,000) although having preferable electrochemical stability, excellent is flexible
Property, but its in electrolyte propylene carbonate act on when be easy to happen swelling, cause electrode structure to deform, at the same its bonding
Power reduces, and causes the cycle performance of battery to be deteriorated, which has limited application of the PVDF in terms of inhibiting silicon-based anode expansion.
Summary of the invention
It is an object of the present invention to provide a kind of high-performance compound binding agent, the silicon-based anode piece based on this binder and its preparations
Method.
In order to achieve the above object, the present invention provides a kind of preparation methods of silicon-based anode piece, which is characterized in that including
Following steps:
Step 1: the Kynoar 10-80wt% for being 1,500,000-300 ten thousand by weight average molecular weight, weight average molecular weight 80
The Kynoar 0-60wt% that ten thousand-140 ten thousand Kynoar 10-70wt% and weight average molecular weight is 200,000-60 ten thousand is logical
Ball mill mixing is crossed, compound binding agent is obtained；
Step 2: the resulting compound binding agent of step 1 being dissolved in organic solvent, obtains adhesive gelatin；
Step 3: dispersing conductive agent in the resulting adhesive gelatin of step 2, obtain conductive gelatin；
Step 4: Si-C composite material powder and organic solvent being added in the resulting conductive gelatin of step 3, electricity is made
Pole slurry；
Step 5: the resulting electrode slurry of step 4 being coated on negative current collector by automatic coating machine, is coated with
There is the collector of electrode slurry；
Step 6: the collector that gained is coated with electrode slurry being subjected to vacuum high-temperature, solvent is gone to handle；
Step 7: roll-in being carried out to resulting cathode pole piece, obtains silicon-based anode piece.
Preferably, the Si-C composite material is the mixture of silicon substrate and carbon-based material.It is highly preferred that described is carbon-based
Material is one of hard carbon, soft carbon, natural graphite and artificial graphite or a variety of.It is highly preferred that the silica-base material is
Micron silicon, nano-silicon aoxidize sub- one of silicon and silica or a variety of.
Preferably, the conductive agent is one of acetylene black, Ketjen black, carbon fiber and Super P.
Preferably, the organic solvent is one of N-Methyl pyrrolidone, acetonitrile and dimethylformamide.
Preferably, the adhesive gelatin mass fraction is 5-50%.It is highly preferred that the adhesive gelatin quality
Score is 5-10%.
Preferably, the specific step of " the resulting compound binding agent of step 1 is dissolved in organic solvent " in the step 2
It suddenly include: that the resulting compound binding agent of step 1 is added in organic solvent, at 10-60 DEG C of temperature, with 100-2500r
min-110-72h is stirred under revolving speed, adhesive gelatin is made.It is highly preferred that " step 1 is resulting multiple in the step 2
Close binder be dissolved in organic solvent " specific steps include: that the resulting compound binding agent of step 1 is added to organic solvent
In, at 15-45 DEG C of temperature, with 100-2500rmin-110-72h is stirred under revolving speed, adhesive gelatin is made.
Preferably, conductive agent mass fraction is 5-20% in the conductive gelatin.
Preferably, the specific steps of described " dispersing conductive agent in the resulting adhesive gelatin of step 2 " include: to
Conductive agent is added in adhesive gelatin, with 100-1500rmin at 10-60 DEG C of temperature-1Revolving speed stir 5-300min.
Preferably, the viscosity of the electrode slurry is 500-25000mPas.
Preferably, the specific preparation steps of the electrode slurry in the step 4 include: to add Si-C composite material powder
It is added in conductive gelatin, in the case where temperature is 10-60 DEG C, with 100-1000rmin-1Revolving speed stirring 5-100min after, be added with
Solvent, with 100-1500rmin-1Revolving speed stirs 10-500min, obtains electrode slurry.
Preferably, the coating process in the step 5 includes: and passes through electrode slurry automatic at 15-60 DEG C of temperature
Coating machine is coated on negative current collector, coating speed 1-8mmin with 10-300 μ m thick-1, slurry moisture content when coating
In 100ppm or less.
Preferably, the specific steps that the vacuum high-temperature goes solvent to handle include: the afflux for being coated with electrode slurry
Body is placed in the baking oven that temperature is 80-130 DEG C, and relative vacuum angle value is less than or equal to -0.1MPa, handles time 10-25h.
Preferably, after the roll-in, cathode pole piece with a thickness of 10-100 μm.
The present invention also provides a kind of compound binding agents, which is characterized in that including weight average molecular weight is 1,500,000-300 ten thousand
Kynoar 10-80wt%, the Kynoar 10-70wt% and weight average molecular weight that weight average molecular weight is 800,000-140 ten thousand
For 200,000-60 ten thousand Kynoar 0-60wt%.
Preferably, the Kynoar 10- that the high-performance compound binding agent is 22000000 by weight average molecular weight
The poly- inclined fluorine that Kynoar 10-70wt% that 80wt%, weight average molecular weight are 10500000, weight average molecular weight are 5700000
Ethylene 10-60wt% composition.
The present invention also provides the preparation methods of above-mentioned high-performance compound binding agent characterized by comprising weight is equal
The Kynoar 10-80wt% that molecular weight is 1,500,000-300 ten thousand, the Kynoar that weight average molecular weight is 800,000-140 ten thousand
The Kynoar 0-60wt% that 10-70wt% and weight average molecular weight are 200,000-60 ten thousand obtains high property by ball mill mixing
It can compound binding agent.
The method comprises the steps of firstly, preparing high-performance compound binding agent (molecular weight are about 2,000,000), solve unimolecule amount polyvinylidene fluoride
Alkene machinability and structural stability are difficult to the problem of optimizing jointly, then propose the silicon-based anode piece based on this binder
Preparation method.The lithium ion battery carbon silicium cathode prepared by high-performance compound binding agent, can solve silicon in the prior art
Material cell high rate performance difference and the short technical problem of cycle life.Prepared silicon-based anode piece is effectively improved electrode of lithium cell
Material property improves the high rate performance and cycle life of battery.
Compared with prior art, the present invention has following technical effect that
1, compound binding agent preparation method is simple in the present invention, merely with the biggish Kynoar of molecular weight difference
High-performance silicon-based negative electrode binder is made, this method is simple and easy, and it is low in cost, it is pollution-free, it is easy to industrialize.
2, compound binding agent has many advantages, such as that structural stability is good in the present invention, and electrolyte ownership is high, different molecular weight
More stable and flexible network frame can be constructed between electrode after Kynoar is compound, therefore it is negative to alleviate silicon substrate
The technical problem of pole material silicon materials dusting and rate charge-discharge performance difference during lithium ion is embedded in.
3, prepared silicon-carbon cathode has excellent mechanical performance in the present invention, especially preferably flexible strong with bonding
Degree greatly improves the technical problem that silicon-carbon cathode pole piece during to roller lamination is also easy to produce crackle, and then reduces
Defect rate has the potential of large-scale production.
4, the compound binding agent prepared by the present invention combine different molecular weight poly (vinylidene fluoride) thermal stability is good, resistance toization
It learns that moral character is good and the advantages such as workability, has effectively widened the operation strategies of its material, and then urge in flexible lithium battery, optics
The technical fields such as change, air cleaning have broad application prospects.
5, high-performance compound binding agent of the invention has excellent structural stability and electrolyte ownership, is able to solve
The technical problem of silicon based anode material silicon materials dusting during lithium ion is embedded in, and efficiently solve under the prior art
The problems such as silicon-carbon cathode cycle performance of preparation is low, high rate performance is poor improves battery performance.
Detailed description of the invention
Fig. 1 is Kynoar (weight average molecular weight 2200000) powder particle SEM figure.
Fig. 2 is Kynoar (weight average molecular weight 1050000) powder particle SEM figure.
Fig. 3 is that the cathode pole piece surface topography SEM of embodiment 1 schemes.
Fig. 4 is the silicon-carbon cathode half-cell multiplying power figure of embodiment 1.
Fig. 5 is Kynoar (weight average molecular weight 570000) powder particle SEM figure.
Fig. 6 is that the cathode pole piece surface topography SEM of embodiment 2 schemes.
Fig. 7 is that the cathode pole piece surface topography SEM of embodiment 3 schemes.
Fig. 8 is that the cathode pole piece surface topography SEM of comparative example schemes.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
(great Jin is fluorinated work VW-770 to the Kynoar that used weight average molecular weight is 2200000 in following embodiment
Type), the Kynoar (5130 type of Su Wei) that weight average molecular weight is 1050000, the polyvinylidene fluoride that weight average molecular weight is 570000
Alkene (A Kema 761A type).
Used negative electrode material powder is Bei Terui (650 type) Si-C composite material powder (SiO in following embodimentx:
C=7:3).
CR2025 type half-cell assemble method described in following embodiment are as follows: pole piece, which is cut into diameter, with slitter is
The disk of 13mm, then (collector of pole piece towards anode cover) is successively stacked by anode cover, pole piece, diaphragm sequence, it is then poured into
Then electrolyte successively stacks lithium piece, gasket, elastic slice, negative electrode casing on diaphragm, finally by the electronic sealing machine of button cell,
Under conditions of sealing pressure and the time is respectively 350N and 20S, it is assembled into CR2025 type button cell.
Embodiment 1
The preparation method of a kind of high-performance compound binding agent and silicon-based anode piece, specific steps are as follows:
(1) the compound Kynoar powder for weighing 3g is put in ball mill, and compound Kynoar powder is by dividing equally again
Son amount is respectively 2200000 and 1050000 Kynoar powder constituent, mass ratio 7:3, then with 1200rmin-1
Compound binding agent is made by ball mill mixing in revolving speed.
(2) by compound binding agent obtained in step (1), it is added in N-Methyl pyrrolidone, at 25 DEG C of temperature,
With 1100rmin-148h is stirred under revolving speed, so that compound binding agent is dissolved in N-Methyl pyrrolidone, mass fraction is made
For 5.5% adhesive gelatin.
(3) mass ratio of addition conductive agent Ketjen black in Xiang Shangshu glue, glue and conductive agent Ketjen black is 18:1, and
With 300rmin at 25 DEG C of temperature-1Revolving speed stir 25min, be scattered in conductive agent in adhesive gelatin, be made conducting resinl
Liquid.
(4) by Bei Terui (650 type) Si-C composite material powder (SiOx: C=7:3) it is added in conductive gelatin, it is conductive
The mass ratio of glue and silicon-carbon composite powder is 12:5, in the case where temperature is 25 DEG C, with 500rmin in blender-1Revolving speed
After stirring 30min, it is 10000mPas that addition N-Methyl pyrrolidone, which adjusts solution viscosity, with 500rmin-1Revolving speed stirring
Electrode slurry is made in 20min.
(5) above-mentioned electrode slurry is coated on negative current collector by automatic coating machine with 75 μ m thicks, wherein being coated with
25 DEG C of temperature, coating speed 2.5mmin-1, slurry moisture content is coated with electrode slurry hereinafter, obtaining in 100ppm when coating
Collector.
(6) collector for being coated with electrode slurry carries out vacuum high-temperature and solvent is gone to handle, and the vacuum high-temperature goes molten
The specific steps of agent processing include: to be coated with the collector of electrode slurry to be placed in temperature be relative vacuum in 100 DEG C of baking oven
Angle value is less than or equal to -0.1MPa, handles time 25h；
(7) roll-in is carried out to the slurry being coated on negative current collector, the compacting surface density for controlling slurry is 2.5gcm-2, after roll-in, cathode pole piece with a thickness of 35 μm, be made negative electrode tab semi-finished product.
(8) the negative electrode tab semi-finished product after roll-in are punched into design size.
Viscosity by SNB series digital display viscosity meter glue is 3200mPas, by silicon-carbon cathode obtained by step 7
It is assembled into CR2025 type half-cell, carries out battery performance test, obtains first circle specific volume when the 0.1C electric discharge of silicon-carbon cathode half-cell
Amount is 632mAhg-1, specific capacity is 327mAhg when 1C discharges-1。
Embodiment 2
The preparation method of a kind of high-performance compound binding agent and silicon-based anode piece, specific steps are as follows:
(1) the compound Kynoar powder for weighing 3.5g is put in ball mill, and compound Kynoar powder is equal by weight
Molecular weight is respectively 2200000 and 1050000 Kynoar powder constituent, mass ratio 4:1, then with 1000r
min-1Compound binding agent is made by ball mill mixing in revolving speed.
(2) by compound binding agent obtained in step 1, it is added in N-Methyl pyrrolidone, at 15 DEG C of temperature, with
1100r·min-136h is stirred under revolving speed, so that compound binding agent is dissolved in N-Methyl pyrrolidone, obtained mass fraction is
10% adhesive gelatin.
(3) mass ratio of addition conductive agent Ketjen black in Xiang Shangshu glue, glue and conductive agent is 15:1, and in temperature 15
With 400rmin at DEG C-1Revolving speed stir 20min, be scattered in conductive agent in adhesive gelatin, be made conductive gelatin.
(4) by Bei Terui (650 type) Si-C composite material powder (SiOx: C=7:3) it is added in conductive gelatin, it is conductive
The mass ratio of liquid and silicon-carbon composite powder is 4:1, in the case where temperature is 30 DEG C, with 500rmin in blender-1Revolving speed stirring
After 25min, it is 9000mPas that addition N-Methyl pyrrolidone, which adjusts solution viscosity, with 500rmin-1Revolving speed stirs 15min,
Electrode slurry is made.
(5) above-mentioned electrode slurry is coated on negative current collector by automatic coating machine with 100 μ m thicks, wherein being coated with
20 DEG C of temperature, coating speed 4mmin-1, slurry moisture content is coated with electrode slurry hereinafter, obtaining in 80ppm when coating
Collector.
(6) collector for being coated with electrode slurry carries out vacuum high-temperature and solvent is gone to handle, and the vacuum high-temperature goes molten
The specific steps of agent processing include: to be coated with the collector of electrode slurry to be placed in temperature be relative vacuum in 120 DEG C of baking oven
Angle value is less than or equal to -0.3MPa, and the processing time is for 24 hours；
(7) roll-in is carried out to the slurry being coated on negative current collector, the compacting surface density for controlling slurry is 3.2gcm-2, after roll-in, cathode pole piece with a thickness of 55 μm, be made negative electrode tab semi-finished product.
(8) the negative electrode tab semi-finished product after roll-in are punched into design size.
Viscosity by SNB series digital display viscosity meter glue is 2400mPas, by silicon-carbon cathode obtained by step 7
It is assembled into CR2025 type half-cell, carries out battery performance test, obtains first circle specific volume when the 0.1C electric discharge of silicon-carbon cathode half-cell
Amount is 610mAhg-1, specific capacity is 282mAhg when 1C discharges-1。
Embodiment 3
The preparation method of a kind of high-performance compound binding agent and silicon-based anode piece, specific steps are as follows:
(1) the compound Kynoar powder for weighing 4g is put in ball mill, and compound Kynoar powder is by dividing equally again
Son amount be respectively 2200000,1050000 and 570000 Kynoar powder constituent, mass ratio 3:2:1, then with
900r·min-1Compound binding agent is made by ball mill mixing in revolving speed.
(2) by compound binding agent obtained in step 1, it is added in N-Methyl pyrrolidone, at 30 DEG C of temperature, with
1000r·min-130h is stirred under revolving speed, so that compound binding agent is dissolved in N-Methyl pyrrolidone, obtained mass fraction is
8% adhesive gelatin.
(3) mass ratio of addition conductive agent Ketjen black in Xiang Shangshu glue, glue and conductive agent is 14:1, and in temperature 30
With 400rmin at DEG C-1Revolving speed stir 15min, be scattered in conductive agent in adhesive gelatin, be made conductive gelatin.
(4) by Bei Terui (650 type) Si-C composite material powder (SiOx: C=7:3) it is added in conductive gelatin, it is conductive
The mass ratio of liquid and silicon-carbon composite powder is 5:1, in the case where temperature is 20 DEG C, with 600rmin in blender-1Revolving speed stirring
After 30min, it is 9000mPas that addition N-Methyl pyrrolidone, which adjusts solution viscosity, with 600rmin-1Revolving speed stirs 15min,
Electrode slurry is made.
(5) above-mentioned electrode slurry is coated on negative current collector by automatic coating machine with 150 μ m thicks, wherein being coated with
23 DEG C of temperature, coating speed 1.0mmin-1, slurry moisture content is coated with electrode slurry hereinafter, obtaining in 90ppm when coating
Collector.
(6) collector for being coated with electrode slurry carries out vacuum high-temperature and solvent is gone to handle, and the vacuum high-temperature goes molten
The specific steps of agent processing include: to be coated with the collector of electrode slurry to be placed in temperature be relative vacuum in 80 DEG C of baking oven
Angle value is less than or equal to -0.2MPa, handles time 20h；
(7) roll-in is carried out to the slurry being coated on negative current collector, the compacting surface density for controlling slurry is 3.8gcm-2, after roll-in, cathode pole piece with a thickness of 65 μm, be made negative electrode tab semi-finished product.
(8) the negative electrode tab semi-finished product after roll-in are punched into design size.
Viscosity by SNB series digital display viscosity meter glue is 2000mPas, by silicon-carbon cathode obtained by step 7
It is assembled into CR2025 type half-cell, carries out battery performance test, obtains first circle specific volume when the 0.1C electric discharge of silicon-carbon cathode half-cell
Amount is 602mAhg-1, specific capacity is 270mAhg when 1C discharges-1。
Comparative example
The preparation method of a kind of unimolecule binder and silicon-based anode piece, specific steps are as follows:
(1) Kynoar of 3g is weighed, molecular weight 1050000 is added in N-Methyl pyrrolidone, in temperature 30
At DEG C, with 800rmin-120h is stirred under revolving speed, the adhesive gelatin that mass fraction is 5.5% is made.
(2) mass ratio of addition conductive agent Ketjen black in Xiang Shangshu glue, glue and conductive agent is 17:1, and in temperature 25
With 900rmin at DEG C-1Revolving speed stir 15min, be scattered in conductive agent in adhesive gelatin, be made conductive gelatin；
(3) Bei Terui (650 type) silicon-carbon composite powder (SiO is added in Xiang Shangshu conduction liquidx: C=7:3), conduction liquid with
The mass ratio of silicon-carbon composite powder is 5:1, with 500rmin-1Revolving speed stirring 20min after, add N-Methyl pyrrolidone tune
Section solution viscosity is 8000mPas, with 500rmin-1Revolving speed stirs 10min, and slurry is made.
(4) above-mentioned electrode slurry is coated on negative current collector by automatic coating machine with 75 μ m thicks, wherein being coated with
40 DEG C of temperature, coating speed 4.5mmin-1, slurry moisture content is coated with electrode slurry hereinafter, obtaining in 95ppm when coating
Collector.
(5) collector for being coated with electrode slurry carries out vacuum high-temperature and solvent is gone to handle, and the vacuum high-temperature goes molten
The specific steps of agent processing include: to be coated with the collector of electrode slurry to be placed in temperature be relative vacuum in 110 DEG C of baking oven
Angle value is less than or equal to -0.1MPa, handles time 12h；
(6) roll-in is carried out to the slurry being coated on negative current collector, the compacting surface density for controlling slurry is 2.7gcm-2, after roll-in, cathode pole piece with a thickness of 35 μm, be made negative electrode tab semi-finished product.
(7) the negative electrode tab semi-finished product after roll-in are punched into design size.
Viscosity by SNB series digital display viscosity meter glue is 1500mPas, by silicon-carbon cathode obtained by step 7
It is assembled into CR2025 type half-cell, carries out battery performance test, obtains first circle specific volume when the 0.1C electric discharge of silicon-carbon cathode half-cell
Amount is 580mAhg-1, specific capacity is 221mAhg when 1C discharges-1。
Test example 1:
The Kynoar applied in embodiment (molecular weight 2200000) is subjected to SEM test, gained spectrogram such as Fig. 1 institute
Show.
Test example 2:
The Kynoar applied in embodiment (molecular weight 1050000) is subjected to SEM test, gained spectrogram such as Fig. 2 institute
Show.
Test example 3:
The high-performance compound binding agent silicon-based anode prepared in embodiment 1 is subjected to SEM test, gained spectrogram such as Fig. 3 institute
Show.
Test example 4:
High-performance compound binding agent silicon-based anode prepared by embodiment 1 is assembled into CR2025 type half-cell, carries out half electricity
The test of pond high rate performance, test results are shown in figure 4.From fig. 4, it can be seen that first when the 0.1C electric discharge of this silicon-carbon cathode half-cell
Circle specific capacity is 632mAhg-1, specific capacity is 327mAhg when 1C discharges-1。
Test example 5:
The Kynoar applied in embodiment (molecular weight 570000) is subjected to SEM test, gained spectrogram such as Fig. 5 institute
Show.
Test example 6:
The high-performance compound binding agent silicon-based anode prepared in embodiment 2 is subjected to SEM test, gained spectrogram such as Fig. 6 institute
Show.
Test example 7:
The high-performance compound binding agent silicon-based anode prepared in embodiment 3 is subjected to SEM test, gained spectrogram such as Fig. 7 institute
Show.
Test example 8:
The unimolecule binder silicon-based anode piece prepared in embodiment 4 is subjected to SEM test, gained spectrogram is as shown in Figure 8.
The above-mentioned description to embodiment is for that can understand and apply the invention convenient for those skilled in the art.
Person skilled in the art obviously easily can make various modifications to this embodiment, and general original described herein
It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to embodiment here, abilities
Field technique personnel announcement according to the present invention, the improvement made for the present invention and modification all should be in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of silicon-based anode piece, which comprises the following steps:
Step 1: the Kynoar 10-80wt% for being 1,500,000-300 ten thousand by weight average molecular weight, weight average molecular weight are 800,000-140
The Kynoar 0-60wt% that ten thousand Kynoar 10-70wt% and weight average molecular weight are 200,000-60 ten thousand passes through ball mill
Mixing obtains compound binding agent；
Step 2: the resulting compound binding agent of step 1 being dissolved in organic solvent, obtains adhesive gelatin；
Step 3: dispersing conductive agent in the resulting adhesive gelatin of step 2, obtain conductive gelatin；
Step 4: Si-C composite material powder and organic solvent being added in the resulting conductive gelatin of step 3, electrode slurry is made
Material；
Step 5: the resulting electrode slurry of step 4 being coated on negative current collector by automatic coating machine, acquisition is coated with electricity
The collector of pole slurry；
Step 6: the collector that gained is coated with electrode slurry being subjected to vacuum high-temperature, solvent is gone to handle；
Step 7: roll-in being carried out to resulting cathode pole piece, obtains silicon-based anode piece.
2. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that the Si-C composite material is silicon
The mixture of base and carbon-based material；The carbon-based material be one of hard carbon, soft carbon, natural graphite and artificial graphite or
It is a variety of；The silica-base material is micron silicon, nano-silicon, aoxidizes sub- one of silicon and silica or a variety of.
3. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that the conductive agent be acetylene black,
One of Ketjen black, carbon fiber and Super P；The organic solvent is N-Methyl pyrrolidone, acetonitrile and dimethyl formyl
One of amine；The mass fraction of the adhesive gelatin is 5-50%；Conductive agent mass fraction in the conductive gelatin
For 5-20%；The viscosity of the electrode slurry is 500-25000mPas.
4. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that in the step 2 " by step
1 resulting compound binding agent is dissolved in organic solvent " specific steps include: to be added to the resulting compound binding agent of step 1
In organic solvent, at 10-60 DEG C of temperature, with 100-2500rmin-110-72h is stirred under revolving speed, adhesive gelatin is made.
5. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that described " disperses conductive agent in
In the resulting adhesive gelatin of step 2 " specific steps include: that conductive agent is added into adhesive gelatin, at 10-60 DEG C of temperature
Under with 100-1500rmin-1Revolving speed stir 5-300min.
6. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that the electrode slurry in the step 4
The specific preparation steps of material include: that Si-C composite material powder is added in conductive gelatin, in the case where temperature is 10-60 DEG C, with
100-1000r·min-1Revolving speed stirring 5-100min after, add organic solvent, with 100-1500rmin-1Revolving speed stirring
10-500min obtains electrode slurry.
7. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that coated in the step 5
Journey includes: that electrode slurry is coated on negative pole currect collecting by automatic coating machine with 10-300 μ m thick at 15-60 DEG C of temperature
Body, coating speed 1-8mmin-1, slurry moisture content is in 100ppm or less when coating.
8. the preparation method of silicon-based anode piece as described in claim 1, which is characterized in that the vacuum high-temperature is gone at solvent
The specific steps of reason include: to be coated with the collector of electrode slurry to be placed in temperature be relative vacuum in 80-130 DEG C of baking oven
Angle value is less than or equal to -0.1MPa, handles time 10-25h.
9. a kind of compound binding agent, which is characterized in that the Kynoar 10- for being 1,500,000-300 ten thousand including weight average molecular weight
80wt%, weight average molecular weight be 800,000-140 ten thousand Kynoar 10-70wt% and weight average molecular weight be 200,000-60 ten thousand it is poly-
Vinylidene 0-60wt%.
10. the preparation method of high-performance compound binding agent as claimed in claim 9 characterized by comprising by weight average molecular weight
For 1,500,000-300 ten thousand Kynoar 10-80wt%, weight average molecular weight is 800,000-140 ten thousand Kynoar 10-70wt%
And it is compound viscous to obtain high-performance by ball mill mixing by the Kynoar 0-60wt% that weight average molecular weight is 200,000-60 ten thousand
Tie agent.
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