CN104600241A - Lithium ion battery positive plate, preparation method of lithium ion battery positive plate, and lithium ion battery - Google Patents
Lithium ion battery positive plate, preparation method of lithium ion battery positive plate, and lithium ion battery Download PDFInfo
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- CN104600241A CN104600241A CN201410790011.4A CN201410790011A CN104600241A CN 104600241 A CN104600241 A CN 104600241A CN 201410790011 A CN201410790011 A CN 201410790011A CN 104600241 A CN104600241 A CN 104600241A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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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
- H01M4/13—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
- H01M4/62—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery positive plate, which comprises a positive current collector and a positive active layer coating the surface of the positive current collector, the positive active layer comprises the following raw materials in parts by mass: 0.9-1.5 parts of a positive binder, 0.6-1 part of carbon nanotubes, and 90-100 parts of positive active materials, the lithium ion battery positive plate selects the carbon nanotubes as a conducting agent, the conductivity of the carbon nanotube is excellent, the tubular structure cannot collapse during repeated charging and discharging processes; compared with a traditional conducting agent, by adopting the carbon nanotubes, the cyclic performance of the battery adopting the lithium ion battery positive plate can be effectively improved, the effects of reducing internal resistance and reducing polarization can also be achieved, so that the battery safety performance of the lithium ion battery positive plate can be improved.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of based lithium-ion battery positive plate and preparation method thereof, and lithium ion battery.
Background technology
Promote the industrialization of notebook, portable power source, electric bicycle, electric tool, electric automobile, become the cutting point of Chinese each industrial structure change adjustment and great-leap-forward development.One of key technology of notebook, portable power source, electric bicycle, electric tool, electric automobile is developed exactly and is produced and meets safety and environmental requirement and the product battery that capacity is high, the life-span is long.
Lithium ion battery compares other batteries, specific power, specific energy and cycle performance has excellent embodiment, therefore also becomes the first-selection of notebook, portable power source, electric bicycle, electric tool, battery for electric automobile.
Along with people are to the raising of this electronic product dependency degree, electronic product function upgrading and diversified expansion, higher requirement is still had to the performance of lithium ion battery, but very convergence theoretical upper limit such as current conventional lithium ion battery its cycle performance, security performance etc.
Summary of the invention
Based on this, be necessary that providing a kind of improves based lithium-ion battery positive plate of cycle performance of lithium ion battery and security performance and preparation method thereof, still further provides a kind of lithium ion battery adopting this based lithium-ion battery positive plate.
A kind of based lithium-ion battery positive plate, comprise plus plate current-collecting body and be coated in the positive-active layer of anode collection surface, comprise the positive electrode active materials of the positive electrode binder of 0.9 ~ 1.5 part, the carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts by the material of mass fraction positive-active layer.
Wherein in an embodiment, positive electrode binder is selected from the one in polyvinylidene fluoride and polytetrafluoroethylene, and positive electrode active materials is selected from least one in LiFePO4, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate and nickel cobalt lithium aluminate.
A preparation method for based lithium-ion battery positive plate, comprises the steps:
According to mass fraction, the positive electrode active materials of the positive pole solvent of 16 ~ 20 parts, the positive electrode binder of 0.9 ~ 1.5 part, the carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts is mixed obtained anode sizing agent;
Anode sizing agent is coated on plus plate current-collecting body and forms positive-active layer, after drying, obtain based lithium-ion battery positive plate.
Wherein in an embodiment, the preparation method of anode sizing agent specifically comprises the steps:
By positive pole solvent and obtained first mixture of positive electrode binder mix and blend;
Carbon nano-tube is added in the first mixture and also stirs obtained second mixture;
Remove the bubble in the second mixture;
Positive electrode active materials is added in the second mixture and also stirs obtained anode sizing agent;
Bubble in removing anode sizing agent;
Anode sizing agent is filtered.
Wherein in an embodiment, anode sizing agent, under 100 ~ 140 DEG C of conditions, is coated on plus plate current-collecting body with the speed of 8 ~ 10m/min.
A kind of lithium ion battery, comprise the based lithium-ion battery positive plate of negative plate, barrier film and claim 1 or 2, negative plate, barrier film and based lithium-ion battery positive plate stack gradually winding.
Wherein in an embodiment, negative plate comprises negative current collector and is coated in the negative electrode active layer of negative pole currect collecting surface, comprises the water of the negative active core-shell material of 90 ~ 95 parts, the cathode conductive agent of 1 ~ 2 part, the negative pole dispersant of 1 ~ 2 part, the negative electrode binder of 3 ~ 5 parts and 80 ~ 90 parts by the material of mass fraction negative electrode active layer.
Wherein in an embodiment, negative active core-shell material is selected from least one in the black carbon of stone, the black alkene of stone and silicon-carbon, cathode conductive agent is acetylene black, and negative pole dispersant is sodium carboxymethylcellulose, and negative electrode binder is selected from least one in polyvinyl alcohol and polytetrafluoroethylene.
Wherein in an embodiment, negative electrode active layer, under 60 ~ 100 DEG C of conditions, is coated on negative current collector with the speed of 8 ~ 10m/min.
This based lithium-ion battery positive plate selects carbon nano-tube as conductive agent, carbon nano-tube conductive is good, its tubular structure there will not be and caves in repeated charge process, compared with conventional conductive agent, carbon nano-tube effectively can improve the cycle performance of the battery using this based lithium-ion battery positive plate, the effect reducing internal resistance, reduce polarization can also be played, thus improve the security performance of the battery using this based lithium-ion battery positive plate.
Accompanying drawing explanation
Fig. 1 is the cutaway view of the based lithium-ion battery positive plate of an execution mode;
Fig. 2 is the schematic flow sheet of the preparation method of the based lithium-ion battery positive plate of an execution mode;
Fig. 3 is the schematic flow sheet of the preparation method of the lithium ion battery of an execution mode;
Fig. 4 is the electric performance test result schematic diagram of the lithium ion battery that the obtained lithium ion battery of embodiment 3 and comparative example obtain.
Embodiment
For the ease of understanding the present invention, will be described more fully the present invention with specific embodiment below.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, provide the object of this embodiment be make the understanding of disclosure of the present invention more comprehensively thorough.
Refer to Fig. 1, a kind of based lithium-ion battery positive plate 10, comprise plus plate current-collecting body 110 and be coated in the positive-active layer 130 on plus plate current-collecting body 110 surface, by mass fraction, the material of positive-active layer 130 comprises the positive electrode active materials of the positive electrode binder of 0.9 ~ 1.5 part, the carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts.
Further, positive electrode binder is selected from the one in polyvinylidene fluoride and polytetrafluoroethylene.
Further, positive electrode active materials is selected from least one in LiFePO4, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate and nickel cobalt lithium aluminate.
Further, by mass fraction, in the material of positive-active layer 130, positive electrode active materials gets 97.37 ~ 98.07 parts.
Positive-active layer 130 generally covers the two-sided of plus plate current-collecting body 110.
This based lithium-ion battery positive plate 10 selects carbon nano-tube as conductive agent, carbon nano-tube conductive is good, its tubular structure there will not be and caves in repeated charge process, compared with conventional conductive agent, carbon nano-tube effectively can improve the cycle performance of the battery using this based lithium-ion battery positive plate 10, the effect reducing internal resistance, reduce polarization can also be played, thus improve the security performance of the battery using this based lithium-ion battery positive plate 10.
Refer to Fig. 2, the preparation method of above-mentioned based lithium-ion battery positive plate 10, comprises the steps:
S10, according to mass fraction, the positive electrode active materials mix and blend of the positive pole solvent of 16 ~ 20 parts, the binding agent of 0.9 ~ 1.5 part, the carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts is obtained anode sizing agent.
When positive electrode binder does not disperse in a solvent completely, will likely with carbon nano-tube, the bonding one-tenth block of positive electrode active materials, thus increase the difficulty that mixes.Therefore each component of anode sizing agent can batch mixed, to improve the efficiency of mix and blend.
Further, positive pole solvent is selected from least one in 1-METHYLPYRROLIDONE and dimethylacetylamide.
Specifically in the present embodiment, step S10 is prepared according to the following steps:
S110, according to mass fraction, by the positive pole solvent of 16 ~ 20 parts, the positive electrode binder mix and blend of 0.9 ~ 1.5 part, obtained first mixture.
Positive electrode binder is well dispersed in positive pole solvent, avoids positive electrode binder one-tenth block bonding with other components.
S120, according to mass fraction, add mix and blend in carbon nano-tube to the first mixture of 0.6 ~ 1 part, obtained second mixture.
S130, the bubble removed in the second mixture.
The method of bubble removing has physical method and chemical method, and physical method comprises low rate mixing, vacuumizes, and chemical method comprises and adds defoamer etc.
Specifically in the present embodiment, the mode of the bubble in removing second mixing is for vacuumizing.
Further, keep vacuum degree when vacuumizing between-0.08 ~-0.1MPa.
Be appreciated that when there is not bubble in the second mixture, or when the bubble produced is not enough to the quality requirement affecting product, step S130 is omissible.
S140, according to mass fraction, the positive electrode active materials of 90 ~ 100 parts is added to mix and blend in the second mixture, obtained anode sizing agent.
Further, by mass fraction, positive electrode active materials gets 97.37 ~ 98.07 parts.
Bubble in S150, removing anode sizing agent.
Step S150 is step S130 in like manner.Specifically in the present embodiment, the mode of the bubble in removing anode sizing agent is for vacuumizing.
Further, keep vacuum degree when vacuumizing between-0.08 ~-0.1MPa.
Be appreciated that when there is not bubble in the second mixture, or when the bubble produced is not enough to the quality requirement affecting product, step S130 is omissible.
S160, anode sizing agent to be filtered.
The object of filtering mainly removes particle in anode sizing agent, and these particles may be insufficient owing to stirring, or component is impure etc., and extraneous factor produces.
Be appreciated that when there is not particle in anode sizing agent, or when the particle existed is not enough to the quality requirement affecting product, step S160 is omissible.
Be appreciated that step S150, S160 are separate, there is no sequencing.
S20, anode sizing agent is coated on plus plate current-collecting body 110 forms positive-active layer 130, obtained positive plate 10 after dry.
Further, for avoiding anode sizing agent to solidify and causing coating step to carry out, according to the actual physics proterties of anode sizing agent, answer rate-determining steps S20 100 ~ 140 DEG C temperature environment and carry out under keeping the speed of 8 ~ 10m/min.
In above-mentioned preparation technology, carbon nano-tube and other compositions are uniformly mixed and make anode sizing agent, be directly coated on plus plate current-collecting body 110 and form positive-active layer 130, namely obtain based lithium-ion battery positive plate 10, therefore preparation technology is simple, can effectively enhance productivity.
A kind of lithium ion battery, comprise negative plate, barrier film and above-mentioned based lithium-ion battery positive plate 10, negative plate, barrier film and based lithium-ion battery positive plate 10 stacks gradually winding.
Further, negative plate comprises negative current collector and is coated in the negative electrode active layer of negative pole currect collecting surface, by mass fraction, the material of negative electrode active layer comprises the water of the negative active core-shell material of 90 ~ 95 parts, the cathode conductive agent of 1 ~ 2 part, the negative pole dispersant of 1 ~ 2 part, the negative electrode binder of 3 ~ 5 parts and 80 ~ 90 parts.
Further, negative active core-shell material is selected from least one in the black carbon of stone, the black alkene of stone and silicon-carbon
Further, cathode conductive agent is acetylene black.
Further, negative pole dispersant is sodium carboxymethylcellulose.
Further, negative electrode binder is selected from least one of polyvinyl alcohol and polytetrafluoroethylene.
Negative electrode active layer generally covers the two-sided of negative current collector.
Further, the material of barrier film is selected from least one in PP, PP PE and PE.
The conductive agent of above-mentioned lithium ion battery using carbon nano-tube as based lithium-ion battery positive plate 10, and specific aim adopts corresponding negative pole to match, by means of the electric conductivity that carbon nano-tube is good, effectively raise the cycle performance of lithium ion battery, and carbon nano-tube can play the effect reducing internal resistance and reduce polarization, thus the security performance of lithium ion battery is made to have also been obtained raising.
Refer to Fig. 3, a kind of preparation method of lithium ion battery, comprises the following steps:
Based lithium-ion battery positive plate 10 is prepared according to above-mentioned steps S10, S20.
S30, according to mass fraction, the negative electrode binder mix and blend of the negative active core-shell material of 90 ~ 95 parts, the cathode conductive agent of 1 ~ 2 part, the negative pole dispersant of 1 ~ 2 part, the water of 80 ~ 90 parts and 3 ~ 5 parts is obtained cathode size.
Negative electrode binder and other components stir simultaneously, increase the difficulty mixed by likely forming bond pad, and therefore in cathode size, each component can batch mixed, to improve the efficiency of mix and blend.
Specifically in the present embodiment, step S30 is prepared according to the following steps:
S310, according to mass fraction, by the negative active core-shell material of 90 ~ 95 parts, the cathode conductive agent of 1 ~ 2 part, the negative pole dispersant of 1 ~ 2 part, the water mix and blend of 80 ~ 90.
S320, according to mass fraction, mix and blend in the negative electrode binder adding 3 ~ 5 parts to the obtained mixture of step S310, obtained cathode size.
Bubble in S330, removing cathode size.
The method of bubble removing has physical method and chemical method, and physical method comprises low rate mixing, vacuumizes, and chemical method comprises and adds defoamer etc.
Specifically in the present embodiment, the mode of the bubble in removing cathode size is for vacuumizing.
Further, keep vacuum degree when vacuumizing between-0.08 ~-0.1MPa.
Be appreciated that when there is not bubble in cathode size, or when the bubble produced is not enough to the quality requirement affecting product, step S330 is omissible.
S340, anticathode slurry filter.
The object of filtering mainly removes particle in cathode size, and these particles may be insufficient owing to stirring, or component is impure etc., and extraneous factor produces.
Be appreciated that when there is not particle in cathode size, or when the particle existed is not enough to the quality requirement affecting product, step S340 is omissible.
Be appreciated that step S330, S340 are separate, there is no sequencing.
S40, cathode size is coated on negative current collector forms negative electrode active layer, obtained negative plate after dry.Further, for avoiding cathode size to solidify and causing coating step to carry out, according to the actual physics proterties of cathode size, answer rate-determining steps S20 60 ~ 100 DEG C temperature environment and carry out under keeping the speed of 8 ~ 10m/min.
S50, by stacked to positive plate 10, barrier film and negative plate and be wound into battery core.
Specifically in the present embodiment, step S50 is prepared according to following steps:
S510, carries out compression process to positive plate 10.
Further, thickness to 135 ~ 170 ± 2 μm are suppressed to positive plate 10.
S520, carries out compression process by negative plate.
Further, anticathode sheet compacting thickness to 150 ~ 175 ± 2 μm.
Be appreciated that step S510, S520 are separate, there is no sequencing.
S530, carries out cutting process by positive plate 10.
Further, wide 57 ~ 58mm, long 400 ~ 700mm are cut into positive plate 10.
S540, carries out cutting process by negative plate.
Further, anticathode sheet cuts into wide 59 ~ 60mm, length is 500 ~ 800mm.
Be appreciated that step S510, S520 are separate, there is no sequencing.
S550, dries the positive plate 10 after above-mentioned repressed process and cutting process.
S560, dries the negative plate after above-mentioned repressed process and cutting process.
Be appreciated that step S550, S560 are separate, there is no sequencing.
Be appreciated that step S550, S560 is omissible.
S570, stacks gradually based lithium-ion battery positive plate 10, barrier film and negative plate, is wound into battery core.
Further, the diameter control of battery core is between 17.45 ~ 17.56mm.
S60, loads housing by battery core, then in housing, injects electrolyte, and by cap sealed, obtains lithium ion battery.
The based lithium-ion battery positive plate 10 made using carbon nano-tube as conductive agent, is assembled into battery jointly with negative plate, and compared with traditional handicraft, preparation process is simple, therefore can effectively enhance productivity.
Below in conjunction with specific embodiment, the lithium ion battery of above-mentioned use carbon nano-tube as conductive agent is described in detail.
Embodiment 1
(1) positive plate 10 is prepared
The 1-METHYLPYRROLIDONE of 16g, the polyvinylidene fluoride of 1.5g are added in size making pot, adopts two speed combination mixer, under high speed 1500r/min, at a slow speed 30r/min condition, stir 30min, obtained first mixture.
Add the carbon nano-tube of 0.6g, adopt two speed combination mixer, under high speed 1500r/min, at a slow speed 30 conditions, stir 60min, obtained second mixture.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Add the mixture of the LiFePO4 of 98.07g and LiMn2O4 1:0.8 proportioning in mass ratio, adopt single rotating speed mixer, rotating speed controls at 1500r/min, stirs 150min, obtained anode sizing agent.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Anode sizing agent is filtered by 150 mesh filter screens.
Under 100 DEG C of conditions, the plus plate current-collecting body 110 anode sizing agent being coated in 18 μm forms positive-active layer 130, and coating speed controls at 10m/min.
(2) negative plate is prepared
Add in size making pot by the acetylene black of black for the stone of 90g alkene, 2g, the sodium carboxymethylcellulose of 2g, the deionized water of 90g, mix and blend 300min, speed of agitator controls at 2200r/min.
Add the polyvinyl alcohol of 5g, stir 60min, speed of agitator controls at 1800r/min, obtained cathode size.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Cathode size is filtered by 150 mesh filter screens.
Under 100 DEG C of conditions, negative current collector cathode size being coated in 7 μm forms negative electrode active layer, and coating speed controls at 10m/min.
(3) battery is prepared
Positive plate 10 and negative plate are suppressed by roll squeezer, make the thickness of positive plate 10 be 135 ± 2 μm, the thickness of negative plate is 150 ± 2 μm.
Positive plate 10 carries out cutting process, makes the wide 58mm of positive plate 10, long 400mm; Negative plate carries out cutting process, makes the wide 60mm of negative plate, long 500mm.
The positive plate 10 cut, negative plate puts into baking oven respectively dries.
With up-coiler, positive plate 10, barrier film and negative plate are wound into battery core in order, the diameter control of battery core is at 17.45mm, and barrier film adopts PE material.
The battery core spooled is loaded housing, in housing, injects electrolyte, cover block, with sealing machine, encapsulation process is carried out to housing, the battery of obtained embodiment 1.
After battery is shelved 12h, first with 0.2C constant-current constant-voltage charging 500min, then battery is shelved 72h in 45 DEG C of environment.After battery is cooled to normal temperature, first with 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.01C, then with 0.2C constant-current discharge to 3V, then with 0.5C constant-current constant-voltage charging to half-full electricity, complete the use pre-treatment work of the battery of embodiment 1.
Embodiment 2
(1) positive plate 10 is prepared
The dimethylacetylamide of 20g, the polytetrafluoroethylene of 0.9g are added in size making pot, adopts two speed combination mixer, under high speed 2000r/min, at a slow speed 40r/min condition, stir 30min, obtained first mixture.
Add the carbon nano-tube of 1g, adopt two speed combination mixer, under high speed 2000r/min, at a slow speed 40r/min condition, stir 60min, obtained second mixture.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Add the nickle cobalt lithium manganate of 97.37g and the nickel cobalt lithium aluminate mixture according to mass ratio 1:1 proportioning, adopt single rotating speed mixer, rotating speed controls at 2200r/min, stirs 120min, obtained anode sizing agent.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Anode sizing agent is filtered by 150 mesh filter screens.
Under 140 DEG C of conditions, the plus plate current-collecting body 110 anode sizing agent being coated in 12 μm forms positive-active layer 130, and coating speed controls at 8m/min.
(2) negative plate is prepared
By the silicon charcoal of 95g and the black alkene of stone mixture, the acetylene black of 1g, the sodium carboxymethylcellulose of 1g, the deionized water of 80g according to mass ratio 0.5:1 proportioning, mix and blend 300min, speed of agitator controls at 1800r/min.
Add the polytetrafluoroethylene of 3g and the polyvinyl alcohol mixture according to volume ratio 1:1 proportioning, stir 60min, speed of agitator controls at 2200r/min, obtained cathode size.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Cathode size is filtered by 150 mesh filter screens.
Under 60 DEG C of conditions, negative current collector cathode size being coated in 11 μm forms negative electrode active layer, and coating speed controls at 8m/min.
(3) battery is prepared
Positive plate 10 and negative plate are suppressed by roll squeezer, make the thickness of positive plate 10 be 170 ± 2 μm, the thickness of negative plate is 175 ± 2 μm.
Positive plate 10 carries out cutting process, makes wide 57mm, long 700mm; Negative plate carries out cutting process, makes the wide 59mm of negative plate, long 800mm.
The positive plate 10 cut, negative plate puts into baking oven respectively dries.
With up-coiler, positive plate 10, barrier film and negative plate are wound into battery core in order, the diameter control of battery core is at 17.56mm, and barrier film adopts PPPE material.
The battery core spooled is loaded housing, in housing, injects electrolyte, cover block, with sealing machine, encapsulation process is carried out to housing, the battery of obtained embodiment 2.
After battery is shelved 12h, first with 0.2C constant-current constant-voltage charging 500min, then battery is shelved 72h in 45 DEG C of environment.After battery is cooled to normal temperature, first with 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.01C, then with 0.2C constant-current discharge to 3V, then with 0.5C constant-current constant-voltage charging to half-full electricity, complete the use pre-treatment work of the battery of embodiment 2.
Embodiment 3
(1) positive plate 10 is prepared
The dimethylacetylamide of 18g, the polyvinylidene fluoride of 1.3g are added in size making pot, adopts two speed combination mixer, under high speed 1800r/min, at a slow speed 37.5r/min condition, stir 30min, obtained first mixture.
Add the carbon nano-tube of 0.85g, adopt two speed combination mixer, under high speed 1800r/min, at a slow speed 35r/min condition, stir 60min, obtained second mixture.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Add the lithium nickelate of 98g, adopt single rotating speed mixer, rotating speed controls at 2000r/min, stirs 140min, obtained anode sizing agent.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Anode sizing agent is filtered by 150 mesh filter screens.
Under 110 DEG C of conditions, the plus plate current-collecting body 110 anode sizing agent being coated in 12.5 μm forms positive-active layer 130, and coating speed controls at 8.5m/min.
(2) negative plate is prepared
By the acetylene black of black for the stone of 94g carbon, 1.6g, the sodium carboxymethylcellulose of 1.5g, the deionized water of 85g, mix and blend 300min, speed of agitator controls at 2000r/min.
Add the polyvinyl alcohol of 4g, stir 60min, speed of agitator controls at 2000r/min, obtained cathode size.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Cathode size is filtered by 150 mesh filter screens.
Under 88 DEG C of conditions, negative current collector cathode size being coated in 9 μm forms negative electrode active layer, and coating speed controls at 8.5m/min.
(3) battery is prepared
Positive plate 10 and negative plate are suppressed by roll squeezer, make the thickness of positive plate 10 be 150 ± 2 μm, the thickness of negative plate is 165 ± 2 μm.
Positive plate 10 carries out cutting process, makes wide 57.4mm, long 420mm; Negative plate carries out cutting process, makes the wide 59.5mm of negative plate, long 590mm.
The positive plate 10 cut, negative plate puts into baking oven respectively dries.
With up-coiler, positive plate 10, barrier film and negative plate are wound into battery core in order, the diameter control of battery core is at 17.47mm, and barrier film adopts PP material.
The battery core spooled is loaded housing, in housing, injects electrolyte, cover block, with sealing machine, encapsulation process is carried out to housing, the battery of obtained embodiment 3.
After battery is shelved 12h, first with 0.2C constant-current constant-voltage charging 500min, then battery is shelved 72h in 45 DEG C of environment.After battery is cooled to normal temperature, first with 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.01C, then with 0.2C constant-current discharge to 3V, then with 0.5C constant-current constant-voltage charging to half-full electricity, complete the use pre-treatment work of the battery of embodiment 3.
Comparative example
(1) positive plate 10 is prepared
The dimethylacetylamide of 18g, the polyvinylidene fluoride of 1.3g are added in size making pot, adopts two speed combination mixer, under high speed 1800r/min, at a slow speed 37.5r/min condition, stir 30min, obtained first mixture.
Add the conduction charcoal of 0.85g, adopt two speed combination mixer, under high speed 1800r/min, at a slow speed 35r/min condition, stir 60min, obtained second mixture.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Add the lithium nickelate of 98g, adopt single rotating speed mixer, rotating speed controls at 2000r/min, stirs 140min, obtained anode sizing agent.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Anode sizing agent is filtered by 150 mesh filter screens.
Under 110 DEG C of conditions, the plus plate current-collecting body 110 anode sizing agent being coated in 12.5 μm forms positive-active layer 130, and coating speed controls at 8.5m/min.
(2) negative plate is prepared
By the acetylene black of black for the stone of 94g carbon, 1.6g, the sodium carboxymethylcellulose of 1.5g, the deionized water of 85g, mix and blend 300min, speed of agitator controls at 2000r/min.
Add the polyvinyl alcohol of 4g, stir 60min, speed of agitator controls at 2000r/min, obtained cathode size.
Size making pot is vacuumized, keeps vacuum degree in pot between-0.08 ~-0.1MPa, to continue to vacuumize 30min.
Cathode size is filtered by 150 mesh filter screens.
Under 88 DEG C of conditions, negative current collector cathode size being coated in 9 μm forms negative electrode active layer, and coating speed controls at 8.5m/min.
(3) battery is prepared
Positive plate 10 and negative plate are suppressed by roll squeezer, make the thickness of positive plate 10 be 150 ± 2 μm, the thickness of negative plate is 165 ± 2 μm.
Positive plate 10 carries out cutting process, makes wide 57.4mm, long 420mm; Negative plate carries out cutting process, makes the wide 59.5mm of negative plate, long 590mm.
The positive plate 10 cut, negative plate puts into baking oven respectively dries.
With up-coiler, positive plate 10, barrier film and negative plate are wound into battery core in order, the diameter control of battery core is at 17.47mm, and barrier film adopts PP material.
The battery core spooled is loaded housing, in housing, injects electrolyte, cover block, with sealing machine, encapsulation process is carried out to housing, the battery of obtained comparative example.
After battery is shelved 12h, first with 0.2C constant-current constant-voltage charging 500min, then battery is shelved 72h in 45 DEG C of environment.After battery is cooled to normal temperature, first with 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.01C, then with 0.2C constant-current discharge to 3V, then with 0.5C constant-current constant-voltage charging to half-full electricity, complete the use pre-treatment work of the battery of comparative example.
The electric performance test of embodiment 3 and comparative example the results are shown in following table.
| Embodiment 3 | Comparative example |
| Same proportioning capacity | 2581mAh | 2558mAh |
| Cycle-index | 300 | 300 |
| Capability retention | 94.69％ | 93.15％ |
Under 25 DEG C of test conditions, same proportioning, same method of testing, embodiment 3 capacity is 2581mAh, and the capacity of comparative example is 2558mAh, and namely embodiment 3 capacity promotes to some extent.
Refer to Fig. 4, embodiment 3 and comparative example circulate after 300 times simultaneously under 25 DEG C of normal temperature conditions, its capability retention is respectively 94.69%, 93.15%, adopts the cycle performance of cycle performance higher than the lithium ion battery of comparative example of the lithium ion battery of carbon nano-tube.
Can find out from contrast test, when other factors are identical, adopt the lithium ion battery of carbon nano-tube and adopt the lithium ion battery of conventional conductive agent, capacitance has larger lifting, and cycle performance is better, and therefore capability retention is also higher.
Because carbon nano-tube conductive is good, its tubular structure there will not be and caves in, therefore compared with conventional conductive agent in repeated charge process, carbon nano-tube effectively can not only improve the cycle performance of battery, can also the internal resistance of cell be reduced, reduce polarization, improve the security performance of battery.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a based lithium-ion battery positive plate, it is characterized in that, comprise plus plate current-collecting body and be coated in the positive-active layer of described anode collection surface, comprise the positive electrode active materials of the positive electrode binder of 0.9 ~ 1.5 part, the carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts by the material of positive-active layer described in mass fraction.
2. based lithium-ion battery positive plate according to claim 1, it is characterized in that, described positive electrode binder is selected from the one in polyvinylidene fluoride and polytetrafluoroethylene, and described positive electrode active materials is selected from least one in LiFePO4, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate and nickel cobalt lithium aluminate.
3. a preparation method for based lithium-ion battery positive plate, is characterized in that, comprises the steps:
According to mass fraction, the described positive electrode active materials of the positive pole solvent of 16 ~ 20 parts, the described positive electrode binder of 0.9 ~ 1.5 part, the described carbon nano-tube of 0.6 ~ 1 part and 90 ~ 100 parts is mixed obtained anode sizing agent;
Described anode sizing agent is coated on described plus plate current-collecting body and forms described positive-active layer, after drying, obtain described based lithium-ion battery positive plate.
4. the preparation method of based lithium-ion battery positive plate according to claim 3, is characterized in that, the preparation method of described anode sizing agent specifically comprises the steps:
By described positive pole solvent and obtained first mixture of described positive electrode binder mix and blend;
Described carbon nano-tube is added in described first mixture and also stirs obtained second mixture;
Remove the bubble in described second mixture;
Described positive electrode active materials is added in described second mixture and also stirs obtained described anode sizing agent;
Remove the bubble in described anode sizing agent;
Described anode sizing agent is filtered.
5. the preparation method of based lithium-ion battery positive plate according to claim 3, is characterized in that, described anode sizing agent, under 100 ~ 140 DEG C of conditions, is coated on described plus plate current-collecting body with the speed of 8 ~ 10m/min.
6. a lithium ion battery, is characterized in that, comprises the based lithium-ion battery positive plate described in negative plate, barrier film and claim 1 or 2, and described negative plate, described barrier film and described based lithium-ion battery positive plate stack gradually winding.
7. lithium ion battery according to claim 6, it is characterized in that, described negative plate comprises negative current collector and is coated in the negative electrode active layer of described negative pole currect collecting surface, comprises the water of the negative active core-shell material of 90 ~ 95 parts, the cathode conductive agent of 1 ~ 2 part, the negative pole dispersant of 1 ~ 2 part, the negative electrode binder of 3 ~ 5 parts and 80 ~ 90 parts by the material of negative electrode active layer described in mass fraction.
8. lithium ion battery according to claim 7, it is characterized in that, described negative active core-shell material is selected from least one in the black carbon of stone, the black alkene of stone and silicon-carbon, described cathode conductive agent is acetylene black, described negative pole dispersant is sodium carboxymethylcellulose, and described negative electrode binder is selected from least one in polyvinyl alcohol and polytetrafluoroethylene.
9. lithium ion battery according to claim 7, is characterized in that, described negative electrode active layer, under 60 ~ 100 DEG C of conditions, is coated on described negative current collector with the speed of 8 ~ 10m/min.
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Effective date of registration: 20170601 Address after: 518119 Beek Industrial Zone, Kwai Chung street, Dapeng New District, Guangdong, Shenzhen Applicant after: SHENZHEN BAK BATTERY CO., LTD. Address before: Kwai Chung street Beek Industrial Park in Longgang District of Shenzhen City, Guangdong province 518119 Applicant before: Shenzhen Bak Battery Co., Ltd. |
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