CN108183236A - A kind of preparation method of lithium ion battery anode glue size - Google Patents
A kind of preparation method of lithium ion battery anode glue size Download PDFInfo
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- CN108183236A CN108183236A CN201810039505.7A CN201810039505A CN108183236A CN 108183236 A CN108183236 A CN 108183236A CN 201810039505 A CN201810039505 A CN 201810039505A CN 108183236 A CN108183236 A CN 108183236A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides a kind of preparation methods of lithium ion battery anode glue size, it is characterised in that the composite dispersing agent is combined for polyvinylidene fluoride with the one or several kinds in polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, polyvinyl alcohol.This anode sizing agent is uniform, it is stable, there is good mobility, under the interaction of composite dispersing agent, carbon nanotube can be fully dispersed in solvent, does not assemble, good conductive network is formed with conductive black and positive active material.Battery prepared by anode sizing agent provided by the invention has excellent high-rate charge-discharge capability and prepares simply, at low cost, convenient for preserving for a long time, is suitable for the production application of large-scale.
Description
Technical field
The present invention relates to field of lithium ion battery anode more particularly to a kind of preparations of lithium ion battery anode glue size
Method.
Background technology
Lithium ion battery is a kind of new high-tech product, and compared with ni-Cd, Ni-MH battery, lithium ion battery has voltage
It is high, bigger than energy, have extended cycle life, have a safety feature, self discharge is small, memory-less effect, can fast charging and discharging, operating temperature model
Many advantages, such as enclosing width.With outstanding representation of the carbon nanotube in lithium ion battery in recent years, people also more it is expected that carbon is received
Mitron can replace conventional conductive agent in rate battery, make more high magnification and the lithium ion battery of safety and stability, with broadening
Lithium ion battery is in the application market of large current density electrical domain.
At present, carbon nanotube has obtained relatively broad application, particularly mobile phone, notebook etc. in lithium ion battery
In digital product.But since carbon nanotube price is considerably beyond conventional carbon black conductive agent, cause use cost higher, and divide
Difficulty is dissipated, carbon nanotube can only be added on a small quantity, although capacity of lithium ion battery and charge-discharge magnification performance have bigger carry
It rises, but performance particularly fast charging and discharging performance cannot still far meet practical application.
In conventional lithium battery anode doped carbon nanometer pipe combined conductive agent technique, carbon pipe poor dispersion is reunited, is led
Electric agent poor dispersion, can not form good conductive network, and charging and discharging lithium battery performance is undesirable.And carbon nanometer used
The dispersion of pipe conductive agent is very high to equipment and abrasive media requirement, using the 2mm even abrasive media of below 1mm.Patent
CN104868125A discloses the abrasive media using 0.8-1.0 mm, using high speed sand mill grinding distribution, but sand mill
Itself is of high cost, and abrasion is big, is added significantly to production cost, and abrasive media and remains in sample, it is difficult to remove, to follow-up
Battery production impacts, and it is difficult to carry out large-scale commercial production to lead to the lithium ion battery containing carbon pipe conductive agent.
Patent CN101757875B is disclosed using the compound of nonionic surface active agent and ionic surfactant
The method of dispersant, but this patent is simply mixed using two kinds of surfactants, and surfactant resistance is big, increases
The resistance of slurry is unfavorable for the high-power charge and discharge of lithium ion battery.
Invention content
Carbon nanotube composite conductive agent dispersion effect in existing anode material of lithium battery is bad, conductance in order to solve by the present invention
The problems such as rate is bad, high processing costs provides a kind of preparation method of lithium ion battery anode glue size.
The preparation method of lithium ion battery anode glue size of the present invention, step are as follows:
1) composite dispersing agent is dissolved in solvent, then adds in the carbon nanotube of pickling purifying in the composite diffusion agent solution,
Dispersion pretreatment is carried out with high speed dispersor;
2) the pretreated carbon nano tube dispersion liquid is disperseed with ball mill, by scattered carbon nano tube dispersion liquid
It pours into dispersion tank;
3) carbon black is added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, with high speed dispersor into
Row shearing dispersion;
4) carbon nanotube after high speed dispersion and the composite dispersion liquid of carbon black are disperseed with ball mill, be made carbon nanotube and
The combined conductive agent slurry of carbon black;
5) primary in combined conductive agent slurry or addition positive active material progress high speed dispersor dispersion several times;
6) slurry ball milling after gained is disperseed measures system viscosity, when system viscosity is no longer reduced with viscosity agent, you can
Stop ball milling, the lithium ion battery anode glue size is made.
Composite dispersing agent is polyvinylidene fluoride and polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, polyvinyl alcohol
In one or several kinds be combined.
Solvent is n-methyl-2-pyrrolidone.
Positive active material is LiFePO4, LiMn2O4, cobalt acid lithium or the tertiary cathode containing elements such as nickel, cobalt, manganese
Active material.
Carbon nanotube is the carbon nanotube of pickling purifying, and the caliber of carbon nanotube is 1-50 nm, and the length of carbon nanotube is
200 nm-2 um。
The weight percent of polyvinylidene fluoride in composite dispersing agent is 20-80%.
Carbon nanotube is single wall or multi-walled carbon nanotube.
Carbon black is the one or several kinds in Super P, acetylene black, Ketjen black or furnace black.
The carbon nanotube, carbon black, composite dispersing agent, positive active material weight part ratio be(0.5-5):(0.5-5):
(1-2.5):(92-93.5).
Solid-to-liquid ratio is 11 in the anode sizing agent:9.
Grinding of the abrasive media for wear-resistant ceramic materials such as diameter 2-30 mm zirconium oxide beads, corundum or agates
Ball, simultaneously containing different size of abrasive media system.
The ball mill is common horizontal or planetary ball mill.
Speed of the ball mill in dispersion is 900-1500 rpm, and vibrations Ball-milling Time is 2-3h, high speed dispersor rotating speed
For 600 rpm, jitter time is no less than 0.5 h.
Lithium ion battery anode glue size composite dispersion liquid provided by the invention is uniform, stablizes, and with good mobility
And dispersibility.The present invention prepares lithium ion battery anode glue size, and it is high first to add in the composite dispersing agent containing polyvinylidene fluoride
Fast dispersion machine is pre-dispersed to carbon nanotube progress, then again with horizontal ball mill or planetary ball mill to carbon nanotube point
It dissipates.The dispersants such as polyvinylidene fluoride and polyvinylpyrrolidone interact, and greatly improve the dispersibility of carbon nanotube,
Composite dispersing agent further improves dispersion effect by absorption on the surface of carbon nanotube simultaneously, carbon nanotube without aggregation, with
After carbon black is compound, good conductive network is constituted in positive electrode.
It adds in carbon black in carbon nano tube dispersion liquid, under vacuum state, carries out shearing dispersion with high speed dispersor, make carbon black
While retention performance, scattered conductive network of carbon nanotubes further supplement and improve, are eventually adding just
Anode sizing agent is prepared in pole active material dispersion.Carbon nanotube good dispersion in anode sizing agent prepared by the present invention is not assembled,
Good conductive network is formed, compared with the single dispersant such as polyvinylpyrrolidone is only added in when carbon pipe disperses, is significantly carried
The high charge-discharge magnification performance of lithium ion battery cell.
Preparation method provided by the invention is low for equipment requirements, and production cost is low, and dispersion effect is good, while because of its slurry system
It is standby convenient, and anode sizing agent dispersion effect can be observed in real time by viscosity measurement, it is easy to operate, it can be suitably used for scale metaplasia
Production, greatly reduces the production cost of lithium ion battery manufacturer, while increase substantially lithium ion battery charge-discharge magnification
Performance.
Description of the drawings
Fig. 1 is that embodiment 1 uses the carbon nanotube of composite dispersing agent preparation and the combined conductive agent slurry of conductive black
SEM schemes.
Fig. 2 is to be schemed using the SEM of the lithium iron phosphate positive material obtained by 1 lithium battery anode slurry of embodiment.
Fig. 3 is the first charge-discharge curve of lithium iron phosphate positive material obtained in embodiment 1.
Fig. 4 is to be schemed using the SEM of the lithium cobaltate cathode material obtained by 2 lithium battery anode slurry of embodiment.
Fig. 5 is the ternary obtained by using 3 lithium battery anode slurry of embodiment(NCM111)The SEM figures of positive electrode.
Fig. 6 is to be schemed using the SEM of the lithium cobaltate cathode material obtained by 2 lithium battery anode slurry of comparative example.
Specific embodiment
Below in conjunction with specific embodiment and comparative example, the present invention will be described in further detail(Alleged number is below
Parts by weight):
Embodiment 1
1)By 2.5 parts of composite dispersing agents(Wherein 0.5 part is polyvinylidene fluoride, and 2 parts are polyvinylpyrrolidone), it is dissolved in 81.8
In part Solvents N-methyl -2-Pyrrolidone, 2 parts of carbon nanotubes of pickling purifying are then added in, with carrying out for high-speed dispersion equipment
Dispersion pretreatment, rotating speed are 600 rpm, jitter time 1h;
2)The pretreated carbon nano tube dispersion liquid is disperseed with ball mill, rotating speed is 900 rpm, and abrasive media is
Different size of zirconium oxide bead, size are 5-20 mm, shake 2 h of ball milling, scattered carbon nano tube dispersion liquid is poured into dispersion
In tank;
3)2 parts of acetylene blacks are added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, use high speed dispersion
Machine carries out shearing dispersion, and dispersion rotating speed is 600rpm, and jitter time is no less than 2 h;
4)By after high speed dispersion carbon nanotube, acetylene black composite dispersion liquid disperseed with ball mill, rotating speed be 1200 rpm,
The different size of corundum pearl equal proportion that abrasive media selects diameter to be respectively tetra- kinds of 5.0 mm, 10 mm, 15 mm and 20 mm is mixed
Zoarium system, shakes 2.5 h of ball milling, and the combined conductive agent slurry of carbon nanotube and conductive black is made;
5)93.5 parts of LiFePO4 is added in combined conductive agent slurry, is dispersed with stirring 3 h of time(LiFePO4 adds in two times
Enter:50 parts for the first time, 43.5 parts for the second time, high-speed stirred is carried out after adding in every time respectively and disperses 1.5 h);
6)By step 5)Gained slurry carries out ball milling, and it is 18500 mpa.s to measure system k value with rotational viscometer, works as system
Viscosity no longer reduces, and lithium battery anode slurry is made.
Lithium battery anode slurry obtained is coated on aluminium foil, the disk of 2 × 2 cm is made after drying using tablet press machine,
After 12 h are dried in vacuo at 110 DEG C, half-cell is assembled into using lithium piece in glove box, evaluates its electrochemical energy, it is real below
It applies example and uses this same method with comparative example.
Various material quality percentages are shown in Table 1 in the present embodiment.It is received in the present embodiment using carbon made from composite dispersing agent
The scanning electron microscope of mitron and conductive black slurry(SEM)As shown in Figure 1, Fig. 1 can be seen that carbon nanotube is well dispersed,
Carbon nanotube and acetylene black are uniformly mixed.Use the lithium iron phosphate positive material obtained by 1 lithium battery anode slurry of embodiment
Scanning electron microscope(SEM)As shown in Fig. 2, Fig. 2 can be seen that the conductive agent of carbon nanotube and acetylene black and positive electrode mix
Uniform, formation conductive network is closed, and carbon nanotube is adsorbed on positive electrode surface well.Ferric phosphate lithium cell test is filled
Discharge-rate performance data is referring to table 2.Ferric phosphate lithium cell test first charge-discharge curve is as shown in Figure 3.
Embodiment 2
1)By 1 part of composite dispersing agent(Wherein 0.5 part of polyvinylidene fluoride and 0.5 part of polyethylene glycol), it is dissolved in 81.8 parts of solvent N-
In N-methyl-2-2-pyrrolidone N, then add in pickling purifying 0.5 part of carbon nanotube, with high-speed dispersion equipment disperse it is pre-
Processing, rotating speed are 600 rpm, jitter time 0.5h;
2)The pretreated carbon nano tube dispersion liquid is disperseed with ball mill, rotating speed is 900 rpm, and abrasive media is
Different size of zirconium oxide bead, size are 5-20 mm, shake 2.5 h of ball milling, scattered carbon nano tube dispersion liquid is poured into point
It dissipates in tank;
3)5 parts by weight SuperP are added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, with height
Fast dispersion machine carries out shearing dispersion, and dispersion rotating speed is 600rpm, and jitter time is no less than 2 h;
4)By after high speed dispersion carbon nanotube, SuperP composite dispersion liquids disperseed with ball mill, rotating speed be 1500 rpm,
Abrasive media selects the different size of zirconium oxide bead equal proportion that diameter is respectively tetra- kinds of 5.0 mm, 10 mm, 15 mm and 20 mm
Mixed system shakes 3 h of ball milling, carbon nanotube and the combined conductive agent slurry of SuperP is made;
5)93.5 parts of cobalt acid lithium is added in combined conductive agent slurry, is dispersed with stirring 3 h of time(Cobalt acid lithium adds in two times:
50 parts for the first time, 43.5 parts for the second time, high-speed stirred is carried out after adding in every time respectively and disperses 1.5 h);
6)By step 5)Gained slurry carries out ball milling, and it is 18500 mpa.s to measure system k value with rotational viscometer, works as system
Viscosity no longer reduces, and lithium battery anode slurry is made.
Various material quality percentages are shown in Table 1 in the present embodiment.Using obtained by the present embodiment lithium battery anode slurry
Lithium cobaltate cathode material scanning electron microscope(SEM)As shown in figure 4, Fig. 4 can be seen that carbon nanotube and the conduction of SuperP
Agent and positive electrode are uniformly mixed, and form conductive network.The charge-discharge magnification performance data of cobalt acid lithium battery test is referring to table 2.
Embodiment 3
1)By 2.5 parts of composite dispersing agents (2 parts of polyvinylidene fluoride, 0.5 part of polyvinyl alcohol) be dissolved in 81.8 parts of Solvents N-methyls-
In 2-Pyrrolidone, 5 parts of carbon nanotubes of pickling purifying are then added in, dispersion pretreatment is carried out with high-speed dispersion equipment, turned
Speed is 600 rpm, jitter time 1.5h;
2)The pretreated carbon nano tube dispersion liquid is disperseed with ball mill, rotating speed is 900 rpm, and abrasive media is
Different size of agate bead, size are 5-20 mm, shake 2.5 h of ball milling, scattered carbon nano tube dispersion liquid is poured into dispersion
In tank;
3)0.5 part of Ketjen black is added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, with high speed point
Scattered machine carries out shearing dispersion, and dispersion rotating speed is 600rpm, under vacuum state, 2 h of jitter time;
4)By after high speed dispersion carbon nanotube, Ketjen black composite guide dispersion liquid disperseed with ball mill, 1100 rpm of rotating speed,
The different size of agate bead equal proportion that abrasive media selects diameter to be respectively tetra- kinds of 5.0 mm, 10 mm, 15 mm and 20 mm is mixed
Zoarium system, shakes 2.5 h of ball milling, and the combined conductive agent slurry of carbon nanotube and Ketjen black is made;
5)92 parts of ternary materials are added in combined conductive agent slurry(NCM111), it is dispersed with stirring 3 h of time(Ternary material is divided to two
Secondary addition:50 parts for the first time, 42 parts for the second time, high-speed stirred is carried out after adding in every time respectively and disperses 1.5 h);
6)2.5 h of slurry ball milling after gained is disperseed measures system k value as 17500 mpa.s, system with viscosity agent
Viscosity no longer reduces, and lithium battery anode slurry is made.
Various material quality percentages are shown in Table 1 in the present embodiment.Lithium battery anode slurry obtained by the present embodiment is made
The ternary obtained(NCM111)Positive electrode scanning electron microscope(SEM)As shown in Fig. 5, Fig. 5 can be seen that carbon nanotube and section
The black conductive agent of qin and positive electrode are uniformly mixed, and form conductive network.Ternary material(NCM111)The charge and discharge of battery testing
High rate performance data are referring to table 2.
It is right to fully demonstrate peptizaiton of the composite dispersing agent in composite conducting slurry and positive electrode in the present invention
It is not added with dispersant and only adds in the electrocondution slurry of single dispersant and positive electrode compares, comparative example 1 is is not added with disperseing
Agent, comparative example 2 is adds in single polyethylene of dispersing agent pyrrolidones.
Comparative example 1
1)2 parts of carbon nanotubes of pickling purifying are added in 81.8 parts of Solvents N-methyl -2-Pyrrolidones, are set with high speed dispersion
Standby carries out dispersion pretreatment, and rotating speed is 600 rpm, 1.5 h of jitter time;
2)The pretreated carbon nano tube dispersion liquid is disperseed with ball mill, rotating speed is 900 rpm, and abrasive media is
Different size of zirconium pearl, size are 5-20 mm, and process of lapping opens cooling circulating water and cools down, and shakes 2.5 h of ball milling, will
Scattered carbon nano tube dispersion liquid is poured into dispersion tank;
3)2 parts of acetylene blacks are added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, with high speed point
Scattered machine carries out shearing dispersion, and dispersion rotating speed is 600 rpm, under vacuum state, 2 h of jitter time;
4)By after high speed dispersion carbon nanotube, acetylene black composite conducting slurry disperseed with ball mill, rotating speed 1000-1100
Rpm, it is respectively different size of zirconium oxide bead of tetra- kinds of 5.0 mm, 10 mm, 15 mm and 20 mm etc. that abrasive media, which selects diameter,
Ratio mixed system shakes 2.5 h of ball milling, and the combined conductive agent slurry of carbon nanotube and acetylene black is made;
5)3 parts of polyvinylidene fluoride and 93 parts of LiFePO4 are added in combined conductive agent slurry, is dispersed with stirring time 3h(Phosphorus
Sour iron lithium adds in two times:50 parts for the first time, 43 parts for the second time, high-speed stirred is carried out after adding in every time respectively and disperses 1.5 h);
6)2.5 h of slurry ball milling after gained is disperseed measures system k value as 19500 mpa.s, system with viscosity agent
Viscosity no longer reduces, and lithium battery anode slurry is made.
Various material quality percentages are shown in Table 1 in this comparative example.The charge and discharge times of obtained ferric phosphate lithium cell test
Rate performance data is referring to table 2.
Comparative example 2
1)2 parts of carbon nanotubes of addition pickling purifying are with 1 part of polyvinylpyrrolidone in 81.8 parts of Solvents N-methyl -2- pyrrolidines
In ketone, dispersion pretreatment is carried out with high-speed dispersion equipment, rotating speed is 600 rpm, 1.5 h of jitter time;
2)The pretreated carbon nano tube dispersion liquid is disperseed with ball mill, rotating speed is 900 rpm, and abrasive media is
Different size of zirconium pearl, size are 5-20 mm, and process of lapping opens cooling circulating water and cools down, and shakes 2.5 h of ball milling, will
Scattered carbon nano tube dispersion liquid is poured into dispersion tank;
3)2 parts of Ketjen blacks are added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, use high speed dispersion
Machine carries out shearing dispersion, and dispersion rotating speed is 600 rpm, under vacuum state, 2 h of jitter time;
4)By after high speed dispersion carbon nanotube, Ketjen black composite conducting slurry disperseed with ball mill, rotating speed 1000-1100
Rpm, it is respectively different size of zirconium oxide bead of tetra- kinds of 5.0 mm, 10 mm, 15 mm and 20mm etc. that abrasive media, which selects diameter,
Ratio mixed system, process of lapping open cooling circulating water and cool down, shake 2.5 h of ball milling, carbon nanotube and section's qin is made
Black combined conductive agent slurry;
5)2 parts of polyvinylidene fluoride and 93 parts of cobalt acid lithium are added in combined conductive agent slurry, is dispersed with stirring time 3h(Cobalt acid
Lithium adds in two times:50 parts for the first time, 43 parts for the second time, high-speed stirred is carried out after adding in every time respectively and disperses 1.5 h);
6)2.5 h of slurry ball milling after gained is disperseed measures system k value as 19000 mpa.s, system with viscosity agent
Viscosity no longer reduces, and lithium battery anode slurry is made.
Various material quality percentages are shown in Table 1 in this comparative example.Using obtained by this comparative example lithium battery anode slurry
Lithium cobaltate cathode material scanning electron microscope(SEM)As shown in fig. 6, Fig. 6 can be seen that conductive agent and positive electrode cannot mix
It closes.The charge-discharge magnification performance data of obtained cobalt acid lithium battery test is referring to table 2.
The present invention compared with being routinely not added with dispersant and single dispersant, improves lithium ion using composite dispersing agent
The problem of carbon nanotube dispersibility is bad in cell positive material.The present invention uses the composite dispersing agent containing polyvinylidene fluoride
Carbon nanotube is disperseed and is stablized, carbon nanotube is substantially increased using the interaction of two kinds of chemical compositions in composite dispersing agent
Dispersibility, and carbon nanotube can be helped preferably to adsorb on the surface of positive electrode, add conductive black formation and lead
Electric network, referring to Fig. 2, so as to substantially increase the charge-discharge magnification performance of the comprehensive performance of battery core, particularly lithium ion battery
Referring to table 2.Fig. 3 is the lithium iron phosphate positive material first charge-discharge curve in embodiment 1, and first charge-discharge efficiency reaches 93%,
Wherein constant-current charge accounting reaches 96%, and 3.22 V are pressed in electric discharge.It is not added in comparative example 1 in dispersant and comparative example 2 using single
The positive electrode that ingredient dispersion agents make, the battery rate charge-discharge hydraulic performance decline of table 2, the capacity of especially high-multiplying power discharge decline
Subtract serious.
Raw material proportioning of the table 1 for the anode sizing agent of embodiment and comparative example, poly- difluoroethylene and polyethylene pyrrole in embodiment
Pyrrolidone adds in when preparing carbon nanotube composite conductive agent as the composite dispersing agent of carbon nanotube, polyvinylpyrrolidone
Deng as dispersant, the defects of oxygen atom of structure can be with above carbon nanotube, which combines, divides carbon nanotube
It dissipates.The defects of fluorine atom of polyvinylidene fluoride structure can also be in carbon nano tube surface is same with reference to what is disperseed to it
When, blending effect can also be generated with dispersants such as polyvinylpyrrolidones, enhance the dispersants such as polyvinylpyrrolidone
Peptizaiton enables the more stable presence in the slurry of obtained carbon nanotube.Meanwhile polyvinylidene fluoride and polyethylene
The dispersants such as pyrrolidones collective effect is bonded in the carbon nanotube of dispersion on the surface of positive electrode, on the surface of positive electrode
The conductive network formed.Polyvinylidene fluoride finally walks together when preparing anode sizing agent with positive active material in comparative example
It is rapid to add in, it is only capable of using as the binding agent of positive electrode.
The anode sizing agent raw material proportioning (digital representation parts by weight) of 1 embodiment and comparative example of table
Table 2 is the lithium ion cell positive electrochemistry cycle and charge and discharge that the different anode sizing agents in embodiment and comparative example make
Electrical performance data, during fast charging and discharging, particularly more than 5C multiplying powers charging and during more than 10C multiplying power dischargings, the appearance in embodiment
Amount holding ratio is apparently higher than comparative example.
2 embodiment and comparative example battery charging and discharging performance of table
Embodiment described above is only presently preferred embodiments of the present invention, is not intended to limit the invention, all the present invention's
All any modification, equivalent and improvement made within spirit and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium ion battery anode glue size, step are as follows:
1) composite dispersing agent is dissolved in solvent, then adds in the carbon nanotube of pickling purifying in the composite diffusion agent solution,
Dispersion pretreatment is carried out with high speed dispersor;
2) the pretreated carbon nano tube dispersion liquid is disperseed with ball mill, by scattered carbon nano tube dispersion liquid
It pours into dispersion tank;
3) carbon black is added in the carbon nano tube dispersion liquid in the high speed dispersion tank, under vacuum state, with high speed dispersor into
Row shearing dispersion;
4) carbon nanotube after high speed dispersion and the composite dispersion liquid of carbon black are disperseed with ball mill, be made carbon nanotube and
The combined conductive agent slurry of carbon black;
5) primary in combined conductive agent slurry or addition positive active material progress high speed dispersor dispersion several times;
6) slurry ball milling after gained is disperseed measures system viscosity, when system viscosity is no longer reduced with viscosity agent, you can
Stop ball milling, the lithium ion battery anode glue size is made;
It is characterized in that the composite dispersing agent is polyvinylidene fluoride and polyvinylpyrrolidone, polyethylene glycol, polyacrylamide
One or several kinds in amine, polyvinyl alcohol are combined.
2. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the solvent is N- methyl -2- pyrroles
Pyrrolidone.
3. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the positive active material is phosphorus
Sour iron lithium, LiMn2O4, cobalt acid lithium or the tertiary cathode active material containing elements such as nickel, cobalt, manganese.
4. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the carbon nanotube is pure for pickling
The carbon nanotube of change, the caliber of carbon nanotube is 1-50 nm, and the length of carbon nanotube is 200 nm-2 um.
5. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that poly- in the composite dispersing agent
The weight percent of vinylidene fluoride is 20-80%.
6. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the carbon nanotube for single wall or
Person's multi-walled carbon nanotube.
7. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the carbon black is Super P, second
One or several kinds in acetylene black, Ketjen black or furnace black.
8. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the carbon nanotube, is answered at carbon black
Close dispersant, the weight part ratio of positive active material is(0.5-5):(0.5-5):(1-2.5):(92-93.5), solid-liquid in slurry
Than being 11:9.
9. such as the preparation method of claim 1 lithium ion battery anode glue size, it is characterised in that the abrasive media is diameter
The mill ball of the wear-resistant ceramic materials such as 2-30 mm zirconium oxide beads, corundum or agate.
10. as claim 1 lithium ion battery anode glue size preparation method, it is characterised in that the ball mill dispersion when
Speed is 900-1500 rpm, and vibrations Ball-milling Time is 2-3h, and high speed dispersor rotating speed is 600 rpm, and jitter time is no less than
0.5 h。
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Cited By (4)
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CN110808376A (en) * | 2019-11-12 | 2020-02-18 | 湖南艾威尔新能源科技有限公司 | Conductive agent and preparation method and application thereof |
CN112072103A (en) * | 2020-08-08 | 2020-12-11 | 江苏天奈科技股份有限公司 | High-conductivity carbon conductive slurry and preparation method thereof |
US20210408595A1 (en) * | 2019-12-26 | 2021-12-30 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device |
US11355744B2 (en) * | 2010-10-28 | 2022-06-07 | Electrovaya Inc. | Lithium ion battery electrode with uniformly dispersed electrode binder and conductive additive |
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